U.S. patent number RE48,770 [Application Number 16/454,802] was granted by the patent office on 2021-10-12 for non-petrochemically derived cationic emulsifiers that are neutralized amino acid esters and related compositions and methods.
This patent grant is currently assigned to INOLEX INVESTMENT CORPORATION. The grantee listed for this patent is Inolex Investment Corporation. Invention is credited to Rocco Burgo.
United States Patent |
RE48,770 |
Burgo |
October 12, 2021 |
Non-petrochemically derived cationic emulsifiers that are
neutralized amino acid esters and related compositions and
methods
Abstract
The invention includes a method of increasing the substantivity
of a personal care composition to hair, skin or nails by preparing
a composition of an aqueous phase, a non-aqueous phase and a
neutralized amino acid ester that is a reaction product of a
neutral amino acid having a non-polar side chain with a long chain
fatty alcohol and is represented by formula (I): ##STR00001##
wherein R.sup.1 is an alkyl group; R.sup.2 is a linear or branched
carbon chain; and the amine group of the amino acid is neutralized
with an acid. The composition is substantially free of
petrochemicals and/or derivatives of petrochemical materials. The
aqueous phase and the non-aqueous phase are emulsified by the
neutralized amino acid ester. Other methods and an emulsifiers that
is the neutralized amino acid ester are included. Because the
neutralized amino acid ester and the compositions do not contain
petrochemical-derived ingredient, the products are natural.
Inventors: |
Burgo; Rocco (Mullica Hill,
NJ) |
Applicant: |
Name |
City |
State |
Country |
Type |
Inolex Investment Corporation |
Wilmington |
DE |
US |
|
|
Assignee: |
INOLEX INVESTMENT CORPORATION
(Wilmington, DE)
|
Family
ID: |
1000005585375 |
Appl.
No.: |
16/454,802 |
Filed: |
June 27, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
12825555 |
Jan 31, 2012 |
8105569 |
|
|
|
61221154 |
Jun 29, 2009 |
|
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Reissue of: |
13187820 |
Jul 21, 2011 |
8287844 |
Oct 16, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61Q
19/00 (20130101); A61K 8/44 (20130101); A61Q
5/12 (20130101); A61Q 3/00 (20130101) |
Current International
Class: |
A61K
8/00 (20060101); A61K 8/18 (20060101); A61Q
5/00 (20060101); A61Q 19/00 (20060101); A61Q
5/12 (20060101); A61K 8/44 (20060101); A61Q
3/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1314717 |
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May 2003 |
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EP |
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46-41286 |
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Dec 1971 |
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JP |
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S6084209 |
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May 1985 |
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JP |
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S6097043 |
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May 1985 |
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JP |
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11240828 |
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Sep 1999 |
|
JP |
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5412908 |
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Nov 2013 |
|
JP |
|
6161624 |
|
Jul 2017 |
|
JP |
|
2010073119 |
|
Jul 2010 |
|
WO |
|
Other References
Notice Requesting Submission of Opinion from Korean Intellectual
Property Office, Korean Patent Application No. 10-2020-7009877,
dated Mar. 29, 2021. cited by applicant .
Extended European Search Report from the European Patent Office,
European Patent Application No. 20191777, dated Feb. 1, 2021. cited
by applicant .
Chimia 57 (2003) 241-247 @ Schweizerische Chemische Gesellschaft
Sylvie Chamoin, Hans-Jorg Roth, Carsten Borek, Aline Jary, and
Hugues Maillot. Automated Parallel Synthesis of N-Alkylated-a-Amino
Methyl Esters in Gram Quantities. Chimia 57 (2003) 241-247. cited
by applicant .
Jong Hyun Cho and B. Moon Kim. LiOH-mediated N-monoalkylation of
a-amino acid esters and a dipeptide ester using activated alkyl
bromides. Tetrahedron Letters 43 (2002) 1273-1276. cited by
examiner .
Chimia 57 (2003) 241-247, .COPYRGT. 0Schweizerische Chemische
Gesellschaft, Sylvie Chamoin, Hans-Jorg Roth, Carsten Borek, Aline
Jary, and Hugues Maillot. Automated Parallel Synthesis of
N-Alkylateda-.alpha.-Amino Methyl Esters in Gram Quantities. Chimia
57 (2003) 241-247. cited by examiner.
|
Primary Examiner: Xu; Ling X
Attorney, Agent or Firm: Cozen O'Connor
Parent Case Text
CROSS REFERENCE TO RELATED .[.APPLICATION.].
.Iadd.APPLICATIONS.Iaddend.
This application .[.in.]. .Iadd.is .Iaddend.a .Iadd.reissue
application of U.S. application Ser. No. 13/187,820, filed Jul. 21,
2011, issued as U.S. Pat. No. 8,287,844 on Oct. 16, 2012, which is
a .Iaddend.continuation of .[.pending.]. U.S. application Ser. No.
12/825,555, filed Jun. 29, 2010, .Iadd.issued as U.S. Pat. No.
8,105,569 on Jan. 31, 2012, .Iaddend.which in turn claims the
benefit under 35 U.S.C. .sctn.119(e) of U.S. provisional patent
application No. 61/221,154, filed Jun. 29, 2009, the entire
disclosures of each of which are incorporated herein by reference.
Claims
I claim:
1. A method of increasing the substantivity of a personal care
composition to hair, skin or nails comprising: preparing a
composition that comprises an aqueous phase, a non-aqueous phase
and a neutralized amino acid ester that is a reaction product of a
neutral amino acid having a non-polar side chain with a long chain
fatty alcohol and is represented by formula (I): ##STR00007##
wherein R.sup.1 is a linear or branched alkyl group; R.sup.2 is a
linear or branched carbon chain; and the amine group of the amino
acid is neutralized with an acid, and wherein the composition is
substantially free of petrochemicals and/or derivatives of
petrochemical materials, and the aqueous phase and the non-aqueous
phase are emulsified by the neutralized amino acid ester; and
applying the personal care composition to a surface of hair, skin
or nails.
2. The method of claim 1, wherein R.sup.1 of formula (I) is chosen
from a branched alkyl and a linear alkyl group.
3. The method of claim 1, wherein R.sup.1 of formula (I) .[.is.].
has 1 to 10 carbon atoms.
4. The method of claim 1, wherein the carbon chain of R.sup.2 in
formula (I) comprises at least one unsaturated carbon atom.
5. The method of claim 1, wherein R.sup.2 of formula (I) .[.is.].
has 10 to 50 carbon atoms.
6. The method of claim 1, wherein the neutral amino acid is chosen
from L-alanine, L-valine, L-leucine, and L-isoleucine.
7. The method of claim 1, wherein the neutral amino acid is
L-isoleucine.
8. The method of claim 1, wherein the neutral amino acid is
obtained from vegetable matter.
9. The method of claim 1, wherein the long chain fatty alcohol is
chosen from the coconut fatty alcohol, capric alcohol, lauryl
alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol,
arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, isostearyl
alcohol, and/or mixtures thereof.
10. The method of claim 1, wherein the amine group of the amino
acid is neutralized by an ethanesulfonic acid that is derived from
an ethanol that is derived from fermentation of vegetable
matter.
11. The method of claim 1, wherein the amine group of the amino
acid is neutralized by an acid chosen from hydrochloric acid,
phosphoric acid, sulfuric acid, boric acid, and nitric acid.
12. The method of claim 1, wherein the personal care composition
further comprise at least one of a surfactant, a colorant, a
pearlizing agent, an acrylate polymer, an antioxidant, an
opacifying agent, mica, an oil, a lipid, a protein, a pH modifier,
a vitamin, a fatty acid, a fatty alcohol, a humectant, and a
conditioning agent.
13. The method of claim 1, wherein the composition is chosen from a
hair detergent, shampoo, rinse, hair cream conditioner,
conditioning shampoo, hair lotions, hair treatment, hair cream,
hair spray, hair liquid, hair wax, hair-styling preparation,
permanent wave liquids, hair colorant, acidic hair colorant, hair
manicure, glaze, skin lotion, milky lotion, face wash, makeup
remover, cleansing lotion, emollient lotion, nourishing cream,
emollient cream, massage cream, cleansing cream, body shampoo, hand
soap, bar soap, shaving creams, sunscreen, sunburn treatment,
deodorants, makeup removing gel, moisture gel, moisture essence, UV
exposure-preventing essence, shaving foam, face powder, foundation,
lipstick, blush, eyeliner, wrinkle and anti-aging cream, eye
shadow, eyebrow pencils, mascara, mouthwash, toothpaste, an oral
care composition, a skin cleansing composition, a textile cleansing
compositions, a dish cleaning composition, a hair or fur cleansing
composition, a deodorant or antiperspirant, a cosmetic, a hair
styling composition, a skin moisturizer, a skin conditioner, a hair
conditioner and a nail conditioner.
