U.S. patent application number 13/994972 was filed with the patent office on 2013-10-10 for personal care compositions including aqueous compositions of viscoelastic surfactants and hydrophobically modified polymers.
This patent application is currently assigned to Akzo Nobel Chemicals International B.V.. The applicant listed for this patent is Elliot Isaac Band, JR., Stuart Peter Robert Holt, Klin A. Rodrigues, Samuel Anthony Vona, Qingwen Wendy Yuan-Huffman, Jian Zhou. Invention is credited to Elliot Isaac Band, JR., Stuart Peter Robert Holt, Klin A. Rodrigues, Samuel Anthony Vona, Qingwen Wendy Yuan-Huffman, Jian Zhou.
Application Number | 20130266531 13/994972 |
Document ID | / |
Family ID | 44202517 |
Filed Date | 2013-10-10 |
United States Patent
Application |
20130266531 |
Kind Code |
A1 |
Yuan-Huffman; Qingwen Wendy ;
et al. |
October 10, 2013 |
PERSONAL CARE COMPOSITIONS INCLUDING AQUEOUS COMPOSITIONS OF
VISCOELASTIC SURFACTANTS AND HYDROPHOBICALLY MODIFIED POLYMERS
Abstract
Personal care compositions, methods for making and uses thereof
include an aqueous viscoelastic composition and a personal care
active ingredient. The viscoelastic composition includes at least
one surfactant and at least one hydrophobically-modified polymers
with low molecular weights.
Inventors: |
Yuan-Huffman; Qingwen Wendy;
(Belle Meade, NJ) ; Rodrigues; Klin A.; (Signal
Mountain, TN) ; Zhou; Jian; (Danbury, CT) ;
Holt; Stuart Peter Robert; (Chicago, IL) ; Band, JR.;
Elliot Isaac; (Pleasantville, NY) ; Vona; Samuel
Anthony; (Highland, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Yuan-Huffman; Qingwen Wendy
Rodrigues; Klin A.
Zhou; Jian
Holt; Stuart Peter Robert
Band, JR.; Elliot Isaac
Vona; Samuel Anthony |
Belle Meade
Signal Mountain
Danbury
Chicago
Pleasantville
Highland |
NJ
TN
CT
IL
NY
NY |
US
US
US
US
US
US |
|
|
Assignee: |
Akzo Nobel Chemicals International
B.V.
Amersfoort
NL
|
Family ID: |
44202517 |
Appl. No.: |
13/994972 |
Filed: |
December 15, 2011 |
PCT Filed: |
December 15, 2011 |
PCT NO: |
PCT/EP2011/072863 |
371 Date: |
June 17, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61423710 |
Dec 16, 2010 |
|
|
|
Current U.S.
Class: |
424/70.16 ;
424/70.17; 424/78.03; 510/119; 510/123; 510/159 |
Current CPC
Class: |
A61K 8/8147 20130101;
C08L 39/00 20130101; C09K 8/68 20130101; C11D 1/94 20130101; C11D
1/92 20130101; E21B 43/26 20130101; C11D 1/29 20130101; A61K 8/84
20130101; C09K 8/604 20130101; C11D 3/3765 20130101; A61K 8/87
20130101; A61Q 19/10 20130101; C11D 17/003 20130101; C08L 33/10
20130101; C08L 33/26 20130101; A61Q 19/00 20130101; C09K 8/88
20130101; A61K 8/8111 20130101; A61Q 5/02 20130101; A61Q 9/02
20130101; A61Q 5/00 20130101; A61Q 5/12 20130101; C09K 2208/30
20130101 |
Class at
Publication: |
424/70.16 ;
424/70.17; 424/78.03; 510/119; 510/159; 510/123 |
International
Class: |
A61K 8/87 20060101
A61K008/87; A61Q 9/02 20060101 A61Q009/02; A61K 8/81 20060101
A61K008/81; A61Q 5/12 20060101 A61Q005/12; A61Q 5/00 20060101
A61Q005/00; A61Q 5/02 20060101 A61Q005/02; A61Q 19/10 20060101
A61Q019/10; A61K 8/84 20060101 A61K008/84; A61Q 19/00 20060101
A61Q019/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 6, 2011 |
EP |
11161261.0 |
Claims
1. A personal care composition comprising: an aqueous viscoelastic
composition comprising: at least one surfactant; at least one
hydrophobically-modified polymer; and a personal care active
ingredient.
2. The personal care composition of claim 1 wherein the at least
one hydrophobically-modified polymer has a number average molecular
weight of from 1000 to 100,000 Da.
3. The personal care composition of claim 1 wherein the at least
one hydrophobically modified polymer, to a level of least 0.1 mol
%, based on the amount of monomer units in the polymer, contains
monomeric units each covalently bonded to a pendant, optionally
alkoxylated, hydrocarbyl group having from 6 to 40 carbon atoms,
said pendant, optionally alkoxylated, hydrocarbyl group being
connected to the backbone of said hydrophobically modified polymer
via a non-ester containing linking group.
4. The personal care composition of claim 1, wherein said pendant,
optionally alkoxylated, hydrocarbyl group has at least 12 carbon
atoms and said hydrophobically modified polymer to a level of from
0.1 to 20 mole %, based on the amount of monomer units in the
polymer, contains monomeric units connected to said pendant,
optionally alkoxylated, hydrocarbyl group.
5. The personal care composition of claim 1, wherein said pendant,
optionally alkoxylated, hydrocarbyl group has at most 11 carbon
atoms and said hydrophobically modified polymer to a level of from
1 to 50 mole %, based on the amount of monomer units in the
polymer, contains monomeric units connected to said pendant,
optionally alkoxylated, hydrocarbyl group
6. The personal care composition according to claim 1, wherein said
pendant, optionally alkoxylated, hydrocarbyl group contains at
least 8 carbon atoms.
7. The personal care composition according to claim 1, wherein said
pendant, optionally alkoxylated, hydrocarbyl group contains at most
32.
8. The personal care composition according to claim 1, wherein said
pendant, optionally alkoxylated, hydrocarbyl group is a branched
alkyl or alkenyl group.
9. The personal care composition according to claim 1, wherein said
hydrophobically modified polymer is present in a concentration
below the overlap concentration of said polymer.
10. The personal care composition according to claim 1, wherein
said hydrophobically modified polymer is obtainable by
copolymerizing at least a first and at least a second ethylenically
unsaturated monomer, wherein a. said first monomer is an
ethylenically unsaturated monomer with a optionally alkoxylated
hydrocarbyl group having from 6 to 40 carbon atoms, being connected
to the unsaturated function of said monomer via a non-ester
containing linkage; b. said second monomer is an ethylenically
unsaturated monomer free from hydrocarbyl groups having 6 or more
carbon atoms connected to the unsaturated function of said monomer;
said first and second monomer being present in a mutual molar ratio
of from 0.1:99.9 to 90:10
11. The personal care composition according to claim 10, wherein
said optionally alkoxylated hydrocarbyl group has at least 12
carbon atoms and said first and second monomers are present in a
molar ratio of from 0.1:99.9 to 20:80.
12. The personal care composition according to claim 10, wherein
said optionally alkoxylated hydrocarbyl group has at most 11 carbon
atoms and said first and second monomers are present in a mutual
molar ratio of from 1:99 to 90:10.
13. The personal care composition according to claim 10, wherein
said second ethylenically unsaturated monomer is selected from the
group consisting of anionic ethylenically unsaturated monomers,
cationic ethylenically unsaturated monomers, non-ionically
ethylenically unsaturated monomers, zwitterionic ethylenically
unsaturated monomers, and mixtures thereof and salts thereof.
14. The personal care composition according to claim 10, wherein
said second ethylenically unsaturated monomer is selected from the
group consisting of (meth)acrylic acid, maleic acid or maleic
anhydride, itaconic acid, 2-acrylamido-2-methyl propane sulfonic
acid, vinyl sulfonic acid, sodium methallyl sulfonate, sulfonated
styrene, allyloxybenzene sulfonic acid and mixtures thereof and
salts thereof.
15. The personal care composition of claim 10 wherein the second
ethylenically unsaturated monomer is dimethylaminoethyl
methacrylate or diallyldimethylammonium chloride.
16. The personal care composition according to claim 1 wherein said
hydrophobically modified polymer has a number average molecular
weight of from 1,500 Da.
17. The personal care composition according to claim 1, wherein
said viscoelastic surfactant is selected from the group consisting
of zwitterionic surfactants, amphoteric surfactants, anionic
surfactants and combinations thereof.
18. The personal care composition according to claim 1, wherein the
weight ratio of hydrophobically modified polymer to viscoelastic
surfactant is from 0.1:100.
19. The personal care composition of claim 1 wherein the ratio of
hydrophobically-modified polymer to surfactant in the final aqueous
viscoelastic composition is from 1:100 to 40:100, based on the
weight of the aqueous viscoelastic composition.
20. The personal care composition of claim 1 wherein the surfactant
is present in the final aqueous viscoelastic composition in a
concentration from about 1 wt % to about 40 wt %, based on the
weight of the total aqueous viscoelastic composition.
21. The personal care composition according to claim 1, further
comprising a member selected from the group consisting of organic
salts, inorganic salt, organic acid and organic acid salts.
22. The personal care composition according to claim 21, wherein
the concentration of said member is from 0.1 to 30% by weight of
the total composition.
23. The personal care composition according to claim 1, further
comprising a chelating agent.
24. The personal care composition of claim 1 wherein the personal
care composition is a hair care formulation.
25. The personal care composition of claim 1 wherein the personal
care composition is a skin care formulation.
26. The personal care composition of claim 1 wherein the aqueous
viscoelastic composition is present in an amount of about 0.1 wt %
to about 10 wt % based on the weight of the personal care
composition (dry basis).
27. A liquid cleansing product for hair or skin comprising an
effective amount of the personal care composition of claim 1.
28. A liquid conditioning product for hair or skin comprising an
effective amount of the personal care composition of claim 1.
29. A shaving preparation comprising an effective amount of the
personal care composition of claim 1.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to personal care compositions
comprising aqueous viscoelastic compositions comprising at least
one viscoelastic surfactant, and at least one hydrophobically
modified polymer.
BACKGROUND OF THE INVENTION
[0002] It is noted that WO 2003/056130 proposes an improvement on
such existing systems and proposes to use a combination of
viscoelastic surfactants and a hydrophobically modified polymer,
wherein the concentration of the hydrophobically modified polymer
is comprised between its overlap concentration c* and its
entanglement concentration c.sub.e. Although the viscoelastic
fluids of WO 2003/056130 have certain commercial value, they
contain high amounts of both surfactant and hydrophobically
modified polymer in order to achieve aqueous compositions with the
desired viscosity. Further, in the polymer, the hydrophobes are
connected to the polymer backbone via a degradable group.
[0003] It is noted that also in U.S. Pat. No. 4,432,881 liquids are
used wherein a water-soluble polymer with hydrophobic groups is
used. The polymers that are taught to be used have a weight
averaged molecular weight of 200,000 to 5 million Dalton.
[0004] The high molecular weight polymers are difficult to dissolve
and difficult to distribute homogeneously in aqueous
formulations.
[0005] Personal cleansing products, such as shampoos, liquid hand
soaps and body washes, not only must be able to clean the desired
surfaces of the body, but they should also be aesthetically
pleasing throughout all aspects of the consumer experience. For
example, it is desirable that such cleansers should also provide
pleasing experiences when dispensing the product, applying it,
creating lather, cleansing, and rinsing the product.
[0006] It is desirable that liquid cleansing products to have a
rich and luxurious aesthetic upon dispensing and application.
Furthermore, consumers often equate a rich and luxurious lather to
the cleansing efficacy of the product. Additionally, consumers have
grown to expect additional benefits from their liquid cleansing
products beyond cleansing. Such additional benefits include
moisturization, conditioning, exfoliation, protection, and delivery
of beneficial active ingredients to the hair and skin. Often times,
these additional benefits are provided to the consumer by
suspension or dispersion of active ingredients throughout the
liquid cleansing product that are effectively deposited upon
application.
[0007] Only low levels of surfactant are typically required to
effectively clean the desired surfaces and that the level of
surfactants in conventional liquid cleansing products vastly
exceeds the required level. These high levels of surfactants are
included in order to achieve several desirable attributes
including: 1) rheological characteristics that are consistent with
the rich and luxurious application aesthetic, 2) the rich and
luxurious lather that consumers equate to product efficacy, and 3)
rheological characteristics that enable shelf stable
suspensions/dispersions of active ingredients.
[0008] In some cases, however, it is not possible to achieve the
desired characteristics solely through increasing the quantity of
surfactant. In these cases, the characteristics can be improved by
addition of salt. Addition of salt to certain surfactant solutions
induces a structural transition from spherical micelles to
worm-like micelles. However, not all surfactant systems are
sensitive to addition of salt in this way. Where salt is not
effective, a variety of other types of components can be added to
the surfactant systems to achieve the desired characteristics.
Examples of such components include water soluble/dispersible
thickeners that effectively thicken the system and chemicals that
can crystallize to form complex three dimensional structures, such
as PEG150 distearate,
[0009] The above thickeners tend to be high molecular weight
species that effectively thicken aqueous systems. Some drawbacks to
these thickeners are that they can be difficult to handle due to
their high viscosity, poor dissolution speed, their relatively high
level usage requirement and their negatively impact the
clarity.
[0010] It is therefore desirable to provide chemicals that can more
easily be incorporated into liquid cleansing products that enable
rheological characteristics of surfactant systems, that enable
suspension of benefit agents and that are consistent with the rich
and luxurious aesthetic that consumers demand, while reducing the
overall level of surfactant required to achieve these benefits.
