U.S. patent application number 14/923991 was filed with the patent office on 2018-01-25 for shampoo composition comprising low viscosity emulsified silicone polymers.
The applicant listed for this patent is The Procter & Gamble Company. Invention is credited to Joseph Harry Jansen, Michael Albert Snyder, Roland Wagner, Martha Janie Weaver.
Application Number | 20180021236 14/923991 |
Document ID | / |
Family ID | 52133212 |
Filed Date | 2018-01-25 |
United States Patent
Application |
20180021236 |
Kind Code |
A1 |
Snyder; Michael Albert ; et
al. |
January 25, 2018 |
SHAMPOO COMPOSITION COMPRISING LOW VISCOSITY EMULSIFIED SILICONE
POLYMERS
Abstract
A shampoo composition including (a) a silicone polymer including
(i) one or more quaternary groups; (ii) at least one silicone block
comprising greater than 200 siloxane units; (iii) at least one
polyalkylene oxide structural unit; and (iv) at least one terminal
ester group, and (b) a detersive surfactant. The silicone polymer
has a viscosity of up to 100,000 mPas. The silicone polymer is a
pre-emulsified dispersion with a particle size of less than about 1
micron.
Inventors: |
Snyder; Michael Albert;
(Mason, OH) ; Jansen; Joseph Harry; (Harrison,
OH) ; Wagner; Roland; (Bonn, DE) ; Weaver;
Martha Janie; (Cincinnati, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
|
Family ID: |
52133212 |
Appl. No.: |
14/923991 |
Filed: |
October 27, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
14039886 |
Sep 27, 2013 |
9198849 |
|
|
14923991 |
|
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Current U.S.
Class: |
510/122 |
Current CPC
Class: |
A61K 8/893 20130101;
A61K 8/585 20130101; A61K 8/894 20130101; A61Q 5/02 20130101; A61K
8/898 20130101 |
International
Class: |
A61K 8/58 20060101
A61K008/58; A61K 8/893 20060101 A61K008/893; A61K 8/894 20060101
A61K008/894; A61K 8/898 20060101 A61K008/898; A61Q 5/02 20060101
A61Q005/02 |
Claims
1. A shampoo composition comprising: a) a silicone polymer
comprising: i. one or more quaternary groups; ii. at least one
silicone block comprising greater than 200 siloxane units; iii. at
least one polyalkylene oxide structural unit; and iv. at least one
terminal ester group wherein said silicone polymer has a viscosity
of from 500 mPas to 100,000 mPas; and b) a detersive
surfactant.
2. The shampoo composition of claim 1, wherein said silicone block
comprises from about 300 to about 600 siloxane units.
3. The shampoo composition of claim 1, wherein said silicone
polymer is present in an amount of from about 0.05% to about 15% by
weight of the composition.
4. The shampoo composition of claim 1, wherein said silicone
polymer is present in an amount of from about 0.1% to about 10% by
weight of the composition.
5. The shampoo composition of claim 1, wherein said silicone
polymer is present in an amount of from about 0.15% to about 5% by
weight of the composition.
6. The shampoo composition of claim 1, wherein said silicone
polymer is defined by the following chemical structure:
M-Y-[--(N.sup.+R.sub.2-T-N.sup.+R.sub.2)--Y-].sub.m-[--(NR.sup.2-A-E-A'-N-
R.sup.2)--Y-].sub.k-M (Ia) wherein: m is an average value of from
above 0 to 100 k is an average value of from above 0 to 50 M
represents a terminal group, comprising terminal ester groups
selected from --OC(O)--Z --OS(O).sub.2--Z --OS(O.sub.2)O--Z
--OP(O)(O--Z)OH --OP(O)(O--Z).sub.2 wherein Z is selected from
monovalent organic residues having up to 40 carbon atoms, wherein A
and A' each are independently selected from a single bond or a
divalent organic group having up to 10 carbon atoms and one or more
hetero atoms, and E is a polyalkylene oxide group of the general
formula:
--[CH.sub.2CH.sub.2O].sub.q--[CH.sub.2CH(CH.sub.3)O].sub.r--[CH.sub.2CH(C-
.sub.2H.sub.5)O].sub.s-- with q=0 to 200, r=0 to 200, s=0 to 200,
and q+r+s=1 to 600, R is selected from monovalent organic groups
having up to 22 carbon atoms and optionally one or more
heteroatoms, and wherein the free valencies at the nitrogen atoms
are bound to carbon atoms, R.sup.2 is selected from hydrogen or R,
Y is a group of the formula: --K--S--K-- and -A-E-A'- or -A'-E-A-,
with ##STR00018## wherein R.sup.1=C.sub.1-C.sub.22-alkyl,
C.sub.1-C.sub.22-fluoralkyl or aryl, n=200 to 1000, K is a bivalent
or trivalent straight chain, cyclic and/or branched
C.sub.2-C.sub.40 hydrocarbon residue which is optionally
interrupted by --O--, --NH--, trivalent N, --NR.sup.1--, --C(O)--,
--C(S)--, and optionally substituted with --OH, wherein T is
selected from a divalent organic group having up to 20 carbon atoms
and one or more hetero atoms.
7. The shampoo composition of claim 6, wherein the K residues in
said --K--S--K-- moiety are identical or different, and are bound
to the silicon atom of the residue S via a C--Si-bond.
8. The shampoo composition of claim 1, wherein said silicone
polymer is defined by the following chemical structure:
M-Y-[--(N.sup.+R.sub.2-T-N.sup.+R.sub.2)--Y-].sub.m-[--(N.sup.+R.sup.2.su-
b.2-A-E-A'-N.sup.+R.sup.2.sub.2)--Y-].sub.k-M (Ib) wherein: m is an
average value of from above 0 to 100 k is an average value of from
above 0 to 50 M represents a terminal group, comprising terminal
ester groups selected from --OC(O)--Z --OS(O).sub.2--Z
--OS(O.sub.2)O--Z --OP(O)(O--Z)OH --OP(O)(O--Z).sub.2 wherein Z is
selected from monovalent organic residues having up to 40 carbon
atoms, wherein A and A' each are independently selected from a
single bond or a divalent organic group having up to 10 carbon
atoms and one or more hetero atoms, and E is a polyalkylene oxide
group of the general formula:
--[CH.sub.2CH.sub.2O].sub.q--[CH.sub.2CH(CH.sub.3)O].sub.r--[CH.sub.2CH(C-
.sub.2H.sub.5)O].sub.s-- with q=0 to 200, r=0 to 200, s=0 to 200,
and q+r+s=1 to 600, R is selected from monovalent organic groups
having up to 22 carbon atoms and optionally one or more
heteroatoms, and wherein the free valencies at the nitrogen atoms
are bound to carbon atoms, R.sup.2 is selected from hydrogen or R,\
Y is a group of the formula: K--S--K-- and -A-E-A'- or -A'-E-A-,
with ##STR00019## wherein R.sup.1=C.sub.1-C.sub.22-alkyl,
C.sub.1-C.sub.22-fluoralkyl or aryl, n=200 to 1000, K is a bivalent
or trivalent straight chain, cyclic and/or branched
C.sub.2-C.sub.40 hydrocarbon residue which is optionally
interrupted by --O--, --NH--, trivalent N, --NR.sup.1--, --C(O)--,
--C(S)--, and optionally substituted with --OH, wherein T is
selected from a divalent organic group having up to 20 carbon atoms
and one or more hetero atoms.
9. The shampoo composition of claim 8, wherein the K residues in
said --K--S--K-- moiety are identical or different, and are bound
to the silicon atom of the residue S via a C--Si-bond.
10. The shampoo composition of claim 8 wherein: m is >0 to 10, k
is >0 to 10, M is --OC(O)--Z, Z is hydrocarbon chain with 0 to
40 carbons q=0-50, r=0-50, q+r is at least 1, s=0, R.sup.2 is
methyl n=300-500
11. The shampoo composition of claim 1, wherein said silicone
polymer has a viscosity of from 500 to 50,000 mPas.
12. The shampoo composition of claim 1, wherein said silicone
polymer has a viscosity of from 500 to 5000 mPas.
13. The shampoo composition of claim 1, wherein said detersive
surfactant is present in an amount of from about 0.5% to about 20%
by weight of the composition.
14. The shampoo composition of claim 1, wherein said silicone
polymer is a pre-emulsified dispersion with a particle size of 0.05
.mu.m to 1 .mu.m.
15. The shampoo composition of claim 1, wherein said silicone
polymer is a pre-emulsified dispersion with a particle size of 0.1
.mu.m to 0.5 .mu.m.
16. The shampoo composition of claim 1, wherein said at least one
silicone block comprises from 300 siloxane united to 500 siloxane
units.
17. The shampoo composition of claim 1, wherein said at least one
silicone block comprises from 200 siloxane united to 500 siloxane
units.
17. The shampoo composition of claim 1 further comprising an
anti-dandruff particulate.
18. A method of providing improved cleaning and conditioning
benefits to hair and/or skin, said method comprising the step of
washing said hair and/or skin with said shampoo composition of
claim 1.
Description
FIELD OF THE INVENTION
[0001] Provided is a shampoo composition comprising (1) a silicone
polymer containing quaternary groups and silicone blocks linked to
alkylene oxides (e.g., ethylene oxide and/or propylene oxide),
wherein the silicone polymer has a viscosity of up to 100,000 mPas,
wherein the silicone polymer is a pre-emulsified dispersion with a
particle size of less than about 1 micron; and (2) a detersive
surfactant.
BACKGROUND OF THE INVENTION
[0002] Silicone polymers are strategically important materials in
hair care, especially in providing conditioning benefits to hair.
Human hair becomes damaged due to, for example, combing, permanent
waves, and/or coloring the hair. Such damaged hair is often left
hydrophilic and/or in a rough condition especially when the hair
dries, compared to non-damaged or less damaged hair. Silicone
polymers consisting of blocks of silicones and alkylene oxide
(e.g., ethylene oxide and propylene oxide groups (EO/PO)) linked
with amine- and quat-functional groups have been used to counteract
the hydrophilic nature of damaged hair. Silicone blocks are
responsible for conditioning and lubrication performance while
amine- and quat-functional groups included in the polymer chain
further aid deposition during rinsing. In particular, optimum
conditioning performance has been observed for silicone blocks of
greater than 200 D units. However these materials generally have
high viscosities as neat materials. In order to achieve the desired
conditioning benefits, these silicone polymers have traditionally
been used in blends with silicone copolyols or other diluents or
solvents.
[0003] Based on the foregoing, there is a need a shampoo
composition which provides even greater improved conditioning
benefits such as smooth feel and reduced friction on wet hair and
dry hair. In addition, there is a need for a shampoo composition
which provides improved conditioning benefits on damaged hair.
SUMMARY OF THE INVENTION
[0004] According to an embodiment of the invention, there is
provided a shampoo composition comprising (a) a silicone polymer
comprising: (i) one or more quaternary groups; (ii) at least one
silicone block comprising greater than 200 siloxane units; (iii) at
least one polyalkylene oxide structural unit; and (iv) at least one
terminal ester group, wherein said silicone polymer has a viscosity
of up to 100,000 mPas, wherein said silicone polymer is a
pre-emulsified dispersion with a particle size of less than about 1
micron; and (b) a detersive surfactant.
[0005] According to another embodiment of the invention, there is
provided a method of providing improved cleaning and conditioning
benefits to hair and/or skin, the method comprising the step of
washing said hair and/or skin with a shampoo composition comprising
(a) a silicone polymer comprising: (i) one or more quaternary
groups; (ii) at least one silicone block comprising greater than
200 siloxane units; (iii) at least one polyalkylene oxide
structural unit; and (iv) at least one terminal ester group,
wherein said silicone polymer has a viscosity of up to 100,000
mPas; and (b) a detersive surfactant.
[0006] These and other features, aspects, and advantages of the
invention will become evident to those skilled in the art from a
reading of the following disclosure.
DETAILED DESCRIPTION OF THE INVENTION
[0007] While the specification concludes with claims which
particularly point out and distinctly claim the invention, it is
believed that the provided invention will be better understood from
the following description.