.Iadd.14. A method of increasing the substantivity of a personal
care composition to hair, skin or nails comprising: preparing a
composition that comprises an aqueous phase, a non-aqueous phase
and a neutralized amino acid ester that is a reaction product of
one or more of L-alanine, L-valine, L-leucine, and L-isoleucine
with a long chain fatty alcohol and is represented by formula (1):
##STR00008## wherein R.sup.1 is a linear or branched alkyl group;
R.sup.2 is a linear or branched carbon chain; and the amine group
of the amino acid is neutralized with an acid, and wherein the
composition is substantially free of petrochemicals and/or
derivatives of petrochemical materials, and the aqueous phase and
the non-aqueous phase are emulsified by the neutralized amino acid
ester; and applying the personal care composition to a surface of
hair, skin or nails..Iaddend.
.Iadd.15. The method of claim 14, wherein the neutral amino acid is
obtained from vegetable matter..Iaddend.
.Iadd.16. The method of claim 14, wherein the long chain fatty
alcohol is chosen from Brassica alcohol, coconut fatty alcohol,
capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol,
stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl
alcohol, isostearyl alcohol, and/or mixtures thereof..Iaddend.
.Iadd.17. The method of claim 14, wherein the amine group of the
amino acid is neutralized by an ethanesulfonic acid that is derived
from an ethanol that is derived from fermentation of vegetable
matter..Iaddend.
.Iadd.18. The method of claim 14, wherein the amine group of the
amino acid is neutralized by an acid chosen from hydrochloric acid,
phosphoric acid, sulfuric acid, boric acid, and
nitric..Iaddend.
.Iadd.19. A method of preparing a personal care composition
comprising preparing a composition that comprises an aqueous phase,
a non-aqueous phase and a neutralized amino acid ester that is a
reaction product of one or more of L-alanine, L-valine, L-leucine,
and L-isoleucine with a long chain fatty alcohol and is represented
by formula (I): ##STR00009## wherein R.sup.1 is a linear or
branched alkyl group; R.sup.2 is a linear or branched carbon chain,
wherein an amine group of the amino acid is neutralized with an
acid, wherein the composition is substantially free of
petrochemicals and/or derivatives of petrochemical materials,
emulsifying the aqueous phase and the non-aqueous phase with the
neutralized amino acid ester, and applying the personal care
composition to a surface of hair, skin or nails..Iaddend.
.Iadd.20. The method of claim 19, wherein the neutral amino acid is
obtained from vegetable matter..Iaddend.
.Iadd.21. The method of claim 19, wherein the long chain fatty
alcohol is chosen from Brassica alcohol, coconut fatty alcohol,
capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol,
stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl
alcohol, isostearyl alcohol, and/or mixtures thereof..Iaddend.
.Iadd.22. The method of claim 19, wherein the amine group of the
amino acid is neutralized by an ethanesulfonic acid that is derived
from an ethanol that is derived from fermentation of vegetable
matter..Iaddend.
.Iadd.23. The method of claim 19, wherein the amine group of the
amino acid is neutralized by an acid chosen from hydrochloric acid,
phosphoric acid, sulfuric acid, boric acid, and nitric..Iaddend.
Description
BACKGROUND OF THE INVENTION
Sales of "natural" products within the personal care industry
continue to show significant growth. Popular culture has driven
this growth by popularizing the idea that there may be potential
adverse effects to the body (toxicity) and to the environment
(pollution, hastening of climate change, and environmental
toxicity) associated with the use of ingredients derived from
fossil fuels. The personal care industry has rapidly advanced its
attempts to identify ingredients described as "renewable" and
"sustainable," that is, ingredients of non-fossil fuel origin for
use in the formulation of virtually all cosmetic product types and
forms.
In many instances, the industry has successfully identified
replacements for many ingredients that are historically of fossil
fuel origin. Examples of this are the replacement of mineral oils,
silicones, and petrochemically-derived synthetic esters with
vegetable oils and natural esters, synthetic fragrances with
essential oils, and petrochemical preservatives with certain
extracts.
Although used in marketing materials, the term "natural" has not
yet been completely defined. However, efforts are underway by
industry trade organizations to give the term a more concise and
consistent meaning. Historically, it has been generally recognized
that materials derived from renewable and/or sustainable, or
otherwise non-fossil fuel sources are considered to be "natural" by
the marketplace. More recently the definition of "natural" has been
further refined. For example, there is a trend within the trade to
prohibit animal-derived materials and plant-derived materials that
are obtained from the use of genetically-modified organisms (GMO)
from use in natural products.
Also, certain chemical processes used in the manufacture of
ingredients, especially those processes that employ petrochemical
solvents, generate unrecoverable waste, and/or consume excessive
resources, are frowned upon or may otherwise be prohibited. The use
of "Green Chemistry" principles in the production of cosmetic and
personal care ingredients is rapidly becoming a positive benefit
that can be exploited in the marketing of products produced using
those principles. Thus, the evolving definition of "natural"
currently includes products that are not petrochemically derived.
However, the other concepts discussed above (non-animal, non-GMO,
Green Chemistry) may be taken into consideration when creating
"natural" products, and to satisfy market demands.
One particular challenge facing formulators of natural products
relates to the identification of suitable emulsifiers. An
emulsifier is a type of surfactant typically used to keep emulsions
(metastable mixtures of immiscible fluids) well dispersed.
Emulsifiers typically have a hydrophobic (water-fearing) and a
hydrophilic (water-loving) moiety. In an emulsion involving an oil
and water, emulsifiers will surround the oil with their hydrophobic
moiety oriented toward the oil, thus forming a protective layer so
that the oil molecules cannot coalesce. This action helps keep the
dispersed phase in small droplets (micelles) and preserves the
emulsion. Emulsifiers may be anionic, nonionic, or cationic. A good
emulsifier for use in a personal care product is one that will
maintain consistent emulsion characteristics such as particle size,
appearance, texture, and viscosity, substantially constant for as
long a period as possible since by their very nature, all emulsions
due to their metastable nature will eventually separate into their
constituent oil soluble and water soluble components. Stability of
the emulsion is highly desirable in most products, since among
other advantages, this stability contributes to an extended shelf
life of the product and the maintenance of its initial aesthetic
properties over time.
Although the vast majority of emulsifiers currently used personal
care products are wholly or partially petrochemically derived such
as polyethylene glycol (PEG) derivatives and amine quaternaries, a
limited number of known emulsifiers may meet the current definition
of natural. However, presently available natural emulsifiers fall
only within the classes of nonionic and anionic emulsifiers.
The natural nonionic emulsifiers are typically partial esters of
long chain fatty acids with a polyol. Examples are long chain
partial esters of sugars, of alkylglucosides, and of polyglycerols.
Although these nonionic emulsifiers can be effective in building
stable emulsions, they do little or nothing to provide any
conditioning and/or aesthetic benefits to the hair or skin because
they are not substantive to these substrates, which are negatively
charged.
The natural anionic emulsifiers are typically the long chain fatty
acid soaps of fatty acids and sulfuric acid esters (sulfates) of
fatty alcohols. These tend to be drying to the skin and provide no
aesthetic or conditioning benefits because, like the hair and skin,
they are negatively charged and therefore tend to be repelled by
these substrates.
Currently there are no known natural cationic emulsifiers. Many
personal care applications require or are greatly improved by the
use of cationic emulsifiers. Owing to the fact that typical
cationic emulsifiers are built from a long chain (hydrophobic)
alkyl group attached to a hydrophilic moiety, they act as
emulsifiers much the same way as the nonionic and anionic
emulsifiers previously described. However, in a cationic
emulsifier, the hydrophilic portion of the molecule is positively
charged. This cationic moiety will electrostatically bind to (be
substantive to) negatively charged substrates such as the hair and
skin. The hydrophobic moiety, which is non-ionic, has no affinity
for the substrate, and will orient away from the substrate creating
a protective layer of fatty material that can provide enhanced
sensory properties. The property of substantivity differentiates
the cationic emulsifiers from anionic and/or nonionic emulsifiers.