SUMMARY OF THE INVENTION
[0011] High molecular weight polymers are generally difficult to
dissolve and difficult to distribute homogeneously in aqueous
formulations. Therefore, another solution is desired. More
specifically, there is a need in the art for aqueous surfactant
based systems with reduced amount of chemicals to obtain a certain
viscosity or compositions with a higher viscosity when the same
amount of chemicals are used, the amounts being based on the weight
of the chemicals in the final composition, thereby further reducing
the costs involved in the use of said fluid and/or expanding the
applications wherein the compositions can be used. Also there is a
need to be able to use polymers that are more easily dispersible in
aqueous formulations.
[0012] It has been found that satisfactory aqueous viscoelastic
compositions can be produced that do not suffer from the drawbacks
of the conventional compositions of the art. More specifically, in
an aspect, the invention provides a personal care composition
comprising an aqueous viscoelastic composition comprising one or
more viscoelastic surfactants in combination with one or more
hydrophobically-modified polymers and a personal care active
ingredient.
BRIEF DESCRIPTION OF THE DRAWING
[0013] The invention is best understood from the following detailed
description when read in connection with the accompanying drawings.
Included in the drawings are the following figures:
[0014] FIG. 1 is chart illustrating the rheology profile determined
by Steady Strain Sweep test for Example 1 and comparative examples
A and B.
[0015] FIG. 2 is chart illustrating the rheology profile determined
by Steady Strain Sweep test for Example 2 and comparative examples
C and D.
[0016] FIG. 3 is a chart illustrating the rheology profile
determined by Steady Strain Sweep test for comparative examples E
and F.
[0017] FIG. 4 is a chart illustrating the rheology profile
determined by Steady Strain Sweep test for Example 5 and
comparative examples H and I.
[0018] FIG. 5 is a chart illustrating the rheology profile
determined by Steady Strain Sweep test for Example 6 and
comparative example J.
[0019] FIG. 6 is a chart illustrating the results of steady state
sweep measurements to determine zero shear viscosity.
[0020] FIG. 7 is a chart illustrating the results of steady state
sweep measurements to determine zero shear viscosity comparing
fitted data to observed data.
[0021] FIG. 8 is a chart showing the results of zero shear
viscosity vs. % salt for 8 dilution experiments at various
surfactant concentrations, four according to the present invention
and four without the polymer-surfactant combination.
[0022] FIG. 9 is a chart showing the results showing Elastic
Modulus as a function of stress for two compositions prepared
according to Examples 10 and 5, respectively.
DETAILED DESCRIPTION
[0023] The invention generally provides a personal care composition
comprising an aqueous viscoelastic composition and a personal care
active ingredient. The viscoelastic composition comprises one or
more viscoelastic surfactants in combination with one or more
hydrophobically-modified polymers.
[0024] In an embodiment, the viscoelastic surfactant is of the
conventional type and can be selected from amine oxide surfactants
including amidoamine oxide surfactants, amphoteric surfactants,
zwitterionic surfactants, anionic surfactants, cationic surfactants
and mixtures of two or more thereof.
[0025] The property of viscoelasticity in general is well known and
reference is made to Hoffmann et al., "Influence of Ionic
Surfactants on the Viscoelastic Properties of Zwitterionic
Surfactant Solutions", Langmuir, 8, 2140-2146, (1992). A useful
test method for viscoelasticity is to apply sinusoidal shear
deformation to the composition and to measure the storage shear
modulus (G') and the loss shear modulus (G'') at a given
temperature. If the elastic component (storage shear modulus G') is
at least as large as the viscous component (loss shear modulus
G''), that is G'.gtoreq.G'', at some point or over some range of
points below a frequency of about 10 rad/sec, typically between
about 0.001 to about 10 rad/sec, more typically between 0.1 to 10
rad/sec, at a given temperature and if G'>10.sup.-2 Pascal,
preferably more than 10.sup.-1 Pascal, the fluid is considered
viscoelastic at that temperature. The definition and rheological
measurement of G' and G'' are generally described in Barnes H. A.
et al., "An Introduction to Rheology", pp. 45-54, Elsevier,
Amsterdam (1997).
[0026] The viscoelastic surfactant is of the conventional type. It
is well known that viscoelastic surfactants provide viscoelasticity
by forming a different type of micelle than the usual spherical
micelles formed by most surfactants. Viscoelastic surfactants form
elongated, often cylindrical, micelles which can be described as
worm-like, thread-like, or rod-like micelles. Typically it is said
that the shape and size of a micelle is a function of the molecular
geometry of its surfactant molecules and solution conditions such
as surfactant concentration, temperature, pH, and ionic strength.
The formation of long, cylindrical micelles creates useful
rheological properties. Viscoelastic surfactant exhibits
shear-thinning behavior, and remain stable despite repeated high
shear applications. By comparison, a typical polymeric thickener
will irreversibly degrade when subjected to high shear
applications. In an embodiment, a viscoelastic surfactant is a
surfactant that forms a visocelastic fluid in an aqueous media.
Amino Oxide and Amidoamine Oxide Viscoelastic Surfactant
[0027] In an embodiment, amine oxide surfactants contemplated for
use in the present invention as viscoelastic surfactants include
those of the following structural formula (I):
##STR00001##
where R.sub.1 is a hydrophobic moiety of alkyl, alkenyl,
cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or
alkylamidoalkyl. R.sub.1 has from about 8 to about 30 carbon atoms
and may be straight or branched chained and saturated or
unsaturated. Examples of long chain alkyl groups include, but not
limited to, octadecenyl (oleyl), octadecyl (stearyl), docosenoic
(erucyl) and the derivatives of tallow, coco, soy and rapeseed
oils.
[0028] R.sub.2 and R.sub.3 are, independently, hydrogen or
aliphatic group (i.e. as opposed to aromatic) having from 1 to
about 30 carbon atoms, preferably from about 1 to about 20 carbon
atoms, more preferably from about 1 to about 10 carbon atoms, and
most preferably from about 1 to about 6 carbon atoms.
Representative aliphatic groups include alkyl, alkenyl, cycloalkyl,
alkylaryl, hydroxyalkyl, carboxyalkyl and
hydroxyalkyl-polyoxyalkylene. The aliphatic group can be straight
or branched chained and saturated or unsaturated.
[0029] In an embodiment, amidoamine oxide surfactants contemplated
for use as viscoelastic surfactants in the present invention
include those of the following structural formula (II):
##STR00002##
where R.sub.1 is a straight or branched chained and saturated or
unsaturated aliphatic group of from about 8 to about 30 carbon
atoms, preferably from about 14 to about 21 carbon atoms. More
preferably, R1 is a fatty aliphatic derived from natural fats and
oils having an iodine value of from about 1 to about 140,
preferably from about 30 to about 90, and more preferably from 40
to about 70. R.sub.1 may be restricted to a single chain length or
may be of mixed chain length such as those groups derived from
natural fats and oils or petroleum stocks. Preferred are tallow
alkyl, hardened tallow alkyl, rapeseed alkyl, hardened rapeseed
alkyl, tall oil alkyl, hardened tall oil alkyl, coco alkyl, oleyl,
or soya alkyl; R.sub.2 is a straight or branched-chained,
substituted or unsubstituted, divalent alkylene group of from 2 to
about 6 carbon atoms, preferably, of 2 to 4 carbon atoms and more
preferably of 3 carbon atoms; R.sub.3 and R.sub.4 are the same or
different and are selected from alkyl or hydroxyalkyl groups of
from 1 to about 4 carbon atoms and are preferably hydroxyethyl or
methyl. Alternatively, R.sub.3 and R.sub.4 in the amidoamine oxide
of formula (II) together with the nitrogen atom to which these
groups are bonded form a heterocyclic ring of up to 6 members; and
R.sub.5 is hydrogen or a C.sub.1-C.sub.4 alkyl or hydroxyalkyl
group.
[0030] Examples of amidoamine oxide contemplated by the present
invention include, but are not limited to, those selected from the
group consisting of tallow amidoalkylamine oxide, hardened tallow
amidoalkylamine oxide, rapeseed amidoalkylamine oxide, hardened
rapeseed amidoalkylamine oxide, tall oil amidoalkylamine oxide,
hardened amidoalkylamine oxide, coco amidoalkylamine oxide, stearyl
amidoalkylamine oxide, oleyl amidoalkylamine oxide, soya
amidoalkylamine oxide, and mixtures thereof. Preferred specific
examples of the amidoamine oxides of the present invention include,
but are not limited to, the following: tallow amidopropyl
dimethylamine oxide, hydrogenated tallow amidopropyl dimethylamine
oxide, soya amidopropyl dimethylamine oxide, oleyl amidopropyl
dimethylamine oxide, erucyl amidopropyl dimethylamine oxide,
rapeseed amidopropyl dimethylamine oxide, hydrogenated rapeseed
amidopropyl dimethylamine oxide, tall oil amidopropyl dimethylamine
oxide, hydrogenated tall oil amidopropyl dimethylamine oxide,
C14-C22 saturated or unsaturated fatty acid amidopropyl
dimethylamine oxides, and mixtures thereof.
Cationic Viscoelastic Surfactant
[0031] A cationic surfactant has a positively charged moiety
regardless of pH. In an embodiment, cationic surfactants
contemplated for use as viscoelastic surfactants in the present
invention include those selected from quaternary salts, certain
amines and combinations thereof.
[0032] In an embodiment, the quaternary salts have the structural
formula (III)
##STR00003##
where R.sub.1 is a hydrophobic moiety of alkyl, alkenyl,
cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or
alkylamidoalkyl. R.sub.1 has from about 8 to about 30 carbon atoms
and may be straight or branched chained and saturated or
unsaturated. Examples of long chain alkyl groups include, but are
not limited to, octadecenyl (oleyl), octadecyl (stearyl),
docosenoic (erucyl) and the derivatives of tallow, coco, soy and
rapeseed oils; R.sub.2, R.sub.3 and R.sub.4 are, independently, at
least partially aliphatic groups having from 1 to about 30 carbon
atoms, preferably from about 1 to about 20 carbon atoms, more
preferably from about 1 to about 10 carbon atoms, and most
preferably from about 1 to about 6 carbon atoms. Representative
aliphatic groups include alkyl, alkenyl, alkylaryl, alkoxyalkyl,
hydroxyalkyl, carboxyalkyl and hydroxyalkyl-polyoxyalkylene. The
aliphatic group can be straight or branched chained and saturated
or unsaturated, and; X.sup.- is a suitable counter-anion. The
counter-anion is typically an inorganic anion such as a sulfate
such as (CH.sub.3).sub.2SO.sub.4.sup.-, a nitrate, a perchlorate or
a halide such as Cr.sup.-, Br.sup.-, or an aromatic organic anion
such as salicylate, naphthalene sulfonate, p- and
m-chlorobenzoates, 3,5-, 3,4-, and 2,4-dichlorobenzoates, t-butyl
and ethyl phenate, 2,6- and 2,5-dichlorophenates,
2,4,5-trichlorophenate, 2,3,5,6-tetrachlorophenate, p-methyl
phenate, m-chlorophenate, 3,5,6-trichloropicolinate,
4-amino-3,5,6-, 2,4-dichlorophenoxyacetate. The amines have the
following structural formula (IV):
##STR00004##
where R.sub.1, R.sub.2 and R.sub.3 have the meaning as defined
above for the quaternary salt residues R.sub.1, R.sub.2 and
R.sub.3, respectively.
Zwitterionic Viscoelastic Surfactant
[0033] The zwitterionic surfactant has a permanently positively
charged moiety in the molecule regardless of pH and a negatively
charged moiety at alkaline pH. In an embodiment, selected
zwitterionic surfactants that are useful as viscoelastic
surfactants in the present invention have the following structural
formula (V):
##STR00005##
where R.sub.1 is hydrophobic moiety of alkyl, alkenyl, cycloalkyl,
alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl.
R.sub.1 has from about 8 to about 30 carbon atoms and may be
straight or branched chained and saturated or unsaturated. Examples
of long chain alkyl groups include, but are not limited to,
octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucyl) and
the derivatives of tallow, coco, soy and rapeseed oils; R.sub.2 and
R.sub.3 are, independently, at least partially aliphatic groups
having from 1 to about 30 carbon atoms, preferably from about 1 to
about 20 carbon atoms, more preferably from about 1 to about 10
carbon atoms, and most preferably from about 1 to about 6 carbon
atoms. Representative aliphatic groups include alkyl, alkenyl,
alkylaryl, alkoxyalkyl, hydroxyalkyl, carboxyalkyl and
hydroxyalkyl-polyoxyalkylene. The aliphatic group can be straight
or branched chained and saturated or unsaturated, and; R.sub.4 is a
hydrocarbyl radical (e.g. alkylene) with a chain length of 1 to 4
carbon atoms. Preferred are methylene or ethylene groups.
[0034] When it is zwitterionic, the surfactant is associated with
both negative and positive counter-ions. Anions are typically as
defined above for X.sup.- for the cationic surfactant. In an
embodiment any cation is suitably elected from Na.sup.+, K.sup.+,
NH4+, and amine salts, such as (CH.sub.3).sub.2NH.sub.2.sup.+.
Amphoteric Viscoelastic Surfactant
[0035] An amphoteric surfactant has both a positively charged
moiety and a negatively charged moiety over a certain pH range
(e.g. typically slightly acidic), only a negatively charged moiety
over a certain pH range (e.g. typically slightly alkaline) and only
a positively charged moiety at a different pH (e.g. typically
moderately acidic).
[0036] In an embodiment, amphoteric surfactants suitable for use as
viscoelastic surfactants in the present invention are represented
by following the structural formula (VI):
##STR00006##
where R.sub.1 is a hydrophobic moiety of alkyl, alkenyl,
cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or
alkylamidoalkyl. R.sub.1 has from about 8 to about 30 carbon atoms
and may be straight or branched chained and saturated or
unsaturated. Examples of long chain alkyl groups include, but are
not limited to, octadecenyl (oleyl), octadecyl (stearyl),
docosenoic (erucyl) and the derivatives of tallow, coco, soy and
rapeseed oils; R.sub.2 has the meaning as defined above for the
residue R.sub.2 of the zwitterionic surfactant; R.sub.3 is a
hydrocarbyl radical (e.g. alkylene) with a chain length of 1 to 4
carbon atoms. Preferred are methylene or ethylene groups.