[0008] In all embodiments of the provided invention, all
percentages are by weight of the total composition, unless
specifically stated otherwise. All ratios are weight ratios, unless
specifically stated otherwise. The number of significant digits
conveys neither a limitation on the indicated amounts nor on the
accuracy of the measurements. All numerical amounts are understood
to be modified by the word "about" unless otherwise specifically
indicated. Unless otherwise indicated, all measurements are
understood to be made at about 25.degree. C. and at ambient
conditions, wherein "ambient conditions" means conditions under
about one atmosphere of pressure and at about 50% relative
humidity. All such weights as they pertain to listed ingredients
are based on the active level and do not include carriers or
by-products that may be included in commercially available
materials, unless otherwise specified.
[0009] The term "comprising," as used herein, means that other
steps and other ingredients which do not affect the end result can
be added. This term encompasses the terms "consisting of" and
"consisting essentially of." The processes of the provided
invention can comprise, consist of, and consist essentially of the
elements and limitations of the invention described herein, as well
as any of the additional or optional ingredients, components,
steps, or limitations described herein.
A. Silicone Polymer Containing Quaternary Groups
[0010] The compositions of the present invention comprise a low
viscosity silicone polymer having a viscosity up to 100,000 mPas.
Without being bound by theory, this low viscosity silicone polymer
provides improved conditioning benefits over conventional silicones
because of the addition of hydrophobic functionalities--quaternary
amines, ethylene oxides/propylene oxides. Compared to previously
disclosed silicones with quaternary functionality, these new
structures are significantly lower in viscosity, so that they don't
have to be blended with other lower viscosity diluents and
dispersants to allow them to be formulated into products. Low
viscosity silicone solvents and diluents can often cause viscosity
and stability tradeoffs in shampoo products. The current invention
eliminates the need for these materials since the silicone polymer
is low enough in viscosity to be added directly or in emulsion
form. The improved conditioning benefits include smooth feel,
reduced friction, and prevention of hair damage, while, in some
embodiments, eliminating the need for a silicone blend.
[0011] Structurally, the silicone polymer is a polyorganosiloxane
compound comprising one or more quaternary ammonium groups, at
least one silicone block comprising greater than 200 siloxane
units, at least one polyalkylene oxide structural unit, and at
least one terminal ester group. In one or more embodiments, the
silicone block may comprise between 300 to 500 siloxane units.
[0012] The silicone polymer is present in an amount of from about
0.05% to about 15%, preferably from about 0.1% to about 10%, more
preferably from about 0.15% to about 5%, and even more preferably
from about 0.2% to about 4% by weight of the composition.
[0013] In a preferred embodiment the polyorganosiloxane compounds
according to the invention have the general formulas (Ia) and
(Ib):
M-Y-[--(N.sup.+R.sub.2-T-N.sup.+R.sub.2)--Y-].sub.m-[--(NR.sup.2-A-E-A'--
NR.sup.2)--Y-].sub.k-M (Ia)
M-Y-[--(N.sup.+R.sub.2-T-N.sup.+R.sub.2)--Y-].sub.m-[--(N.sup.+R.sup.2.s-
ub.2-A-E-A'-N.sup.+R.sup.2.sub.2)--Y-].sub.k-M (Ib)
wherein: [0014] m is >0, preferred 0.01 to 100, more preferred
0.1 to 100, even more preferred 1 to 100, specifically 1 to 50,
more specifically 1 to 20, even more specifically 1 to 10, [0015] k
is 0 or an average value of from >0 to 50, or preferably from 1
to 20, or even more preferably from 1 to 10, [0016] M represents a
terminal group, comprising terminal ester groups selected from
[0017] --OC(O)--Z [0018] --OS(O).sub.2--Z [0019] --OS(O.sub.2)O--Z
[0020] --OP(O)(O--Z)OH [0021] --OP(O)(O--Z).sub.2 [0022] wherein Z
is selected from monovalent organic residues having up to 40 carbon
atoms, optionally comprising one or more hetero atoms; [0023] A and
A' each are independently from each other selected from a single
bond or a divalent organic group having up to 10 carbon atoms and
one or more hetero atoms, and [0024] E is a polyalkylene oxide
group of the general formula:
[0024]
--[CH.sub.2CH.sub.2O].sub.q--[CH.sub.2CH(CH.sub.3)O].sub.r--[CH.s-
ub.2CH(C.sub.2H.sub.5)O].sub.s-- [0025] wherein q=0 to 200, r=0 to
200, s=0 to 200, and q+r+s=1 to 600. [0026] R.sup.2 is selected
from hydrogen or R, [0027] R is selected from monovalent organic
groups having up to 22 carbon atoms and optionally one or more
heteroatoms, and wherein the free valencies at the nitrogen atoms
are bound to carbon atoms, [0028] Y is a group of the formula:
[0028] --K--S--K-- and -A-E-A'- or -A'-E-A-, [0029] with
[0029] ##STR00001## [0030] wherein R1=C.sub.1-C.sub.22-alkyl,
C.sub.1-C.sub.22-fluoralkyl or aryl; n=200 to 1000, and these can
be identical or different if several S Groups are present in the
polyorganosiloxane compound; [0031] K is a bivalent or trivalent
straight chain, cyclic and/or branched C.sub.2-C.sub.40 hydrocarbon
residue which is optionally interrupted by --O--, --NH--, trivalent
N, --NR.sup.1--, --C(O)--, --C(S)--, and optionally substituted
with --OH, wherein R.sup.1 is defined as above, [0032] T is
selected from a divalent organic group having up to 20 carbon atoms
and one or more hetero atoms.
[0033] The residues K may be identical or different from each
other. In the --K--S--K-- moiety, the residue K is bound to the
silicon atom of the residue S via a C--Si-bond.
[0034] Due to the possible presence of amine groups
(--(NR.sup.2-A-E-A'-NR.sup.2)--) in the polyorganosiloxane
compounds, they may have protonated ammonium groups, resulting from
the protonation of such amine groups with organic or inorganic
acids. Such compounds are sometimes referred to as acid addition
salts of the polyorganosiloxane compounds according to the
invention.
[0035] In a preferred embodiment the molar ratio of the quaternary
ammonium groups b) and the terminal ester groups c) is less than
100:20, even more preferred is less than 100:30 and is most
preferred less than 100:50. The ratio can be determined by
.sup.13C-NMR.
[0036] In a further embodiment, the polyorganosiloxane composition
may comprise: (A) at least one polyorganosiloxane compound,
comprising (i) at least one polyorganosiloxane group, (ii) at least
one quaternary ammonium group, (iii) at least one terminal ester
group, and (iv) at least one polyalkylene oxide group (as defined
before); and (B) at least one polyorganosiloxane compound,
comprising at least one terminal ester group, different from
compound (A).
[0037] In the definition of component (A) it can be referred to the
description of the polyorganosiloxane compounds of the invention.
The polyorganosiloxane compound (B) differs from the
polyorganosiloxane compound (A) preferably in that it does not
comprise quaternary ammonium groups. Preferred polyorganosiloxane
compounds (B) result from the reaction of monofunctional organic
acids, in particular carboxylic acids, and polyorganosiloxane
containing bisepoxides.
[0038] In the polyorganosiloxane compositions according to the
invention the weight ratio of compound (A) to compound (B) is
preferably less than 90:10. Or in other words, the content of
component (B) is at least 10 weight percent. In a further preferred
embodiment of the polyorganosiloxane compositions according to the
invention in compound (A) the molar ratio of the quaternary
ammonium groups (ii) and the terminal ester groups (iii) is less
than 100:10, even more preferred is less than 100:15 and is most
preferred less than 100:20.
[0039] The silicone polymer has a viscosity at 20.degree. C. and a
shear rate of 0.1 s.sup.-1 (plate-plate system, plate diameter 40
mm, gap width 0.5 mm) of less than 100,000 mPas (100 Pas). In
further embodiments, the viscosities of the neat silicone polymers
may range from 500 to 100,000 mPas, or preferably from 500 to
70,000 mPas, or more preferably from 500 to 50,000 mPas, or even
more preferably from 500 to 20,000 mPas. In further embodiments,
the viscosities of the neat polymers may range from 500 to 10,000
mPas, or preferably 500 to 5000 mPas determined at 20.degree. C.
and a shear rate of 0.1 s.sup.-1.
[0040] In addition to the above listed silicone polymers, preferred
embodiments are provided below. For example, in the polyalkylene
oxide group E of the general formula:
--[CH.sub.2CH.sub.2O].sub.q--[CH.sub.2CH(CH.sub.3)O].sub.r--[CH.sub.2CH(-
C.sub.2H.sub.5)O].sub.s-- [0041] wherein the q, r, and s indices
may be defined as follows: [0042] q=0 to 200, or preferably from 0
to 100, or more preferably from 0 to 50, or even more preferably
from 0 to 20, [0043] r=0 to 200, or preferably from 0 to 100, or
more preferably from 0 to 50, or even more preferably from 0 to 20,
[0044] s=0 to 200, or preferably from 0 to 100, or more preferably
from 0 to 50, or even more preferably from 0 to 20, [0045] and
q+r+s=1 to 600, or preferably from 1 to 100, or more preferably
from 1 to 50, or even more preferably from 1 to 40.
[0046] For polyorganosiloxane structural units with the general
formula S:
##STR00002##
R.sup.1=C.sub.1-C.sub.22-alkyl, C.sub.1-C.sub.22-fluoralkyl or
aryl; n=from 200 to 1000, or preferably from 300 to 500, K (in the
group --K--S--K--) is preferably a bivalent or trivalent straight
chain, cyclical or branched C.sub.2-C.sub.20 hydrocarbon residue
which is optionally interrupted by --O--, --NH--, trivalent N,
--NR.sup.1--, --C(O)--, --C(S)--, and optionally substituted with
--OH.
[0047] In specific embodiments, R.sup.1 is C.sub.1-C.sub.18 alkyl,
C.sub.1-C.sub.18 fluoroalkyl and aryl. Furthermore, R.sup.1 is
preferably C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.6 fluoroalkyl and
aryl. Furthermore, R.sup.1 is more preferably C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 fluoroalkyl, even more preferably
C.sub.1-C.sub.4 fluoroalkyl, and phenyl. Most preferably, R.sup.1
is methyl, ethyl, trifluoropropyl and phenyl.
[0048] As used herein, the term "C.sub.1-C.sub.22 alkyl" means that
the aliphatic hydrocarbon groups possess from 1 to 22 carbon atoms
which can be straight chain or branched. Methyl, ethyl, propyl,
n-butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, isopropyl,
neopentyl and 1,2,3-trimethyl hexyl moieties serve as examples.
[0049] Further as used herein, the term "C.sub.1-C.sub.22
fluoroalkyl" means aliphatic hydrocarbon compounds with 1 to 22
carbon atoms which can be straight chain or branched and are
substituted with at least one fluorine atom. Monofluormethyl,
monofluoroethyl, 1,1,1-trifluorethyl, perfluoroethyl,
1,1,1-trifluoropropyl, 1,2,2-trifluorobutyl are suitable
examples.
[0050] Moreover, the term "aryl" means unsubstituted or phenyl
substituted once or several times with OH, F, Cl, CF.sub.3,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.7
cycloalkyl, C.sub.2-C.sub.6 alkenyl or phenyl. Aryl may also mean
naphthyl.
[0051] For the embodiments of the polyorganosiloxanes, the positive
charges resulting from the ammonium group(s), are neutralized with
inorganic anions such as chloride, bromide, hydrogen sulfate,
sulfate, or organic anions, like carboxylates deriving from
C.sub.1-C.sub.30 carboxylic acids, for example acetate, propionate,
octanoate, especially from C.sub.10-C.sub.18 carboxylic acids, for
example decanoate, dodecanoate, tetradecanoate, hexadecanoate,
octadecanoate and oleate, alkylpolyethercarboxylate,
alkylsulphonate, arylsulphonate, alkylarylsulphonate,
alkylsulphate, alkylpolyethersulphate, phosphates derived from
phosphoric acid mono alkyl/aryl ester and phosphoric acid
dialkyl/aryl ester. The properties of the polyorganosiloxane
compounds can be, inter alia, modified based upon the selection of
acids used.
[0052] The quaternary ammonium groups are usually generated by
reacting the di-tertiary amines with an alkylating agents, selected
from in particular di-epoxides (sometimes referred to also as
bis-epoxides) in the presence of mono carboxylic acids and
difunctional dihalogen alkyl compounds.