It is substantivity that facilitates the conditioning benefits of
the end product. Therefore, in addition to being excellent
emulsifiers, cationic emulsifiers also deliver the benefits of
improving the aesthetics of formulations that include them, and
allowing the formulation of personal care products that can
condition, moisturize, and repair the skin, hair, or nails.
Cationic emulsifiers, unlike anionic and nonionic materials are
therefore multifunctional.
Cationic emulsifiers, when used in hair care applications such as
cream conditioners, provide excellent conditioning benefits such as
improvement in application aesthetics, creaminess and richness of
the conditioner, and improvements in such application properties as
softening, anti-static behavior, fly-away, wet combing, and dry
combing. When cationic emulsifiers, are used in skin care
preparations, they are known to provide what is known in the
industry as a "dry, light, powdery" skin feel that is a distinct
advantage in many skin care products. Exemplary traditional
cationic emulsifiers include quaternized cationic emulsifiers such
as cetrimonium chloride, behentrimonium chloride and
distearyldimonium chloride, and amidoamines such as
stearamidopropyl dimethylamine and behenamidopropyl
dimethylamine.
All of the traditional cationic emulsifiers are petrochemically
derived; therefore, all of these cationic emulsifiers are not
considered to be natural and therefore cannot be used in the
formulation of natural products. Accordingly, there is a need in
the art for natural cationic emulsifiers that have performance and
use characteristics and substantivity similar to the traditional
cationic emulsifiers.
BRIEF SUMMARY OF THE INVENTION
The invention includes personal care compositions containing a
cationic neutralized amino acid ester emulsifier but that is
substantially free of petrochemicals and/or derivatives of
petrochemical materials and which exhibits performance
characteristics (such as substantivity to skin and hair, shelf
stability and conditioning/lubrication capabilities) comparable to
compositions containing petrochemicals and/or derivatives of
petrochemicals, and/or superior to those exhibited by other
non-petrochemical containing compositions.
Specifically, the invention may include a method of increasing the
substantivity of a personal care composition to hair, skin or
nails. The method includes preparing a composition that comprises
an aqueous phase, a non-aqueous phase and a neutralized amino acid
ester that is a reaction product of a neutral amino acid having a
non-polar side chain with a long chain fatty alcohol and is
represented by formula (I):
##STR00002## wherein R.sup.1 is a linear or branched alkyl group;
R.sup.2 is a linear or branched carbon chain; and the amine group
of the amino acid is neutralized with an acid. The composition is
substantially free of petrochemicals and/or derivatives of
petrochemical materials. The aqueous phase and the non-aqueous
phase are emulsified by the neutralized amino acid ester. The
method also includes applying the personal care composition to a
surface of hair, skin or nails, wherein the composition exhibits
increased substantivity on the surface relative to the
substantivity of a composition that does not contain the
neutralized amino acid ester and which is substantially free of
petrochemicals and/or derivatives of petrochemical materials.
Also included is a method of emulsifying a personal care
composition having an aqueous phase and an non-aqueous phase that
includes preparing a composition that comprises an aqueous phase, a
non-aqueous phase and a neutralized amino acid ester that is a
reaction product of a neutral amino acid having a non-polar side
chain with a long chain fatty alcohol and is represented by formula
(I):
##STR00003## wherein R.sup.1 is a linear or branched alkyl group;
R.sup.2 is a linear or branched carbon chain; and the amine group
of the amino acid is neutralized with an acid. The composition is
substantially free of petrochemicals and/or derivatives of
petrochemical materials.
The invention provides additionally a method of conditioning,
lubricating, or repairing the skin, hair or nails comprising
applying a neutralized amino acid ester to a surface of skin, hair
or nails, wherein the neutralized amino acid ester is a product of
a reaction of a neutral amino acid having a non-polar side chain
with a long chain fatty alcohol represented by the structure of
formula (I):
##STR00004## wherein R.sup.1 is a linear or branched alkyl group;
R.sup.2 is a linear or branched carbon chain; and the amine group
of the amino acid is neutralized with an acid.
A cationic emulsifier is provided. The emulsifier includes a
neutralized amino acid ester derived from the reaction of a neutral
amino acid having a non-polar side chain with a long chain fatty
alcohol (such as the ester represented by formula I,) wherein the
emulsifier is substantially free of petrochemicals and/or
derivatives of petrochemical materials.
The invention includes a neutralized amino acid ester emulsifier
that is obtained from the reaction of a neutral amino acid having a
non-polar side chain with a long chain fatty alcohol. The ester of
the invention may have a structure represented by formula (I):
##STR00005## wherein R.sup.1 is a linear or branched alkyl group;
R.sup.2 is a linear or branched carbon chain; and the amine group
of the amino acid is neutralized with an acid. Also included is a
personal care composition comprising the ester described above.
Methods provided by the invention include methods of conditioning
the hair or skin, comprising topical application of the personal
care composition containing the ester and methods of forming an
emulsion comprising the incorporation of the neutralized amino acid
ester of the invention, and methods of stabilizing and improving
the texture of an emulsion comprising incorporation of a
neutralized amino acid ester of the invention with other
neutralized amino acid ester(s) of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing summary, as well as the following detailed
description of preferred embodiments of the invention, will be
better understood when read in conjunction with the appended
drawings. It should be understood that the invention is not limited
to the precise arrangements and instrumentalities shown. In the
drawings:
FIG. 1 shows an infrared spectrum of Brassicyl L-isoleucinate
esylate (BLIE);
FIGS. 2-9 are graphical representations of the pH of various
inventive formulations and control formulations over time at room
temperature;
FIG. 10 is a graph showing the results of a colorimetric analysis
of sample hair, untreated and treated with the inventive and
commercially available, non-natural control compositions;
FIG. 11 is a graphical representation of the wet combing
evaluations of untreated hair and hair treated with the inventive
compositions and two commercially available, non-natural
compositions;
FIG. 12 is a graphical representation of data obtained from
brushing experiments of human hair treated with a conditioner of
the invention and comparative conditioners;
FIG. 13 is a graphical representation of data obtained from static
electricity evaluation of human hair, untreated and treated with
the inventive compositions and two commercially available,
non-natural compositions;
FIG. 14 is a chart showing several formulations of the
invention;
FIG. 15 is a chart showing the initial pH values and viscosities of
the formulations of FIG. 14; and
FIGS. 16-23 are graphical representations of the pH changes over
time of the formulations of FIG. 14 as evaluated at room
temperature;
FIGS. 24-31 are graphical representations of the pH changes over
time of the formulations of FIG. 14 as evaluated at 5.degree.
C.;
FIGS. 32-39 are graphical representations of the pH changes over
time of the formulations of FIG. 14 as evaluated at 45.degree. C.;
and
FIGS. 40-47 are graphical representations of the pH changes over
time of the formulations of FIG. 14 as evaluated at 50.degree.
C.
DETAILED DESCRIPTION OF THE INVENTION
This invention includes neutralized amino acid ester cationic
emulsifiers and compositions that are natural, as they are not
derived from petrochemical materials, and also may be produced from
non-animal derived and non-GMO reactants, and prepared by processes
that utilize Green Chemistry principles. Because of the ester's
cationic structure, it is well suited for personal care
applications, particularly for compositions used in the
conditioning of hair and skin. At the time of the invention, no
other personal care compositions containing a cationic emulsifier
that was not petrochemically-derived were known. Accordingly, up to
the time of discovery of the invention, no natural personal care
compositions exhibited the performance characteristics provided by
a cationic emulsifier and expected by the consumer, particularly
with respect to substantivity, skin feel, and shelf stability.
The invention encompasses personal care compositions that contain
this emulsifying ester, particularly hair and skin conditioning
compositions. Such natural compositions may be substantially free
of petrochemicals, petrochemical derivatives, materials derived
from genetically modified organisms (such as GMO plant materials),
and/or any animal materials or derivatives.
In addition, the neutralized amino acid ester has been found to be
non-toxic to animals (including humans) and plants, unlike some
cationic emulsifiers that may harm wildlife and/or plants when
discharged into the environment.
The invention includes methods of increasing the substantivity
(absorbance to a negatively charged substrate, such as hair, skin
and nails) of a personal care composition that is substantially
free of petrochemicals, petrochemical derivatives, and/or materials
derived from genetically modified organisms (such as GMO plant
materials), and/or any animal materials or derivatives; therefore
the composition itself is natural.
The neutralized amino acid ester of the invention is derived from
the esterification of (i) an amino acid having a non-polar side
chain wherein the amine group of the amino acid has been
neutralized with an acid; with (ii) a long chain fatty alcohol. In
particular, suitable amino acid esters are derived from the
esterification of a neutral amino acid with a non-polar side chain
with a long chain fatty alcohol.
The amino acid ester of the invention may be represented by the
structure of formula (I):
##STR00006##
In (I), R.sup.1 represents an alkyl group, which may be branched or
linear. It may have one to ten carbon atoms or two to six carbon
atoms.
R.sup.2 represents a carbon chain that may be linear or branched.
It may contain ten to fifty carbon atoms or twenty-four to
thirty-two carbon atoms. The chain of R.sup.2 may contain at least
one unsaturated carbon atom. In an embodiment, R.sup.2 is an alkyl
group having eight to twenty four carbon atoms.
Amino acids for the formation of the ester include any that are
neutral. In an embodiment, one may select L-alanine, L-valine,
L-leucine and L-isoleucine. Particularly preferred, in some
embodiments of the invention, is L-isoleucine.
It is preferred that the selected neutral amino acid is not derived
from animal sources or GMO sources. In an embodiment, it may be
preferred that the amino acid(s) are synthetic and/or derived from
plants, algae, or other non-animal organisms. They may be obtained,
for example, from vegetable matter by a fermentation process.
To obtain the ester of the invention, the amine group of the amino
acid is neutralized with an acid, and is reacted with a long chain
fatty alcohol. Suitable fatty alcohols may be linear and/or
branched and may additionally be saturated and/or unsaturated. It
may be preferred that the fatty alcohol contains about ten to about
fifty or about twenty-four to about thirty-two carbon atoms. In an
embodiment, linear and/or branched fatty alcohols containing from
about twelve to about twenty-two carbon atoms may be preferred.
Examples of suitable fatty alcohols include lauryl alcohol,
myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol,
isostearyl alcohol, arachidyl alcohol, behenyl alcohol and mixtures
or combinations thereof. It is advisable that the fatty alcohols
are derived from non-petrochemical sources.
The amine group of the amino acid ester may be fully or partially
neutralized by an acid, to facilitate its cationic behavior. Any
acid may be used, including organic and inorganic acids. Suitable
acids include, without limitation, mineral acids, amino acids,
hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, and
nitric acid. Suitable organic acids may be citric acid,
ethanesulfonic acid, acetic acid, formic acid, and oxalic acid.
Suitable amino acids may include glutamic acid and aspartic acid.
In an embodiment, one may prefer ethanesulfonic acid that is
derived from non-GMO ethanol.
An exemplary preferred neutralized amino acid ester may be
Brassicyl L-isoleucine esylate (BLIE) or leucine isostearyl ester
esylate (LIEE). Brassicyl L-isoleucine esylate (BLIE) may be
derived from the esterification of Brassica alcohol with
L-isoleucine esylate. L-isoleucine esylate may be prepared by
reacting the amine group on isoleucine with ethanesulfonic acid.
Brassica alcohol is a fatty alcohol that is derived from the
splitting of high erucic acid rapeseed oil obtained from the
Brassica genus of plants followed by hydrogenation. Brassica
alcohol consists predominantly of stearyl (C.sub.18), arachidyl
(C.sub.20) and behenyl (C.sub.22) alcohols with minor quantities of
lower and higher alkyl chain length alcohols.
The neutralized amino acid ester of the invention may be
synthesized by methods commonly known in the art.
The invention also includes personal care compositions that contain
the neutralized amino acid ester; such compositions may contain a
non-aqueous phase and an aqueous phase that are emulsified by the
ester. The compositions are preferably substantially free of
petrochemical or petrochemical derivatives. To form such
compositions, an exemplary process may be mixing or otherwise
incorporating the neutralized amino acid ester with other
ingredients of the composition to formulate the finished
product.
In an exemplary hair conditioner base formulation, the neutralized
amino acid ester is mixed with fatty alcohol and an emollient and
is warmed to about 75.degree. C. to about 85.degree. C. This
mixture is then added to hot water and allowed to cool slowly with
agitation. In such compositions, the neutralized amino acid ester
of the invention serves multiple roles--it emulsifies the aqueous
and non-aqueous phases of the invention, it increases the
substantively of the personal care composition to skin, hair or
nails, and it conditions/lubricates the surfaces of the hair, skin
or nail substrates to which it is applied.
The composition of the invention may be formulated to be any type
of personal care composition, cosmetic, or pharmaceutical delivery
formulation (for example, to deliver therapeutic agents to the skin
or gums).
Other suitable compositions may include a hair detergent, hair
cream conditioner, shampoo, rinse, conditioning shampoo, hair
lotions, hair treatment, hair cream, hair spray, hair liquid, hair
wax, hair-styling preparation, permanent wave liquids, hair
colorant, acidic hair colorant, hair manicure, glaze, skin lotion,
milky lotion, face wash, makeup remover, cleansing lotion,
emollient lotion, nourishing cream, emollient cream, massage cream,
cleansing cream, body shampoo, hand soap, bar soap, shaving creams,
sunscreen, sunburn treatment, deodorants, makeup removing gel,
moisture gel, moisture essence, UV exposure-preventing essence,
shaving foam, face powder, foundation, lipstick, blush, eyeliner,
wrinkle and anti-aging cream, eye shadow, eyebrow pencils, mascara,
mouthwash, toothpaste, an oral care composition, a skin cleansing
composition, a textile cleansing compositions, a dish cleaning
composition, a hair or fur cleansing composition, a deodorant or
antiperspirant, a cosmetic, a hair styling composition, a skin
moisturizer, a skin conditioner, a hair conditioner and a nail
conditioner.
The compositions may include various additives, as are known in the
personal care composition art. Suitable additives include various
anionic surfactants, cationic surfactants, amphoteric surfactants,
nonionic surfactants, waxes, other oils and fats and derivatives
thereof, fatty acid esters of varying chain lengths, synthetic oils
and fats, polymers, alcohols, polyhydric alcohols, extracts useful
for providing fragrance, amino acids, nucleic acids, vitamins,
hydrolyzed proteins and derivatives thereof, glycerine and
derivates thereof, enzymes, anti-inflammatory and other
medicaments, microbiocides, antifungals, antiseptics, antioxidants,
UV absorbers, dyes and pigments, sunscreen active agents, chelating
agents, sweat retardants, oxidizers, pH balancing agents, glyceryl
monoesters, moisturizers, peptides and derivatives thereof,
anti-aging actives, hair growth promoters, anti-cellulite actives
and the like acceptable for use in formulations for human use.
Others include EDTA, glutamic acid, glycerine, panthenol, stearyl
alcohol, cetyl alcohol, cyclomethicone, dimethicone, pH adjustment
additives, and preferably a water base.
Methods that are included within the scope of the invention include
methods of conditioning the hair and/or skin by applying the
personal care compositions described above. It may be desirable
that the composition is in the form of an oil-in-water emulsion,
but can also be in a form of, for example, creams, lotions,
solutions, gels, pastes, mousses, sprays and combinations thereof.
The proportion of the neutralized amino acid ester used in the hair
condition composition is preferably from about 0.1 to about 10.0
weight percent, and more preferably from about 0.25 to about 5.0
weight percent.
The compositions may contain a single neutralized amino acid ester
or more than one. In an embodiment, the preferred neutralized amino
acid ester may be leucine isostearyl ester esylate (LIEE) or
Brassicyl L-isoleucinate esylate (BLIE). In some embodiments, it
may be preferred to include a mixture of LIEE and BLIE. LIEE and
BLIE may be included in any proportion, including, for example, in
parts by weight, 1:1, 1:2, 1:3, 1:4, 1:5; `1:6; 1:7; 1:8; 1:9; and
1:10.
Also included are methods of forming an emulsion that includes
incorporating the amino acid ester of the invention into a mixture
containing at least an aqueous phase and non-aqueous phase.
EXAMPLES
Example 1
Synthesis of Brassicyl L-Isoleucinate Esylate (BLIE)
To a one liter round bottom flask affixed with vapor column, total
condenser, nitrogen sparge and agitator, 508.5 grams (1.629 moles)
of Brassicyl alcohol and 106.9 grams (0.8147 moles) of L-isoleucine
were charged. The mixture was warmed to 90.degree. C. with
stirring, and 134.5 grams (0.8551 moles) of a 70% solution of
ethanesulfonic acid was added dropwise over about a twenty-minute
period. The mixture was then heated to 140.degree. C. and was held
for about 16 hours. The mixture was then cooled to 90.degree. C.
and the excess of ethanesulfonic acid was neutralized with 1.8
grams of sodium carbonate dissolved in 5.6 grams of water. The
mixture was then dried under hard vacuum for about one hour. The
mixture was then cooled to about 70.degree. C. and flaked off,
yielding a pale yellow solid product.
Acid value was determined on the product using ASTM (American
Society of Testing and Materials, West Conshohocken, Pa.) official
method number D-972, the contents of which are incorporated herein
by reference, and was found to be 2.67 mg KOH/g (95.9% conversion.)
The amine value was determined through the use of multi-endpoint
titration with base using a modern automatic titrator. In the
method, a sample is weighed and dissolved in un-neutralized
denatured ethanol. The mixture is then titrated with dilute sodium
hydroxide to the appearance of two endpoints, the first being
related to the consumption of carboxylate, and the second being
related to the titration of the amine salt. The value found was
64.3 mg KOH/g. The infrared spectrum was determined using a
Perkin-Elmer (Waltham, Mass.) Spectrum 100 FT-IR spectrophotometer
fitted with a Pike (Madison, Wis.) MIRacle ATR (Attenuated Total
Reflectance) accessory with ZnSe crystal. The spectrum is displayed
in FIG. 1, and shows a prominent peak at 1745 cm-1 indicative of
ester and the absence of any peak at 1670-1640 cm-1 indicative of
the absence of amide. The melting point was determined using an SRS
(Stanford Research Systems, Inc. Sunnyvale, Calif.) EZMelt
automated melting point apparatus and was found to be 55.degree.
C.
Example 2
Additional analogs of BLIE were prepared and analyzed using the
general methods described in Example 1, and the properties are
summarized in Table 1.
TABLE-US-00001 TABLE 1 Amine Value Acid Value (mg Melting Point
Amino Acid Fatty Alcohol (mg KOH/g) KOH/g) (.degree. C.) L-Alanine
Coconut 0.0 106.6 78 L-Alanine Brassicyl (Hyd.) 3.4 71.9 99
L-Alanine Stearyl 5.5 114.6 114 L-Alanine Isostearyl 1.7 76.9 Paste
at R.T. L-Valine Coconut 2.5 109.0 Paste at R.T. L-Valine Brassicyl
(Hyd.) 0.4 67.2 60 L-Valine Stearyl 0.0 75.6 62 L-Valine Isostearyl
1.2 73.7 Liquid at R.T. L-Leucine Coconut 2.0 97.7 Liquid at R.T.
Leucine Brassicyl (Hyd.) 3.5 65.4 62 L-Leucine Stearyl 2.1 73.0 59
L-Leucine Isostearyl 1.8 72.1 Liquid at R.T. L-Isoeucine Coconut
5.3 103.1 Liquid at R.T. L-Isoeucine Stearyl 1.1 72.8 53
Example 3
To demonstrate the emulsification behavior achieved by the present
invention, an exemplary hair conditioning base formulation was
prepared. The composition of the formulation is shown in Table
2.
TABLE-US-00002 TABLE 2 Ingredients % w/w Part A Deionized water
90.40 L-Arginine 0.20 Part B Stearyl alcohol 5.90 Brassicyl
L-Isoleucinate Esylate 3.50 Total 100.00
The formulation was prepared using the following procedure. Part A,
deionized water and L-arginine were combined in a vessel with
propeller agitation and heated to about 70 to about 75.degree. C.
and agitated until a clear solution was obtained. In a separate
vessel, stearyl alcohol, cetyl alcohol, and Brassicyl
L-isoleucinate esylate (BLIE) were combined and heated to about
70.degree. C. to about 75.degree. C., then agitated until a uniform
mixture was obtained. The contents of the second vessel were added
to the first, and agitated at a temperature of about 70 to about
75.degree. C. until a milky dispersion was obtained (about 10
minutes.) The mixture was then allowed to cool with sweep agitation
to about 30.degree. C. to about 35.degree. C. Agitation was then
stopped, and the completed conditioner formulation was poured off
to containers. What resulted was a white, creamy emulsion that
showed no signs of instability for 1 month at 45.degree. C.
Example 4
To illustrate the ability of the invention to create stable
emulsions, a stability study was performed. Forty-four formulations
were prepared using the general method described in Example 3.
TABLE-US-00003 TABLE 3 Formula 1 2 3 4 5 6 7 8 Ingredients % w/w %
w/w % w/w % w/w % w/w % w/w % w/w % w/w Deionized Water 88.20 86.20
84.20 82.20 88.03 85.99 83.95 81.90 L-Arginine 0.00 0.00 0.00 0.00
0.17 0.21 0.25 0.30 KB Natural 8.00 10.00 12.00 14.00 8.00 10.00
12.00 14.00 Natural Oil 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Preservative 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 100.00 100 100
100 100.00 100.00 100.00 100.00 Formula 9 10 11 12 13 14 15 16
Ingredients % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt
% wt/wt Deionized Water 88.02 88.01 88.01 87.98 85.98 87.96 85.95
85.93 Arginine 0.18 0.19 0.202 0.216 0.22 0.235 0.25 0.27 BLIE 2.79
2.98 3.17 3.39 3.49 3.73 3.97 4.24 Cetyl Alcohol 2.60 2.51 2.41
2.305 3.255 2.135 3.015 2.88 Stearyl Alcohol 2.60 2.51 2.41 2.305
3.255 2.135 3.015 2.88 Natural Oil 3.00 3.00 3.00 3.00 3.00 3.00
3.00 3.00 Preservative 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80
100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Formula 17
18 19 20 21 22 23 24 Ingredients % wt/wt % wt/wt % wt/wt % wt/wt %
wt/wt % wt/wt % wt/wt % wt/wt Deionized Water 83.938 83.92 83.902
83.883 81.886 81.864 81.843 81.818 Arginine 0.262 0.28 0.298 0.317
0.314 0.336 0.357 0.382 BLIE 4.19 4.48 4.76 5.09 4.89 5.22 5.56
5.93 Cetyl Alcohol 3.905 3.76 3.62 3.455 4.55 4.39 4.22 4.035
Stearyl Alcohol 3.905 3.76 3.62 3.455 4.55 4.39 4.22 4.035 Natural
Oil 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Preservative 0.80 0.80
0.80 0.80 0.80 0.80 0.80 0.80 100.00 100.00 100.00 100.00 100.00
100.00 100.00 100.00 Formula 25 26 27 28 29 30 31 32 Ingredients %
wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt
Deionized Water 88.11 86.09 84.08 82.05 88.09 88.09 88.09 88.07
Arginine 0.085 0.105 0.124 0.147 0.1068 0.114 0.1212 0.1296 BLIE
2.67 3.33 4.00 4.67 2.79 2.98 3.17 3.39 Cetyl Alcohol 2.67 3.33
4.00 4.67 2.605 2.51 2.41 2.305 Stearyl Alcohol 2.67 3.33 4.00 4.67
2.605 2.51 2.41 2.305 Natural Oil 3.00 3.00 3.00 3.00 3.00 3.00
3.00 3.00 Preservative 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80
100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Formula 33
34 35 36 37 38 39 40 Ingredients % wt/wt % wt/wt % wt/wt % wt/wt %
wt/wt % wt/wt % wt/wt % wt/wt Deionized Water 86.07 88.06 86.05
86.04 84.07 84.06 84.051 84.041 Arginine 0.132 0.141 0.15 0.1602
0.131 0.14 0.149 0.159 BLIE 3.49 3.73 3.97 4.24 4.19 4.48 4.76 5.09
Cetyl Alcohol 3.255 2.135 3.015 2.88 3.905 3.76 3.62 3.455 Stearyl
Alcohol 3.255 2.135 3.015 2.88 3.905 3.76 3.62 3.455 Natural Oil
3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Preservative 0.80 0.80 0.80
0.80 0.80 0.80 0.80 0.80 100.00 100.00 100.00 100.00 100.00 100.00
100.00 100.00 Formula 41 42 43 44 Ingredients % wt/wt % wt/wt %
wt/wt % wt/wt Deionized Water 81.42 82.032 82.022 82.01 Arginine
0.785 0.168 0.178 0.191 BLIE 4.89 5.22 5.56 5.93 Cetyl Alcohol 4.55
4.39 4.22 4.035 Stearyl Alcohol 4.55 4.39 4.22 4.035 Natural Oil
3.00 3.00 3.00 3.00 Preservative 0.80 0.80 0.80 0.80 100.00 100.00
100.00 100.00
The pH and viscosity at 25.degree. C. were performed on each of the
formulations, and the results are found in Table 4. The pH was
measured using an Orion 420A pH meter with a glass electrode that
was calibrated using aqueous buffer solutions. The clean, dry
electrode was placed in each sample at 25.degree. C. for
approximately 1 minute and the pH was recorded directly from the
meter display. The viscosity was determined using a Brookfield RVT
dial viscometer with helipath stand and T-bar spindles. The test
emulsion was equilibrated at 25.degree. C. before taking each
measurement. The spindle was attached to the instrument and lowered
into the test formula. The viscometer and helipath stand were
turned on and the viscosity measurement was recorded after a period
of 60 seconds.
TABLE-US-00004 TABLE 4 Formula 1 2 3 4 5 6 7 8 9 10 11 pH 4.25 4.35
4.4 4.48 5.38 5.66 5.73 5.76 4.92 4.97 5.02 Viscosity 18500 20000
22800 66500 41000 54000 69000 75500 4000 6000 7000 Formula 12 13 14
15 16 17 18 19 20 21 22 pH 4.98 5.15 4.94 5.39 5.33 5.16 5.23 5.22
5.16 5.24 5.33 Viscosity 11500 35500 9000 6000 43500 57000 61000
47000 54000 51000 77000 Formula 23 24 25 26 27 28 29 30 31 32 33 pH
5.55 5.54 5.09 5.26 5.27 5.49 5.05 5.16 4.99 4.98 5.17 Viscosity
69000 80000 35000 59000 73000 83000 23000 16000 25000 27000 4600- 0
Formula 34 35 36 37 38 39 40 41 42 43 44 pH 4.99 5.05 5.07 5.11
5.14 4.87 4.84 5.3 5.17 5.08 5.07 Viscosity 24000 42000 47500 91000
65000 18000 72000 92000 Too thick Too thick 81000
All formulations were transferred to canisters to test for
stability. Stability is defined as the ability of the emulsion to
retain its initial, creamy uniform texture, and to not separate.
The test was performed at room temperature for a period of four
weeks. Formulation pH was monitored weekly. FIGS. 2 through 9 show
the pH as a function of storage time. In each case, pH changed very
little over the entire course of the study for all formulations,
and all formulations retained their initial physical form and
characteristics.
Example 5
To demonstrate the conditioning properties of the inventive
cationic emulsifiers, a model hair conditioning formulation was
prepared to test for the reduction in flyaway hair. The composition
of the inventive formulation (Inventive Formulation A) is shown in
Table 5 below:
TABLE-US-00005 TABLE 5 Inventive Formulation A Ingredients % w/w
Part A Deionized water 88.060 L-Arginine 0.141 BLIE 3.730 Part B
Stearyl alcohol 2.135 Cetyl Alcohol 2.135 Almond Oil 3.000 Part C
Preservative 0.800 Total 100.000
The Inventive Formulation A was tested against industry leader
commercial products Pantene Pro-V Daily Moisture Renewal and Gamier
Fructis Fortifying Cream Conditioner. The cationic emulsifier
utilized in Pantene Pro-V Daily Moisture Renewal is
stearamidopropyl dimethylamine, while the Gamier Fructis Fortifying
Cream Conditioner utilizes behentrimonium chloride.
Ten tresses of hair were washed with Pantene clarifying shampoo and
rinsed under deionized water for 1 minute. The tresses were combed,
and were immersed in conditioner for 1 minute, then rinsed under
deionized water for 1 minute and hung to dry for 2 hours. The
tresses were then dried with a hair dryer on low for 5 minutes and
hung to dry another 15 minutes. The width at the bottom of the
tress was recorded, it was combed 20 times, and the width was
recorded again. The data obtained are recorded in Tables 6, 7, and
8.
TABLE-US-00006 TABLE 6 Inventive Pre comb Post-comb Formulation A
width (cm) width (cm) Difference % Fly Away 1 5.0 7.3 2.3 31.51 2
4.3 5.4 1.1 20.37 3 5.7 5.8 0.1 1.72 4 4.8 6.2 1.4 22.58 5 5.2 6.8
1.6 23.53 6 5.3 5.9 0.6 10.17 7 5.2 4.4 -0.8 -18.18 8 4.3 4.8 0.5
10.42 9 4.5 6.2 1.7 27.42 10 4.9 5.1 0.2 3.92 Average 4.92 5.79
0.87 13.35
TABLE-US-00007 TABLE 7 Pre comb width Post-comb Pantene (cm) width
(cm) Difference % Fly Away 1 4.1 5.5 1.4 25.45 2 4.5 5.1 0.6 11.76
3 3.9 4.2 0.3 7.14 4 2.9 4.5 1.6 35.56 5 4.5 5.3 0.8 15.09 6 3.9
4.2 0.3 7.14 7 4.1 5.3 1.2 22.64 8 4.5 5.5 1.0 18.18 9 4.1 4.1 0.0
0.00 10 3.2 4.3 1.1 25.58 Average 4.0 4.8 0.8 16.86
TABLE-US-00008 TABLE 8 Pre comb width Post-comb width Garnier (cm)
(cm) Difference % Fly Away 1 3.0 4.3 1.3 30.23 2 2.9 4.8 1.9 39.58
3 3.7 4.4 0.7 15.91 4 3.1 4.3 1.2 27.91 5 2.1 3.2 1.1 34.38 6 3.0
3.9 0.9 23.08 7 2.9 3.3 0.4 12.12 8 3.2 4.2 1.0 23.81 9 2.2 3.3 1.1
33.33 10 3.0 4.1 1.1 26.83 Average 2.9 4.0 1.1 26.72
The results show that there was less fly-away using Inventive
Formulation A when compared with Pantene and Gamier conditioners.
Therefore, the Inventive Formulation A is just as effective, if not
more effective, than Pantene and Gamier (both of which contain
petrochemicals and/or petrochemical-derived materials) at
conditioning hair.
Example 6
The Rubine Dye Test was used to evaluate the sub stantivity of
Inventive Formulation A versus market standards Pantene and Garnier
as in Example 5. Rubine Dye is an anionic dye which will readily
react with cationic materials. When light blonde hair or wool is
treated with a cationic conditioner and rinsed, the hair or wool
turns reddish pink when dipped into a dilute solution of Rubine
Dye. This study was performed to evaluate the deposition of Direct
Red, an anionic dye solution, onto conditioned hair to measure the
degree of cationic charge due to substantivity of the conditioner
to the hair.
A stock dye solution was prepared by combining deionized water
(99.37%,) Direct Red 80 dye (0.50%) and glacial acetic acid (0.13%)
until a uniform solution was obtained. This solution was further
diluted by mixing the stock dye solution with deionized water at a
ratio of one to four to create the Test Dye Solution. Prebleached
hair was glued to plastic strips weighing 0.60+/-0.02 grams each.
Ten swatches were prepared for each conditioner to be tested. Each
swatch was individually wet under warm running water, then washed
with two grams of cationic conditioner for one minute. Each sample
was then rinsed under warm running water for two minutes and excess
water was removed by blotting with a paper towel. Each hair sample
was then immersed in 200 ml if Test Dye Solution for 10 seconds,
then rinsed under running water for 5 seconds. Excess water was
removed by blotting between two paper towels and then hung to dry.
Qualitative and quantitative comparisons of dye uptake and relative
substantivity of each cationic conditioner was evaluated using a
digital camera and Minolta Chroma Meter. FIG. 10 shows the level of
color as determined by the Minolta Chroma Meter in terms of delta
E. The Minolta Chroma Meter measures chromaticity, tristimulus
values, color difference, correlated color temperature and the
illuminance of light sources. The delta E value is given by
equation below. Higher delta E relates to higher color.
.DELTA.E=.DELTA.L.sup.2+.DELTA.a.sup.2+.DELTA.b.sup.2
The results of this study indicate that Formulation A performs
comparably to behentrimonium chloride (Garnier) and stearamidopropl
dimethylamine (Pantene) based conditioners. The Formulation A
conditioner was slightly more substantive than the Pantene, but
less than Gamier, and well within commercially acceptable
parameters. The results are expressed as .DELTA.E, which accounts
for variations in tone and hue versus the unconditioned
tresses.
Example 7
Exemplary formulations for hair and skin care compositions are
shown below (formulations A to M). None contains petrochemicals
and/or petrochemical-derived materials.
A. Daily Conditioner for Normal Hair
TABLE-US-00009 Ingredients % w/w Part A Deionized water 84.05
L-Arginine 0.15 BLIE 4.50 Part B Stearyl alcohol 3.75 Cetyl Alcohol
3.75 Caprylic/Capric Triglycerides 3.00 Part C Preservative 0.80
Total 100.00
B. Intense Moisturizing Hair Conditioner
TABLE-US-00010 Ingredients % w/w Part A Deionized water 74.34
L-Arginine 0.16 BLIE 5.20 Glycerine 5.00 Part B Cetearyl Alcohol
7.50 Helianthus Annuus (Sunflower) Seed Oil 6.50 Hydrolyzed Silk
Protein 0.50 Part C Preservative 0.80 Total 100.00
C. Leave-In Hair Conditioning Treatment
TABLE-US-00011 Ingredients % w/w Part A Deionized water 89.11
L-Arginine 0.14 BLIE 3.75 Part B Cetyl Alcohol 2.10 Stearyl Alcohol
2.10 Olea Europaea (Olive) Fruit Oil 2.00 Part C Preservative 0.80
Total 100.00
D. Rich Conditioning Treatment (Hair)
TABLE-US-00012 Ingredients % w/w Part A Deionized water 81.05
L-Arginine 0.15 BLIE 4.50 Part B Cetyl Alcohol 3.75 Stearyl Alcohol
3.75 Olea Europaea (Olive) Fruit Oil 2.00 Part C Preservative 0.80
Total 100.00
E. Baby Lotion (Skin)
TABLE-US-00013 Ingredients % w/w Part A Deionized water 80.25
L-Arginine 00.25 Glycerin 2.00 Part B BLIE 3.00 Brassica Alcohol
3.00 Brassica Glycerides 2.00 Heptyl Undecylenate 4.00 Helianthus
Annuus (Sunflower) Seed Oil 4.00 Glyceryl Monocaprylate 1.00 Part C
Natural Fragrance 0.30 Total 100.00
F. Rich Body Butter (Skin)
TABLE-US-00014 Ingredients % w/w Part A Deionized water 68.04
L-Arginine 0.16 Glycerine 4.00 Aloe Barbadensis Leaf Juice 1.00
Part B BLIE 5.20 Cetyl Alcohol 3.50 Behenyl Alcohol 3.50 Heptyl
Undecylenate 5.00 Olea Europaea (Olive) Fruit Oil 7.00
Butyrospermum Parkii (Shea) Butter 1.50 Part C Preservative 0.80
Natural Fragrance 0.30 Total 100.00
G. Conditioning Cream (Hair)
TABLE-US-00015 Ingredients % w/w Part A Deionized water 85.30
L-Arginine 0.15 Glycerine 0.50 Part B BLIE 3.70 Brassica Alcohol
6.55 Helianthus Annuus (Sunflower) Seed Oil 3.00 Part C
Preservative 0.80 Total 100.00
H. Deep Conditioning Treatment (Hair)
TABLE-US-00016 Ingredients % w/w Part A Deionized water 76.55
L-Arginine 0.25 Glycerine 0.50 Part B BLIE 4.00 Brassica Alcohol
7.00 Heptyl Undecylenate 3.00 Caprylic/Capric Triglyceride 1.00
Cetyl Alcohol 5.00 Polyester-11 0.50 Part C Keratin Amino Acids
1.00 Glyceryl Monocaprylate 1.20 Total 100.00
I. Moisturizing Conditioner for Curly Hair
TABLE-US-00017 Ingredients % w/w Part A Deionized water 75.05
L-Arginine 0.25 Sorbitol 2.00 Glyceryl Monocaprylate 1.00 Panthenol
0.50 Glycerine 2.50 Polyester-11 0.50 Part B BLIE 4.00 Cetearyl
Alcohol 10.00 Caprylic/Capric Triglyceride 1.00 Olea Europaea
(Olive) Oil 2.00 Part C Hydrolyzed Wheat Protein 1.00 Total
100.00
J. Light Daily Conditioner (Hair)
TABLE-US-00018 Ingredients % w/w Part A Deionized water 89.20
L-Arginine 0.20 Glycerine 0.50 Glyceryl Monocaprylate 1.00 Part B
BLIE 1.80 Brassica Alcohol 3.20 Heptyl Undecylenate 1.00 Cetyl
Alcohol 3.00 Part C Natural Fragrance 0.10 Total 100.00
K. Leave-In Conditioning Spary (Hair)
TABLE-US-00019 Ingredients % w/w Part A Deionized water 91.25
L-Arginine 0.15 Glycerine 0.50 Glyceryl Monocaprylate 1.00 Part B
BLIE 1.25 Brassica Alcohol 2.25 Heptyl Undecylenate 1.00 Cetyl
Alcohol 1.50 Olea Europaea (Olive) Oil 0.50 Part C Hydrolyzed Silk
Protein 0.50 Natural Fragrance 0.10 Total 100.00
L. Deluxe Moisturizier
TABLE-US-00020 Ingredients % w/w Part A Deionized water 56.85
L-Arginine 0.15 Glycerine 5.00 Part B BLIE 4.50 Brassica Alcohol
4.50 Brassica Glycerides 3.00 Caprylic/Capric Triglyceride 25.00
Glyceryl Monocaprylate 1.00 Total 100.00
M. Sprayable Hydrating Lotion (Skin)
TABLE-US-00021 Ingredients % w/w Part A Deionized water 84.30
L-Arginine 0.20 Glycerine 5.00 Glyceryl Monocaprylate 1.00 Part B
BLIE 2.05 Brassica Alcohol 2.05 Brassica Glycerides 1.40
Caprylic/Capric Triglyceride 4.00 Total 100.00
Example 8
Two conditioning formulations in accordance with the invention were
prepared specifically to evaluate the aesthetic characteristics of
the formulations. Each was prepared with out any petrochemical
materials. Formulation K included both leucine isostearyl ester
esylate (LIEE) and Brassicyl L-isoleucinate esylate (BLIE).
Formulation C included BLIE only.
The formulations were prepared simultaneously using the following
procedure. With reference to Table 8 below, Part A, deionized
water, glycerine and arginine were combined in a vessel with
propeller agitation and heated to about 70 to about 75.degree. C.
and agitated until a clear solution was obtained. In a separate
vessel, Brassica alcohol, cetyl alcohol, heptyl undecylenate,
caprylic/capric triglyceride, glyceryl monocaprylate and Brassicyl
L-isoleucinate esylate (BLIE) were combined and heated to about
70.degree. C. to about 75.degree. C., then agitated until a uniform
mixture was obtained. The contents of the second vessel were added
to the first, and agitated at a temperature of about 70 to about
75.degree. C. until a milky dispersion was obtained (about 10
minutes.) The mixture was then allowed to cool with sweep agitation
to about 30.degree. C. to about 35.degree. C. Agitation was then
stopped, and the completed conditioner formulation was poured off
to containers.
TABLE-US-00022 TABLE 8 K C Ingredients % w/w % w/w Part A Deionized
water 77.05 78.05 L-Arginine 0.25 0.25 Glycerine 0.50 0.50 Part B
BLIE 4.00 4.00 Brassica Alcohol 7.00 7.00 Heptyl Undecylenate 3.00
3.00 Caprylic/Capric Triglyceride 1.00 1.00 Cetyl Alcohol 5.00 5.00
Leucine Isostearyl Ester Esylate 1.00 0 Glyceryl Monocaprylate 1.20
1.20 Total 100.00 100.00
Test formula K was a milky, creamy emulsion while hot and cooled to
a smooth uniform emulsion with a glossy finish. Test formula C was
thicker and the resulting emulsion was grainy and dull in
appearance. Test formula C, without LIEE, was less stable at
elevated temperature. Test formula K was stable for 90 days at
25.degree. C. and 45.degree. C.
Example 9
A conditioning cream in accordance with the invention was prepared
by incorporating the ingredients of Part A (Table 9, below) and
Part B (Table 9, below), and subsequently mixing Parts A and B
together.
TABLE-US-00023 TABLE 9 Conditioning Cream Ingredients % w/w Part A
Deionized water 85.30 L-Arginine 0.15 Glycerin 0.50 Part B BLIE
3.70 Brassica Alcohol 6.55 Helianthus Annuus (Sunflower) Seed Oil
3.00 Part C Preservative 0.80 Total 100.00
The resulting conditioning cream was evaluated against commercially
available products (containing petrochemical derivatives) for
various performance characteristics in Examples 10-12.
Example 10
Wet Combining Evaluation
The primary technical function of most conditioning products is to
lubricate the hair surface, and in doing so to facilitate
manageability and mediate degrading feel properties. Thus,
protection, conditioning, and manageability properties of a product
may be evaluated through combing experiments that quantify the
lubrication magnitude. Accordingly, the conditioning cream of
Example 9 ("CC9") was evaluated for these properties in a wet
combing study. Virgin (un-colored or unbleached) European medium
brown hair test tresses (supplied by International Hair Importers)
were prepared to be 1 inch wide, 8 inches long and contained 3
grams of hair.
To eliminate any structural differences in the hair, each tress was
initially bleached using a 6% hydrogen peroxide solution at pH of
10.2. The tresses were left in contact with the bleach solution for
50 minutes under controlled temperature conditions (40.degree. C.).
At the end of this process, tresses were thoroughly rinsed under an
Intellifaucet (Hass Mfg. Co., Averill Park, N.Y.) set at 37.degree.
C. with a flow rate of 1.0 GPM.
Internal control condition creams were selected from commercially
available products that have previously been determined to
represent performance extremes for different attributes.
Comparative Conditioner 1 ("CC1") was a bargain brand product that
previous studies have consistently shown to be a relatively poor at
providing surface lubrication. Control Conditioner 2 ("CC2") was
the moisturizing variant of a commercially successful hair care
brand that has consistently shown high levels of surface
lubrication. Each of CC1 and CC2 contains petrochemical
materials.
Each tress was treated with one of the CC9, CC1 or CC2. All tress
treatment was performed using an Intellifaucet set at 37.degree. C.
with a flow rate of 1.0 GPM. Tresses were first wetted for 30
seconds. Conditioner was syringe-applied to the hair at a dosage of
15% of the tress weight (i.e., 0.45 g product on a 3 gram tress).
The product was massaged into the tress for 30 seconds, and then
allowed to remain on the hair for additional 30 seconds. The
product was then rinsed under the Intellifaucet for 30 seconds. A
negative control consisting of a tress that was not treated with
any conditioning cream was also evaluated.
Each tress was subjected to a wet combing evaluating performed in
accordance with the widely used method first proposed by Garcia
& Diaz (JSCC, 27, (1976) 379-398-Combability Measurements on
Hair,) the contents of which are incorporated here in by reference.
Wet combing experiments were performed using an Instron 5500 series
tensile tester equipped with Bluehill software. Eight replicate
hair tresses are used for each sample to ensure statistical
relevance.
The results of the wet combing evaluations are shown below, and are
plotted graphically in FIG. 11.
TABLE-US-00024 Results of Wet Combing Evaluation Treatment N Mean
Std Dev Std Err Mean Unconditioned Hair 8 64.3 1.40 0.50 A CC1 8
21.7 1.61 0.57 B CC9 8 18.0 2.06 0.73 C CC2 8 14.3 1.41 0.50 D
Levels not connected by same letter are significantly
different.
As can be seen from the results, Conditioner of Example 9 (CC9) has
properties about intermediate relative to the properties of the two
commercial control formulations. Thus, CC9 provides a wet combing
performance that is comparable to many commercially available
bodifying/volumizing conditioners.
Example 11
CC9 was evaluated for its surface lubrication properties. Repeated
brushing experiments provide a means to evaluate a conditioning
products' ability to provide surface lubrication, therefore
reducing hair snags, entanglements and abrasion which in turn
reduces fiber (hair) breakage. The results of such tests are
expressed as a count of the number of broken fibers as a function
of combing/brushing cycles. Tresses were bleached and treated with
CC9, CC1 and CC2 as described in Example 10, above. Each tress was
brushed 10,000 times with subsequent counting of broken fibers.
Brushing was performed using a repeated combing/brushing device, to
ensure uniform application of brushing force across all tress
samples. Eight replicate tresses were used. The results are shown
below and are plotted graphically in FIG. 12.
TABLE-US-00025 Treatment N Mean Std Dev Std Err Mean Unconditioned
Hair 10 197.9 16.46 5.21 A CC1 10 61.3 5.87 1.86 B CC2 10 43.5 4.09
1.29 C CC9 10 40.7 5.03 1.59 C Levels not connected by same letter
are significantly different
The data demonstrate that CC9 protects against breakage at a level
comparable to the positive control (CC2). Results suggest an
approximate 80% reduction in the amount of breakage relative to
Unconditioned Hair.
Example 12
CC9 was evaluated for its ability to reduce static electricity
build up in hair. Under low humidity conditions, hair has an
especially low conductivity and so charges resulting from standard
grooming practices (such as heat styling and brushing) are not
readily dissipated. Many conditioner products aim to reduce static
electricity build-up, although the mechanism by which charge is
reduces has not yet been definitively elucidated. It appears likely
that there is a contribution from lubrication (which reduces the
amount of charge build up), and also an increased surface
conductivity arising from the deposition of cationic surfactants
(which facilitates charge dissipation).
Hair tresses were bleached and treated with CC9, CC1, and CC2, as
described in Example 10. The method of Lunn and Evans (JSCC,
(1977), 28, 549-569) (the contents of which are incorporated herein
by reference) were used to quantify the anti-static benefit. Hair
tresses were equilibrated at low humidity and then brushed. An
appropriately placed sensor provided real-time measurement of the
static build-up. Eight tresses were evaluated per sample. Untreated
tresses were also evaluated. The results are shown below and are
plotted graphically in FIG. 13.
TABLE-US-00026 Treatment N Mean Std Dev Std Err Mean Unconditioned
Hair 10 1452.0 216.6 68.48 A CC1 10 483.0 93.2 29.48 B CC2 10 148.6
47.0 14.87 C CC9 10 116.4 26.5 8.38 C Levels not connected by same
letter are significantly different
As can been seen from the results, CC9 provides comparable
protection against static flyaway as the positive control.
Example 13
Forty-four formulations of the invention were prepared to evaluate
longer term shelf stability of the formula. The formulations 1-44
were prepared by mixing together the ingredients as set out in FIG.
14.
In each of formulations 9-24, the ingredient called out as "Base I"
is: behenyl alcohol 57.61%, stearyl alcohol 57.61%, isoleucine
14.25%, and ethane sulfonic acid 17.94%. In each of formulations
1-8 and 25-28, the ingredient called out as "Base II" is: Base I
33.26%, cetyl alcohol 33.26%, stearyl alcohol 33.26%, and sodium
carbonate 0.22%.
The initial physical properties of pH and viscosity for each
formulation were evaluated and are shown in FIG. 15. Each
formulation was split into several samples, which were maintained
at room temperature, 5.degree. C., 45.degree. C. or 50.degree. C.
and pH (an indicator of stability) was re-evaluated at time points
of various duration. The results are shown graphically in FIGS.
16-47.
While it has been shown and described several embodiments in
accordance with the invention and use thereof, it is understood
that the same is not limited thereto, but is susceptible to many
changes and modifications to one possessing ordinary skill in the
art, and therefore we do not wish to be limited to the details
shown and described herein, but intend to cover all such
modifications as are encompassed by the scope of the appended
claims.
* * * * *