Anionic Viscoelastic Surfactant
[0037] An anionic surfactant has a negatively charged moiety
regardless of pH. In an embodiment, the anionic surfactants
contemplated for use as viscoelastic surfactants in the present
invention include those of the following structural formulas (VII),
(VIII) and/or (VIII).
R--Z (VII)
R--X--Y--Z (VIII)
R--Y--Z (VIII)
where R is the hydrophobic moiety of alkyl, alkenyl, cycloalkyl,
alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl.
Preferably, R is a saturated or unsaturated, straight or branched
alkyl chain of at least 8 carbon atoms, and in another embodiment
from 8 to 30 carbon atoms. Examples of long alkyl chain groups
include, but not limited to, octadecenyl (oleyl), lauryl, octadecyl
(stearyl), docosenoic (erucyl) and the derivatives of tallow, coco,
soy and rapeseed oils; Z is the negatively charged hydrophilic head
of the surfactant. Z is suitably selected from the group consisting
of carboxylate COO.sup.-, sulfonate SO.sub.3.sup.-, sulfate
SO.sub.4.sup.- phosphonate, phosphate, and combinations thereofln
an embodiment, Z may be a carboxylate group COO.sup.- or a
sulfonate group SO.sub.3.sup.-; X is a stabilizing group. X is
preferably a cleavable bond. Preferably, X is an ester, amid,
reverse ester or reverse amide group; Y is a space group, which
separates the cleavable group X and the hydrophilic head of the
surfactant. Y is preferably a linear, saturated or unsaturated
hydrocarbon chain of 1, 2 or 3 carbon atoms or a branched,
saturated or unsaturated hydrocarbon chain where the main chain is
of 1, 2 or 3 carbon atoms, possibly incorporating an aromatic
ring.
[0038] Optionally, the surfactant of the invention may be dimeric
or oligomeric. In such case, the formula of the surfactant is
[R--Z].sub.n, or [R--X--Y--Z].sub.n, where n is 2-10, preferably 2
or 3. An example of an oligomeric anionic surfactant is
oligomerized oleic acid which generally leads to complex mixtures
of dimeric and trimeric products. Commercially available oligomers,
such as the Empol.TM. series of dimmers and trimers are suitable
for use in accordance with the present invention.
[0039] When the surfactant is anionic, the counter-ion is typically
Na.sup.+, K.sup.+, NH.sub.4.sup.+, or amine salt such as
(CH.sub.3).sub.2NH.sub.2.sup.+.
[0040] These mono-, di- or oligomeric carboxylates or sulfonates
form viscoelastic aqueous compositions in the presence of salt.
[0041] Preferably the surfactants that are used are biodegrable,
more preferably readily biodegradable, when testing using
conventional tests such as OECD 306 A-F.
[0042] Surfactants suitable in the present invention include those
known in the art for use in personal care compositions, and include
nonionic, anionic, cationic, and amphoteric surfactants. Classes of
surfactants useful in personal care compositions, such as personal
cleansing compositions, of the present invention include the
following: alcohols, alkanolamides, alkylaryl sulfonates, alkylaryl
sulfonic acids, alkylbenzenes, amine acetates, amine oxides,
amines, sulfonated amines and amides, betaines, block polymers,
carboxylated alcohol or alkylphenol ethoxylates, diphenyl sulfonate
derivatives, ethoxylated alcohols, ethoxylated alkylphenols,
ethoxylated amines and/or amides, ethoxylated fatty acids,
ethoxylated fatty esters and oils, fatty esters (other than glycol,
glycerol, etc.), fluorocarbon-based surfactants, glycerol esters,
glycol esters, heterocyclics, imidazolines and imidazoline
derivatives, isethionates, lanolin-based derivatives, lecithin and
lecithin derivatives, lignin and lignin derivatives, methyl esters,
monoglycerides and derivatives, olefin sulfonates, phosphate
esters, phosphorous organic derivatives, polymeric
(polysaccharides, acrylic acid, acrylamide), propoxylated and
ethoxylated fatty acids, propoxylated and ethoxylated fatty
alcohols, propoxylated and ethoxylated alkyl phenols, protein-based
surfactants, quaternary surfactants, sarcosine derivatives,
silicone-based surfactants, soaps, sorbitan derivative, sucrose and
glucose esters and derivatives, sulfates and sulfonates of oils and
fatty acids, sulfates and sulfonates ethoxylated alkyl phenols,
sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of
fatty esters, sulfonates of benzene, cumene, toluene and xylene,
sulfonates of condensed naphthalenes, sulfonates of dodecyl and
tridecyl benzenes, sulfonates of naphthalene and alkyl naphthalene,
sulfonates of petroleum, sulfosuccinamates, sulfosuccinates and
derivatives.
[0043] Anionic surfactants suitable for use in the personal care
compositions are the alkyl and alkyl ether sulfates. These
materials have the respective formulae--ROSO.sub.3M and
RO(C.sub.2H.sub.4O).sub.xSO.sub.3M wherein R is alkyl or alkenyl of
from about 8 to about 18 carbon atoms, x is an integer having a
value of from 1 to 10, and M is a cation, such as ammonium,
alkanolamine such as triethanolamine, monovalent metal, such as
sodium or potassium, and polyvalent metal cation, such as magnesium
or calcium. The cation M should be selected such that the anionic
surfactant component is water soluble. Solubility of the surfactant
depends upon the particular anionic surfactants and cations
chosen.
[0044] In an embodiment, R has from about 8 to about 18 carbon
atoms in both the alkyl and alkyl ether sulfates. In another
embodiment, R has from about 10 to about 16 carbon atoms. In even
another embodiment, R has from about 12 to about 14 carbon atoms.
The alkyl ether sulfates are typically made as condensation
products of ethylene oxide and monohydric alcohols having from
about 8 to about 24 carbon atoms. The alcohols can be synthetic or
they can be derived from fats (e.g., coconut oil, palm kernel oil,
tallow). In an embodiment, lauryl alcohol and straight chain
alcohols derived from coconut oil or palm kernel oil are preferred.
Such alcohols are reacted with between about 0 and about 10,
preferably from about 2 to about 5, more preferably about 3, molar
proportions of ethylene oxide, and the resulting mixture of
molecular species having, for example, an average of 3 moles of
ethylene oxide per mole of alcohol, is sulfated and
neutralized.
[0045] Specific non-limiting examples of alkyl ether sulfates which
can be used in the personal care compositions of the present
invention include, but are not limited to, sodium and ammonium
salts of coconut alkyl triethylene glycol ether sulfate, tallow
alkyl triethylene glycol ether sulfate, and tallow alkyl
hexaoxyethylene sulfate. In an embodiment, alkyl ether sulfates are
those comprising a mixture of individual compounds, wherein the
compounds in the mixture have an average alkyl chain length of from
about 10 to about 16 carbon atoms and an average degree of
ethoxylation of from about 1 to about 4 moles of ethylene
oxide.
[0046] Other suitable anionic surfactants are the water-soluble
salts of organic/sulfuric acid reaction products conforming to the
formula--[R.sup.1--SO.sub.3-M] where R.sup.1 is a straight or
branched chain, saturated, aliphatic hydrocarbon radical having
from about 8 to about 24, preferably about 10 to about 18, carbon
atoms; and M is a cation, such as ammonium, alkanolamine such as
triethanolamine, monovalent metal, such as sodium or potassium, and
polyvalent metal cation, such as magnesium or calcium. The cation M
should be selected such that the anionic surfactant component is
water soluble. Non limiting examples of such surfactants are the
salts of an organic sulfuric acid reaction product of a hydrocarbon
of the methane series, including iso-, neo-, and n-paraffins,
having from about 8 to about 24 carbon atoms, preferably about 12
to about 18 carbon atoms and a sulfonating agent (e.g., SO.sub.3,
H.sub.2SO.sub.4) obtained by known sulfonation methods such as
bleaching and hydrolysis. Preferred are alkali metal and ammonium
sulfonated C.sub.10 to C.sub.18 n-paraffins.
[0047] Still other suitable anionic surfactants are the reaction
products of fatty acids esterified with isethionic acid and
neutralized with sodium hydroxide where, for example, the fatty
acids are derived from coconut oil or palm kernel oil; sodium or
potassium salts of fatty acid amides of methyl tauride in which the
fatty acids, for example, are derived from coconut oil or palm
kernel oil. Other similar anionic surfactants are described in U.S.
Pat. Nos. 2,486,921, 2,486,922 and 2,396,278, each of which is
incorporated by reference in its entirety herein.
[0048] Succinates are another type of anionic surfactant suitable
for use in the personal care compositions of the present invention.
Examples include disodium N-octadecylsulfosuccinnate; disodium
lauryl sulfosuccinate; diammonium lauryl sulfosuccinate;
tetrasodium N-(1,2-carboxyethyl)-N-octadecyl sulfosuccinate; diamyl
ester of sodium sulfosuccinic acid; dihexyl ester of sodium
sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic
acid.
[0049] Other suitable anionic surfactants include olefin sulfonates
having about 10 to about 24 carbon atoms. In this context the term
"olefin sulfonates" refers to compounds produced by sulfonation of
.alpha.-olefins by means of uncomplexed sulfur trioxide, followed
by neutralization of the acid reaction mixture in conditions such
that any sulfones formed in the reaction are hydrolyzed to give the
corresponding hydroxy alkane sulfonates. The sulfur trioxide can be
liquid or gaseous, and is usually, but not necessarily, diluted by
inert diluents (e.g., by liquid SO.sub.2, chlorinated hydrocarbons,
etc.) when used in the liquid form, or by air, nitrogen, gaseous
SO.sub.2, etc., when used in the gaseous form. Those
.alpha.-olefins from which the olefin sulfonates are derived are
mono-olefins having from about 10 to about 24 carbon atoms, and
preferably from about 12 to about 16 carbon atoms. Preferably, they
are straight chain olefins. In addition to true alkene sulfonates
and a proportion of hydroxy alkane sulfonates, the olefin
sulfonates can contain minor amounts of other materials, such as
alkene disulfonates, depending upon reaction conditions, proportion
of reactants, nature of the starting olefins and impurities in the
olefin stock, and side reactions during the sulfonation process.
Combinations of .alpha.-olefins are also contemplated for use in
the present invention. A non-limiting example of such an
.alpha.-olefin sulfonate mixture is described in U.S. Pat. No.
3,332,880, which is incorporated by reference in its entirety
herein.
[0050] Another class of anionic surfactants suitable for use in the
personal care compositions are the .beta.-alkyloxy alkane
sulfonates. Examples of suitable anionic surfactants for use in the
personal care compositions 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, arumonium 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, and combinations thereof.
[0051] Suitable amphoteric or zwitterionic detersive surfactants
for use in the personal care composition herein include those which
are known for use in hair care or other personal care cleansing
composition, and which contain a group that is anionic at the pH of
the personal care composition.
[0052] Amphoteric surfactants suitable for use in the personal care
composition are well known in the art, and include those
surfactants broadly described as derivatives of aliphatic secondary
and tertiary amines in which the aliphatic radical can be straight
or branched chain, wherein at least one of the aliphatic
substituents contains from about 8 to about 18 carbon atoms and at
least one contains an anionic water solubilizing group such as
carboxy, sulfonate, sulfate, phosphate, or phosphonate.
[0053] Zwitterionic surfactants suitable for use in the personal
care composition are well known in the art, and include those
surfactants broadly described as derivatives of aliphatic
quaternary ammonium, phosphonium, and sulfonium compounds in which
the aliphatic radicals are straight or branched chain, and wherein
at least one of the aliphatic substituents contains from about 8 to
about 18 carbon atoms and at least one contains an anionic group
such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
Zwitterionic surfactants such as betaines are preferred.
[0054] Non-limiting examples of other nonionic, anionic,
zwitterionic, amphoteric or additional surfactants suitable for use
in the personal care compositions are described in McCutcheon's
Emulsifiers and Detergents 1989 Annual, MC Publishing, Glen Rock,
N.J., as well as U.S. Pat. Nos. 3,929,678 and 2,528,378, each of
which is incorporated by reference in its entirety herein.
[0055] Surfactants in the present invention can be used alone or in
combination.
Hydrophobically Modified Polymers
[0056] The hydrophobically modified polymers can be anionic
hydrophobically modified polymer or cationic hydrophobically
modified polymer or non-ionic hydrophobically modified polymer or
zwitterionic hydrophobically modified polymer.
[0057] The at least one hydrophobically modified polymer is formed
from polymerization of ethylenically unsaturated monomers using
polymerization conditions known to those skilled in the art.
[0058] The hydrophobically modified polymers have a number average
molecular weight of from 1,000, preferably from 1,500, for more
preferably from 2,500, to 100,000, more preferably to 90,000 and
more preferably to 50,000, and even more preferably to 25,000 Da.
In the context of this invention, the polymer molecular weights are
as determined with size exclusion chromatography using HPLC grade
water comprising 0.025M NaH.sub.2PO.sub.4, 0.025M
Na.sub.2HPO.sub.4, and 0.01M of sodium azide which was filtered
through a 0.2 .mu.m filter as the eluent and four separation
columns, G6000PWxI 7.8 mm.times.30 cm, G4000PWxI 7.8 mm.times.30
cm, G3000PWxI 7.8 mm.times.30 cm, and TSKgel Guard PWxI 6.0
mm.times.4 cm as the G2500 Guard column (all ex Tosoh Bioscience).