[0053] In a preferred embodiment the polyorganosiloxane compounds
are of the general formulas (Ia) and (Ib):
M-Y-[--(N.sup.+R.sub.2-T-N.sup.+R.sub.2)--Y-].sub.m-[--(NR.sup.2-A-E-A'--
NR.sup.2)--Y-].sub.k-M (Ia)
M-Y-[--(N.sup.+R.sub.2-T-N.sup.+R.sub.2)--Y-].sub.m-[--(N.sup.+R.sup.2.s-
ub.2-A-E-A'-N.sup.+R.sup.2.sub.2)--Y-].sub.k-M (Ib) [0054] wherein
each group is as defined above; however, the repeating units are in
a [0055] statistical arrangement (i.e., not a block-wise
arrangement).
[0056] In a further preferred embodiment the polyorganosiloxane
compounds may be also of the general formulas (IIa) or (IIb):
M-Y-[-(--N.sup.+R.sub.2--Y-].sub.m-[--(NR.sup.2-A-E-A'-NR.sup.2)--Y-].su-
b.k-M (IIa)
M-Y-[-(--N.sup.+R.sub.2--Y-].sub.m-[--(N.sup.+R.sup.2.sub.2-A-E-A'-N.sup-
.+R.sup.2.sub.2)--Y-].sub.k-M (IIb) [0057] wherein each group is as
defined above. Also in such formula the repeating units are usually
in a statistical arrangement (i.e not a block-wise arrangement).
[0058] wherein, as defined above, M is [0059] --OC(O)--Z, [0060]
--OS(O).sub.2--Z [0061] --OS(O.sub.2)O--Z [0062] --OP(O)(O--Z)OH
[0063] --OP(O)(O--Z).sub.2 [0064] Z is a straight chain, cyclic or
branched saturated or unsaturated C.sub.1-C.sub.20, or preferably
C.sub.2 to C.sub.18, or even more preferably a hydrocarbon radical,
which can be interrupted by one or more --O--, or --C(O)-- and
substituted with --OH. In a specific embodiment, M is --OC(O)--Z
resulting from normal carboxylic acids in particular with more than
10 carbon atoms like for example dodecanoic acid.
[0065] In a further embodiment, the molar ratio of the
polyorganosiloxane-containing repeating group --K--S--K-- and the
polyalkylene repeating group -A-E-A'- or -A'-E-A- is between 100:1
and 1:100, or preferably between 20:1 and 1:20, or more preferably
between 10:1 and 1:10.
[0066] In the group --(N.sup.+R.sub.2-T-N.sup.+R.sub.2)--, R may
represent a monovalent straight chain, cyclic or branched
C.sub.1-C.sub.20 hydrocarbon radical, which can be interrupted by
one or more --O--, --C(O)-- and can be substituted by --OH, T may
represent a divalent straight-chain, cyclic, or branched
C.sub.1-C.sub.20 hydrocarbon radical, which can be interrupted by
--O--, --C(O)-- and can be substituted by hydroxyl.
[0067] The above described polyorganosiloxane compounds comprising
quaternary ammonium functions and ester functions may also contain:
1) individual molecules which contain quaternary ammonium functions
and no ester functions; 2) molecules which contain quaternary
ammonium functions and ester functions; and 3) molecules which
contain ester functions and no quaternary ammonium functions. While
not limited to structure, the above described polyorganosiloxane
compounds comprising quaternary ammonium functions and ester
functions are to be understood as mixtures of molecules comprising
a certain averaged amount and ratio of both moieties.
[0068] Various monofunctional organic acids may be utilized to
yield the esters. Exemplary embodiments include C.sub.1-C.sub.30
carboxylic acids, for example C.sub.2, C.sub.3, C.sub.8 acids,
C.sub.10-C.sub.18 carboxylic acids, for example C.sub.12, C.sub.14,
C.sub.16 acids, saturated, unsaturated and hydroxyl functionalized
C.sub.18 acids, alkylpolyethercarboxylic acids, alkylsulphonic
acids, arylsulphonic acids, alkylarylsulphonic acids,
alkylsulphuric acids, alkylpolyethersulphuric acids, phosphoric
acid mono alkyl/aryl esters and phosphoric acid dialkyl/aryl
esters.
[0069] Further performance improvements can be achieved by
pre-dispersing the silicone polymer in a small particle emulsion
(less than 1 micron) prior to adding it to the shampoo base.
[0070] The term "emulsion" in this patent application describes any
stable emulsion or dispersion of the silicone polymer, separately
prepared and used as one of the components of a shampoo
composition.
[0071] Stable means that the viscosity, particle size, and other
important characteristics of the emulsion do not significantly
change over reasonable time under exposure to typical temperature,
moisture, pressure, shear, light and other environmental conditions
that the pre-emulsion is exposed during packing, storage, and
transportation
[0072] Making the small particle emulsion may require
pre-emulsifying the silicone polymer before their addition to the
shampoo composition. A non-limiting example of a method of making
is provided below. All oil soluble components are mixed in a
vessel. Heat may be applied to allow mixture to liquidify. All
water soluble components are mixed in a separate vessel and heated
to about same temperature as the oil phase. The oil phase and
aqueous phase are mixed under a high shear mixer (example, Turrax
mixer by IKA) The particle size of the conditioning active is in
the range of 0.01-5 .mu.m, more preferred 0.05-1 .mu.m, most
preferred 0.1-0.5 .mu.m. High energy mixing device may be used to
achieve desired particle size. High energy mixing device include,
but not limited to Microfluidizer from Microfluidics Corp.,
Sonolator from Sonic Corp., Colloid mill from Sonic Corp.
[0073] The emulsifiers which may be selected for each the silicone
may be guided by the Hydrophilic-Lipophilic-Balance value (HLB
value) of emulsifiers. Suitable range of HLB value may be 6-16,
alternatively 8-14. Emulsifiers with a HLB higher than 10 are water
soluble. Emulsifiers with low HLB are lipid soluble. To obtain
suitable HLB value, a mixture of two or more emulsifiers may be
used. Suitable emulsifiers include non-ionic, cationic, anionic and
amphoteric emulsifiers.
[0074] The concentration of the emulsifier in the emulsion should
be sufficient to provide desired the emulsification of the
conditioning active to achieve desired particle size and emulsion
stability, and generally ranges from about 0.1 wt %-about 50 wt %,
from about 1 wt %-about 30 wt %, from about 2 wt %-about 20 wt %,
for example.
[0075] The use of a pre-emulsified dispersion of the silicone may
present multiple advantages including: (i) The small particle size
of the silicones in the emulsion leads to more even deposition and
reduces island-like spotty deposits; and (ii) the more even
deposition is more favorable for providing smoothness for hair/skin
surfaces, easier combing, and enhanced hair volume.
B. Detersive Surfactant
[0076] The shampoo composition of the present invention includes a
detersive surfactant, which provides cleaning performance to the
composition. The detersive surfactant in turn comprises an anionic
surfactant, amphoteric or zwitterionic surfactants, or mixtures
thereof. Various examples and descriptions of detersive surfactants
are set forth in U.S. Pat. No. 6,649,155; U.S. Patent Application
Publication No. 2008/0317698; and U.S. Patent Application
Publication No. 2008/0206355, which are incorporated herein by
reference in their entirety.
[0077] The concentration of the detersive surfactant component in
the shampoo composition should be sufficient to provide the desired
cleaning and lather performance, and generally ranges from about 2
wt % to about 50 wt %, from about 5 wt % to about 30 wt %, from
about 8 wt % to about 25 wt %, or from about 10 wt % to about 20 wt
%. Accordingly, the shampoo composition may comprise a detersive
surfactant in an amount of about 5 wt %, about 10 wt %, about 12 wt
%, about 15 wt %, about 17 wt %, about 18 wt %, or about 20 wt %,
for example.
[0078] Anionic surfactants suitable for use in the compositions are
the alkyl and alkyl ether sulfates. Other suitable anionic
surfactants are the water-soluble salts of organic, sulfuric acid
reaction products. Still other suitable anionic surfactants are the
reaction products of fatty acids esterified with isethionic acid
and neutralized with sodium hydroxide. Other similar anionic
surfactants are described in U.S. Pat. Nos. 2,486,921; 2,486,922;
and 2,396,278, which are incorporated herein by reference in their
entirety.
[0079] Exemplary anionic surfactants for use in the shampoo
composition include ammonium lauryl sulfate, ammonium laureth
sulfate, triethylamine lauryl sulfate, triethylamine laureth
sulfate, triethanolamine lauryl sulfate, triethanolamine laureth
sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth
sulfate, diethanolamine lauryl sulfate, diethanolamine laureth
sulfate, lauric monoglyceride sodium sulfate, sodium lauryl
sulfate, sodium laureth sulfate, potassium lauryl sulfate,
potassium laureth sulfate, sodium lauryl sarcosinate, sodium
lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium
cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate,
sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl
sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl
sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl
sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene
sulfonate, sodium cocoyl isethionate and combinations thereof. In a
further embodiment of the present invention, the anionic surfactant
is sodium lauryl sulfate or sodium laureth sulfate.
[0080] Suitable amphoteric or zwitterionic surfactants for use in
the shampoo composition herein include those which are known for
use in shampoo or other personal care cleansing. Concentrations of
such amphoteric surfactants range from about 0.5 wt % to about 20
wt %, and from about 1 wt % to about 10 wt %. Non limiting examples
of suitable zwitterionic or amphoteric surfactants are described in
U.S. Pat. Nos. 5,104,646 and 5,106,609, which are incorporated
herein by reference in their entirety.
[0081] Amphoteric detersive surfactants suitable for use in the
shampoo composition include those surfactants broadly described as
derivatives of aliphatic secondary and tertiary amines in which the
aliphatic radical can be straight or branched chain and wherein one
of the aliphatic substituents contains from about 8 to about 18
carbon atoms and one contains an anionic group such as carboxy,
sulfonate, sulfate, phosphate, or phosphonate. Exemplary amphoteric
detersive surfactants for use in the present shampoo composition
include cocoamphoacetate, cocoamphodiacetate, lauroamphoacetate,
lauroamphodiacetate, and mixtures thereof.
[0082] Zwitterionic detersive surfactants suitable for use in the
shampoo composition include those surfactants broadly described as
derivatives of aliphatic quaternaryammonium, phosphonium, and
sulfonium compounds, in which the aliphatic radicals can be
straight or branched chain, and wherein one of the aliphatic
substituents contains from about 8 to about 18 carbon atoms and one
contains an anionic group such as carboxy, sulfonate, sulfate,
phosphate or phosphonate. In another embodiment, zwitterionics such
as betaines are selected.
[0083] Non limiting examples of other anionic, zwitterionic,
amphoteric or optional additional surfactants suitable for use in
the compositions are described in McCutcheon's, Emulsifiers and
Detergents, 1989 Annual, published by M. C. Publishing Co., and
U.S. Pat. Nos. 3,929,678, 2,658,072; 2,438,091; 2,528,378, which
are incorporated herein by reference in their entirety.
[0084] In an embodiment, the composition comprises an anionic
surfactant and a non-ionic co-surfactant. In another embodiment the
surfactant system is free, or substantially free of sulfate
materials. Suitable sulfate free surfactants are disclosed in WO
publication 2011/120780 and WO publication 2011/049932.
C. Deposition Polymer
[0085] The shampoo composition may also comprise a cationic
deposition polymer. These cationic deposition polymers can include
at least one of (a) a cationic guar polymer, (b) a cationic
non-guar galactomannan polymer, (c) a cationic tapioca polymer, (d)
a cationic copolymer of acrylamide monomers and cationic monomers,
and/or (e) a synthetic, non-crosslinked, cationic polymer, which
may or may not form lyotropic liquid crystals upon combination with
the detersive surfactant (f) a cationic cellulose polymer.
Additionally, the cationic deposition polymer can be a mixture of
deposition polymers.
[0086] (1) Cationic Guar Polymers
[0087] According to an embodiment of the present invention, the
shampoo composition comprises a cationic guar polymer, which is a
cationically substituted galactomannan (guar) gum derivatives. Guar
gum for use in preparing these guar gum derivatives is typically
obtained as a naturally occurring material from the seeds of the
guar plant. The guar molecule itself is a straight chain mannan,
which is branched at regular intervals with single membered
galactose units on alternative mannose units. The mannose units are
linked to each other by means of .beta.(1-4) glycosidic linkages.
The galactose branching arises by way of an .alpha.(1-6) linkage.