Polyacrylic acid sodium salt standards (ex American Polymer
Standards Corporation) were used for calibration. The polymers are
prepared in water at a concentration of 0.1% w/w. The weight
average (Mw) and number average molecular weight (Mn) of the
standards are:
TABLE-US-00001 1. Mw 1,300 Dalton Mn 830 Dalton 2. Mw 8,300 Dalton
Mn 6200 Dalton 3. Mw 83,400 Dalton Mn 47,900 Dalton 4. Mw 495,000
Dalton Mn 311,300 Dalton 5. Mw 1,700,000 Dalton Mn 1,100,000
Dalton
[0059] Injection column was 450 .mu.L for the standard and sample.
Inject the standards and build a first-order or second-order
calibration curve. Choose the curve with the best fit and within
the range of the sample molecular weight. Run time was 60 minutes
per injection for standard and sample.
[0060] Surprisingly, such low molecular weight polymers, that in
themselves are typically not thickeners, were found to interact
with the viscoelastic surfactants in a way that led to an increased
viscosity which is much higher than the viscosity of solution of
pure viscoelastic surfactant of the same concentration.
[0061] According to a non-binding theory, the
hydrophobically-modified polymers of the invention, notably its
pendant hydrophobic chains, interact in an improved way with the
surfactant micelles. This interaction conceivably increases the
worm- or rod-like micelle size, and/or cross-linked the micelles,
so that a higher viscosity is achieved. As a result, an aqueous
viscoelastic structure that satisfies the required rheology profile
is obtained using less amount of chemicals than previously
possible. At the same time the lower molecular weight polymers
allow easier handling of the polymer itself and faster preparation
of the compositions of the invention.
[0062] The hydrophobically-modified polymer has a backbone and,
attached to said backbone, randomly or not, pendant hydrophobic
chains. The polymer can be charged or non-charged, depending on the
monomers used and the pH of the aqueous composition in which it is
used. If too many hydrophobic groups are present, the
water-solubility decreases. If it is too low, the interaction with
the viscoelastic surfactant will become impaired. In an embodiment
of the invention the amount of hydrophobic monomer-derived units is
about 0.1 mole % or more. In another embodiment it is about 0.5
mole % or more and in a further embodiment it is about 1 mole % or
more of all the monomer units comprised in the polymer.
[0063] To a level of at least 0.1 mole %, based on the amount of
monomer units in the polymer, the hydrophobically modified polymer
comprises monomeric units each covalently bonded to a pendant,
optionally alkoxylated, hydrocarbyl group having from 6 to 40
carbon atoms, said pendant, optionally alkoxylated, hydrocarbyl
group being connected to the backbone of said hydrophobically
modified polymer via a non-ester containing linking group.
[0064] The pendant, optionally alkoxylated, hydrocarbyl group has
from 6, preferably from 8, more preferably from 11, for example
from 14, to 40, preferably to 32, more preferred to 24 carbon
atoms. The pendant hydrocarbyl group is typically a straight,
branched or cyclic, saturated or unsaturated hydrocarbyl, such as a
linear or branched alkyl, alkenyl, cycloalkyl, aryl, alkylaryl,
alkenylaryl or an alkoxylated derivative thereof. The hydrocarbyl
group can optionally be alkoxylated, such as obtained by
ethoxylating, propoxylating and/or butoxylating the alcohol or acid
corresponding to the hydrocarbyl group. If alkoxylated, the
alkyleneoxy group(s) will be located between the hydrocarbyl group
and the polymer backbone. Examples of pendant hydrocarbyl groups
include behenyl, stearyl, lauryl, 2-etylhexyl, 2-propylheptyl,
2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl,
2-dodecylhexadecyl, 2-tetradecyloctadecyl or their alkoxylated
derivatives, or the alkyl group of oleyl, coco, soya, erucyl or
tallow acids or alcohols or amines and their alkoxylated
derivatives. When the hydrocarbyl is alkoxylated, the carbon atoms
in the alkyleneoxy-groups are included in the carbon atom count of
the hydrocarbyl group, except for the carbon atoms of any
ethyleneoxy-groups, which due to the hydrophilicity of the
ethyleneoxy group are not included in the carbon atom count of the
hydrocarbyl group. To illustrate, an ethoxylated dodecyl group is
an alkoxylated hydrocarbyl group having 12 carbon atoms, whereas
hexyl propoxylated with 3 propoxylenoxy groups is an alkoxylated
hydrocarbyl group having 15 (6+9) carbon atoms.
[0065] Suitably, the hydrophobically-modified polymer is
synthesized by copolymerization of one or more hydrophilic, one or
more hydrophobic monomers, and optionally one or more other
nonionic monomers. The monomers used can be copolymerized in any
sequence. In an embodiment at least acrylic acid is used as a
hydrophilic monomer. In another embodiment the hydrophobic monomer
is selected from monomers that result in pendant hydrophobic chain,
pendant of the backbone of said polymer, having at least 8 carbon
atoms in said pendant chain. In an embodiment of the invention the
amount of hydrophobic monomer-derived units is about 0.1 mole % or
more. In another embodiment it is about 0.5 mole % or more and in a
further embodiment it is about 1 mole % or more of all the monomer
units comprised in the polymer.
[0066] In another embodiment of the invention the pendant,
optionally alkoxylated hydrocarbyl group comprises an alkyl
function with at most 11 carbon atoms and the hydrophobically
modified polymer contains, to a level, of from 0.1, such as from
such as from 0.5, for example from 1, to 20, such as to 10, for
example to 5 mole %, based on the amount of monomer units in the
polymer, monomeric units connected to such pendant, optionally
alkoxylated, hydrocarbyl group.
[0067] The pendant, optionally alkoxylated hydrocarbyl group is
connected to the backbone of the hydrophobically modified polymer
by via a non-ester containing linking group. Non-ester containing
linking groups may be a direct bond or:
##STR00007##
wherein R.sub.4 is a hydrocarbylene group having 1 to 10 carbon
atoms, preferably CH.sub.2, and the top bond of the linking group
is connected to the polymer backbone and the bottom bond is
connected to the pendant, optionally alkoxylated hydrocarbyl group.
Preferably, the non-ester containing linking group is a, but not
limited to, urea, urethane, imide, or amide containing linking
group, more preferably a urea or urethane containing linking
group.
[0068] The polymers of the invention can be produced by
copolymerizing suitable monomers, as described above, but they can
also be produced by modification of a polymer. Hence in an
embodiment of the invention, the polymer is produced in a
conventional way by reacting a functional polymer with a
hydrophobic modification agent, such as reacting a copolymer of
maleic anhydride, including polyisobutylene succinic acid
copolymers (PIBSA), with a fatty amine.
[0069] Alternatively, the hydrophobically modified polymer may be
produced by reacting a functional polymer with a hydrophobic
modification agent.
[0070] The hydrophobically modified polymer is suitably free from,
or contains at most 1, preferably at most 0.1, more preferably at
most 0.01 mole % based on the amount of monomer units in the
polymer, of monomeric units connected to pendant, optionally
alkoxylated, hydrocarbyl group having at least 10, preferably at
least 8, more preferably at least 6 carbon atoms connected to the
backbone of said hydrophobically modified polymer via an ester
containing linking group.
[0071] The hydrophobically modified polymer may obtained by
copolymerizing at least a first and at least a second ethylenically
unsaturated monomer, wherein said first monomer is an ethylenically
unsaturated monomer with an optionally alkoxylated hydrocarbyl
group having from 6, preferably from 8, more preferably from 11 to
40, preferably to 32, more preferably to 24 carbon atoms being
connected to the unsaturated function of said monomer via a
non-ester containing linkage, preferably a urea, urethane, imide
and amide containing linkage, more preferably a urea or urethane
containing linkage; and said second monomer is an ethylenically
unsaturated monomer free from hydrocarbyl groups having at least
11, preferably at least 8, more preferably at least 6 carbon atoms
connected to the unsaturated function of the monomer. The first and
second monomers are present in a molar ratio of from 0.1:99.9 to
90:10.
[0072] When the optionally alkoxylated hydrocarbyl group has at
least 12 carbon atoms, the first and second monomers are usually
present in a molar ratio of from 0.1:99.9 to 20:80; preferably from
0.5:99.5 to 10:90, more preferably from 1:99 to 5:95.
[0073] When the optionally alkoxylated hydrocarbyl group has at
most 11 carbon atoms, the first and second monomers are usually
present in a mutual molar ratio of from 1:99 to 90:10; preferably
from 5:95 to 70:30, more preferably from 10:90 to 50:50. In another
embodiment the hydrophobically-modified polymer is obtained by
first copolymerizing a monomer mixture comprising at least a
hydrophobic and a hydrophilic monomer and reacting the resulting
copolymer with further hydrophilic or hydrophobic reagents as to
refine its properties.
[0074] Monomers with an optionally alkoxylated hydrocarbyl group
having from 6 to 40 carbon atoms connected to the unsaturated
function thereof via a non-ester containing linkage (herein also
referred to hydrophobe-bearing monomers) include those with the
following structure (VIIII)
##STR00008##
where R1, R2, and R3 are independently selected from H, CH.sub.3,
COOH, and CH.sub.2COOH, X is a direct bond or
##STR00009##
wherein R.sub.4 is a hydrocarbylene group having from 1 to 10
carbon atoms, preferably CH.sub.2, the top bond of X is connected
to the double bond in (VIII) and the bottom bond of X is connected
to R.sub.hy, and R.sub.hy is the optionally alkoxylated hydrocarbyl
group having from 6, preferably from 8, more preferably form 11 to
40, preferably to 32, more preferably to 24 carbon atoms.
[0075] Hydrophobe-bearing monomers of the above type are
commercially available or can be obtained by methods well known in
the art, for example by reacting a ethylenically unsaturated
isocyanate, such as allyl-isocyanate or
3-isopropyl-benzyl-.alpha.,.alpha.-dimethyl-isocyanate, with an
alcohol or amine containing a hydrocarbyl group (optionally
alkoxylated) having from 6 to 40 carbon atoms, by reacting an
ethylenically unsaturated acid monomer, such as acrylic acid, with
an amine containing a hydrocarbyl group (optionally alkoxylated)
having from 6 to 40 carbon atoms. Other methods to synthesize such
monomers are well known to the person skilled in the art of organic
synthesis.
[0076] Examples of hydrophobe-bearing monomers where the hydrophobe
is linked to the double bond of the monomer include t-octyl
acrylamide, n-octyl acrylamide, lauryl acrylamide, stearyl
acrylamide, behenyl acrylamide, 1-allyl naphthalene, 2-allyl
naphthalene, 1-vinyl naphthalene, 2-vinyl naphthalene, styrene,
.alpha.-methyl styrene, 3-methyl styrene, 4-propyl styrene, t-butyl
styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl
styrene and 4-(phenyl butyl) styrene.
[0077] The ethylenically unsaturated monomer free from hydrocarbyl
groups having 11 or more, preferably 8 or more, more preferably 6
or more carbon atoms connected to the unsaturated function of the
monomer, i.e. the second monomer, may be anionic ethylenically
unsaturated monomers, cationic ethylenically unsaturated monomers,
non-ionically ethylenically unsaturated monomers, zwitterionic
ethylenically unsaturated monomers, mixtures thereof and salts
thereof.
[0078] In an embodiment, the hydrophobically modified polymer is
anionic and is synthesized from at least one first ethylenically
unsaturated hydrophobe-bearing monomer and at least one second
ethylenically unsaturated monomer that is anionic and referred to
as an anionic ethylenically unsaturated monomer hereforth. In
another embodiment, the hydrophobically modified polymer is
cationic and is synthesized from at least one first ethylenically
unsaturated hydrophobe-bearing monomer and at least one second
ethylenically unsaturated monomer that is cationic and referred to
as a cationic ethylenically unsaturated monomer hereforth. In yet
another embodiment, a the hydrophobically modified polymer is
non-ionic and is synthesized from at least one first ethylenically
unsaturated hydrophobe-bearing monomer and at least one second
ethylenically unsaturated monomer that is non-ionic and referred to
as a non-ionic ethylenically unsaturated monomer hereforth. In a
further embodiment, a the hydrophobically modified polymer is
zwitterionic and is synthesized from at least one first
ethylenically unsaturated hydrophobe-bearing monomer and at least
one second ethylenically unsaturated monomer that is zwitterionic
and referred to as a zwitterionic ethylenically unsaturated monomer
hereforth. In this embodiment, the polymer contains positive and
negative charges which are on the same monomer repeat unit. In yet
another embodiment, the hydrophobically modified polymer is
zwitterionic and synthesized from at least one first ethylenically
unsaturated hydrophobe-bearing monomer and at least one anionic
ethylenically unsaturated second monomer and at least one cationic
ethylenically unsaturated second monomer and at least one
hydrophobe-bearing monomer. In this embodiment, the polymer
contains positive and negative charges which are on different
monomer repeat units.
[0079] Herein an anionic ethylenically unsaturated monomer is
defined as any monomer that is capable of introducing a negative
charge to the hydrophobically modified polymer. These anionic
ethylenically unsaturated monomers include of acrylic acid,
methacrylic acid, ethacrylic acid, .alpha.-chloro-acrylic acid,
.alpha.-cyano acrylic acid, .beta.-methyl-acrylic acid (crotonic
acid), .alpha.-phenyl acrylic acid, .beta.-acryloxy propionic acid,
sorbic acid, .alpha.-chloro sorbic acid, angelic acid, cinnamic
acid, p-chloro cinnamic acid, .beta.-styryl acrylic acid
(1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid,
citraconic acid, mesaconic acid, glutaconic acid, aconitic acid,
fumaric acid, tricarboxy ethylene, 2-acryloxypropionic acid,
2-acrylamido-2-methyl propane sulfonic acid (AMPS), vinyl sulfonic
acid, sodium methallyl sulfonate, sulfonated styrene,
allyloxybenzene sulfonic acid and their salts. The preferred salts
of hydrophilic acid monomers are sodium, potassium or ammonium
salts. Moieties such as maleic anhydride or acrylamide that can be
derivatized to an acid-containing group can be used. Combinations
of acid-containing hydrophilic monomers can also be used. In one
aspect the acid-containing hydrophilic monomer is acrylic acid,
maleic acid, itaconic acid, methacrylic acid, 2-acrylamido-2-methyl
propane sulfonic acid, vinyl sulfonic acid, sodium methallyl
sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid or
mixtures thereof and their salts.