Cationic derivatives of the guar gums are obtained by reaction
between the hydroxyl groups of the polygalactomannan and reactive
quaternary ammonium compounds. The degree of substitution of the
cationic groups onto the guar structure must be sufficient to
provide the requisite cationic charge density described above.
[0088] According to one embodiment, the cationic guar polymer has a
weight average MWt. of less than about 2.5 million g/mol, and has a
charge density of from about 0.05 meq/g to about 2.5 meq/g. In an
embodiment, the cationic guar polymer has a weight average MWt. of
less than 1.5 million g/mol, or from about 150 thousand to about
1.5 million g/mol, or from about 200 thousand to about 1.5 million
g/mol, or from about 300 thousand to about 1.5 million g/mol, or
from about 700,000 thousand to about 1.5 million g/mol. In one
embodiment, the cationic guar polymer has a charge density of from
about 0.2 to about 2.2 meq/g, or from about 0.3 to about 2.0 meq/g,
or from about 0.4 to about 1.8 meq/g; or from about 0.5 meq/g to
about 1.7 meq/g.
[0089] According to one embodiment, the cationic guar polymer has a
weight average MWt. of less than about 1 million g/mol, and has a
charge density of from about 0.1 meq/g to about 2.5 meq/g. In an
embodiment, the cationic guar polymer has a weight average MWt. of
less than 900 thousand g/mol, or from about 150 thousand to about
800 thousand g/mol, or from about 200 thousand to about 700
thousand g/mol, or from about 300 thousand to about 700 thousand
g/mol, or from about 400 thousand to about 600 thousand g/mol. from
about 150 thousand to about 800 thousand g/mol, or from about 200
thousand to about 700 thousand g/mol, or from about 300 thousand to
about 700 thousand g/mol, or from about 400 thousand to about 600
thousand g/mol. In one embodiment, the cationic guar polymer has a
charge density of from about 0.2 to about 2.2 meq/g, or from about
0.3 to about 2.0 meq/g, or from about 0.4 to about 1.8 meq/g; or
from about 0.5 meq/g to about 1.5 meq/g.
[0090] In an embodiment, the composition comprises from about 0.01%
to less than about 0.7%, or from about 0.04% to about 0.55%, or
from about 0.08% to about 0.5%, or from about 0.16% to about 0.5%,
or from about 0.2% to about 0.5%, or from about 0.3% to about 0.5%,
or from about 0.4% to about 0.5%, of cationic guar polymer (a), by
total weight of the composition.
[0091] The cationic guar polymer may be formed from quaternary
ammonium compounds. In an embodiment, the quaternary ammonium
compounds for forming the cationic guar polymer conform to the
general formula 1:
##STR00003##
wherein where R.sup.3, R.sup.4 and R.sup.5 are methyl or ethyl
groups; R.sup.6 is either an epoxyalkyl group of the general
formula 2:
##STR00004##
or R.sup.6 is a halohydrin group of the general formula 3:
##STR00005##
wherein R.sup.7 is a C.sub.1 to C.sub.3 alkylene; X is chlorine or
bromine, and Z is an anion such as Cl--, Br--, I-- or
HSO.sub.4--.
[0092] In an embodiment, the cationic guar polymer conforms to the
general formula 4:
##STR00006##
wherein R.sup.8 is guar gum; and wherein R.sup.4, R.sup.5, R.sup.6
and R.sup.7 are as defined above; and wherein Z is a halogen. In an
embodiment, the cationic guar polymer conforms to Formula 5:
##STR00007##
Suitable cationic guar polymers include cationic guar gum
derivatives, such as guar hydroxypropyltrimonium chloride. In an
embodiment, the cationic guar polymer is a guar
hydroxypropyltrimonium chloride. Specific examples of guar
hydroxypropyltrimonium chlorides include the Jaguar.RTM. series
commercially available from Rhone-Poulenc Incorporated, for example
Jaguar.RTM. C-500, commercially available from Rhodia. Jaguar.RTM.
C-500 has a charge density of 0.8 meq/g and a MWt. of 500,000
g/mole. Jaguar.RTM. C-17, which has a cationic charge density of
about 0.6 meq/g and a MWt. of about 2.2 million g/mol and is
available from Rhodia Company. Jaguar.RTM. C 13S which has a MWt.
of 2.2 million g/mol and a cationic charge density of about 0.8
meq/g (available from Rhodia Company). Other suitable guar
hydroxypropyltrimonium chloride are: guar hydroxypropyltrimonium
chloride which has a charge density of about 1.1 meq/g and a MWt.
of about 500,000 g/mole is available from ASI, a charge density of
about 1.5 meq/g and a MWt. of about 500,000 g/mole is available
from ASI. Other suitable guar hydroxypropyltrimonium chloride are:
Hi-Care 1000, which has a charge density of about 0.7 meq/g and a
MWt. of about 600,000 g/mole and is available from Rhodia; N-Hance
3269 and N-Hance 3270, which has a charge density of about 0.7
meq/g and a MWt. of about 425,000 g/mole and is available from ASI;
N-Hance 3196, which has a charge density of about 0.8 and a M. Wt.
Of about 1,100,000 g/mole and is available from ASI. AquaCat CG518
has a charge density of about 0.9 meq/g and a MWt. of about 50,000
g/mole and is available from ASI. BF-13, which is a borate (boron)
free guar of charge density of about 1.1 meq/g and M. Wt. of about
800,000 and BF-17, which is a borate (boron) free guar of charge
density of about 1.7 meq/g and M. Wt. of about 800,000 both
available from ASI.
[0093] (2) Cationic Non-Guar Galactomannan Polymers
[0094] The shampoo compositions of the present invention may
comprise a galactomannan polymer derivative having a mannose to
galactose ratio of greater than 2:1 on a monomer to monomer basis,
the galactomannan polymer derivative selected from the group
consisting of a cationic galactomannan polymer derivative and an
amphoteric galactomannan polymer derivative having a net positive
charge. As used herein, the term "cationic galactomannan" refers to
a galactomannan polymer to which a cationic group is added. The
term "amphoteric galactomannan" refers to a galactomannan polymer
to which a cationic group and an anionic group are added such that
the polymer has a net positive charge.
[0095] Galactomannan polymers are present in the endosperm of seeds
of the Leguminosae family. Galactomannan polymers are made up of a
combination of mannose monomers and galactose monomers. The
galactomannan molecule is a straight chain mannan branched at
regular intervals with single membered galactose units on specific
mannose units. The mannose units are linked to each other by means
of .beta.(1-4) glycosidic linkages. The galactose branching arises
by way of an .alpha. (1-6) linkage. The ratio of mannose monomers
to galactose monomers varies according to the species of the plant
and also is affected by climate. Non Guar Galactomannan polymer
derivatives of the present invention have a ratio of mannose to
galactose of greater than 2:1 on a monomer to monomer basis.
Suitable ratios of mannose to galactose can be greater than about
3:1, and the ratio of mannose to galactose can be greater than
about 4:1. Analysis of mannose to galactose ratios is well known in
the art and is typically based on the measurement of the galactose
content.
[0096] The gum for use in preparing the non-guar galactomannan
polymer derivatives is typically obtained as naturally occurring
material such as seeds or beans from plants. Examples of various
non-guar galactomannan polymers include but are not limited to Tara
gum (3 parts mannose/1 part galactose), Locust bean or Carob (4
parts mannose/1 part galactose), and Cassia gum (5 parts mannose/1
part galactose).
[0097] In one embodiment of the invention, the non-guar
galactomannan polymer derivatives have a M. Wt. from about 1,000 to
about 10,000,000, and/or form about 5,000 to about 3,000,000.
[0098] The shampoo compositions of the present invention may
include galactomannan polymer derivatives which have a cationic
charge density from about 0.5 meq/g to about 7 meq/g. In one
embodiment of the present invention, the galactomannan polymer
derivatives have a cationic charge density from about 1 meq/g to
about 5 meq/g. The degree of substitution of the cationic groups
onto the galactomannan structure should be sufficient to provide
the requisite cationic charge density.
[0099] In one embodiment of the present invention, the
galactomannan polymer derivative is a cationic derivative of the
non-guar galactomannan polymer, which is obtained by reaction
between the hydroxyl groups of the polygalactomannan polymer and
reactive quaternary ammonium compounds. Suitable quaternary
ammonium compounds for use in forming the cationic galactomannan
polymer derivatives include those conforming to the general
formulas 1-5, as defined above.
[0100] Cationic non-guar galactomannan polymer derivatives formed
from the reagents described above are represented by the general
formula 6:
##STR00008##
wherein R is the gum. The cationic galactomannan derivative can be
a gum hydroxypropyltrimethylammonium chloride, which can be more
specifically represented by the general formula 7:
##STR00009##
[0101] In another embodiment of the invention, the galactomannan
polymer derivative is an amphoteric galactomannan polymer
derivative having a net positive charge, obtained when the cationic
galactomannan polymer derivative further comprises an anionic
group.
[0102] In one embodiment of the invention the cationic non-guar
galactomannan has a ratio of mannose to galactose is greater than
about 4:1, a MWt. of about 100,000 to about 500,000, and/or from
about 150,000 to about 400,000 and a cationic charge density from
about 1 meq/g to about 5 meq/g, and/or from 2 meq/g to about 4
meq/g and is a derived from a cassia plant.
[0103] The shampoo compositions of the present invention may
comprise at least about 0.05% of a galactomannan polymer derivative
by weight of the composition. In one embodiment of the present
invention, the shampoo compositions comprise from about 0.05% to
about 2%, by weight of the composition, of a galactomannan polymer
derivative.
[0104] (3) Cationically Modified Starch Polymer
[0105] The shampoo compositions of the present invention may
comprise water-soluble cationically modified starch polymers. As
used herein, the term "cationically modified starch" refers to a
starch to which a cationic group is added prior to degradation of
the starch to a smaller molecular weight, or wherein a cationic
group is added after modification of the starch to achieve a
desired molecular weight. The definition of the term "cationically
modified starch" also includes amphoterically modified starch. The
term "amphoterically modified starch" refers to a starch
hydrolysate to which a cationic group and an anionic group are
added.
[0106] The shampoo compositions of the present invention may
comprise cationically modified starch polymers at a range of about
0.01% to about 10%, and/or from about 0.05% to about 5%, by weight
of the composition.
[0107] The cationically modified starch polymers disclosed herein
have a percent of bound nitrogen of from about 0.5% to about
4%.
[0108] The cationically modified starch polymers for use in the
shampoo compositions of the present invention may have a molecular
weight from about 850,000 to about 15,000,000 and/or from about
900,000 to about 5,000,000. As used herein, the term "molecular
weight" refers to the weight average molecular weight. The weight
average molecular weight may be measured by gel permeation
chromatography ("GPC") using a Waters 600E HPLC pump and Waters 717
auto-sampler equipped with a Polymer Laboratories PL Gel MIXED-A
GPC column (Part Number 1110-6200, 600.times.7.5 mm, 20 .mu.m) at a
column temperature of 55.degree. C. and at a flow rate of 1.0
ml/min (mobile phase consisting of Dimethylsulfoxide with 0.1%
Lithium Bromide), and using a Wyatt DAWN EOS MALLS (multi-angle
laser light scattering detector) and Wyatt Optilab DSP
(interferometric refractometer) detectors arranged in series (using
a dn/dc of 0.066), all at detector temperatures of 50.degree. C.,
with a method created by using a Polymer Laboratories narrow
dispersed Polysaccharide standard (Mw=47,300), with an injection
volume of 200 .mu.l.
[0109] The shampoo compositions of the present invention may
include cationically modified starch polymers which have a charge
density of from about 0.2 meq/g to about 5 meq/g, and/or from about
0.2 meq/g to about 2 meq/g. The chemical modification to obtain
such a charge density includes, but is not limited to, the addition
of amino and/or ammonium groups into the starch molecules.
Non-limiting examples of these ammonium groups may include
substituents such as hydroxypropyl trimmonium chloride,
trimethylhydroxypropyl ammonium chloride,
dimethylstearylhydroxypropyl ammonium chloride, and
dimethyldodecylhydroxypropyl ammonium chloride. See Solarek, D. B.,
Cationic Starches in Modified Starches: Properties and Uses,
Wurzburg, O. B., Ed., CRC Press, Inc., Boca Raton, Fla. 1986, pp
113-125. The cationic groups may be added to the starch prior to
degradation to a smaller molecular weight or the cationic groups
may be added after such modification.
[0110] The cationically modified starch polymers may have a degree
of substitution of a cationic group from about 0.2 to about 2.5. As
used herein, the "degree of substitution" of the cationically
modified starch polymers is an average measure of the number of
hydroxyl groups on each anhydroglucose unit which is derivatized by
substituent groups. Since each anhydroglucose unit has three
potential hydroxyl groups available for substitution, the maximum
possible degree of substitution is 3. The degree of substitution is
expressed as the number of moles of substituent groups per mole of
anhydroglucose unit, on a molar average basis. The degree of
substitution may be determined using proton nuclear magnetic
resonance spectroscopy (".sup.1H NMR") methods well known in the
art. Suitable .sup.1H NMR techniques include those described in
"Observation on NMR Spectra of Starches in Dimethyl Sulfoxide,
Iodine-Complexing, and Solvating in Water-Dimethyl Sulfoxide",
Qin-Ji Peng and Arthur S. Perlin, Carbohydrate Research, 160
(1987), 57-72; and "An Approach to the Structural Analysis of
Oligosaccharides by NMR Spectroscopy", J. Howard Bradbury and J.
Grant Collins, Carbohydrate Research, 71, (1979), 15-25.
[0111] The source of starch before chemical modification can be
chosen from a variety of sources such as tubers, legumes, cereal,
and grains. Non-limiting examples of this source starch may include
corn starch, wheat starch, rice starch, waxy corn starch, oat
starch, cassaya starch, waxy barley, waxy rice starch, glutenous
rice starch, sweet rice starch, amioca, potato starch, tapioca
starch, oat starch, sago starch, sweet rice, or mixtures
thereof.
[0112] In one embodiment of the present invention, cationically
modified starch polymers are selected from degraded cationic maize
starch, cationic tapioca, cationic potato starch, and mixtures
thereof. In another embodiment, cationically modified starch
polymers are cationic corn starch and cationic tapioca.
[0113] The starch, prior to degradation or after modification to a
smaller molecular weight, may comprise one or more additional
modifications. For example, these modifications may include
cross-linking, stabilization reactions, phosphorylations, and
hydrolyzations. Stabilization reactions may include alkylation and
esterification.
[0114] The cationically modified starch polymers may be
incorporated into the composition in the form of hydrolyzed starch
(e.g., acid, enzyme, or alkaline degradation), oxidized starch
(e.g., peroxide, peracid, hypochlorite, alkaline, or any other
oxidizing agent), physically/mechanically degraded starch (e.g.,
via the thermo-mechanical energy input of the processing
equipment), or combinations thereof.
[0115] An optimal form of the starch may be one which is readily
soluble in water and forms a substantially clear (%
Transmittance.gtoreq.80 at 600 nm) solution in water. The
transparency of the composition is measured by Ultra-Violet/Visible
(UV/VIS) spectrophotometry, which determines the absorption or
transmission of UV/VIS light by a sample, using a Gretag Macbeth
Colorimeter Color i 5 according to the related instructions. A
light wavelength of 600 nm has been shown to be adequate for
characterizing the degree of clarity of cosmetic compositions.
[0116] Suitable cationically modified starch may be available from
known starch suppliers. Also suitable for use in the present
invention is nonionic modified starch that could be further
derivatized to a cationically modified starch as is known in the
art. Other suitable modified starch starting materials may be
quaternized, as is known in the art, to produce the cationically
modified starch polymer suitable for use in the invention.
[0117] (4) Cationic Copolymer of an Acrylamide Monomer and a
Cationic Monomer
[0118] According to an embodiment of the present invention, the
shampoo composition may comprise a cationic copolymer of an
acrylamide monomer and a cationic monomer, wherein the copolymer
has a charge density of from about 1.0 meq/g to about 3.0 meq/g. In
an embodiment, the cationic copolymer is a synthetic cationic
copolymer of acrylamide monomers and cationic monomers.
[0119] In an embodiment, the cationic copolymer comprises: [0120]
(i) an acrylamide monomer of the following Formula AM:
[0120] ##STR00010## [0121] where R.sup.9 is H or C.sub.1-4 alkyl;
and R.sup.10 and R.sup.11 are independently selected from the group
consisting of H, C.sub.1-4 alkyl, CH.sub.2OCH.sub.3,
CH.sub.2OCH.sub.2CH(CH.sub.3).sub.2, and phenyl, or together are
C.sub.3-6cycloalkyl; and [0122] (ii) a cationic monomer conforming
to Formula CM:
##STR00011##
[0122] where k=1, each of v, v', and v'' is independently an
integer of from 1 to 6, w is zero or an integer of from 1 to 10,
and X.sup.- is an anion.
[0123] In an embodiment, cationic monomer conforming to Formula CM
and where k=1, v=3 and w=0, z=1 and X.sup.- is Cl.sup.- to form the
following structure:
##STR00012##
The above structure may be referred to as diquat. In another
embodiment, the cationic monomer conforms to Formula CM and wherein
v and v'' are each 3, v'=1, w=1, y=1 and X.sup.- is Cl.sup.-, such
as:
##STR00013##
The above structure may be referred to as triquat.
[0124] In an embodiment, the acrylamide monomer is either
acrylamide or methacrylamide.
[0125] In an embodiment, the cationic copolymer (b) is AM:TRIQUAT
which is a copolymer of acrylamide and
1,3-Propanediaminium,N-[2-[[[dimethyl[3-[(2-methyl-1-oxo-2-propenyl)amino-
]propyl]ammonio]acetyl]amino]ethyl]2-hydroxy-N,N,N',N'-pentamethyl-,
trichloride. AM:TRIQUAT is also known as polyquarternium 76 (PQ76).
AM:TRIQUAT may have a charge density of 1.6 meq/g and a MWt. of 1.1
million g/mol.
[0126] In an alternative embodiment, the cationic copolymer is of
an acrylamide monomer and a cationic monomer, wherein the cationic
monomer is selected from the group consisting of:
dimethylaminoethyl (meth)acrylate, dimethylaminopropyl
(meth)acrylate, ditertiobutylaminoethyl (meth)acrylate,
dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl
(meth)acrylamide; ethylenimine, vinylamine, 2-vinylpyridine,
4-vinylpyridine; trimethylammonium ethyl (meth)acrylate chloride,
trimethylammonium ethyl (meth)acrylate methyl sulphate,
dimethylammonium ethyl (meth)acrylate benzyl chloride,
4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethyl
ammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl
(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride,
diallyldimethyl ammonium chloride, and mixtures thereof.
[0127] In an embodiment, the cationic copolymer comprises a
cationic monomer selected from the group consisting of: cationic
monomers include trimethylammonium ethyl (meth)acrylate chloride,
trimethylammonium ethyl (meth)acrylate methyl sulphate,
dimethylammonium ethyl (meth)acrylate benzyl chloride,
4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethyl
ammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl
(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride,
and mixtures thereof.
[0128] In an embodiment, the cationic copolymer is water-soluble.
In an embodiment, the cationic copolymer is formed from (1)
copolymers of (meth)acrylamide and cationic monomers based on
(meth)acrylamide, and/or hydrolysis-stable cationic monomers, (2)
terpolymers of (meth)acrylamide, monomers based on cationic
(meth)acrylic acid esters, and monomers based on (meth)acrylamide,
and/or hydrolysis-stable cationic monomers. Monomers based on
cationic (meth)acrylic acid esters may be cationized esters of the
(meth)acrylic acid containing a quaternized N atom. In an
embodiment, cationized esters of the (meth)acrylic acid containing
a quaternized N atom are quaternized dialkylaminoalkyl
(meth)acrylates with C1 to C3 in the alkyl and alkylene groups. In
an embodiment, the cationized esters of the (meth)acrylic acid
containing a quaternized N atom are selected from the group
consisting of: ammonium salts of dimethylaminomethyl
(meth)acrylate, dimethylaminoethyl (meth)acrylate,
dimethylaminopropyl (meth)acrylate, diethylaminomethyl
(meth)acrylate, diethylaminoethyl (meth)acrylate; and
diethylaminopropyl (meth)acrylate quaternized with methyl chloride.
In an embodiment, the cationized esters of the (meth)acrylic acid
containing a quaternized N atom is dimethylaminoethyl acrylate,
which is quaternized with an alkyl halide, or with methyl chloride
or benzyl chloride or dimethyl sulfate (ADAME-Quat). In an
embodiment, the cationic monomer when based on (meth)acrylamides
are quaternized dialkylaminoalkyl(meth)acrylamides with C1 to C3 in
the alkyl and alkylene groups, or dimethylaminopropylacrylamide,
which is quaternized with an alkyl halide, or methyl chloride or
benzyl chloride or dimethyl sulfate.
[0129] In an embodiment, the cationic monomer based on a
(meth)acrylamide is a quaternized dialkylaminoalkyl(meth)acrylamide
with C1 to C3 in the alkyl and alkylene groups. In an embodiment,
the cationic monomer based on a (meth)acrylamide is
dimethylaminopropylacrylamide, which is quaternized with an alkyl
halide, especially methyl chloride or benzyl chloride or dimethyl
sulfate.
[0130] In an embodiment, the cationic monomer is a
hydrolysis-stable cationic monomer. Hydrolysis-stable cationic
monomers can be, in addition to a
dialkylaminoalkyl(meth)acrylamide, all monomers that can be
regarded as stable to the OECD hydrolysis test. In an embodiment,
the cationic monomer is hydrolysis-stable and the hydrolysis-stable
cationic monomer is selected from the group consisting of:
diallyldimethylammonium chloride and water-soluble, cationic
styrene derivatives.
[0131] In an embodiment, the cationic copolymer is a terpolymer of
acrylamide, 2-dimethylammoniumethyl (meth)acrylate quaternized with
methyl chloride (ADAME-Q) and
3-dimethylammoniumpropyl(meth)acrylamide quaternized with methyl
chloride (DIMAPA-Q). In an embodiment, the cationic copolymer is
formed from acrylamide and acrylamidopropyltrimethylammonium
chloride, wherein the acrylamidopropyltrimethylammonium chloride
has a charge density of from about 1.0 meq/g to about 3.0
meq/g.
[0132] In an embodiment, the cationic copolymer has a charge
density of from about 1.1 meq/g to about 2.5 meq/g, or from about
1.1 meq/g to about 2.3 meq/g, or from about 1.2 meq/g to about 2.2
meq/g, or from about 1.2 meq/g to about 2.1 meq/g, or from about
1.3 meq/g to about 2.0 meq/g, or from about 1.3 meq/g to about 1.9
meq/g.
[0133] In an embodiment, the cationic copolymer has a MWt. from
about 100 thousand g/mol to about 2 million g/mol, or from about
300 thousand g/mol to about 1.8 million g/mol, or from about 500
thousand g/mol to about 1.6 million g/mol, or from about 700
thousand g/mol to about 1.4 million g/mol, or from about 900
thousand g/mol to about 1.2 million g/mol.
[0134] In an embodiment, the cationic copolymer is a
trimethylammoniopropylmethacrylamide chloride-N-Acrylamide
copolymer, which is also known as AM:MAPTAC. AM:MAPTAC may have a
charge density of about 1.3 meq/g and a MWt. of about 1.1 million
g/mol. In an embodiment, the cationic copolymer is AM:ATPAC.
AM:ATPAC may have a charge density of about 1.8 meq/g and a MWt. of
about 1.1 million g/mol.
[0135] (5) Cationic Synthetic Polymer
[0136] According to an embodiment of the present invention, the
shampoo composition may comprise a cationic synthetic polymer that
may be formed from
[0137] i) one or more cationic monomer units, and optionally
[0138] ii) one or more monomer units bearing a negative charge,
and/or
[0139] iii) a nonionic monomer,
wherein the subsequent charge of the copolymer is positive. The
ratio of the three types of monomers is given by "m", "p" and "q"
where "m" is the number of cationic monomers, "p" is the number of
monomers bearing a negative charge and "q" is the number of
nonionic monomers
[0140] In one embodiment, the cationic polymers are water soluble
or dispersible, non-crosslinked, synthetic cationic polymers having
the following structure:
##STR00014##
where A, may be one or more of the following cationic moieties:
##STR00015##
where @=amido, alkylamido, ester, ether, alkyl or alkylaryl; where
Y=C1-C22 alkyl, alkoxy, alkylidene, alkyl or aryloxy; where
.psi.=C1-C22 alkyl, alkyloxy, alkyl aryl or alkyl arylox; where
Z=C1-C22 alkyl, alkyloxy, aryl or aryloxy; where R1=H, C1-C4 linear
or branched alkyl; where s=0 or 1, n=0 or .gtoreq.1; where T and
R7=C1-C22 alkyl; and where X--=halogen, hydroxide, alkoxide,
sulfate or alkylsulfate.