[0080] Cationic polymers can be obtained by (co)polymerizing a
cationic monomer or by functionalizing a polymer after
polymerization. Cationic ethylenically unsaturated monomers are
ethylenically unsaturated monomers which are capable of introducing
a positive charge to the hydrophobically-modified copolymer. In an
embodiment of the present invention, the cationic ethylenically
unsaturated monomer has at least one amine functionality. The
cations in the polymer may be obtained by forming amine salts of
all or a portion of the amine functionality, and/or by quaternizing
all or a portion of the amine functionality to form quaternary
ammonium salts, or by oxidizing all or a portion of the amine
functionality to form N-oxide groups. As used herein, the term
"amine salt" means that the nitrogen atom of the amine
functionality is covalently bonded to from one to three organic
groups and from three to one protons, such that there are 4 bonds
to the nitrogen and it is associated with an anion. As used herein,
the term "quaternary ammonium salt" means that a nitrogen atom of
the amine functionality is covalently bonded to four organic groups
and is associated with an anion.
[0081] Monomers that can form cations include, but are not limited
to, N,N-dialkylaminoalkyl (meth)acrylate, N-alkylanninoalkyl
(meth)acrylate, N,N-dialkylanninoalkyl (meth)acrylamide and
N-alkylaminoalkyl (meth)acrylamide, where the alkyl groups are
independently C.sub.1-18 cyclic compounds such as 1-vinyl imidazole
and the like. Aromatic amine containing monomers such as vinyl
pyridine may also be used. Furthermore, monomers such as vinyl
formamide, vinyl acetamide and the like which generate amine
moieties on hydrolysis may also be used. Preferably the cationic
ethylenically unsaturated monomer is N,N-dimethylaminoethyl
methacrylate, tert-butyl aminoethyl methacrylate and
N,N-dimethylaminopropyl methacrylamide. Cationic ethylenically
unsaturated monomers that may be used include the quarternized
derivatives of the above monomers as well as
diallyldimethylammonium chloride also known as
dimethyldiallylammonium chloride, (meth)acrylamidopropyl
trimethylammonium chloride, 2-(meth)acryloyloxy ethyl trimethyl
ammonium chloride, 2-(meth)acryloyloxy ethyl trimethyl ammonium
methyl sulfate, 2-(meth)acryloyloxyethyltrimethyl ammonium
chloride, N,N-Dimethylaminoethyl (meth)acrylate methyl chloride
quaternary, methacryloyloxy ethyl betaine as well as other betaines
and sulfobetaines, 2-(meth)acryloyloxy ethyl dimethyl ammonium
hydrochloride, 3-(meth)acryloyloxy ethyl dimethyl ammonium
hydroacetate, 2-(meth)acryloyloxy ethyl dimethyl cetyl ammonium
chloride, 2-(meth)acryloyloxy ethyl diphenyl ammonium chloride and
others.
[0082] As used herein, the term "nonionic ethylenically unsaturated
monomer" means an ethylenically unsaturated monomer which does not
introduce a charge to the hydrophobically-modified copolymer. These
nonionic ethylenically unsaturated monomers include, but are not
limited to, acrylamide, styrene, acylonitrile rmethacrylamide,
N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide such as
N,N-dimethylacrylamide, hydroxyalkyl(meth)acrylates,
alkyl(meth)acrylates such as, methylacrylate and
methylmethacrylate, vinyl acetate, acrylonitrile, vinyl morpholine,
vinyl pyrrolidone, vinyl caprolactum, ethoxylated alkyl, alkaryl or
aryl monomers such as methoxypolyethylene glycol (meth)acrylate,
allyl glycidyl ether, allyl alcohol, glycerol (meth)acrylate,
monomers containing silane, silanol and siloxane functionalities
and others. In an embodiment the non-ionic hydrophobically modified
polymer contains vinyl alcohol which is typically generated by
hydrolysis of vinyl acetate after the hydrophobically modified
polymer has been formed. The nonionic ethylenically unsaturated
monomer is preferably water soluble.
[0083] As used herein, the term "zwitterionic ethylenically
unsaturated monomer" means an ethylenically unsaturated monomer
which introduces both a positive and a negative charge in the same
monomer repeat unit of the hydrophobically modified copolymer. The
zwitterionic ethylenically unsaturated monomers include amine
oxides carboxybetaine, sulfobetaine, and phosphobetaine monomers.
Examples of amine oxides include, but are not limited to, vinyl
pyridine-N-oxide and tert-butyl-aminoethylmethacrylate-N-oxide. It
is understood that the monomer, say N-vinyl pyridine, can be
copolymerized and then the pyridine moiety is oxidized to the amine
oxide. Examples of carboxybetaine monomers include, but are not
limited to,
N,N'-dimethyl-N-methacryloyloxyethyl-N-(2-carboxyethyl)ammonium,
(2-(2-acrylamido-2-methylpropyldimethylammonio)ethanoate,
6-(2-acrylamido-2-methylpropyl dimethyl-ammonia)hexanoate,
4-(N,N-diallyl-N-methylammonio)butanoate, and others. Examples of
sulfobetaine monomers include, but are not limited to,
sulfopropyldimethylammonioethyl methacrylate,
sulfoethyldimethylammonioethyl methacrylate,
sulfobutyldimethylammonioethyl methacrylate, sulfohydroxy
propyl-dimethylammonioethyl methacrylate, sulfopropyldimethyl
ammoniopropylacrylamide,
sulfopropyldimethylammoniopropylmethacrylamide,
sulfohydroxypropyldimethyl-ammoniopropylmethacrylamide,
sulfopropyldimethylammonioethyl acrylate,
sulfopropyl-diethylammonioethoxyethyl methacrylate,
2-vinyl-1-(3-sulfopropyl)pyridinium betaine,
4-vinyl-l-(3-sulfopropyl)pyridinium betaine,
l-vinyl-3-(3sulfopropyl)imidazolium betaine,
sulfopropylmethyldiallylammonium betaine,
3-(N,N-diallyl-N-methylammonio)propane-sulfonate, and others.
[0084] As mentioned before, a zwitterionic hydrophobically modified
polymer can be synthesized by copolymerizing an anionic
ethylenically unsaturated monomer and a cationic ethylenically
unsaturated monomer with a hydrophobe-bearing monomer. Any
combination of anionic and cationic monomers may be used. However,
the preferred anionic monomer will introduce a sulfonate group to
the copolymer.
[0085] A polymer of the present invention may comprise further
monomers in addition to those mentioned above.
[0086] It should be noted that the hydrophobically modified
polymers of the invention are not conventional thickeners, due to
their low molecular weight. In an embodiment of the invention, the
number average molecular weight of the polymers, neutralized or
not, may for example be chosen such that they do not thicken a 4 wt
% KCl solution in water when used at concentrations of 2 wt % in
said KCl solution, at a temperature of 25.degree. C. In another
embodiment, the molecular weight of the polymer is chosen such that
an aqueous solution of 2 wt % of the polymer and 4 wt % of KCl has
a viscosity of 100 or less, preferably 50 or less, most preferably
16 mPas or less at a shear rate of 100 sec.sup.-1 and a temperature
of 25.degree. C. Optionally, the polymers are neutralized.
[0087] Because of the exceptional properties observed for the
compositions of the invention with the viscoelastic surfactant and
the specific polymer, it is possible to reduce the amount of
surfactant and/or polymer. It was also surprisingly found that the
increased viscosity can be achieved at a polymer concentration that
is lower than the overlap concentration c*. The polymer overlap
concentration c* is a threshold concentration when polymer coils
begin to densely pack in a solvent. In a dilute polymer solution
where polymer concentration is below c*, the polymer coils are
separated. In a polymer solution where the polymer concentration is
above c*, the polymer coils are densely packed. The detailed
definition of c* is described by Pierre-Gilles de Gennes in
"Scaling Concept on Polymer Physics", pp. 76-77, Cornell University
Press, Ithaca and London (1979). c* is measured by the plot of
viscosity versus concentration. At low concentrations, the plot
will follow a linear path and once the c* is reached, the slope of
the line drastically increases. For the purposes herein, the
polymer overlap concentration c* is measured at 25.degree. C. at
atmospheric pressure in the solvent. Accordingly, in an embodiment
it may be desired for economic and environmental reasons to use the
polymers of the invention at a polymer concentration that is below
the overlap concentration c*. Further, it is noted that the
polymers of the invention were found to interact with viscoelastic
surfactants in such a way that the combined use leads to increased
viscosities at high temperature (tested up to 100.degree. C.) and
pressures (tested up to 25 bara.)
[0088] If the combination of viscoelastic surfactant and polymer of
the invention is supplied in a concentrated form, it is preferably
in an aqueous, essentially salt-free form. Such an aqueous
concentrate has the advantage of having a low viscosity and related
easy dilution. Typical aqueous concentrates comprise one or more
glycols, such as propylene glycol, so that the viscoelastic
surfactant is more easily dissolved in the concentrate. Typically,
the amount of viscoelastic surfactant in such a concentrate is
within the range of greater than 10% w/w, preferably 10-60% w/w,
whereas the amount of polymer ranges from about 5-30% w/w, based on
the weight of the concentrate. By the term essentially salt-free it
is meant that the salt concentration is less than 0.01% w/w,
otherwise the viscosity becomes unacceptably high.
[0089] For personal care applications, the viscoelastic surfactant
is used in an amount below about 40% w/w, preferentially, below
about 20% w/w of the final viscoelastic aqueous composition. Also
the viscoelastic surfactant is suitably used in an amount of about
1% w/w or more. In an embodiment it is about 5% w/w or more, while
in another embodiment it is about 7% w/w or more, all being based
on the weight of the total viscoelastic aqueous composition.
[0090] In general, the hydrophobically modified polymer is used in
an amount of 10% w/w or less. In an embodiment of the invention, it
is 5% w/w or less. In another embodiment it is 2% or less, while in
a further embodiment it is 1% w/w or less. The polymer is to be
used in an amount of at least 0.01% w/w. All of these amounts are
based on the weight of the total viscoelastic aqueous
composition.
[0091] The weight ratio of hydrophobically modified polymer to
viscoelastic surfactant is usually from 0.1:100, preferably from
1:100, more preferably from 3:100, to 100:50, preferably to
100:100, more preferably to 50:100. The viscoelastic compositions
of the invention may also comprise one or more chelating agents.
Particularly when the aqueous formulations or the area where the
compositions are used has a lot of hardness ions, the use of
chelating agents for such ions was found to be beneficial. Without
wishing to be bound by theory, it is thought that these hardness
ions tend to precipitate the hydrophobically modified polymer in
the aqueous solution. The addition of chelating agents, according
to said theory, prevents the precipitation of these hydrophobically
modified polymers and preserves the performance of the mixture of
these polymers and viscoelastic surfactants in high hardness
aqueous solutions.
[0092] For purposes of this invention, a chelating agent is
described as any material that will chelate hardness ions, such as
calcium and magnesium, in aqueous solutions. Chelating agents
include but are not limited to (S,S)-ethylenediaminesuccinic acid
trisodium salt, N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium
salt, L-aspartate-(N,N)-diacetic acid tetrasodium salt,
N-2-hydroxyethyliminodiacetic acid disodium salt,
methylglycinediacetic acid trisodium salt,
ethylenediaminetetraacetic acid, nitorilotriacetic acid,
diethylenetriaminepentaacetic acid,
hydroxyethylethylenediaminetriacetic acid,
triethylenetetraminehexaacetic acid, 1,3-propanediaminetetraacetic
acid, 1,3-diamino-2-hydroxypropanetetraacetic acid,
dihydroxyethylglycine, glycol ether diamine tetraacetic acid,
hydroxyethanediphosphonic acid, aminotrimethylenephosphonic acid,
1,2,4-butanetricarboxylic acid,
dihydroxyethylethylenediaminediacetic acid, sodium gluconate,
sodium glucoheptonate, inositol hexaphosphate, hydroxyethanoic
acid, 2-hydroxypropanoic acid, 2-hydroxysuccinic acid,
2,3-dihydroxybutanedioic acid, and
2-hydroxy-1,2,3-propanetricarboxylic acid and their salts. The
preferred chelating agents are aminocarboxylates, such as
(S,S)-ethylenediaminesuccinic acid trisodium salt,
N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt,
L-aspartate-(N,N)-diacetic acid tetrasodium salt,
N-2-hydroxyethyliminodiacetic acid disodium salt,
methylglycinediacetic acid trisodium salt,
ethylenediaminetetraacetic acid, nitrilotriacetic acid, and their
salts. For purposes of this invention, a high hardness aqueous
solution is defined as a solution with a hardness of greater than
100 ppm expressed as CaCO.sub.3, more preferably greater than 250
ppm as CaCO.sub.3, and most preferably greater than 500 ppm as
CaCO.sub.3.
[0093] In addition to the aqueous viscoelastic solution, the
personal care compositions of the present invention also include a
personal care active ingredient. In hair care formulations, the
personal care active ingredients may provide beneficial properties
to hair such as improved cleanliness, fragrance, improved shine,
improved wet combability, improved dry combability, improved wet
feel, improved dry feel, improved strength, or improved color. In
skin care formulations, the personal care active ingredients may
provide beneficial properties to skin such as improved cleanliness,
fragrance, preparation for shaving, improved smoothness, improved
appearance, reduced wrinkle, improved color, or improved tone. Such
active ingredients include, without limitation, thickeners,
emulsifiers, aesthetic modifiers, UV filters, humectants (such as
hydroxyethyl urea, available from Akzo Nobel Surface Chemistry
under the trademark HYDROVANCE.RTM.), lubricants, skin whitening
ingredients, silicones, powders, de-viscosifying agents,
moisturizers, emollients, solvents, chelating agents, vitamins,
antioxidants, botanical extracts, pH adjusting agents,
preservatives, fragrances, waterproofing agents, anti-aging agents,
firming forming polymers, toning agents, dyes, pigments, colors,
polymers, conditioning agents, rheology modifiers, surfactants,
opacifiers, foaming agents, heat generating agents and/or
effervescing agents, glitter and decorative beads and shapes. In an
embodiment of the invention, the personal care composition may be a
hair care formulation, such as a shampoo or a conditioner, or a
skin care formulation such as a body wash or shave preparation.
[0094] The active ingredient will be present in the personal care
composition from about 0.01 to about 10% of the total formula
weight. In an embodiment of this invention the active ingredient
will be present from about 0.1 to about 5 percent by weight based
on the total weight of the personal care formulation (dry basis).
In another embodiment, the active viscoelastic aqueous composition
will be present from about 0.3 to 4% of the total weight of
personal care formulation (dry basis).
[0095] The viscoelastic aqueous composition will be present from
about 0.1 to about 10 wt % of the total personal care formulation
(dry basis). In an embodiment of this invention the viscoelastic
aqueous composition will be present from about 0.2 to about 5 wt %
of the total personal care formulation (dry basis). In another
embodiment, the viscoelastic aqueous composition will be present
from about 0.3 to 4 wt % of the total weight of the personal care
formulation (dry basis).
[0096] In an embodiment, salt can be added to the formulation to
assist in increasing viscosity. Typical levels of salt that can be
added to the personal care composition will be from about 0.1 to
about 10% based on the total weight of the composition. Typical
salts will be, for example, alkaline metal and alkaline earth
cations of common anions (e.g. sulfate, chloride, bromide, nitrate,
phosphate, carbonate, and mixtures thereof). In another embodiment
the salt will be sodium chloride, calcium chloride or mixtures
thereof. In yet another embodiment the salt will be present in an
amount from about 1 to about 5 percent based on the total weight of
the composition.
[0097] With the exception of the information in the examples, or
where otherwise indicated, all numbers or expressions referring to
quantities of ingredients, reaction conditions, and the like, used
in the specification and claims are to be understood as modified in
all instances by the term "about". Further, where numerical ranges
are disclosed they are meant to be continuous ranges that include
every value between the minimum and maximum value as presented. Wt
% and % w/w mean percent by weight.
[0098] The invention will now be further described in connection
with the following Examples which are not intended to limit the
scope thereof. Unless otherwise stated, all parts and percentages
refer to parts and percentages by weight. All numbers given relate
to the amount of active material. So if in the examples 10% w/w of
a chemical is specified, then the amount to be used of the supplied
product is to be increased if the product is supplied in a diluted
form.
EXAMPLES
[0099] Except where indicated otherwise, the viscosity of samples
has been determined over a broad shear rate range using a
stress-controlled rheometer SR-5000 (from Rheometric Scientific,
which is now TA Instruments). The sample was placed between two
circular parallel plates of 25 mm or 40 mm in diameter and
evaluated at a temperature of 25.degree. C. Typically the initial
stress was 0.5 Pa and the final stress was in the 150-400 Pa range,
depending on the viscosity of the sample, with the lower final
stress selected for samples with lower viscosity. In the linear
sweep mode a stress increment of 0.5-2 Pa was applied.
[0100] Aromox.RTM. APA-TW is a commercial tallowalkylamidopropyl
dimethyl amine oxide supplied by AkzoNobel.
[0101] POLYFLOS.RTM. HM 21 is a hydrophobically modified
hydroxypropyl guar gum supplied by Lambed spa, and was used as
received. This polymer was used as a comparison for the polymers of
the invention.
Preparation of Hydrophobically-Modified Polymer R7-33-43
Synthesis of Behenyl Alcohol Urethane of m-TMI Monomer
[0102] 75 g of behenyl alcohol (available from Cognis) was melted
and added to a reactor and heated to 95.degree. C. and sparged with
nitrogen for 4 hours to remove any water. The nitrogen sparge was
discontinued and the reaction temperature lowered to 78.degree. C.
0.3 g of monomethyl ether hydroquinone (MEHQ) inhibitor and 0.3
grams of Stannous 2-ethylhexanoate (FASCAT.RTM. 2003 available from
Arkema Inc, Philadelphia, Pa.) were then added to the reactor. 47.6
g of 3-isopropenyl-.alpha.,.alpha.-dimethylbenzyl isocyanate (m-TMI
available from Cytec, Stamford, Conn.) was then slow added to the
reactor over a period of 30 minutes. A slight exotherm was observed
which raised the temperature to 78 to 83.degree. C. After the
addition, the reactor was held at 80.degree. C. for an additional
30 minutes. The final product was a liquid which cooled down to a
solid at room temperature.
Synthesis of the Polymer R7-33-43
[0103] An initial charge of 40.8 g of water and 153.5 g of
isopropyl alcohol were added to a 1 liter glass reactor. The
reactor contents were heated to reflux (approximately 82 to
84.degree. C.). In a separate beaker, 142 g of acrylic acid was
warmed to 55.degree. C. and then 60 g of the behenyl alcohol
urethane of m-TMI of the previous step was added with stirring.
This warm mixture was added to the reactor at reflux over a period
of 2.5 hours. A solution of 1.9 g of sodium persulfate dissolved in
60 g of water was simultaneously added but over said period of 2.5
hours. The reaction temperature was maintained at about 85.degree.
C. for one hour. A scavenge feed (to minimize residual monomer)
containing 0.175 g of sodium persulfate dissolved in 10 g of water
was then added to the reactor over 30 minutes and maintained for an
additional 30 minutes. The reactor was then set up for distillation
which was carried out at increased temperature and/or reduced
pressure, to ensure a controlled distillation without polymer
degradation. A small amount of ANTIFOAM.RTM. 1400 (0.12 g) (from
Dow Chemical) was added to suppress any foam generated during
distillation. The alcohol (the cosolvent) was removed from the
polymer solution by azeotropic distillation. During the
distillation, about 1350 g of water was added. Approximately, 263 g
of a mixture of water and isopropyl alcohol were distilled off.
After distillation was completed, the reaction mixture was cooled
and 21.8 g of 50% NaOH was added. The final product had a pH of 2.2
and solids of 13.3 percent.
Preparation of Hydrophobically-Modified Polymer R7-33-61
Synthesis of Armeen 18D m-TMI Monomer
[0104] 70 g of octadecylamine (Armeen.RTM. 18D available from
AkzoNobel Surface Chemistry) was melted and added to a reactor and
heated to 90.degree. C. The liquid octadecylamine was sparged with
nitrogen for 4 hours to remove any water in the material. The
nitrogen sparge was discontinued and the reaction temperature
lowered to 78.degree. C. 0.3 g of monomethyl ether hydroquinone
(MEHQ) inhibitor and 0.3 grams of Stannous 2-ethylhexanoate
(FASCAT.RTM. 2003 available from Arkema Inc, Philadelphia, Pa.)
were then added to the reactor. 52.2 g of
3-isopropenyl-.alpha.,.alpha.-dimethylbenzyl isocyanate (m-TMI
available from Cytec, Stamford, Conn.) was then slowly added to the
reactor over a period of 45 minutes. A slight exotherm was observed
which raised the temperature to 80 to 83.degree. C. After the
addition, the reactor was held at 80.degree. C. for an additional
30 minutes. The final product was a liquid which cooled down to a
solid at room temperature.
Synthesis of the Polymer R7-33-61
[0105] An initial charge of 38 g of water and 150 g of isopropyl
alcohol were added to a 1 liter glass reactor. The reactor contents
were heated to reflux (approximately 82 to 84.degree. C.). In a
separate beaker, 142 g of acrylic acid was warmed to 55.degree. C.
and then 58.4 g of the Armeen 18D m-TMI monomer was added with
stirring. This warm mixture was added to the reactor at reflux over
a period of 2.5 hours. A solution of 1.9 g of sodium persulfate
dissolved in 61 g of water was simultaneously added but over a
period of 2.5 hours. The reaction temperature was maintained at
about 85.degree. C. for one hour. A scavenge feed containing 0.17 g
of sodium persulfate dissolved in 10 g of water was then added to
the reactor over 30 minutes and held at temperature for an
additional 30 minutes. The reactor was then set up for
distillation. A small amount of ANTIFOAM.RTM. 1400 (0.12 g) (from
Dow Chemical) was added to suppress any foam generated during
distillation. The alcohol cosolvent was removed from the polymer
solution by azeotropic distillation. During the distillation, about
1080 g of water was added. Approximately, 251 g of a mixture of
water and isopropyl alcohol were distilled off. After distillation
was completed, the reaction mixture was cooled. The final product
had a pH of 2.5 and solids of 15.7 percent.
Preparation of Hydrophobically-Modified Polymer R7-36-72
Synthesis of 2-Decyl-Tetradecanol m-TMI Monomer
[0106] 150 g of 2-decyl-tetradecanol (branched alcohol)
[Isofol.RTM. 24 (97.5%) (available from Sasol, Houston, Tex.)] was
added to a 500 ml reactor and heated to 80.degree. C. The reactor
contents were sparged with nitrogen for 4 hours to remove any water
in the material. The nitrogen sparge was discontinued and the
reaction temperature lowered to 68.degree. C. 0.33 g of monomethyl
ether hydroquinone (MEHQ) inhibitor and 0.33 g of Stannous
2-ethylhexanoate (FASCAT 2003 available from Arkema Inc,
Philadelphia, Pa.) were then added to the reactor. 82.5 g of
3-isopropenyl-.alpha.,.alpha.-dimethylbenzyl isocyanate (m-TMI
available from Cytec, Stamford, Conn.) was then slowly added to the
reactor over a period of 30 minutes. A slight exotherm was observed
which raised the temperature to 70 to 71.degree. C. After the
addition, the reactor was held at 72.degree. C. for an additional
60 minutes. The final product was a liquid.
Synthesis of the Polymer R7-36-72
[0107] An initial charge of 43 g of water and 133 g of isopropyl
alcohol were added to a 1 liter glass reactor. The reactor contents
were heated to reflux (approximately 82 to 84.degree. C.). A first
monomer solution of 33 g of acrylic acid, 20.11 g of
2-decyl-tetradecanol m-TMI monomer (synthesized above), 9,9 g of
isopropyl alcohol and 4.1 g of hydroxypropyl methacrylate was added
to the reactor at reflux over a period of 75 minutes. A second
monomer solution containing 12.8 grams of 50% 2-acrylamido-2-methyl
propane sulfonic acid, sodium salt in 20 g of water was added
concurrently over a period of 75 minutes. An initiator solution of
0.97 g of sodium persulfate dissolved in 28.3 g of water was
simultaneously added but over a period of 90 minutes. The reaction
temperature was maintained at about 85.degree. C. for one hour. A
scavenge feed containing 0.15 g of sodium persulfate dissolved in
10 g of water was then added to the reactor over 30 minutes and the
temperature was held for an additional 30 minutes. The reactor was
then set up for distillation and a small amount of ANTIFOAM.RTM.
1400 (0.12 g) (from Dow Chemical) was added to suppress any foam
generated during distillation. The alcohol cosolvent was removed
from the polymer solution by azeotropic distillation.
Approximately, 185 g of a mixture of water and isopropyl alcohol
were distilled off. During the distillation, about 242 g of water
was added to replace the distillate and keep the viscosity at a
manageable level. After distillation was completed, the reaction
mixture was cooled and 7 g of 50% NaOH in 15 g of water was added.
The final product had a pH of 4.2 and solids of 16.9 percent.
Preparation of Polymer R7-33-158
[0108] An initial charge of 77 g of water and 100 g of isopropanol
were added to a 1 liter glass reactor. The reactor contents were
heated to 82.degree. C. A first solution which is a mixture of 72.7
g of acrylic acid and 21.6 g of an N-octadecyl acrylamide dissolved
in 50 g of isopropanol was added to the reactor over a period of 80
minutes. A second solution of 0.97 g of sodium persulfate dissolved
in 46 g of water was simultaneously added at the same time but over
a period of 90 minutes. After the second solution addition was
completed, a solution of 0.09 g of sodium persulfate dissolved in
14 g of water was then added over a period of 10 minutes. The
reactor was then set up for distillation. The alcohol cosolvent was
removed from the polymer solution by azeotropic distillation.
During the distillation, 450 g of water was dripped in and
approximately, 303 g of a mixture of water and alcohol were
distilled off. The final product was a clear colorless viscous
solution with a pH of 2.6 and a solids content of 19.9%.
Preparation of Polymer R7-33-28
[0109] An initial charge of 72.9 g of water and 50.9 g of ethanol
were added to a 500 ml glass reactor. The reactor contents were
heated to reflux (approximately 82 to 84.degree. C.). A mixture of
38.1 g of acrylic acid and 5.55 g of lauryl methacrylate was added
to the reactor at reflux over a period of 3 hours. A solution of
0.6 g of sodium persulfate dissolved in 32 g of water was
simultaneously added but over a period of 4 hours. The reaction
temperature was maintained at about 85.degree. C. for 30 minutes.
The reactor was then set up for distillation. The alcohol cosolvent
was removed from the polymer solution by azeotropic distillation.
During the distillation, 38.8 g of 50% NaOH dissolved in 70 g of
water was dripped in added. Approximately, 99.3 g of a mixture of
water and ethanol were distilled off. The final product has 25.25%
solid and pH=7.5.
Preparation of Polymer J3-9-46
[0110] An initial charge of 150 g diallyldimethylammonium chloride
(65% Aldrich commercial material further concentrated to 88% by
removal of water), 150 g isopropyl alcohol, and 32.2 g
2-decyl-tetradecanol m-TMI monomer (synthesized above) was added to
a 1 liter glass reactor fitted with a condenser for reflux. An
initiator feed consisting of Esperox 28 in isopropyl alcohol (16.4
g in a total volume of 100 mL) was prepared. The reaction was
maintained in the range of 83 to 87.degree. C., to allow for reflux
of IPA, while the initiator solution was added over a period of 2
hr. Following the initiator slow addition, the reaction was
maintained at 83.degree. C. (refluxing IPA) for 2.5 hours. The
reaction was cooled below the reflux temperature, and the reactor
was then fitted with a Dean-Stark trap to allow for collection and
removal of distillate. IPA/water was removed from 81 to 86.degree.
C. while the reaction volume was replenished with water from an
addition funnel to maintain an acceptable viscosity. Total
distillate collection up to this point was 194 g, while the added
water was 350 g. Because of intense foaming, 195 g additional water
was added to the reaction, and the reaction mixture was then
transferred to a Roto-Vap apparatus, where an additional 110 g of
distillate was removed under vacuum at 55.degree. C. The weight of
the final material after being subjected to distillation was 690 g.
This was a pink-tinted, lightly cloudy liquid with a pH of 4 and
consisting of 23% active polymer by weight.
TABLE-US-00002 TABLE 1 Analysis of the hydrophobically modified
polymers compared with the conventional POLYFLOS .RTM. HM 21.
POLYFLOS .RTM. R7-33-43 R7-33-61 R7-36-72 R7-33-28 R7-33-158 HM 21
M.sub.w (Da) 16131 19775 8459 29956 19528 537550 M.sub.n (Da) 2735
3199 1488 4095 2750 13641 Dispersity = 5.9 6.2 5.7 7.3 7.1 39.4
M.sub.w/M.sub.n
Example 1 and Comparative Examples A-B
Rheology of Aromox APA-TW and Hydrophobically Modified Polymer
R7-33-43
[0111] Samples A, B, and 1 were made based on the amount shown in
Table 2.
TABLE-US-00003 TABLE 2 Sample Preparation of Aromox APA-TW +
R7-33-43 Wt. of Wt of Wt of Aromox 4% KCl Polymer APA-TW Solution
Ex. Description (g) (g) (g) pH A 3 wt % (active) Aromox None 2.1270
27.9093 9.72 APA-TW, no polymer, in 4% KCl B 0.2 wt % (active)
R7-33- 0.4956 None 29.7272 11.56 43, no surfactant, in 4% KCl 1 3
wt % (active) Aromox 0.4502 2.0939 27.5104 10.30 APA-TW + 0.2 wt %
(active) R7-33-43, in 4% KCl
[0112] For samples A, B and 1, a strain-controlled rheometer ARES
(from Rheometric Scientific, which is now TA Instruments) was used
to conduct the Steady Strain Rate Sweep at 25.degree. C., with an
initial strain rate of 0.01 s.sup.-1 and a final strain rate of 100
s.sup.-1. Data was collected, 10 data points per strain rate
decade. Parallel plates of diameter of 25 mm were used, and
temperature was controlled by peltier heating.
[0113] The rheology profile is graphed in FIG. 1. Clearly sample 1
shows significantly higher viscosity than sample A and sample B,
indicating a synergistic viscosity increase achieved by combination
of Aromox APA-TW and R7-33-43 polymer (a polymer with a urethane
linkage) in 4% KCl. The same synergistic viscosity increase was
also found at 50.degree. C. and at 80.degree. C.
[0114] In a separate rheology test at 25.degree. C., a dynamic
frequency of 10.sup.-1 to 10.sup.2 rad/s was used and for the
solution of Example 1 G' was higher than G'' over the whole range,
indicating the solution showed viscoelastic behavior.
Example 2 and Comparative Examples C-D
Rheology of Aromox APA-TW and Hydrophobically Modified Polymer
R7-33-61
[0115] Samples C, D, and 2 were made based on the amount shown in
Table 3.
TABLE-US-00004 TABLE 3 Sample Preparation of Aromox APA-TW +
R7-33-61 Wt. of Wt of Wt of Aromox 4% KCl Polymer APA-TW Solution
Ex. Description (g) (g) (g) pH C 3 wt % (active) Aromox None 2.1270
27.9093 9.72 APA-TW, no polymer, in 4% KCl D 0.2 wt % (active)
R7-33- 0.3992 None 29.6257 11.25 61, no surfactant, in 4% KCl 2 3
wt % (active) Aromox 0.3834 2.0971 27.5424 10.00 APA-TW + 0.2 wt %
(active) R7-33-61, in 4% KCl
[0116] For samples C, D and 2, a strain-controlled rheometer ARES
(from Rheometric Scientific, which is now TA Instruments) was used
to conduct the Steady Strain Rate Sweep at 25.degree. C., with an
initial strain rate of 0.01 s.sup.-1 and a final strain rate of 100
s.sup.-1. Data was collected, 10 data points per strain rate
decade. Parallel plates of diameter of 25 mm were used, and
temperature was controlled by peltier heating.
[0117] The rheology profile is graphed in FIG. 2. Again, sample 2
shows significantly higher viscosity than sample C and sample D,
indicating a synergistic viscosity increase achieved by combination
of Aromox APA-TW and R7-33-61 polymer (a polymer with a urea
linkage) in 4% KCl. The same synergistic viscosity increase was
also found at 50.degree. C. and at 80.degree. C.
[0118] In a separate rheology test at 25.degree. C., a dynamic
frequency of 10.sup.-1 to 10.sup.2 rad/s was used and for the
solution of Example 2 G' was higher than G'' over the whole range,
indicating the solution showed viscoelastic behavior.
Comparative Examples E and F
[0119] Rheology of Aromox.RTM. APA-TW and POLYFLOS.RTM. HM 21.
Formulations were as shown in Table 4.
TABLE-US-00005 TABLE 4 Sample Preparation of Aromox APA-TW +
POLYFLOS .RTM. HM 21 Wt. of Wt of Wt of Aromox 4% KCl Polymer
APA-TW Solution Ex. Description (g) (g) (g) pH E 3 wt % (active)
Aromox None 2.1000 27.9326 11.27 APA-TW, no polymer, 4% KCl F 3 wt
% (active) Aromox 0.0774 2.0985 27.8268 11.81 APA-TW + 0.2 wt %
(active) POLYFLOS .RTM. HM 21 in 4% KCl
[0120] The rheology profile is graphed in FIG. 3. The result show
that samples E and F overlay very well with each other, indicating
no rheological synergy upon combination of POLYFLOS.RTM. HM 21 with
Aromox APA-TW in 4% KCl.
[0121] It is pointed out that the polymer in accordance with the
invention (R7-33-43 of Example 1) has a much lower molecular weight
than the conventional thickener POLYFLOS.RTM. HM 21 of the
Comparative example F, see the Table 1 above. Hence it is
surprising to see that the use of conventional hydrophobic polymers
does not lead to the viscosities observed when using polymers of
the invention.
Examples 3 and 4 and Comparative Example G
Rheology of Aromox APA-TW, Polymer R7-33-43 and Polymer
R7-33-61
[0122] Here the performance of an amine-oxide viscoelastic
surfactant in combination with the hydrophobically modified
polymers R7-33-43 and R7-33-61 was investigated for an aqueous
environment containing 4% KCl at elevated temperature (93.degree.
C. (200.degree. F.)) and at an elevated pressure (27.5 bar (400
psi)), to mimic oil-well-stimulation conditions. The amounts of
surfactant and polymer used as well as the results obtained are
presented in the following Table 5, with the viscosity being
determined after two hours at shear rate of 100 s.sup.-1, using a
Grace M5600 rheometer at said pressure and temperature with rotor
R1 and bob B5.
TABLE-US-00006 TABLE 5 Sample preparation of samples G, 3 and 4
HTHP Viscos- Wt. of ity at Wt of Aromox Wt of 93.degree. C./ Poly-
APA- KCl 2 hr mer TW solu- (mPa- Ex. Description (g) (g) tion (g)
pH s) G 3 wt % (active) 0.0000 6.9683 93.0322 10.58 12.49 Aromox
APA- TW, no polymer, in 4% KCl 3 3 wt % (active) 1.5275 7.1534
91.5231 11.72 210.84 Aromox APA- TW + 0.2 wt % (active) R7-33- 43,
in 4% KCl 4 3 wt % (active) 1.2661 6.9709 91.7554 10.68 82.35
Aromox APA- TW + 0.2 wt % (active) R7-33- 61, in 4% KCl
[0123] Clearly, also in a KCl-containing aqueous formulation and at
high temperature and pressure, the combination of viscoelastic
surfactant and hydrophobically modified polymer according to the
invention gave a very high viscosity, even when polymer used in a
small amount and despite the low molecular weight of the
polymer.
Example 5 and Comparative Examples H and I
Rheology of Aromox APA-TW and Polymer R-36-72
[0124] Here, the performance of an amine-oxide viscoelastic
surfactant in combination with hydrophobically modified polymer
R7-36-72 was investigated for an aqueous environment containing 4%
w/w KCl and an amount of CaCl.sub.2 of 2,776 ppm (0.2776% w/w) at
25.degree. C. The amounts of surfactant and polymer used as well as
the results obtained are presented in the Table 6.
TABLE-US-00007 TABLE 6 Sample preparation of samples H, I and 5 Wt.
of Wt. of Aromox Wt. of Polymer APA-TW 4% KCl Ex. Description (g)
(g) (g) pH H 3 wt % (active) Aromox 0.0000 2.0852 27.9146 10.91
APA-TW, no polymer, in brine of CaCl.sub.2/KCl I 0.2 wt % (active)
R7- 0.3714 0.0000 29.6453 10.26 36-72, no Aromox APA-TW, in brine
of CaCl.sub.2/KCl 5 3 wt % (active) Aromox 0.3857 2.1083 27.5273
10.06 APA-TW + 0.2 wt % (active) R7-36-72, in brine of
CaCl.sub.2/KCl
[0125] The combination in accordance with the invention gave a
higher viscosity than the use of the surfactant or polymer alone,
showing the synergistic behavior, despite the low molecular weight
of the polymer and the small quantity in which it was used, as is
demonstrated in FIG. 4. Polymer R7-36-72 contained AMPS monomer
that provided tolerance to Calcium brine.
Example 6 and Comparative Example J
Rheology of Aromox APA-TW and Polymer R-33-43 with EDTA
[0126] In these examples the experiment of Example 5 was repeated,
except that hydrophobically modified polymer R7-33-43 was used,
while also using the well-known chelate EDTA (Dissolvine NA) in the
composition. Samples 6 and J were prepared according to the amount
shown in Table 7.
TABLE-US-00008 TABLE 7 sample preparation, samples 6 and J Wt. of
Poly- Wt. of Wt. of mer Aromox Dissolvine R7-33- APA- NA Wt. of
Descrip- 43 TW (EDTA) Brine Ex. tion (g) (g) (g) (g) pH J 3 wt %
0.0000 2.0917 0.3356 27.5758 9.93 (active) Aromox APA- TW + EDTA,
no polymer, in brine of CaCl.sub.2/ KCl 6 3 wt % 0.4624 2.0940
0.3320 27.1467 9.80 (active) Aromox APA- TW + 0.2 wt % (active) R7-
33-43 + EDTA, in brine of CaCl.sub.2/ KCl
[0127] FIG. 5 shows the viscosity of these formulations. The
results show that the combination of viscoelastic surfactant and
low molecular weight hydrophobically modified polymer gives
exceptionally high viscosity at low concentrations also in the
presence of a chelate.
Example 7 and Comparative Example K
Rheology of Aromox APA-TW and Polymer R7-33-158
[0128] Samples 7 and K were prepared according to the amounts
indicated in Table 8
TABLE-US-00009 TABLE 8 Preparation of samples 7 and K Wt. of Wt. of
Polymer Aromox Wt. of R7-33-158 APA-TW 4% KCl Ex. Description (g)
(g) (g) pH K 3 wt % (active) Aromox 0.0000 2.1270 27.9093 9.72
APA-TW, no polymer, in 4% KCl 7 3 wt % (active) Aromox 0.3026
2.1022 27.6135 12.06 APA-TW + 0.2 wt % R7-33-158, in 4% KCl
[0129] For sample K, a strain-controlled rheometer ARES (from
Rheometric Scientific, which is now TA Instruments) was used to
conduct the Steady Strain Rate Sweep at 25.degree. C., with an
initial strain rate of 0.01 s.sup.-1 and a final strain rate of 100
s.sup.-1. Data was collected, 10 data points per strain rate
decade. Parallel plates of diameter of 25 mm were used, and
temperature was controlled by peltier heating.
[0130] FIG. 6 shows the viscosity of these samples. One can see
from the overlap rheology profiles that the viscosity of sample 7
is higher than that of sample K in the shear rate range tested. The
blend of Aromox APA-TW and polymer R7-33-158 (a polymer with an
amide linkage between the pendant hydrophobe and the backbone) has
higher viscosity than Aromox APA-TW alone.
Comparative Examples L and M
Rheology of Aromox APA-TW and Polymer R7-33-28
[0131] Samples L and M was prepared according to the amounts
indicated in Table 9.
TABLE-US-00010 TABLE 9 Preparation of samples L and M Wt. of Wt. of
Polymer Aromox Wt. of R7-33-28, APA-TW 4% KCl Ex # Description (g)
(g) (g) pH L 3 wt % (active) Aromox 0.0000 2.1270 27.9093 9.72
APA-TW, no polymer, in 4% KCl M 3 wt % (active) APA- 0.2335 2.1150
27.6778 8.71 TW + 0.2 wt % (active) R7-33-28, in 4% KCl
[0132] For samples L and M, a strain-controlled rheometer ARES
(from Rheometric Scientific, which is now TA Instruments) was used
to conduct the Steady Strain Rate Sweep at 25.degree. C., with an
initial strain rate of 0.01 s.sup.-1 and a final strain rate of 100
s.sup.-1. Data was collected, 10 data points per strain rate
decade. Parallel plates of diameter of 25 mm were used, and
temperature was controlled by peltier heating.
[0133] FIG. 7 shows the viscosity of these samples. One can see
from the overlap rheology profiles that the viscosity of sample M
is lower than that of sample L. The blend of Aromox APA-TW and
polymer R7-33-28 (a polymer with an ester linkage between the
pendant hydrophobe and the backbone) has lower viscosity than
Aromox APA-TW alone. In this case, blending VES and polymer showed
a "negative" rheology synergy.
Example 8 and Comparative Example N
Viscoelasticity of Aromox APA-TW and Polymer R7-33-43
[0134] Samples 8 and N was prepared according to the amounts
indicated in the following Table 10.
TABLE-US-00011 TABLE 10 preparation of samples 8 and N Wt. of Wt.
of Aromox Wt. of Polymer APA-TW 4% KCl Ex # Description (g) (g) (g)
pH N 3 wt % (active) Aromox 0.0000 2.1100 27.9126 10.17 APA-TW, no
polymer, in 4% KCl 8 3 wt % (active) Aromox 0.4585 2.0974 27.4362
9.26 APA-TW + 0.2 wt % (active) R7-33-43, in 4% KCl
[0135] Dynamic Frequency Sweep was tested using a stress-controlled
rheometer SR-5000 (originally made by Rheometrics) at 25.degree.
C., with initial frequency of 0.01 rad/s and final frequency of 100
rad/s, and stress=1 Pa. Parallel plates of diameter of 40 mm were
used, and temperature was controlled by peltier heating. 10 data
points were collected within each decade of frequency. The results
are shown in FIGS. 8 and 9
[0136] From FIG. 8, one can see the significant difference of the
G' and G'' profile between the two samples. Sample N had no
polymer, and its G', G'' crossover frequency was roughly 3 rad/s.
The sample showed viscoelasticity, or G'>G'', only at
frequencies that are higher than 3 rad/s. Sample 8 was the blend of
Aromox APA-TW and polymer R7-33-43, and its G', G'' crossover
frequency was roughly 0.02 rad/s. The sample showed
viscoelasticity, or G'>G'', at frequencies that are higher than
0.02 rad/s. Therefore, the VES-polymer blend showed much wider
frequency range where viscoelastcity was demonstrated.
[0137] From FIG. 9, one can see the significant difference in the
phase angle between these two samples. Sample N had no polymer, and
its phase angle is mostly higher than 45 degrees. Its phase angle
was only below 45 degrees at frequency higher than 3 rad/s,
indicating that it only has viscoelastic characteristics at
frequencies higher than 3 rad/s. Sample 8 was the blend of Aromox
APA-TW and polymer R7-33-43, and its phase angle was below 45
degrees at frequencies higher than 0.02 rad/s. This is another data
to support that the VES-polymer blend is more viscoelastic than VES
alone.
Example 9 and Comparative Example O
Viscoelasticity of Aromox APA-TW and Polymer J3-9-46
[0138] Samples 9 and O were prepared according to the amounts
indicated in the following Table 11.
TABLE-US-00012 TABLE 11 Preparation of samples 9 and O Wt. of Wt.
of Aromox Wt. of pH Polymer APA-TW 4% KCl Mea- Ex. Description (g)
(g) (g) sured O 3 wt % (active) Aromox 0.0000 2.1270 27.9093 9.72
APA-TW, no polymer, in 4% KCl 9 3 wt % (active) Aromox 0.4505
3.5028 46.0249 7.75 APA-TW + 0.2% (active) J3-9-46, in 4% KCl
[0139] For sample O, a strain-controlled rheometer ARES (from
Rheometric Scientific, which is now TA Instruments) was used to
conduct the Steady Strain Rate Sweep at 25.degree. C., with an
initial strain rate of 0.01 s.sup.-1 and a final strain rate of 100
s.sup.-1. Data was collected, 10 data points per strain rate
decade. Parallel plates of diameter of 25 mm were used, and
temperature was controlled by peltier heating.
[0140] FIG. 10 shows the results from these experiments. For sample
0, a strain-controlled rheometer ARES (from Rheometrics, which is
now TA Instrument) was used to conduct the Steady Strain Rate Sweep
at 25.degree. C., with an initial strain rate of 0.01 s.sup.-1 and
a final strain rate of 100 s.sup.-1. Data was collected, 10 data
points per strain rate decade. Parallel plates of diameter of 25 mm
were used, and temperature was controlled by peltier heating. For
sample 9, a stress-controlled rheometer SR-5000 (from Rheometrics,
which is now TA Instrument) was used to conduct the Steady Stress
Sweep at 25.degree. C., with an initial stress of 0.1 Pa, a final
stress of 40 Pa, and a linear stress increment of 0.5 Pa. Parallel
plates of diameter of 40 mm were used, and temperature was
controlled by peltier heating.
[0141] One can see from the overlap rheology profiles that the
viscosity of sample 9 is higher than that of sample O in the shear
rate range tested. The blend of Aromox APA-TW and polymer J3-9-46
(a cationic hydrophobically modified polymer) has higher viscosity
than Aromox APA-TW alone.
Example 10
Anionic/Betaine Surfactant-Polymer Dilution Experiments
[0142] Sodium lauryl ether sulfate and cocamidopropyl betaine were
chosen as exemplary surfactants. They were used in a constant ratio
to each other of 4:1 respectively. A series of eight dilution
experiments were conducted. The compositions of the two series of
experiments are found in Table 12 shown below. Sodium Chloride was
the salt used in all the samples in Example 10. The first four
dilution experiments (labeled 1-4) represent "no polymer controls".
The latter four dilution experiments (labeled 5-8) contain
different levels of a polymer R7-36-72 of the current invention.
Columns A-D represent fixed levels of surfactant (column A for 15%
surfactant, B for 10% surfactant, C for 7.5% surfactant, and D for
6% surfactant). In Table 13, the zero shear viscosities are shown
to correlate with the dilution experiments described in Table
12.
TABLE-US-00013 TABLE 12 A B C D Mass % Mass % Mass % Mass % Initial
First Second Third Sample Dilution Dilution Dilution 1 % Surfactant
15 10 7.5 6 % Salt 8 5.33 4 3.2 % Water 77 84.67 88.5 90.8 2 %
Surfactant 15 10 7.5 6 % Salt 6 4 3 2.4 % Water 79 86 89.5 91.6 3 %
Surfactant 15 10 7.5 6 % Salt 3 2 1.5 1.2 % Water 82 88 91 92.8 4 %
Surfactant 15 10 7.5 6 % Salt 2 1.33 1 0.8 % Water 83 88.67 91.5
93.2 5 % Surfactant 15 10 7.5 6 % Salt 8 5.33 4 3.2 % Polymer 0.4
0.267 0.2 0.159 % Water 76.6 84.403 88.3 90.641 6 % Surfactant 15
10 7.5 6 % Salt 6 4 3 2.4 % Polymer 0.4 0.267 0.2 0.159 % Water
78.6 85.733 89.3 91.44 7 % Surfactant 15 10 7.5 6 % Salt 3 2 1.5
1.2 % Polymer 0.4 0.267 0.2 0.159 % Water 80.6 87.06 90.3 92.241 8
% Surfactant 15 10 7.5 6 % Salt 2 1.33 1 0.8 % Polymer 0.4 0.267
0.2 0.159 % Water 82.6 88.403 91.3 93.041
TABLE-US-00014 TABLE 13 Zero Shear Viscosity (Pa-s) - Surfactant +
Polymer R7-36-72 Experiment # A B C D 1 0.004 54 115 16 2 6 173 31
0.4 3 130 157 0.7 0.007 4 0.001 0.001 0.001 0.001 5 0.7 22 170 58 6
1.3 188 138 1.7 7 31 492 5.4 0.001 8 209 17 0.001 0.001 Comparisons
to determine influence of polymer at different salt levels can be
made between the dilution experiment pairs of 1 and 5, 2 and 6, 3
and 7, and 4 and 8.
Zero Shear Viscosity
[0143] Zero shear viscosities were obtained from either a plot of
viscosity vs. shear rate or fitting the data to Cross model.
Viscosities were measured using a stress-controlled rheometer
SR-5000 (from Rheometric Scientific, which is now TA Instruments) a
stress controlled rheometer utilizing a 25 mm diameter parallel
plate configuration and 1 mm gap. Steady state stress sweep
measurements were carried out at 25.degree. C. a data at different
shear rate were obtained.
[0144] The zero shear viscosity was obtained by averaging the
values at the viscosity plateau at the lower end of the shear rate
range. For cases when the value does not reach plateau, the data
was fitted to the Cross model. The fitting was carried out using
the solver module of the MS Excel and setting the criterion to
minimize the sum of the percentage differences between the observed
and fitted data. According to the Cross model viscosity is related
to shear rate by the following equation:
.eta. = .eta. .infin. + .eta. 0 - .eta. .infin. 1 + ( C .gamma. . )
m ##EQU00001##
.eta..sub.0=zero shear viscosity, .eta._=viscosity at very high
rate, =shear rate, C and m are constants.
Calculated Variables of Cross Model
TABLE-US-00015 [0145] .eta..sub.0 0.41 Pa-s .eta..sub..infin.
0.0404 Pa-s C 0.01 m 0.97
[0146] The plot in FIG. 11 displays the results of zero shear
viscosity vs. % salt for the 8 dilution experiments from example
10. In this case, experiments #5-8 relate to experiments employing
R7-36-72 as the polymer of the present invention.
[0147] These data demonstrate that R7-36-72 can effectively
increase the zero shear viscosity for the sodium lauryl ether
sulfate/cocamidopropyl betaine mixture over all surfactant levels
to levels higher than can be achieved without polymer.
Additionally, it can generally be seen that the peak viscosity of
the system can be achieved with lower salt levels than in the
absence of the polymer of the present invention. Furthermore, it
can be observed that the zero shear viscosity of a high surfactant
containing system can be achieved at substantially lower surfactant
content by the addition of the polymer of the present invention
with the appropriate level of salt.
[0148] The peak viscosity achieved for each surfactant level is
provided in Table 14 below. Peak viscosity refers to the highest
viscosity achieved over the entire salt range that was tested.
TABLE-US-00016 TABLE 14 Peak Zero Shear R7-36-72 Testing in
Surfactant System Viscosity (Pa-s) 6% surfactant without polymer 16
6% surfactant with polymer 58 7.5% surfactant without polymer 115
7.5% surfactant with polymer 170 10% surfactant without polymer 173
10% surfactant with polymer 429 15% surfactant without polymer 130
15% surfactant with polymer 209
[0149] Comparing samples with and without polymer shows that in all
cases, the addition of polymer enables higher zero shear
viscosities. Additionally, comparing 15% surfactant without polymer
(130 Pa-s) to 10% surfactant without polymer (173 Pa-s) and 10%
surfactant with polymer (429 Pa-s) shows that it is possible to
achieve higher zero shear viscosities with lower levels of
surfactant by addition of the polymer of the present invention and
the appropriate level of salt.
Example 10
Stress Sweep and Elastic Modulus Measurement
Stress Sweep
[0150] Dynamic stress sweep were also evaluated using the
Rheometric Scientific rheometer and same plate configuration as for
steady state stress sweep. Measurement was carried out at a
frequency of 1 Hz. These values allow us to investigate yield
stress, storage (elastic) and loss (viscous) modulus. Figure below
shows a typical example.
Elastic Modulus Results
[0151] Composition 1 containing 7.5% of surfactant, 3% Sodium
Chloride, and 0% polymer was prepared and evaluated according to
Example 10. Composition 2 containing 7.5% surfactant, 3% Sodium
Chloride, and 0.2% R7-36-72 was prepared and evaluated according to
Example 5.
[0152] The results are found in FIG. 9 showing Elastic Modulus as a
function of Stress.
[0153] These data demonstrate that addition of the polymer of the
present invention can dramatically increase the elastic modulus and
yield stress of surfactant systems.
Example 12
Foam Evaluation
[0154] Foam property was evaluated by creating a foam using a
blender and the measuring the time taken for half of total liquid
to drain from the foam matrix.
Procedure:
[0155] Prepare a 0.035% solution of each of the formulation by
diluting with water. A total of 200 ml of the 0.035% solution were
transferred to a blender (Oster Fusion, 3 speed blender). Blend the
solution at medium speed for 30 sec. Transfer the resulting foam
quickly into a 1000 ml cylinder and measure the volume of foam
created.
Example 13
Influence of Polymer on Foam Volume
[0156] Shampoo 1 containing 7.5% surfactant, 3% salt was prepared
and evaluated for its foam height. Second, shampoo 2 containing
7.5% surfactant, 3% salt, and 0.25% polymer R7-36-72 was prepared
and evaluated for its foam height. Finally, a Shampoo 3, a deep
cleansing shampoo from a leading brand that is estimated to contain
15% total surfactants, was evaluated for its foam height. The
results are summarized in Table 10 below.
TABLE-US-00017 TABLE 10 Product Name Foam Height Standard Deviation
Shampoo 1 782 mL 30 mL Shampoo 2 845 mL 2 mL Shampoo 3 802 mL 3
mL
[0157] These data demonstrate that the polymers of the present
invention enhance the foam characteristics of shampoo.
Additionally, these data demonstrate that it is possible to exceed
the foam characteristics of a shampoo with .about.15% surfactant
with one that contains only 7.5% surfactant by addition of the
polymer of the present invention.
[0158] All documents cited in the Detailed Description of the
Invention are, in relevant part, incorporated herein by reference;
the citation of any document is not to be construed as an admission
that it is prior art with respect to the present invention.
[0159] While particular embodiments of the present invention have
been illustrated and described herein, the invention is not
intended to be limited to the details shown. Rather, various
modifications may be made in the details within the range and scope
of equivalents of the claims and without departing from the spirit
and scope of the invention.
* * * * *