[0141] Where the monomer bearing a negative charge is defined by
R2'=H, C1-C4 linear or branched alkyl and R3 as:
##STR00016##
where D=O, N, or S; where Q=NH.sub.2 or O; where u=1-6; where
t=0-1; and where J=oxygenated functional group containing the
following elements P, S, C.
[0142] Where the nonionic monomer is defined by R2''=H, C1-C4
linear or branched alkyl, R6=linear or branched alkyl, alkyl aryl,
aryl oxy, alkyloxy, alkylaryl oxy and .beta. is defined as
##STR00017##
and where G' and G'' are, independently of one another, O, S or
N--H and L=0 or 1.
[0143] Examples of cationic monomers include aminoalkyl
(meth)acrylates, (meth)aminoalkyl (meth)acrylamides; monomers
comprising at least one secondary, tertiary or quaternary amine
function, or a heterocyclic group containing a nitrogen atom,
vinylamine or ethylenimine; diallyldialkyl ammonium salts; their
mixtures, their salts, and macromonomers deriving from
therefrom.
[0144] Further examples of cationic monomers include
dimethylaminoethyl (meth)acrylate, dimethylaminopropyl
(meth)acrylate, ditertiobutylaminoethyl (meth)acrylate,
dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl
(meth)acrylamide, ethylenimine, vinylamine, 2-vinylpyridine,
4-vinylpyridine, trimethylammonium ethyl (meth)acrylate chloride,
trimethylammonium ethyl (meth)acrylate methyl sulphate,
dimethylammonium ethyl (meth)acrylate benzyl chloride,
4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethyl
ammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl
(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride,
diallyldimethyl ammonium chloride.
[0145] Suitable cationic monomers include those which comprise a
quaternary ammonium group of formula --NR.sub.3.sup.+, wherein R,
which is identical or different, represents a hydrogen atom, an
alkyl group comprising 1 to 10 carbon atoms, or a benzyl group,
optionally carrying a hydroxyl group, and comprise an anion
(counter-ion). Examples of anions are halides such as chlorides,
bromides, sulphates, hydrosulphates, alkylsulphates (for example
comprising 1 to 6 carbon atoms), phosphates, citrates, formates,
and acetates.
[0146] Suitable cationic monomers include trimethylammonium ethyl
(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate
methyl sulphate, dimethylammonium ethyl (meth)acrylate benzyl
chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylate chloride,
trimethyl ammonium ethyl (meth)acrylamido chloride, trimethyl
ammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethyl
ammonium chloride.
[0147] Additional suitable cationic monomers include trimethyl
ammonium propyl (meth)acrylamido chloride.
[0148] Examples of monomers bearing a negative charge include alpha
ethylenically unsaturated monomers comprising a phosphate or
phosphonate group, alpha ethylenically unsaturated monocarboxylic
acids, monoalkylesters of alpha ethylenically unsaturated
dicarboxylic acids, monoalkylamides of alpha ethylenically
unsaturated dicarboxylic acids, alpha ethylenically unsaturated
compounds comprising a sulphonic acid group, and salts of alpha
ethylenically unsaturated compounds comprising a sulphonic acid
group.
[0149] Suitable monomers with a negative charge include acrylic
acid, methacrylic acid, vinyl sulphonic acid, salts of vinyl
sulfonic acid, vinylbenzene sulphonic acid, salts of vinylbenzene
sulphonic acid, alpha-acrylamidomethylpropanesulphonic acid, salts
of alpha-acrylamidomethylpropanesulphonic acid, 2-sulphoethyl
methacrylate, salts of 2-sulphoethyl methacrylate,
acrylamido-2-methylpropanesulphonic acid (AMPS), salts of
acrylamido-2-methylpropanesulphonic acid, and styrenesulphonate
(SS).
[0150] Examples of nonionic monomers include vinyl acetate, amides
of alpha ethylenically unsaturated carboxylic acids, esters of an
alpha ethylenically unsaturated monocarboxylic acids with an
hydrogenated or fluorinated alcohol, polyethylene oxide
(meth)acrylate (i.e. polyethoxylated (meth)acrylic acid),
monoalkylesters of alpha ethylenically unsaturated dicarboxylic
acids, monoalkylamides of alpha ethylenically unsaturated
dicarboxylic acids, vinyl nitriles, vinylamine amides, vinyl
alcohol, vinyl pyrolidone, and vinyl aromatic compounds.
[0151] Suitable nonionic monomers include styrene, acrylamide,
methacrylamide, acrylonitrile, methylacrylate, ethylacrylate,
n-propylacrylate, n-butylacrylate, methylmethacrylate,
ethylmethacrylate, n-propylmethacrylate, n-butylmethacrylate,
2-ethyl-hexyl acrylate, 2-ethyl-hexyl methacrylate,
2-hydroxyethylacrylate and 2-hydroxyethylmethacrylate.
[0152] The anionic counterion (X--) in association with the
synthetic cationic polymers may be any known counterion so long as
the polymers remain soluble or dispersible in water, in the shampoo
composition, or in a coacervate phase of the shampoo composition,
and so long as the counterions are physically and chemically
compatible with the essential components of the shampoo composition
or do not otherwise unduly impair product performance, stability or
aesthetics. Non limiting examples of such counterions include
halides (e.g., chlorine, fluorine, bromine, iodine), sulfate and
methylsulfate.
[0153] In one embodiment, the cationic polymer described herein
aids in providing damaged hair, particularly chemically treated
hair, with a surrogate hydrophobic F-layer. The microscopically
thin F-layer provides natural weatherproofing, while helping to
seal in moisture and prevent further damage. Chemical treatments
damage the hair cuticle and strip away its protective F-layer. As
the F-layer is stripped away, the hair becomes increasingly
hydrophilic. It has been found that when lyotropic liquid crystals
are applied to chemically treated hair, the hair becomes more
hydrophobic and more virgin-like, in both look and feel. Without
being limited to any theory, it is believed that the lyotropic
liquid crystal complex creates a hydrophobic layer or film, which
coats the hair fibers and protects the hair, much like the natural
F-layer protects the hair. The hydrophobic layer returns the hair
to a generally virgin-like, healthier state. Lyotropic liquid
crystals are formed by combining the synthetic cationic polymers
described herein with the aforementioned anionic detersive
surfactant component of the shampoo composition. The synthetic
cationic polymer has a relatively high charge density. It should be
noted that some synthetic polymers having a relatively high
cationic charge density do not form lyotropic liquid crystals,
primarily due to their abnormal linear charge densities. Such
synthetic cationic polymers are described in WO 94/06403 to Reich
et al. The synthetic polymers described herein can be formulated in
a stable shampoo composition that provides improved conditioning
performance, with respect to damaged hair.
[0154] Cationic synthetic polymers that can form lyotropic liquid
crystals have a cationic charge density of from about 2 meq/gm to
about 7 meq/gm, and/or from about 3 meq/gm to about 7 meq/gm,
and/or from about 4 meq/gm to about 7 meq/gm. In some embodiments,
the cationic charge density is about 6.2 meq/gm. The polymers also
have a M. Wt. of from about 1,000 to about 5,000,000, and/or from
about 10,000 to about 2,000,000, and/or from about 100,000 to about
2,000,000.
[0155] In another embodiment of the invention cationic synthetic
polymers that provide enhanced conditioning and deposition of
benefit agents but do not necessarily form lytropic liquid crystals
have a cationic charge density of from about 0.7 meq/gm to about 7
meq/gm, and/or from about 0.8 meq/gm to about 5 meq/gm, and/or from
about 1.0 meq/gm to about 3 meq/gm. The polymers also have a M. Wt.
of from about 1,000 to about 5,000,000, from about 10,000 to about
2,000,000, and from about 100,000 to about 2,000,000.
[0156] The concentration of the cationic polymers ranges about
0.025% to about 5%, from about 0.1% to about 3%, and/or from about
0.2% to about 1%, by weight of the shampoo composition.
[0157] (6) Cationic Cellulose Polymers
[0158] Suitable cationic cellulose polymers may be salts of
hydroxyethyl cellulose reacted with trimethyl ammonium substituted
epoxide, referred to in the industry (CTFA) as Polyquarternium 10
and available from Dwo/Amerchol Corp. (Edison, N.J., USA) in their
Polymer LR, JR, and KG series of polymers. Other suitable types of
cationic cellulose include the polymeric quaternary ammonium salts
of hydroxyethyl cellulose reacted with lauryl dimethyl
ammonium-substituted epoxide referred to in the industry (CTFA) as
Polyquarternium 24. These materials are available from Dow/Amerchol
Corp. under the tradename Polymer LM-200. Other suitable types of
cationic cellulose include the polymeric quaternary ammonium salts
of hydroxyethyl cellulose reacted with lauryl dimethyl
ammonium-substituted epoxide and trimethyl ammonium substituted
epoxide referred to in the industry (CTFA) as Polyquarternium 67.
These materials are available from Dow/Amerchol Corp. under the
tradename SoftCAT Polymer SL-5, SoftCAT Polymer SL-30, Polymer
SL-60, Polymer SL-100, Polymer SK-L, Polymer SK-M, Polymer SK-MH,
and Polymer SK-H.
[0159] In an embodiment, the shampoo composition may comprise a
plurality of cationic conditioning polymers. According to one
embodiment, where two cationic conditioning polymers are present,
the weight ratio of a first cationic conditioning polymer to a
second cationic conditioning polymer is from about 1000:1 to about
2:1. In an embodiment, the weight ratio of the first cationic
conditioning polymer to the second cationic conditioning polymer is
from about 1000:1 to about 4:1. In an embodiment, weight ratio of
the first cationic conditioning polymer to the second cationic
conditioning polymer is from about 800:1 to about 4:1, or from
about 500:1 to about 4:1, or from about 100:1 to about 5:1, or from
about 100:1 to about 6:1, or from about 50:1 to about 6.5:1, or
from about 50:1 to about 7:1, or from about 50:1 to about 8.3:1, or
from about 50:1 to about 16.7:1.
D. Carrier
[0160] The shampoo compositions can be in the form of pourable
liquids (under ambient conditions). Such compositions may comprise
a carrier, which is present at a level of from about 20 wt % to
about 95 wt %, or even from about 60 wt % to about 85 wt %. The
carrier may comprise water, or a miscible mixture of water and
organic solvent, and in one aspect may comprise water with minimal
or no significant concentrations of organic solvent, except as
otherwise incidentally incorporated into the composition as minor
ingredients of other essential or optional components.
[0161] The carrier useful in embodiments of the shampoo
compositions of the present invention includes water and water
solutions of lower alkyl alcohols and polyhydric alcohols. The
lower alkyl alcohols useful herein are monohydric alcohols having 1
to 6 carbons, in one aspect, ethanol and isopropanol. Exemplary
polyhydric alcohols useful herein include propylene glycol,
hexylene glycol, glycerin, and propane diol.
E. Optional Ingredients
[0162] In accordance with embodiments of the present invention, the
shampoo composition may further comprise one or more optional
ingredients, including benefit agents Suitable benefit agents
include, but are not limited to conditioning agents, silicone
emulsions, anti-dandruff actives, gel networks, chelating agents,
and, natural oils such as sun flower oil or castor oil. Additional
suitable optional ingredients include but are not limited to
perfumes, perfume microcapsules, colorants, particles,
anti-microbials, foam busters, anti-static agents, rheology
modifiers and thickeners, suspension materials and structurants, pH
adjusting agents and buffers, preservatives, pearlescent agents,
solvents, diluents, anti-oxidants, vitamins and combinations
thereof.
[0163] Such optional ingredients should be physically and
chemically compatible with the components of the composition, and
should not otherwise unduly impair product stability, aesthetics,
or performance. The CTFA Cosmetic Ingredient Handbook, Tenth
Edition (published by the Cosmetic, Toiletry, and Fragrance
Association, Inc., Washington, D.C.) (2004) (hereinafter "CTFA"),
describes a wide variety of nonlimiting materials that can be added
to the composition herein.
[0164] 1. Silicones
[0165] The shampoo composition may further comprise one or more
silicone conditioning agents in addition to the silicone quaternary
polymers disclosed in Section A. The additional silicone
conditioning agent may comprise volatile silicone, non-volatile
silicone, or combinations thereof. The concentration of the
silicone conditioning agent typically ranges from about 0.01% to
about 10%, by weight of the composition, from about 0.1% to about
8%, from about 0.1% to about 5%, and/or from about 0.2% to about
3%. Non-limiting examples of suitable silicone conditioning agents,
and optional suspending agents for the silicone, are described in
U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646, and U.S.
Pat. No. 5,106,609, which descriptions are incorporated herein by
reference. The silicone conditioning agents for use in the
compositions of the present invention can have a viscosity, as
measured at 25.degree. C., from about 20 to about 2,000,000
centistokes ("csk"), from about 1,000 to about 1,800,000 csk, from
about 50,000 to about 1,500,000 csk, and/or from about 100,000 to
about 1,500,000 csk.
The dispersed silicone conditioning agent particles typically have
a volume average particle diameter ranging from about 0.01
micrometer to about 50 micrometer. For small particle application
to hair, the volume average particle diameters typically range from
about 0.01 micrometer to about 4 micrometer, from about 0.01
micrometer to about 2 micrometer, from about 0.01 micrometer to
about 0.5 micrometer. For larger particle application to hair, the
volume average particle diameters typically range from about 5
micrometer to about 125 micrometer, from about 10 micrometer to
about 90 micrometer, from about 15 micrometer to about 70
micrometer, and/or from about 20 micrometer to about 50
micrometer.
[0166] Additional material on silicones including sections
discussing silicone fluids, gums, and resins, as well as
manufacture of silicones, are found in Encyclopedia of Polymer
Science and Engineering, vol. 15, 2d ed., pp 204-308, John Wiley
& Sons, Inc. (1989), incorporated herein by reference.
[0167] Silicone emulsions suitable for use in the embodiments of
the present invention include, but are not limited to, emulsions of
insoluble polysiloxanes prepared in accordance with the
descriptions provided in U.S. Pat. No. 4,476,282 and U.S. Patent
Application Publication No. 2007/0276087. Accordingly, suitable
insoluble polysiloxanes include polysiloxanes such as alpha, omega
hydroxy-terminated polysiloxanes or alpha, omega alkoxy-terminated
polysiloxanes having a molecular weight within the range from about
50,000 to about 500,000 g/mol. The insoluble polysiloxane can have
an average molecular weight within the range from about 50,000 to
about 500,000 g/mol. For example, the insoluble polysiloxane may
have an average molecular weight within the range from about 60,000
to about 400,000; from about 75,000 to about 300,000; from about
100,000 to about 200,000; or the average molecular weight may be
about 150,000 g/mol. The insoluble polysiloxane can have an average
particle size within the range from about 30 nm to about 10 micron.
The average particle size may be within the range from about 40 nm
to about 5 micron, from about 50 nm to about 1 micron, from about
75 nm to about 500 nm, or about 100 nm, for example.
[0168] The average molecular weight of the insoluble polysiloxane,
the viscosity of the silicone emulsion, and the size of the
particle comprising the insoluble polysiloxane are determined by
methods commonly used by those skilled in the art, such as the
methods disclosed in Smith, A. L. The Analytical Chemistry of
Silicones, John Wiley & Sons, Inc.: New York, 1991. For
example, the viscosity of the silicone emulsion can be measured at
30.degree. C. with a Brookfield viscometer with spindle 6 at 2.5
rpm. The silicone emulsion may further include an additional
emulsifier together with the anionic surfactant.
[0169] Other classes of silicones suitable for use in compositions
of the present invention include but are not limited to: i)
silicone fluids, including but not limited to, silicone oils, which
are flowable materials having viscosity less than about 1,000,000
csk as measured at 25.degree. C.; ii) aminosilicones, which contain
at least one primary, secondary or tertiary amine; iii) cationic
silicones, which contain at least one quaternary ammonium
functional group; iv) silicone gums; which include materials having
viscosity greater or equal to 1,000,000 csk as measured at
25.degree. C.; v) silicone resins, which include highly
cross-linked polymeric siloxane systems; vi) high refractive index
silicones, having refractive index of at least 1.46, and vii)
mixtures thereof.
[0170] 2. Organic Conditioning Materials
[0171] The shampoo composition may also comprise at least one
organic conditioning material such as oil or wax, either alone or
in combination with other conditioning agents, such as the
silicones described above. The organic material can be
non-polymeric, oligomeric or polymeric. It may be in the form of
oil or wax and may be added in the formulation neat or in a
pre-emulsified form. Some non-limiting examples of organic
conditioning materials include, but are not limited to: i)
hydrocarbon oils; ii) polyolefins, iii) fatty esters, iv)
fluorinated conditioning compounds, v) fatty alcohols, vi) alkyl
glucosides and alkyl glucoside derivatives; vii) quaternary
ammonium compounds; viii) polyethylene glycols and polypropylene
glycols having a molecular weight of up to about 2,000,000
including those with CTFA names PEG-200, PEG-400, PEG-600,
PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M and mixtures
thereof.
[0172] 3. Emulsifiers
[0173] A variety of anionic and nonionic emulsifiers can be used in
the shampoo composition of the present invention. The anionic and
nonionic emulsifiers can be either monomeric or polymeric in
nature. Monomeric examples include, by way of illustrating and not
limitation, alkyl ethoxylates, alkyl sulfates, soaps, and fatty
esters and their derivatives. Polymeric examples include, by way of
illustrating and not limitation, polyacrylates, polyethylene
glycols, and block copolymers and their derivatives. Naturally
occurring emulsifiers such as lanolins, lecithin and lignin and
their derivatives are also non-limiting examples of useful
emulsifiers.
[0174] 4. Chelating Agents
[0175] The shampoo composition can also comprise a chelant.
Suitable chelants include those listed in A E Martell & R M
Smith, Critical Stability Constants, Vol. 1, Plenum Press, New York
& London (1974) and A E Martell & R D Hancock, Metal
Complexes in Aqueous Solution, Plenum Press, New York & London
(1996) both incorporated herein by reference. When related to
chelants, the term "salts and derivatives thereof" means the salts
and derivatives comprising the same functional structure (e.g.,
same chemical backbone) as the chelant they are referring to and
that have similar or better chelating properties. This term include
alkali metal, alkaline earth, ammonium, substituted ammonium (i.e.
monoethanolammonium, diethanolammonium, triethanolammonium) salts,
esters of chelants having an acidic moiety and mixtures thereof, in
particular all sodium, potassium or ammonium salts. The term
"derivatives" also includes "chelating surfactant" compounds, such
as those exemplified in U.S. Pat. No. 5,284,972, and large
molecules comprising one or more chelating groups having the same
functional structure as the parent chelants, such as polymeric EDDS
(ethylenediaminedisuccinic acid) disclosed in U.S. Pat. No.
5,747,440.
[0176] Levels of the EDDS chelant in the shampoo compositions can
be as low as about 0.01 wt % or even as high as about 10 wt %, but
above the higher level (i.e., 10 wt %) formulation and/or human
safety concerns may arise. In an embodiment, the level of the EDDS
chelant may be at least about 0.05 wt %, at least about 0.1 wt %,
at least about 0.25 wt %, at least about 0.5 wt %, at least about 1
wt %, or at least about 2 wt % by weight of the shampoo
composition. Levels above about 4 wt % can be used but may not
result in additional benefit.
[0177] 5. Anti-Dandruff Agent
[0178] According to an embodiment, the shampoo composition
comprises an anti-dandruff active, which may be an anti-dandruff
active particulate. The anti-dandruff active can be selected from
the group consisting of: pyridinethione salts; azoles, such as an
imidazole such as ketoconazole, econazole, climbazole and elubiol;
selenium sulphide; coal tar, particulate sulfur; keratolytic agents
such as salicylic acid; and mixtures thereof. In an embodiment, the
anti-dandruff particulate is a pyridinethione salt.
[0179] Pyridinethione particulates are suitable particulate
anti-dandruff actives. In an embodiment, the anti-dandruff active
is a 1-hydroxy-2-pyridinethione salt and is in particulate form. In
an embodiment, the concentration of pyridinethione anti-dandruff
particulate ranges from about 0.01 wt % to about 5 wt %, or from
about 0.1 wt % to about 3 wt %, or from about 0.1 wt % to about 2
wt %. In an embodiment, the pyridinethione salts are those formed
from heavy metals such as zinc, tin, cadmium, magnesium, aluminium
and zirconium, generally zinc, typically the zinc salt of
1-hydroxy-2-pyridinethione (known as "zinc pyridinethione" or
"ZPT"), commonly 1-hydroxy-2-pyridinethione salts in platelet
particle form. In an embodiment, the 1-hydroxy-2-pyridinethione
salts in platelet particle form have an average particle size of up
to about 20 microns, or up to about 5 microns, or up to about 2.5
microns. Salts formed from other cations, such as sodium, may also
be suitable. Pyridinethione anti-dandruff actives are described,
for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No. 3,236,733;
U.S. Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat. No.
4,345,080; U.S. Pat. No. 4,323,683; U.S. Pat. No. 4,379,753; and
U.S. Pat. No. 4,470,982.
[0180] The anti-dandruff active can also be selected from
polyvalent metal salts of pyrithione, the composition further
comprises one or more anti-fungal and/or anti-microbial actives.
Embodiments of the present invention may also comprise a
combination of anti-microbial actives.
[0181] In an embodiment, the composition comprises an effective
amount of a zinc-containing layered material. In an embodiment, the
composition comprises from about 0.001 wt % to about 10 wt %, or
from about 0.01 wt % to about 7 wt %, or from about 0.1 wt % to
about 5 wt % of a zinc-containing layered material (ZLMs), by total
weight of the composition.
[0182] Many ZLMs occur naturally as minerals. In an embodiment, the
ZLM is selected from the group consisting of: hydrozincite (zinc
carbonate hydroxide), aurichalcite (zinc copper carbonate
hydroxide), rosasite (copper zinc carbonate hydroxide), and
mixtures thereof. Related minerals that are zinc-containing may
also be included in the composition. Natural ZLMs can also occur
wherein anionic layer species such as clay-type minerals (e.g.,
phyllosilicates) contain ion-exchanged zinc gallery ions. All of
these natural materials can also be obtained synthetically or
formed in situ in a composition or during a production process.
[0183] Another common class of ZLMs, which are often, but not
always, synthetic, is layered double hydroxides or hydroxy double
salts. In an embodiment, the composition comprises basic zinc
carbonate. Basic zinc carbonate, which also may be referred to
commercially as "Zinc Carbonate" or "Zinc Carbonate Basic" or "Zinc
Hydroxy Carbonate", is a synthetic version consisting of materials
similar to naturally occurring hydrozincite.
[0184] In embodiments having a zinc-containing layered material and
a pyrithione or polyvalent metal salt of pyrithione, the ratio of
zinc-containing layered material to pyrithione or a polyvalent
metal salt of pyrithione is from about 5:100 to about 10:1, or from
about 2:10 to about 5:1, or from about 1:2 to about 3:1.
[0185] 6. Gel Networks
[0186] The shampoo composition may also comprise fatty alcohol gel
networks. These gel networks are formed by combining fatty alcohols
and surfactants in the ratio of from about 1:1 to about 40:1, from
about 2:1 to about 20:1, and/or from about 3:1 to about 10:1. The
formation of a gel network involves heating a dispersion of the
fatty alcohol in water with the surfactant to a temperature above
the melting point of the fatty alcohol. During the mixing process,
the fatty alcohol melts, allowing the surfactant to partition into
the fatty alcohol droplets. The surfactant brings water along with
it into the fatty alcohol. This changes the isotropic fatty alcohol
drops into liquid crystalline phase drops. When the mixture is
cooled below the chain melt temperature, the liquid crystal phase
is converted into a solid crystalline gel network. The gel network
contributes a stabilizing benefit to hair compositions. In
addition, they deliver conditioned feel benefits.
[0187] The fatty alcohol can be included in the fatty alcohol gel
network at a level by weight of from about 0.05 wt % to about 14 wt
%. For example, the fatty alcohol may be present in an amount
ranging from about 1 wt % to about 10 wt %, and/or from about 6 wt
% to about 8 wt %.
[0188] The fatty alcohols useful herein include those having from
about 10 to about 40 carbon atoms, from about 12 to about 22 carbon
atoms, from about 16 to about 22 carbon atoms, and/or about 16 to
about 18 carbon atoms. These fatty alcohols can be straight or
branched chain alcohols and can be saturated or unsaturated.
Nonlimiting examples of fatty alcohols include cetyl alcohol,
stearyl alcohol, behenyl alcohol, and mixtures thereof. Mixtures of
cetyl and stearyl alcohol in a ratio of from about 20:80 to about
80:20 are suitable.
[0189] Gel network preparation: A vessel is charged with water and
the water is heated to about 74.degree. C. Cetyl alcohol, stearyl
alcohol, and SLES surfactant are added to the heated water. After
incorporation, the resulting mixture is passed through a heat
exchanger where the mixture is cooled to about 35.degree. C. Upon
cooling, the fatty alcohols and surfactant crystallized to form a
crystalline gel network. Table 3 provides the components and their
respective amounts for the gel network composition.
TABLE-US-00001 TABLE 3 Gel network components Ingredient Wt. %
Water 78.27% Cetyl Alcohol 4.18% Steary Alcohol 7.52% Sodium
laureth-3 sulfate (28% Active) 10.00%
5-Chloro-2-methyl-4-isothiazolin-3-one, Kathon CG 0.03%
Product Form
[0190] The shampoo compositions of the present invention may be
presented in typical shampoo formulations. They may be in the form
of solutions, dispersion, emulsions, powders, talcs, encapsulated,
spheres, spongers, solid dosage forms, foams, and other delivery
mechanisms. The compositions of the embodiments of the present
invention may be hair tonics, leave-on hair products such as
treatment, and styling products, rinse-off hair products such as
shampoos, and treatment products; and any other form that may be
applied to hair.
[0191] According to one embodiment, the shampoo compositions may be
provided in the form of a porous, dissolvable solid structure
having a percent open cell content of from about 80% to about 100%,
such as those disclosed in U.S. Patent Application Publication Nos.
2009/0232873; and 2010/0179083, which are incorporated herein by
reference in their entirety.
[0192] The shampoo composition can have a viscosity of 4,000 cP to
20,000 cP, or from about 6,000 cP to about 12,000 cP, or from about
8,000 cP to about 11,000 cP, measured at 26.6.degree. C. with a
Brookfield R/S Plus Rheometer at 2 s.sup.-1. cP means
centipoises.
Method of Making
[0193] The shampoo compositions are generally prepared by
conventional. Such methods include mixing of the ingredients in one
or more steps to a relatively uniform state, with or without
heating, cooling, application of vacuum, and the like. The
compositions are prepared such as to optimize stability (physical
stability, chemical stability, photostability) and/or delivery of
the active materials. The shampoo composition may be in a single
phase or a single product, or the shampoo composition may be in a
separate phases or separate products. If two products are used, the
products may be used together, at the same time or
sequentially.
Method of Use
[0194] The shampoo compositions of the present invention can be
applied to the hair and rinsed off with water.
Examples
[0195] The exemplified compositions can be prepared by conventional
formulation and mixing techniques. It will be appreciated that
other modifications of the hair care composition within the skill
of those in the hair care formulation art can be undertaken without
departing from the spirit and scope of this invention. All parts,
percentages, and ratios herein are by weight unless otherwise
specified. Some components may come from suppliers as dilute
solutions. The amount stated reflects the weight percent of the
active material, unless otherwise specified.
[0196] Table 1 includes examples of specific structures for the
silicone quaternary polymers described in Section A of this
application.
TABLE-US-00002 TABLE 1 Silicone Silicone Silicone Quaternary
Quaternary Quaternary Variable Polymer A Polymer B Polymer C M
lauric ester lauric ester lauric ester Y K--S--K K--S--K K--S--K K
CH.sub.2--CHOH--CH.sub.2--O--C.sub.3H.sub.6
CH.sub.2--CHOH--CH.sub.2--O--C.sub.3H.sub.6
CH.sub.2--CHOH--CH.sub.2--O--C.sub.3H.sub.6 S PDMS block PDMS block
PDMS block with 368 with 368 with 368 siloxane units siloxane units
siloxane units R, R.sup.2 methyl methyl methyl T C.sub.6H.sub.12
C.sub.6H.sub.12 C.sub.6H.sub.12 A CH.sub.2--COO-- CH.sub.2--COO--
CH.sub.2--COO-- A' CO--CH.sub.2 CO--CH.sub.2 CO--CH.sub.2 E
Ethylene oxide Ethylene Propylene (CH.sub.2--CH.sub.2--O) oxide
(CH.sub.2--CH.sub.2--O) oxide (CH.sub.2--CH(CH.sub.3)--O) with
average with with average degree of average degree of ethoxylation
degree of propoxylation of 2 ethoxylation of 3.5 of 34 Ratio of 1:1
9:1 9:1 silicone blocks:alkylene oxide blocks Total 4700 mPa s 2800
mPa s 2600 mPa s. Viscosity Silicone Silicone Quaternary Quaternary
Variable Polymer D Polymer E M lauric ester lauric ester Y K--S--K
K--S--K K CH.sub.2--CHOH--CH.sub.2--O--C.sub.3H.sub.6
CH.sub.2--CHOH--CH.sub.2--O--C.sub.3H.sub.6 S PDMS block PDMS block
with 450 with 368 siloxane units siloxane units R, R.sup.2 methyl
methyl T C.sub.6H.sub.12 C.sub.6H.sub.12 A CH.sub.2--COO--
CH.sub.2--COO-- A' CO--CH.sub.2 CO--CH.sub.2 E Propylene Ethylene
oxide (CH.sub.2--CH(CH.sub.3)--O) oxide (CH.sub.2--CH.sub.2--O)
with average with degree of average propoxylation degree of of 3.5
ethoxylation of 2 Ratio of 9:1 7:3 silicone blocks:alkylene oxide
blocks Total 5400 mPa s. 6000 mPa s. Viscosity
[0197] The following examples in Table 2 illustrate embodiments of
silicone emulsions as described in Section A of this
Application.
TABLE-US-00003 TABLE 2 Silicone Emulsion A B C D E Water q.s. q.s.
q.s. q.s. q.s. Sodium Laureth Sulfate.sup.1 5.0 -- -- 5.0 5.0
C11-15 Pareth-5.sup.2 -- 1.4 1.0 C11-15 Pareth-12.sup.3 -- 2.0
Silicone Quaternary 20.0 Polymer A Silicone Quaternary 10.0 Polymer
B Silicone Quaternary 10.0 Polymer C Silicone Quaternary 20.0
Polymer D Silicone Quaternary 20.0 Polymer E .sup.1Sodium Laureth-1
Sulfate, from Stepan .sup.2Tergitol 15-S-5, from The Dow Chemical
Company .sup.3Tergitol 15-S-12, from The Dow Chemical Company
[0198] The following examples in Table 3 illustrate embodiments of
the present invention wherein the silicone polymer is
emulsified.
TABLE-US-00004 TABLE 3 11 12 13 14 15 16 17 18 19 20 Water q.s.
q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. Sodium Laureth 13.0
12.0 10.5 10.5 10.5 10.5 10.5 12.0 12.0 12.0 Sulfate.sup.1 Sodium
Lauryl 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Sulfate.sup.2
CMEA.sup.3 -- -- 0.8 -- -- -- 0.8 -- -- Cocoamidopropyl 1.7 1.7 1.0
1.0 1.0 1.0 1.0 1.7 1.7 1.0 Betaine.sup.4 Guar Hydroxypropyl 0.325
0.3 -- -- -- -- -- 0.30 -- -- Trimonium Chloride.sup.5
Polyquaternium-10.sup.6 0.075 -- -- -- -- -- -- -- 0.30 --
Polyquaternium-6.sup.7 0.075 -- 0.25 -- -- -- -- -- -- -- Silicone
Emulsion A 5.0 2.5 Silicone Emulsion B 3.75 2.5 Silicone Emulsion C
2.5 5.0 Silicone Emulsion D 5.0 1.25 Silicone Emulsion E 1.25 3.75
Glycerine.sup.8 0.5 0.5 -- -- -- -- -- -- -- -- EGDS.sup.9 -- --
1.5 -- -- -- 1.5 -- -- -- Trihydroxystearin.sup.10 0.1 0.1 -- 0.1
0.1 0.1 -- 0.1 0.1 0.1 Fragrance, Up to Up Up Up Up Up Up Up Up Up
preservatives, 3% to to to to to to to to to viscosity adjustment
3% 3% 3% 3% 3% 3% 3% 3% 3% .sup.1Sodium Laureth-1 Sulfate, from
Stepan .sup.2Sodium Lauryl Sulfate, from P&G .sup.3Ninol Comf,
from Stepan .sup.4Amphosol HCA-B, from Stepan .sup.5NHance-3196,
from ASI .sup.6Ucare Polymer KG-30M, from The Dow Chemical Company
.sup.7Mirapol 100, from Rhodia Inc. .sup.8Superol V Glycerine USP,
from P&G .sup.9EGDS pure, from Evonik .sup.10Thixcin R from
Elementis
Data
[0199] Referring to Table 4, Applicants have surprisingly found
that Applicants' emulsified silicone polymer (QAS 4996) in shampoo
shows statistically significant improved dry conditioning
performance when compared to corresponding emulsified
polydimethylsilicone (PDMS) benchmarks.
TABLE-US-00005 TABLE 4 Friction Composition Force (g) Shampoo with
1% Silicone Quaternary Polymer C - 218.97 A milled emulsion Shampoo
with 1% PDMS (330,000 cs) - milled 237.63 B emulsion Shampoo with
1% PDMS (5,000 cs) - milled 259.74 B emulsion *Compositions sourced
from Momentive Performance Materials
[0200] The measurements in Table 4 were taken by measuring the
friction force (g) using the Instron Friction Method (IFM).
Instron Friction Method (IFM)
[0201] Dry conditioning performance is evaluated by hair friction
force measured by an instrument named Instron Tester (Instron Mini
55, Instron, Inc.; Canton, Mass., USA). [0202] First, a 20 g hair
switch is cleaned with tap water running at about 1.5 gpm at about
100.degree. F. [0203] 2 ml of Pantene Fine Hair Solutions Flat to
Volume Shampoo is then applied to the hair switch using a syringe,
applying half of the syringe to the front and half of the syringe
to the back of the switch. [0204] The Flat to Volume Shampoo is
then massaged into the hair using a milking motion with a thumb on
the front of the switch and fingers on the back for 30 seconds.
[0205] The switch is then rinsed with tap water running at about
1.5 gpm at about 100.degree. F. for 30 seconds while massaging the
hair using a milking motion with a thumb on the front and fingers
on the back of the switch. [0206] The shampoo procedure is
repeated. [0207] 2 ml of the shampoo comprising a conditioning
composition is then applied to the hair using a syringe, applying
half of the syringe to the front and half of the syringe to the
back of the switch. [0208] The conditioning composition is then
massaged into the hair using a milking motion with a thumb on the
front of the switch and fingers on the back for 30 seconds. [0209]
The switch is allowed to rest for 30 seconds. [0210] The hair
switch is then rinsed with tap water running at about 1.5 gpm at
about 100.degree. F. for 30 seconds while massaging the hair using
a milking motion with a thumb on the front and fingers on the back
of the switch. [0211] Excess water is removed from the switch by
using fingers as a squeegee, running the fingers down the switch
twice. [0212] The switch is hung on a cart and taken to a CT/CH
room set at about 70.degree. F. and about 50% room humidity to dry
and equilibrate overnight. [0213] The friction force (g) between
the hair surface and a foam pad along the hair is measured using
the Instron Mini 55.
[0214] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm"
[0215] Every document cited herein, including any cross referenced
or related patent or application and any patent application or
patent to which this application claims priority or benefit
thereof, is hereby incorporated herein by reference in its entirety
unless expressly excluded or otherwise limited. The citation of any
document is not an admission that it is prior art with respect to
any invention disclosed or claimed herein or that it alone, or in
any combination with any other reference or references, teaches,
suggests or discloses any such invention. Further, to the extent
that any meaning or definition of a term in this document conflicts
with any meaning or definition of the same term in a document
incorporated by reference, the meaning or definition assigned to
that term in this document shall govern.
[0216] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *