U.S. patent application number 15/887327 was filed with the patent office on 2019-08-08 for hair coloring compositions and methods thereof.
This patent application is currently assigned to KAO USA INC.. The applicant listed for this patent is KAO USA INC.. Invention is credited to Vincent FISCHER, Chris OWENS, Adam SCHROTT.
Application Number | 20190240133 15/887327 |
Document ID | / |
Family ID | 65276062 |
Filed Date | 2019-08-08 |
United States Patent
Application |
20190240133 |
Kind Code |
A1 |
SCHROTT; Adam ; et
al. |
August 8, 2019 |
HAIR COLORING COMPOSITIONS AND METHODS THEREOF
Abstract
A hair coloring composition that includes about 5 to 25 wt. % of
a first monosaccharide having 2 to 4 carbon atoms, up to about 10
wt. % of a second monosaccharide having 2 to 4 carbon atoms, about
0.1 to 5 wt. % of a surfactant, and about 0.1 to 5 wt. % of a
delivery agent, each based on a total weight of the hair coloring
composition. A method for coloring hair, that involves applying the
hair coloring composition onto the hair, and optionally applying
heat to the hair at a dyeing temperature of 30 to 205.degree.
C.
Inventors: |
SCHROTT; Adam; (Hebron,
KY) ; OWENS; Chris; (Ft. Thomas, KY) ;
FISCHER; Vincent; (Saint Petersburg, FL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
KAO USA INC. |
Cincinnati |
OH |
US |
|
|
Assignee: |
KAO USA INC.
Cincinnati
OH
|
Family ID: |
65276062 |
Appl. No.: |
15/887327 |
Filed: |
February 2, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61K 8/4973 20130101;
A61K 8/342 20130101; A61Q 5/065 20130101; A61K 8/046 20130101; A61K
8/345 20130101; A45D 2019/0066 20130101; A61K 8/35 20130101; A45D
2200/155 20130101; A61K 8/604 20130101; A61Q 5/10 20130101; A61K
8/60 20130101 |
International
Class: |
A61K 8/60 20060101
A61K008/60; A61K 8/34 20060101 A61K008/34; A61K 8/49 20060101
A61K008/49; A61K 8/04 20060101 A61K008/04; A61Q 5/10 20060101
A61Q005/10 |
Claims
1. A hair coloring composition, comprising: about 5 to 25 wt. % of
a first monosaccharide having 2 to 4 carbon atoms; up to about 10
wt. % of a second monosaccharide having 2 to 4 carbon atoms; about
0.1 to 5 wt. % of a surfactant; and about 0.1 to 5 wt. % of a
delivery agent, each based on a total weight of the hair coloring
composition.
2. The hair coloring composition of claim 1, wherein the first
monosaccharide is dihydroxyacetone.
3. The hair coloring composition of claim 1, wherein the second
monosaccharide is erythrulose.
4. The hair coloring composition of claim 1, which has about 5 to
10 wt. % of the first monosaccharide and about 0.001 to 1 wt. % of
the second monosaccharide, each based on a total weight of the hair
coloring composition.
5. The hair coloring composition of claim 1, wherein a weight ratio
of the first monosaccharide to the second monosaccharide is 10:1 to
1,000:1.
6. The hair coloring composition of claim 1, wherein the surfactant
is at least one nonionic surfactant selected from the group
consisting of an alkyl pyranoside and a polyoxyalkylene ether of a
fatty alcohol.
7. The hair coloring composition of claim 1, wherein the surfactant
is a mixture of decyl glucoside and ceteareth-25.
8. The hair coloring composition of claim 1, wherein the delivery
agent is a dianhydrohexitol, a C.sub.1 to C.sub.4 monoalkoxy
substituted dianhydrohexitol, or a C.sub.1 to C.sub.4 dialkoxy
substituted dianhydrohexitol.
9. The hair coloring composition of claim 1, wherein the delivery
agent is dimethyl isosorbide.
10. The hair coloring composition of claim 1, further comprising
about 60 to 90 wt. % of water, and about 0.5 to 5 wt. % of an
organic solvent, each based on a total weight of the hair coloring
composition.
11. The hair coloring composition of claim 1, further comprising at
least one of the following additives: up to about 3 wt. % of a
preservative, up to about 3 wt. % of an acidulant, about 1 to 10
wt. % of a conditioning agent, and up to about 1 wt. % of a
fragrance, each based on a total weight of the hair coloring
composition.
12. The hair coloring composition of claim 1, which has a pH of
about 2 to 5.
13. The hair coloring composition of claim 11, wherein the
conditioning agent is present, and is glycerin.
14. The hair coloring composition of claim 1, which is in the form
of a foam.
15. A method for coloring hair, comprising: applying the hair
coloring composition of claim 1 onto the hair.
16. The method of claim 15, further comprising applying heat to the
hair at a dyeing temperature of 30 to 205.degree. C.
17. The method of claim 16, wherein the dyeing temperature is 30 to
60.degree. C.
18. The method of claim 16, wherein the dyeing temperature is more
than 60.degree. C. and up to 205.degree. C.
19. The method of claim 15, wherein the hair coloring composition
is in the form of a foam.
20. The method of claim 15, wherein the hair coloring composition
is not applied to skin.
Description
BACKGROUND OF THE INVENTION
Field of the Invention
[0001] The present invention relates to hair coloring compositions
and methods of coloring hair using the hair coloring
compositions.
Discussion of the Background
[0002] The "background" description provided herein is for the
purpose of generally presenting the context of the disclosure. Work
of the presently named inventors, to the extent it is described in
this background section, as well as aspects of the description
which may not otherwise qualify as prior art at the time of filing,
are neither expressly nor impliedly admitted as prior art against
the present invention.
[0003] The appearance of gray hair typically begins around the age
of 30 and is a top hair care concern for both men and women.
Graying hair may lead to an emotional reaction including feelings
of loss of strength, loss of youthfulness, and loss of vitality,
particularly so for women with graying hair. Therefore many
consumers choose to cover up gray hair by full coverage hair dyes
or by blending of gray hairs into naturally pigmented hair.
[0004] In attempts to cover gray hair, some consumers select box
colors or do-it-yourself sprays because such systems can be applied
at home. However, technology limitations often make the resulting
dyed hair appear flat or without preferred multi-tones, resulting
in an unnatural look. Moreover, such box colors or spray systems
can be difficult to apply and may result in unwanted staining of
the scalp.
[0005] The use of salon services, while generally providing a more
natural looking, multi-tonal coloration, can be cost and time
prohibitive for many consumers and is perceived to cause hair
damage due to repeated and prolonged exposure to chemical
treatments.
[0006] Further, many consumers are generally skeptical of hair dyes
due to the perceived effects of harsh chemicals, such as oxidizing
agents, on hair structure and general follicle health.
[0007] In view of the forgoing, there is a need for a hair coloring
composition that can be easily applied at home in a consumer
friendly amount of time for providing long lasting, deep, rich,
multi-tonal, natural-looking dyed hair without the use of harsh
treatment chemicals (e.g., oxidizing agents) or staining of the
scalp.
SUMMARY OF THE INVENTION
[0008] Accordingly, it is one object of the present invention to
provide novel hair coloring compositions.
[0009] It is another object of the present disclosure to provide
novel methods for coloring hair by applying the hair coloring
compositions onto the hair.
[0010] These and other objects, which will become apparent during
the following detailed description, have been achieved by the
inventors' discovery that the following hair coloring compositions
can be easily applied at home with short application times to
provide a deep, rich, long lasting, multi-tonal color, while
minimizing staining of the scalp and without the use of harsh
oxidizing agents.
[0011] Thus, the present invention provides:
[0012] (1) A hair coloring composition, comprising:
[0013] about 5 to 25 wt. % of a first monosaccharide having 2 to 4
carbon atoms;
[0014] up to about 10 wt. % of a second monosaccharide having 2 to
4 carbon atoms;
[0015] about 0.1 to 5 wt. % of a surfactant; and
[0016] about 0.1 to 5 wt. % of a delivery agent, each based on a
total weight of the hair coloring composition.
[0017] (2) The hair coloring composition of (1), wherein the first
monosaccharide is dihydroxyacetone.
[0018] (3) The hair coloring composition of (1), wherein the second
monosaccharide is erythrulose.
[0019] (4) The hair coloring composition of (1), which has about 5
to 10 wt. % of the first monosaccharide and about 0.001 to 1 wt. %
of the second monosaccharide, each based on a total weight of the
hair coloring composition.
[0020] (5) The hair coloring composition of (1), wherein a weight
ratio of the first monosaccharide to the second monosaccharide is
10:1 to 1,000:1.
[0021] (6) The hair coloring composition of (1), wherein the
surfactant is at least one nonionic surfactant selected from the
group consisting of an alkyl pyranoside and a polyoxyalkylene ether
of a fatty alcohol.
[0022] (7) The hair coloring composition of (1), wherein the
surfactant is a mixture of decyl glucoside and ceteareth-25.
[0023] (8) The hair coloring composition of (1), wherein the
delivery agent is a dianhydrohexitol, a C.sub.1 to C.sub.4
monoalkoxy substituted dianhydrohexitol, or a C.sub.1 to C.sub.4
dialkoxy substituted dianhydrohexitol.
[0024] (9) The hair coloring composition of (1), wherein the
delivery agent is dimethyl isosorbide.
[0025] (10) The hair coloring composition of (1), further
comprising
[0026] about 60 to 90 wt. % of water, and
[0027] about 0.5 to 5 wt. % of an organic solvent, each based on a
total weight of the hair coloring composition.
[0028] (11) The hair coloring composition of (1), further
comprising at least one of the following additives:
[0029] up to about 3 wt. % of a preservative,
[0030] up to about 3 wt. % of an acidulant,
[0031] about 1 to 10 wt. % of a conditioning agent, and
[0032] up to about 1 wt. % of a fragrance, each based on a total
weight of the hair coloring composition.
[0033] (12) The hair coloring composition of (1), which has a pH of
about 2 to 5.
[0034] (13) The hair coloring composition of (11), wherein the
conditioning agent is present, and is glycerin.
[0035] (14) The hair coloring composition of (1), which is in the
form of a foam.
[0036] (15) A method for coloring hair, comprising:
[0037] applying the hair coloring composition of (1) onto the
hair.
[0038] (16) The method of (15), further comprising applying heat to
the hair at a dyeing temperature of 30 to 205.degree. C.
[0039] (17) The method of (16), wherein the dyeing temperature is
30 to 60.degree. C.
[0040] (18) The method of (16), wherein the dyeing temperature is
more than 60.degree. C. and up to 205.degree. C.
[0041] (19) The method of (15), wherein the hair coloring
composition is in the form of a foam.
[0042] (20) The method of (15), wherein the hair coloring
composition is not applied to skin.
[0043] The foregoing paragraphs have been provided by way of
general introduction, and are not intended to limit the scope of
the following claims. The described embodiments, together with
further advantages, will be best understood by reference to the
following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
[0044] In the following description, it is understood that other
embodiments may be utilized and structural and operational changes
may be made without departure from the scope of the present
embodiments disclosed herein.
Definitions
[0045] As used herein, the term "fatty" describes a long-chain
hydrophobic portion of a compound made up of hydrogen and anywhere
from 6 to 26 carbon atoms, which may be fully saturated or
partially unsaturated, and optionally attached to a functional
group such as a hydroxyl group or a carboxyl group. Fatty alcohols,
fatty acids, fatty esters, fatty amides, and fatty hydrocarbon oils
are examples of materials which contain a fatty portion. When the
material contains a carbon-containing functional group, as is the
case in a fatty acid which contains a carboxylic acid group
(--COOH), the 6 to 26 carbon count refers to only the hydrophobic
portion attached to the carbon-containing function group.
Therefore, stearic acid, which has 18 carbons total, has a fatty
portion with 17 carbon atoms.
[0046] As used herein, "polyoxyalkylene" describes a polyether
group derived from polymerization of one or more alkylene oxides
having 2 to 4 carbon atoms, and specifically includes
polyoxyethylene (derived from ethylene oxide), polyoxypropylene
(derived from propylene oxide), and polyoxybutylene (derived from
butylene oxide), as well as mixtures thereof.
[0047] When referencing hair coloring compositions, the phrase
"substantially free", unless otherwise specified, describes an
amount of a particular component present in the hair coloring
composition being less than about 1 wt. %, preferably less than
about 0.5 wt. %, more preferably less than about 0.1 wt. %, even
more preferably less than about 0.05 wt. %, yet even more
preferably 0 wt. %, relative to a total weight of the hair coloring
composition.
[0048] As used herein, the terms "optional" or "optionally" means
that the subsequently described event(s) can or cannot occur or the
subsequently described component(s) may or may not be present
(e.g., 0 wt. %).
[0049] Various hair coloring composition ingredients are listed
throughout the present disclosure and are organized according to
their primary or most desired function, benefit, or use. However,
categorization of an ingredient under a particular function,
benefit, or use is not meant to limit that ingredient to only that
function, benefit, or use. For example, listing of benzyl alcohol
as a preservative does not limit the usefulness of benzyl alcohol
to only that of a preservative, since benzyl alcohol can also
impart other beneficial attributes, such as acting as a fragrance
and/or a solvent.
[0050] When referencing "hair" or "keratin fibers" herein, it is to
be recognized that hair exists on many different mammals (e.g.,
human) on many different body parts, and application of the hair
coloring compositions herein is not limited to hair found on a
specific body part. For example, the hair coloring compositions may
be applied for dyeing of hair found on the head/scalp including the
crown and side of the head, facial hair, and the like. Preferably,
the hair being dyed is located on the head or scalp.
Hair Coloring Composition
[0051] The present disclosure is directed to hair coloring
compositions that are substantially free of, preferably completely
free of (0 wt. %) harsh oxidizing agents, are easy to apply without
staining the scalp, and that provide rich, multi-tonal,
natural-looking dyed hair. The hair coloring compositions may be
used to dye hair of any color to a different shade or color, or
preferably to restore gray hair to an original hair color, for
example, yellow or brown.
[0052] The hair coloring compositions therefore contain components
which enable dyeing of keratin fibers without damaging the keratin
fibers, as well as components which facilitate delivery of active
ingredients and allow the hair coloring compositions to be easily
applied at home to provide natural looking dyed hair. Such
compositions generally include the following components: a
dyestuff, which is preferably a mixture monosaccharides having 2 to
4 carbon atoms, a surfactant, a delivery agent, and optionally
water, an organic solvent, a preservative, an acidulant, a
conditioning agent, and a fragrance. In preferred embodiments, all
components are compatible with the dyestuff (i.e., do not react
with or cause the dyestuff to react) and are homogeneously
dispersed or dissolved uniformly throughout the hair coloring
composition.
[0053] The hair coloring composition may be in a form chosen from a
liquid, a solution, an emulsion, a cream, a gel, a paste, a mousse,
a foam, or any other form that is suitable for topical application
to keratin fibers. Preferably, the hair coloring composition is in
the form of a foam, and is therefore easy to apply to hair
follicles, including hair follicle roots, while minimizing contact
with the scalp to avoid staining of the skin.
Dyestuff
[0054] To act as an effective hair dye (e.g., for gray hair), the
hair coloring composition herein includes a "dyestuff", which is
any colored molecule that, when it is brought into contact with the
keratin material, colors this material, or any non-colored molecule
that, in contact with the keratin material, reacts with and colors
the keratin material without the aid of an additional chemical
agent, for example, without the aid of an oxidizing agent.
[0055] The amount of dyestuff present in the hair coloring
composition may vary depending on the color shade desired and the
quantity and nature of the other components, however, the dyestuff
is typically present in amounts of at least about 1 wt. %,
preferably at least about 2 wt. %, more preferably at least about 3
wt. %, even more preferably at least about 4 wt. %, yet even more
preferably at least about 5 wt. %, and up to about 35 wt. %,
preferably up to about 25 wt. %, preferably up to about 20 wt. %,
preferably up to about 15 wt. %, preferably up to about 10 wt. %,
more preferably up to about 8 wt. %, even more preferably up to
about 7 wt. %, yet even more preferably up to about 6 wt. %, based
on a total weight of the hair coloring composition.
[0056] In preferred embodiments, the dyestuff is a monosaccharide.
Monosaccharides, such as dihydroxyacetone, react with amino acids
naturally occurring in keratin materials and, by virtue of a
Maillard reaction, form melanoids which produce a color change to
the keratin material (Bobin et al. J. Soc. Cosmet. Chem., 35 pages
265-272, 1984; Maillard L. C., C. R. Acad. Sci. 154, 66-68,
1912--each incorporated herein by reference in its entirety).
Advantageously, such color change is produced without the need for
additional chemical agents (e.g., oxidizing agents) to drive the
reaction. Different amino acids react with different
monosaccharides differently to produce a variety of tones of
coloration from yellow to brown. Any monosaccharide capable of
reacting with amino acids found in keratin fibers (e.g., naturally
occurring amino acids) to produce a colored keratin material, can
be employed as the dyestuff herein. The monosaccharide may be an
aldose having 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms,
more preferably 3 to 4 carbon atoms, even more preferably 3 carbon
atoms, a ketose having 3 to 6 carbon atoms, preferably 4 to 5
carbon atoms, more preferably 3 to 4 carbon atoms, including
mixtures such aldoses and/or ketoses. Exemplary monosaccharides
include, but are not limited to, glycolaldehyde, glyceraldehyde,
dihydroxyacetone (DHA), erythrulose, meso-tartaric aldehyde,
glucose, gulose, xylose, fructose, ribose, arabinose, allose,
talose, altrose, idose, mannose, galactose, and erythrose. Such
monosaccharides produce natural looking color shades when applied
to hair owing at least partially to the multi-tone color variations
produced by reaction with various amino acids. Further advantages
of employing monosaccharides as the dyestuff component herein, is
that the monosaccharides are derivatives of, or are closely related
to, physiologically harmless naturally occurring vegetable
compounds, and the colors produced are integral with the keratin
fibers themselves (Maillard reaction products) and are thus
resistant to washing.
[0057] In preferred embodiments, a mixture of monosaccharides is
used, for example a mixture of a first monosaccharide and a second
monosaccharide which is different from the first monosaccharide.
The first monosaccharide is preferably a ketose having 2 to 4
carbon atoms, preferably three carbon atoms. In preferred
embodiments, the first monosaccharide is dihydroxyacetone. The
first monosaccharide may be present in amounts of from about 5 wt.
%, preferably from about 5.5 wt. %, more preferably from about 6
wt. %, even more preferably from about 6.5 wt. %, and up to about
25 wt. %, preferably up to about 20 wt. %, preferably up to about
15 wt. %, preferably up to about 10 wt. %, more preferably up to
about 9 wt. %, even more preferably up to about 8 wt. %, yet even
more preferably up to about 7 wt. %, based on the total weight of
the hair coloring composition. The second monosaccharide is
preferably a ketose having 2 to 4 carbon atoms, preferably four
carbon atoms. In preferred embodiments, the second monosaccharide
is erythrulose. The second monosaccharide may be present in amounts
of from about 0.001 wt. %, preferably from about 0.01 wt. %, more
preferably from about 0.1 wt. %, even more preferably from about
0.5 wt. %, and up to about 10 wt. %, preferably up to about 8 wt.
%, preferably up to about 6 wt. %, preferably up to about 4 wt. %,
more preferably up to about 3 wt. %, even more preferably up to
about 2 wt. %, yet even more preferably up to about 1 wt. %, based
on the total weight of the hair coloring composition.
[0058] The inventors have unexpectedly found that use of a single
monosaccharide (e.g., dihydroxyacetone) often produces an unnatural
dye result, for example an orange tone, but that a mixture of
monosaccharides (e.g., dihydroxyacetone and erythrulose) provides a
rich, long lasting dye with natural-looking multi-tonal colors.
[0059] While the weight ratio of the first monosaccharide (e.g.,
dihydroxyacetone) to the second monosaccharide (e.g., erythrulose)
may be varied depending on color shade, and the desired length of
coloration, the weight ratio is typically from 10:1, preferably
from 50:1, preferably from 100:1, preferably from 200:1, preferably
from 300:1, more preferably from 400:1, even more preferably from
500:1, yet even more preferably from 600:1, and up to 1,000:1,
preferably up to 900:1, more preferably up to 800:1, even more
preferably up to 700:1.
[0060] In preferred embodiments, the hair coloring compositions are
substantially free of dyestuffs other monosaccharides, which
includes being substantially free of, preferably completely free of
(i.e., 0 wt. %) acid dyes, decoctions or extracts, direct dyes,
and/or pigments which provide color. Alternatively, the hair
coloring compositions may include other dyestuffs such as acid
dyes, decoctions or extracts, direct dyes, and/or pigments in
amounts listed previously.
[0061] Examples of acid dyes which may be useful dyestuffs include,
but are not limited to, Yellow No. 203 (D&C Yellow No. 10,
color index (CI) given as CI 47005), Orange No. 205 (D&C Orange
No. 4, CI 15510), Red No. 227 (D&C Red No. 33, CI 17200),
Violet No. 401 (Ext. D&C Violet No. 2, CI 07301), and Black No.
401, CI 20470). Combinations of these acid dyes can be used, for
example, Orange 4+Yellow 10+External Violet 2, Orange 4+Red
33+External Violet 2, Orange 4+Red 33+External Violet 2, or Orange
4+Red 3.
[0062] Extracts or decoctions may also be employed herein as
dyestuffs, and are preferably extracts or decoctions from plant
sources, for example, henna-based extracts, melanin, curcumin,
caramels, malva extracts, hibiscus extracts, green teas, ginsengs,
annattos, beta-carotenes, walnut extracts (e.g., black walnut),
Menthe piperta, Melva silvestris, Cynara Scolymus, Theasinensis,
Juglans regia, Lawsonia inermis, Castanea vulgaris, Asorum
europaeum, Leonurus cardiac, Ballotafoetida, Ocimum basilicum,
Stachys ojficinalis, Brunella vulgaris, Calamintha ojficinalis,
Thymus vulgaris, Rosmarinus ojficinalis, Humulus lupulus, Vaccinium
myrtillus, Arctotaphylosuva-ursi, Calluna vulgaris, Artemisian
abisinthium, Artemisia vulgaris, Artemisia abrotonum, Artemisia
glacialis, Artimesia mutellina, Artemisia spicata, Chamamelum
nobile, Fraxinus excelsior, Syringa vulgaris, Jasminium
grandiflorum, Lythrum salicaria, Althaea ojficinalis, Hysopus
ojficinalis, Origanum majorana, Salvia officinalis, Melissa
officinalis, Melittis melissophylum, Lavandula ojficinalis, Quercus
robur, Fagus sylvatica, Nepta cataria, Origanum dictamus, Thymus
serpyllum, Cichorium intybus L., and Gymnema sylvestre.
[0063] The hair coloring composition may include direct dyes as the
dyestuff component. Various classes of direct dyes may be employed,
such as indole-based dyes (e.g., isatin, 5,6-dihydroxy indole,
indigo); pyrimidine-based dyes (e.g., alloxan); indane-based dyes
(e.g., ninhydrin); nitrobenzene-based dyes (e.g.,
1,4-diamino-2-nitrobenzene,
1-amino-2-nitro-4-.beta.-hydroxyethylaminobenzene,
1-amino-2-nitro-4-bis(.beta.-hydroxyethyl)aminobenzene,
1,4-bis(.beta.-hydroxyethylamino)-2-nitrobenzene,
1,2-diamino-4-nitrobenzene, or the corresponding nitropyridine
variants); quinone-based dyes (e.g., anthraquinone,
1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone,
1-aminopropylamino-4-methylaminoanthraquinone,
1-aminopropylaminoanthraquinone,
5-.beta.-hydroxyethyl-1,4-diaminoanthraquinone,
2-aminoethylaminoanthraquinone,
1,4-bis(.beta.,.gamma.-dihydroxypropylamino)anthraquinone, lawsone,
juglone, alizarin, purpurin, carminic acid, kermesic acid,
spinulosin, Disperse Red 15, Solvent Violet 13, Disperse Violet 1,
Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse
Blue 3, Disperse Red 11, Disperse Blue 7, Basic Blue 22, Disperse
Violet 15, Basic Blue 99); azo-based dyes (e.g.,
1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1H-imidazolium
chloride, 1,3-dimethyl-2-[(4-aminophenyl]azo]-1H-imidazolium
chloride, 1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium
methyl sulfate, Disperse Red 17, Basic Red 22, Basic Red 76, Basic
Yellow 57, Basic Brown 16, Basic Brown 17, Disperse Black 9);
azine-based dyes (e.g., Basic Blue 17, Basic Red 2);
triarylmethane-based dyes (e.g., Basic Green 1, Basic Violet 3,
Basic Violet 14, Basic Blue 7, Basic Blue 26, and those disclosed
in EP 3034065 A1--which is incorporated herein by reference in its
entirety; indoamine-based dyes (e.g.,
2-.beta.-hydroxyethylamino-5-[bis(.beta.-4'-hydroxyethyl)
amino]anilino-1,4-benzoquinone,
2-.beta.-hydroxyethylamino-5-(2'-methoxy-4'-amino)anilino-1,4-benzoquinon-
e,
3-N-(2'-chloro-4'-hydroxy)phenylacetamino-6-methoxy-1,4-benzoquinoneimi-
ne,
3-N-(3'-chloro-4'-methylamino)phenylureido-6-methyl-1,4-benzoquinoneim-
ine,
3-[4'-N-(ethylcarbamylmethyl)amino]phenylureido-6-methyl-1,4-benzoqui-
noneimine); catechol-based dyes (e.g., purpurogallin,
protocatechaldehyde); fluorescent dyes, such as those of the
naphthalimide, cationic or non-cationic coumarin,
xanthenodiquinolizine, azaxanthene, naphtholactam, azlactone,
oxazine, thiazine, or dioxazine families, or polycationic
fluorescent dyes of the azo, azomethine or methine families, for
example those disclosed in US 2006/0005326--which is incorporated
herein by reference in its entirety.
[0064] The dyestuff may also be a pigment, such as white or colored
pigments, lakes, and pearlescent agents or flakes. Exemplary
pigments include, but are not limited to, titanium dioxide, which
may or may not be surface-treated, zirconium oxide, cerium oxide,
iron oxide or chromium oxide, manganese violet, ultramarine blue,
chromium hydrate, ferric blue, and organic pigments (e.g.,
nitroso-, xanthene-, quinolone-, phthalocyanin-, isoindolinone-,
isoindoline-, quinacridone-perinone-, perylene-,
diketopyrrolopyrrole-, thioindigo-, dioxazine-, and
quinophthalone-based organic pigments).
Surfactant
[0065] The hair coloring composition of the present disclosure may
include one or more surfactants, which may be nonionic, amphoteric,
anionic, or cationic surfactants, preferably nonionic surfactants,
and may act as detergents, wetting agents, emulsifiers, foaming
agents, and/or dispersants. The surfactant advantageously provides
the hair coloring composition with good foamability and workability
for ease of application, and may aid consistent application,
coating, and delivery of the dyestuff to the hair follicles to
provide the dyed hair with a long lasting, natural look,
particularly when combined with the monosaccharide dyestuffs
disclosed herein. The amount of surfactant present in the hair
coloring composition may range from about 0.1 wt. %, preferably
from about 0.5 wt. %, more preferably from about 1 wt. %, even more
preferably from about 1.5 wt. %, yet even more preferably from
about 2 wt. %, and up to about 10 wt. %, preferably up to about 5
wt. %, more preferably up to about 4.5 wt. %, even more preferably
up to about 4 wt. %, yet even more preferably up to about 3 wt. %,
based on the total weight of the hair coloring composition.
[0066] The hair coloring compositions preferably include at least
one nonionic surfactant, such as an alkyl pyranoside; a
polyoxyalkylene ether of a fatty alcohol, a polyol, or an ester; an
ethylene oxide/propylene oxide copolymer; and/or a fatty amide.
[0067] Alkyl pyranoside surfactants are pyranose-based
monosaccharides having a glycosidic bond to fatty alcohols having 6
to 26 carbon atoms, preferably 7 to 24 carbon atoms, more
preferably 8 to 22 carbon atoms, even more preferably 9 to 20
carbon atoms, yet even more preferably 10 to 18 carbon atoms. The
alkyl pyranoside may be formed by any combination of a
pyranose-based monosaccharide, for example, allose, altrose,
galactose, glucose, gulose, idose, mannose, and talose, as well as
anhydro-, deoxy-, heteroatom-substituted-, or dehydro-variants
thereof, with a fatty alcohol having 6 to 26 carbon atoms, either
saturated or unsaturated, for example, 1-hexanol,
3-methyl-3-pentanol, 1-heptanol, 1-octanol, pelargonic alcohol,
1-decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol,
myristyl alcohol, pentadecyl alcohol, cetyl alcohol, palmitoleyl
alcohol, heptadecyl alcohol, stearyl alcohol, oleyl alcohol,
nonadecyl alcohol, arachidyl alcohol, heneicosyl alcohol, behenyl
alcohol, erucyl alcohol, lignoceryl alcohol, ceryl alcohol, as well
as mixtures thereof (e.g., cetearyl alcohol, which is a mixture of
cetyl and stearyl alcohols). Specific examples include, but are not
limited to, hexyl glucoside, octyl glucoside, octyl galactoside,
decyl glucoside, decyl galactoside, isodecyl glucoside, isoundecyl
glucoside, lauryl glucoside, cetearyl glucoside, coco glucoside,
and isotridecyl glucoside, as well as mixtures thereof, with decyl
glucoside being the most preferred.
[0068] The surfactant may also be one or more non-ionic surfactants
of the following types: a polyoxyalkylene ether of a fatty alcohol,
for example, laureth-3, ceteareth-6, ceteareth-11, ceteareth-15,
ceteareth-16, ceteareth-17, ceteareth-18, ceteareth-20,
ceteareth-23, ceteareth-25, ceteareth-27, ceteareth-28,
ceteareth-30, isoceteth-20, laureth-9/myreth-9, and PPG-3 caprylyl
ether, as well as mixtures thereof, preferably ceteareth-25 is
used; a polyoxyalkylene ether of a polyol (e.g., glycerin, glucose,
sorbitol, etc.). specific examples include, but are not limited to,
glycereth-7 caprylate/caprate, glycereth-2 cocoate, PEG-7 glyceryl
cocoate, glycereth-7, glycereth-7-triacetate, glycereth-5-lactate,
glycereth-7-diisononanoate, methyl gluceth-10, and polysorbates
such as polysorbate-20, polysorbate-40, polysorbate-60,
polysorbate-80; and/or a polyoxyalkylene ether of an ester
exemplified by PEG-14 laurate, PEG-15 laurate, PEG-20 laurate,
PEG-32 laurate, PEG-75 laurate, and PEG-150 laurate, including
mixtures thereof.
[0069] Ethylene oxide/propylene oxide copolymers may also be
included in the hair coloring compositions as nonionic surfactants,
for example, PPG-12-buteth-16, PPG-3-buteth-5, PPG-5-buteth-7,
PPG-7-buteth-10, PPG-9-buteth-12, PPG-12-buteth-16,
PPG-15-buteth-20, PPG-20-buteth-30, PPG-28-buteth-35, and
PPG-33-buteth-45.
[0070] Examples of fatty amides or polyoxyalkylene fatty amides
which may be used as nonionic surfactants herein include, but are
not limited to, cocoamide DEA, cocamide MEA, cocamide MIPA,
cocamidopropylamine oxide, PEG-6 cocamide, trideceth-2 carboxamide
MEA, PEG-4 rapeseedamide, and the like.
[0071] In preferred embodiments, the surfactant is a mixture of an
alkyl pyranoside and a polyoxyalkylene ether of a fatty alcohol,
for example in a weight ratio of from about 1:1, or from about
1.5:1, or from about 1.8:1, and up to about 3:1, or up to about
2:1. More preferably, the surfactant is a mixture of decyl
glucoside and ceteareth-25, for example, in the above weight ratio
ranges.
[0072] Amphoteric surfactants are preferably not included in the
hair coloring composition, but when present, can be selected from
imidazoline sulfonates, carboxylates, or phosphates (e.g., alkyl
hydroxy ethyl imidazoline sulfonates, disodium lauroamphodiacetate,
sodium lauroampho PG-acetate phosphate), amidosultaines (e.g.,
lauramidopropyl hydroxysultaine, cocamidopropyl hydroxysultaine,
oleamidopropyl hydroxysultaine), betaines (e.g.,
cocamidopropylphosphobetaine, lauric/myristic pyrophosphobetaine,
cocamidopropyl betaine), and the like, as well as mixtures of such
materials.
[0073] The hair coloring compositions are preferably substantially
free of anionic surfactants, however, when present, suitable
anionic surfactants include, but are not limited to, sulfates of
fatty alcohols or polyoxyalkylene ethers of fatty alcohols,
phosphates of fatty alcohols or polyoxyalkylene ethers of fatty
alcohols, sodium salts of fatty acids, acylamino acids, and
lactylates. Specific examples of anionic surfactants that can be
optionally included in the hair coloring compositions herein
include, but are not limited to, sodium lauryl sulfate, sodium
laureth sulfate, cetyl phosphate, sodium stearate, sodium behenoyl
lactylate, sodium isostearoyl lactylate, sodium caproyl lactylate,
sodium laureth-5 carboxylate, sodium laureth-6 carboxylate, sodium
laureth-11 carboxylate, sodium stearate, dicetyl phosphate,
ceteth-10-phosphate, sodium cocoyl taurate, sodium methyl cocoyl
taurate, and sodium methyl oleoyl taurate.
[0074] The hair coloring compositions are preferably substantially
free of cationic surfactants. However, in some embodiments,
cationic surfactants are present, such as protonated fatty amines,
that is, fatty amine salts derived from primary, secondary or
tertiary fatty amines in combination with an acid. For example,
protonated fatty amines of stearamidopropyldimethylamine,
stearamidopropyldiethylamine, stearamidoethyldiethylamine,
stearamidoethyldimethylamine, palmitamidopropyldimethylamine,
palmitamidopropyldiethylamine, palmitamidoethyldiethylamine,
palmitamidoethyldimethylamine, behenamidopropyldimethylamine,
behenamidopropyldiethylmine, behenamidoethyldiethylamine,
behenamidoethyldimethylamine, arachidamidopropyldimethylamine,
arachidamidopropyldiethylamine, arachidamidoethyldiethylamine,
arachidamidoethyldimethylamine, and mixtures thereof.
Delivery Agent
[0075] The hair coloring compositions of the present disclosure may
include a delivery agent, which is a material capable of aiding the
penetration of, and enhancing uniform delivery of, the dyestuff
(and other components of the hair coloring composition) into the
keratin fiber so that a deeper, longer-lasting, natural hair
coloration can be achieved.
[0076] In preferred embodiments, the delivery agent is a
dianhydrohexitol or a derivative thereof, which includes monoalkoxy
substituted dianhydrohexitols and dialkoxy substituted
dianhydrohexitols. Dianhydrohexitols (i.e.,
1,4;3,6-dianhydrohexitols) are by-products of the starch industry
most often obtained by dehydration of D-hexitols. These chiral
biomass-derived products exist as three main isomers, namely
isosorbide (I), isomannide (II), and isoidide (III), depending on
the configuration of the two hydroxyl groups (derived from
D-glucose, D-mannose, and L-fructose, respectively), and any of
these isomers or derivatives of any of these isomers may be
employed as the delivery agent herein, including mixtures.
##STR00001##
[0077] In preferred embodiments, a monoalkoxy substituted
dianhydrohexitol or a dialkoxy substituted dianhydrohexitol is
used, which is a dianhydrohexitol where one hydroxyl group is
substituted to form an alkoxy group or a dianhydrohexitol where
both hydroxyl groups are substituted to form two alkoxy groups
(which can be the same or different), respectively. As used herein,
"alkoxy" substitution includes straight chain, branched, cyclic, or
(poly)oxyalkylene-type, alkoxy groups, either saturated or
unsaturated, having up to 10 carbon atoms, preferably up to 8
carbon atoms, preferably up to 4 carbon atoms, for example 1 to 4
carbon atoms, and specifically includes: acyclic alkoxy groups such
as methoxy, ethoxy, propoxy, allyloxy, isopropoxy, butoxy,
isobutoxy, secondary butoxy, tertiary butoxy, pentoxy, isopentoxy,
hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy; cyclic alkoxy
groups (having 3 to 10 carbon atoms) including cyclopropyloxy,
cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy
groups; and (poly)oxyalkylene-type alkoxy groups such as
polyoxyethylene (--O--(CH.sub.2--CH.sub.2--O).sub.n--R),
polyoxypropylene (--O--(CH.sub.2--CH(CH.sub.3)--O).sub.n--R), and
polyoxybutylene (--O--(CH.sub.2--CH(CH.sub.2CH.sub.3)--O).sub.n--R)
groups having up to 5 repeating units, i.e., n is from 1 to 5,
wherein R is H or a C.sub.1 to C.sub.3 alkyl group (e.g., methyl,
ethyl, n-propyl, isopropyl). Preferably, the delivery agent is a
C.sub.1 to C.sub.4 monoalkoxy substituted dianhydrohexitol, or a
C.sub.1 to C.sub.4 dialkoxy substituted dianhydrohexitol, most
preferably a C.sub.1 to C.sub.4 dialkoxy substituted
dianhydrohexitol. In the case of a dialkoxy substituted
dianhydrohexitol, the carbon count refers to a total number of
carbon atoms for each alkoxy substituent, and thus "a C.sub.1 to
C.sub.4 dialkoxy substituted dianhydrohexitol" refers to compounds
where each alkoxy substituent has 1 to 4 carbon atoms,
independently of the other alkoxy substituent.
[0078] Examples of dianhydrohexitols or derivatives thereof
suitable for use as delivery agents herein include, but are not
limited to, isosorbide, isomannide, and isoidide, methyl
isosorbide, dimethyl isosorbide, ethyl isosorbide, diethyl
isosorbide, propyl isosorbide, dipropyl isosorbide, monoisopropyl
isosorbide, diisopropyl isosorbide, methylethyl isosorbide,
methylpropyl isosorbide, ethylpropyl isosorbide, butyl isosorbide,
dibutyl isosorbide, isobutyl isosorbide, diisobutyl isosorbide,
methylbutyl isosorbide, ethylbutyl isosorbide, propylbutyl
isosorbide, methyl isomannide, methyl isoidide, dimethyl
isomannide, and dimethyl isoidide. In preferred embodiments, the
delivery agent is dimethyl isosorbide (a C.sub.1 dialkoxy
substituted dianhydrohexitol). In addition to aiding delivery of
the dyestuff (and/or other components of the hair coloring
composition), the unsubstituted and alkoxy substituted
dianhydrohexitols disclosed herein are particularly advantageous
because they are soluble in water, biologically harmless, and may
enhance the health and appearance of hair follicles to which they
are applied.
[0079] Other acceptable delivery agents that may be used as
delivery agents in lieu of, or in addition to the dianhydrohexitols
or derivatives thereof, include pyrrolidinone, caprylyl
pyrrolidone, N-methylpyrrolidone, lauryl pyrrolidone, propylene
carbonate, 2-benzyloxyethanol, gamma-butyrolactone, phenylethanol,
diethyl glycol-monoethylether, polyethylene glycols (e.g., PEG-4,
PEG-6, PEG-8, PEG-10, PEG-12, PEG-32), isopentyldiol,
ethoxydiglycol, and the like, as well as mixtures thereof.
[0080] In some embodiments, the amount of delivery agent present in
the hair coloring composition is from about 0.1 wt. %, preferably
from about 0.5 wt. %, preferably from about 1 wt. %, preferably
from about 1.5 wt. %, preferably from about 2 wt. %, and up to
about 5 wt. %, preferably up to about 4 wt. %, preferably up to
about 3 wt. %, preferably up to about 2.5 wt. %, based on a total
weight of the hair coloring composition.
Solvent
[0081] In some embodiments, the hair coloring composition of the
present disclosure is an aqueous composition or an oil-in-water
(o/w) emulsion where the continuous phase is aqueous. Therefore, in
preferred embodiments, the hair coloring composition further
includes water in amounts of at least about 60 wt. %, more
preferably at least about 65 wt. %, even more preferably at least
about 70 wt. %, yet even more preferably at least about 75 wt. %,
and up to about 95 wt. %, preferably up to about 90 wt. %, more
preferably up to about 85 wt. %, even more preferably up to about
80 wt. %, based on a total weight of the hair coloring
composition.
[0082] In addition to water, the hair coloring composition may
optionally include at least one organic solvent which may aid
solubilization of components not sufficiently soluble in water,
adjust the surface properties of the hair coloring composition for
enhanced workability, foamability, and/or foam stability, or to
generally provide a medium suitable for the dyeing operation. The
at least one organic solvent, may be chosen from, for example, a
C.sub.1 to C.sub.4 lower alkanol, for example, methanol, ethanol
(e.g., denatured alcohol), isopropanol, butanol; polyols and polyol
ethers, for example, glycol, 1,3-propanediol, 1,3-butanediol,
2-butoxyethanol, propylene glycol, butylene glycol, hexylene
glycol, isoprene glycol, diethylene glycol, dipropylene glycol,
ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
propylene glycol monomethyl ether, diethylene glycol monomethyl
ether, diethylene glycol monoethyl ether, as well as mixtures
thereof. Preferably, the organic solvent is ethanol. When present,
the organic solvent may be included in the hair coloring
compositions in an amount ranging from about 0.5 wt. %, preferably
from about 1 wt. %, more preferably from about 1.5 wt. %, even more
preferably from about 2 wt. %, yet even more preferably from about
2.5 wt. %, and up to about 10 wt. %, preferably up to about 5 wt.
%, preferably up to about 4.5 wt. %, more preferably up to about 4
wt. %, even more preferably up to about 3.5 wt. %, yet even more
preferably up to about 3 wt. %, based on a total weight of the hair
coloring composition.
Preservative
[0083] The hair coloring composition may optionally further include
a preservative. For example, the preservative may be selected to
kill bacteria that might otherwise be sustained or multiplied in
the composition, or to prevent degradation or chemical breakdown
(e.g., oxidative degradation) of the composition. Preservatives
suitable for use in cosmetic formulations are well-known to those
skilled in the art. In this respect, the preservative chosen may be
varied depending on the particular components present in the hair
coloring composition. Illustrative of suitable preservatives
include ethylparaben, propylparaben, methylparaben, EDTA or salts
thereof (such as disodium EDTA), phenoxyethanol, DMDM hydantoin,
benzyl alcohol,
ethyldibromoglutaronitrile-phenoxyethanol/polyquaternium-7 (Euxyl
K-400, Calgon), imidazolidinyl urea, diazolidinyl urea,
benzalkonium chloride, benzethonium chloride, sodium benzoate,
sorbic acid and the like, or combinations thereof. Preferably, the
preservative is at least one of methylparaben, sodium benzoate, and
benzyl alcohol, most preferably a mixture of these preservatives.
When present, the preservative may be included herein in amounts of
up to about 5 wt. %, preferably up to about 4 wt. %, preferably up
to about 3 wt. %, preferably up to about 2 wt. %, preferably up to
about 1 wt. %, for example from about 0.001 wt. % to about 3 wt. %,
or 0.1 wt. % to about 2 wt. %, or 0.2 wt. % to about 1 wt. %, based
on a total weight of the hair coloring composition.
Acidulant
[0084] The hair coloring compositions disclosed herein may be
optionally formulated to include an acidulant for adjusting the pH
to be more acidic/less alkaline. Additionally, depending on the
chemical structure, the acidulant may act as a chelating agent
and/or a buffering agent to neutralize minerals, enhance the
activity of any preservatives present, and to stabilize active
ingredients (e.g., the dyestuff). When the acidulant contains
.alpha.-hydroxy acid functionality, the acidulant may also confer
moisturizing and smoothing effects to the hair coloring
composition.
[0085] When present, the acidulant may be included herein in
amounts of up to about 5 wt. %, preferably up to about 4 wt. %,
preferably up to about 3 wt. %, preferably up to about 2 wt. %,
preferably up to about 1 wt. %, for example from about 0.001 wt. %
to about 3 wt. %, or 0.02 wt. % to about 2 wt. %, or 0.1 wt. % to
about 1 wt. %, or 0.2 wt. % to about 0.5 wt. %, based on a total
weight of the hair coloring composition. The pH of the hair
coloring composition may be varied, but is preferably less than 5,
for example, at least 2, preferably at least 2.5, more preferably
at least 3, even more preferably at least 3.5, and up to 5,
preferably up to 4.5, more preferably up to 4.
[0086] The acidulant employed herein may be an inorganic acid or an
organic acid, and specifically includes, but is not limited to,
hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic
acids such as fumaric acid, acetic acid, and .alpha.-hydroxy acids
such as tartaric acid, citric acid, and lactic acid, as well as
mixtures thereof. Preferably citric acid is used.
Conditioning Agent
[0087] The hair coloring compositions of the present disclosure may
also optionally include one or more conditioning agents, which may
act as a moisturizer, emollient, occlusive agent, and/or humectant
for the hair. Any suitable conditioning agent known to those of
ordinary skill in the art may be employed herein. If included in
the hair coloring composition, the amount of conditioning agent is
typically less than about 15 wt. %, preferably less than about 10
wt. %, more preferably less than about 8 wt. %, or from about 0.1
wt. %, preferably from about 1 wt. %, more preferably from about 2
wt. %, even more preferably from about 4 wt. %, and up to about 10
wt. %, preferably up to about 8 wt. %, more preferably up to about
6 wt. %, even more preferably up to about 5 wt. %, based on a total
weight of the hair coloring composition.
[0088] In preferred embodiments, the conditioning agent employed
herein is a monomeric polyol, preferably a monomeric polyol having
at least three hydroxyl groups (e.g., glycerin, erythritol,
pentaerythritol, threitol, arabitol, xylitol, ribitol). In most
preferred embodiments, the conditioning agent is glycerin. The hair
coloring compositions may be substantially free of, or
alternatively may include, retinyl palmitate, petrolatum, gelatin,
guar hydroxypropyl trimonium chloride, natural botanicals and
extracts thereof such as chamomile recutita, sambucus nigra,
primula veris, helianthus annuus, urtica dioica (i.e., nettle).
olea europaea (i.e., olive), aloe (e.g., barbadensis gel), kelp
(e.g., sea kelp), phospholipids), and the like, or combinations
thereof.
[0089] In some embodiments, the hair coloring compositions are
substantially free of conditioning agents of the following types: a
quaternary ammonium compound, a fatty material (e.g., fatty
alcohols, fatty acids, fatty hydrocarbon oils, and fatty esters),
and a silicone. However, such conditioning agents may optionally be
included herein. Suitable quaternary ammonium compounds include
cetyltrimethylammonium chloride, behenyltrimethylammonium chloride,
behentrimonium methosulfate, cetylpyridinium chloride,
tetramethylammonium chloride, tetraethylammonium chloride,
octyltrimethylammonium chloride, dodecyltrimethylammonium chloride,
hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium
chloride, decyldimethylbenzylammonium chloride,
stearyldimethylbenzylammonium chloride, didodecyldimethylammonium
chloride, dioctadecyldimethylammonium chloride,
tallowtrimethylammonium chloride, dihydrogenated tallow dimethyl
ammonium chloride (e.g., Arquad 2HT-75, available from Akzo Nobel),
cocotrimethylammonium chloride, PEG-2-oleammonium chloride, and the
like, as well as the corresponding bromides or hydroxides
thereof.
[0090] Fatty materials which provide acceptable hair conditioning
effects include fatty alcohols or corresponding carboxylic acids
(i.e., fatty acid, for example, stearic acid), fatty hydrocarbon
oils, and/or a fatty esters. Exemplary fatty alcohols have been
listed previously, with preferred fatty alcohols being cetyl
alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof
(e.g., cetearyl alcohol). Fatty acids may include, but are not
limited to, caprylic acid, capric acid, lauric acid, myristic acid,
palmitic acid, stearic acid, arachidic acid, behenic acid,
lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid,
sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic
acid, linoelaidic acid, .alpha.-inolenic acid, arachidonic acid,
eicosapentaenoic acid, erucic acid, and docosahexaenoic acid. Fatty
hydrocarbon oils include paraffin oil, mineral oil, saturated and
unsaturated dodecane, saturated and unsaturated tridecane,
saturated and unsaturated tetradecane, saturated and unsaturated
pentadecane, saturated and unsaturated hexadecane, and the like, as
well as mixtures thereof. Branched-chain isomers of these
compounds, as well as higher chain length hydrocarbons, can also be
used. Suitable fatty esters are characterized by having at least
one fatty aliphatic chain derived from a fatty acid, a fatty
alcohol, or both. Fatty esters herein may be monoesters of the
formula R.sup.1COOR.sup.2 in which at least one of R.sup.1 and
R.sup.2 is an alkyl or alkenyl radical having 6 to 26 carbon atoms,
preferably 7 to 24 carbon atoms, more preferably 8 to 22 carbon
atoms, even more preferably 9 to 20 carbon atoms, yet even more
preferably 10 to 18 carbon atoms, and where the sum of carbon atoms
combined in R.sup.1 and R.sup.2 is from 7 to 52 carbon atoms, for
example, cetyl octanoate and lauryl lactate. Diesters and triesters
containing at least one fatty aliphatic portion can also be used.
Particularly preferred fatty esters are mono-, di-, and
tri-glycerides, more specifically the mono-, di-, and tri-esters of
glycerol and at least one fatty acid, for example, glyceryl mono-,
di-, or tri-stearate, cocoa butter, palm stearin, sunflower oil,
soyabean oil and coconut oil.
[0091] Suitable silicone conditioning agents are
polydiorganosiloxanes, in particular polydimethylsiloxanes
(dimethicones), polydimethylsiloxanes having hydroxyl end groups
(dimethiconols), amino-functional polydimethylsiloxanes
(amodimethicones), polyoxyalkylene functionalized
polydimethylsiloxanes (dimethicone copolyols), and mixtures
thereof. Exemplary silicones include cyclomethicone,
phenyltrimethicone, alkyl dimethicone, fluorinated silicones,
dimethicone, PEG-3 dimethicone, PEG-7 dimethicone, PEG-8
dimethicone, PEG-9 dimethicone, PEG-10 dimethicone, PEG-12
dimethicone, PEG-14 dimethicone, PEG-17 dimethicone, PEG/PPG-3/10
dimethicone, PEG/PPG-4/12 dimethicone, PEG/PPG-6/11 dimethicone,
PEG/PPG-8/14 dimethicone, PEG/PPG-14/4 dimethicone, PEG/PPG-15/15
dimethicone, PEG/PPG-16/2 dimethicone, PEG/PPG-17/18 dimethicone,
PEG/PPG-18/18 dimethicone, PEG/PPG-19/19 dimethicone, PEG/PPG-20/6
dimethicone, PEG/PPG-20/15 dimethicone, PEG/PPG-20/20 dimethicone,
PEG/PPG-20/23 dimethicone, PEG/PPG-20/29 dimethicone, PEG/PPG-22/23
dimethicone, PEG/PPG-22/24 dimethicone, PEG/PPG-23/6 dimethicone,
PEG/PPG-25/25 dimethicone and PEG/PPG-27/27 dimethicone, and the
like, and combinations thereof.
Fragrance
[0092] The hair coloring compositions of the present disclosure may
be optionally formulated to include one or more fragrances known to
those of ordinary skill in the cosmetics arts to impart a pleasant
scent or to help mask any malodorous components that may be present
in the hair coloring compositions. Non-limiting examples of
compounds used as fragrances herein include dihydrocitronellyl
nitrile, 2,2,6-trimethylcyclohexane carboxylic acid ethyl ester
(i.e., Thesaron, available from Takasago International
Corporation),
2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol racemic
or optically active form, preferably (E)-(R)-form (i.e.,
Levosandol, available from Takasago International Corporation),
2,2,6-trimethylcyclohexyl-3-hexanol, cyclohexadecenone,
1-(2-methyl-2-propenyloxy)-2,2,4-trimethylpentan-3-ol,
1-phenyl-2,2,4-trimethyl-3-pentanone, 4,8-dimethyl-7-nonen-2-ol,
2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol
racemic or optically active form, preferably (E)-(R)-form,
tri(cis-3-hexenyl) orthoformate, 4-ethoxy-2-methyl-butanethiol,
5-methoxy-3-methyl-3-pentanethiol, thioglycerin, dibutyl sulfide,
thiogeraniol, thiocineol, limonenethiol,
2-methyl-4-propyl-1,3-oxathian, 4-methoxy-2-methyl-2-butanethiol,
terpene hydrocarbons such as p-cymene, terpinolene, myrcene, and
.beta.-caryophylene, aldehydes such as heptanal, octanal,
benzaldehyde, salicylic aldehyde, citronellal,
.alpha.-hexylcinnamic aldehyde and lilial, esters such as methyl
jasmonate, methyl dihydrojasmonate, .gamma.-nonyllactone,
.gamma.-decalactone and coumarin, ethers such as anisole, p-cresyl
methyl ether, .beta.-naphthol methyl ether, and .beta.-naphthol
ethyl ether, ketones such as menthone, acetophenone,
.alpha.-damascone, .beta.-damascone, .alpha.-ionone, .beta.-ionone,
methyl ionone, irone, dihydrojasmone, cis-jasmone, muscone and
civetone, alcohols such as cis-3-hexenol, heptanol, 2-octanol,
benzyl alcohol, citronellol, geraniol, terpineol,
tetrahydrogeraniol, anise alcohol, phenylethyl alcohol, phenoxy
ethanol, santalol, sandalmysore core, bacdanol, ebanol, polysantol,
and natural essential oils such as orange oil, lemon oil, lime oil,
patchouli oil, cyprus oil, sandalwood oil, peppermint oil,
spearmint oil, and anise oil, and the like, as well as mixtures
thereof.
[0093] In some embodiments, the fragrance is present in amounts of
up to about 3 wt. %, preferably up to about 2 wt. %, preferably up
to about 1 wt. %, preferably up to about 0.5 wt. %, preferably up
to about 0.3 wt. %, preferably up to about 0.2 wt. %, preferably up
to about 0.1 wt. %, preferably up to about 0.01 wt. %, based on a
total weight of the hair coloring composition.
Other Optional Ingredients
[0094] Various optional ingredients frequently used in topical
formulations such as propellants, vehicles, adjuvants, anti-aging
components, proteins, rheology control agents, dispersants,
thickeners, film-forming agents, sequestering agents, cleansing
agents, vitamins, botanicals, and sunscreen agents, as well as
other classes of materials whose presence may be cosmetically,
medicinally or otherwise desirable, can also optionally be included
at their conventional art-established usage levels. In preferred
embodiments, the hair coloring compositions are substantially free
of such optional ingredients, however, when included, non-limiting
examples which can be used include film-forming and moisturizing
materials such as hydrolyzed wheat protein/wheat oligosaccharides
(e.g., Cropeptide W by Croda Inc.), hydrolyzed corn protein,
hydrolyzed wheat gluten, hydrolyzed yeast protein, hydrolyzed
vegetable protein, hydrolyzed soy protein, hydrolyzed rice protein,
and hydrolyzed potato protein; cleansing agents and emollients such
as polyethylene glycol derivatives of castor oil, for example,
PEG-40 castor oil (Surfactol 365, available from Vertellus), PEG-45
castor oil, PEG-50 castor oil, PEG-60 castor oil, and PEG-100
castor oil; sunscreens or UV light absorbing compounds
octyldimethyl PABA, benzophenone-4, DEA methoxycinnamate,
2-phenyl-benzimidazole-5-sulfonic acid, and triethanolamine
salicylate; thickeners such as carbomer and C.sub.10-C.sub.30
alkylacrylate cross-polymer; film forming polycationic polymers
such as polyquaternium-1, polyquaternium-2, polyquaternium-4,
polyquaternium-5, polyquaternium-6, polyquaternium-7,
polyquaternium-8, polyquaternium-9, and polyquaternium-10; and
thickening agents such as modified cellulose polymers, for example,
hydroxyethyl cellulose and methyl cellulose.
[0095] In preferred embodiments, the hair coloring composition
includes 5 to 10 wt. % of a first monosaccharide having 2 to 4
carbon atoms (e.g., dihydroxyacetone), 0.001 to 0.5 wt. % of a
second monosaccharide having 2 to 4 carbon atoms (e.g.,
erythrulose); 0.1 to 3 wt. % of a surfactant, which is a mixture of
an alkyl pyranoside (e.g., decyl glucoside) and a polyoxyalkylene
ether of a fatty alcohol (e.g., ceteareth-25); 0.1 to 1 wt. % of a
delivery agent, which is a C.sub.1 to C.sub.4 dialkoxy substituted
dianhydrohexitol (e.g., dimethyl isosorbide), and 70 to 85 wt. %
water, with the balance optionally including one or more of an
organic solvent (e.g., ethanol), a preservative (e.g., a mixture of
methylparaben, sodium benzoate, and benzyl alcohol), an acidulant
(e.g., citric acid), a conditioning agent (e.g., glycerin), and/or
a fragrance.
[0096] In preferred embodiments, the hair coloring composition
includes 5 to 10 wt. % of a first monosaccharide having 2 to 4
carbon atoms (e.g., dihydroxyacetone), 0.001 to 0.5 wt. % of a
second monosaccharide having 2 to 4 carbon atoms (e.g.,
erythrulose); 0.1 to 3 wt. % of a surfactant, which is a mixture of
an alkyl pyranoside (e.g., decyl glucoside) and a polyoxyalkylene
ether of a fatty alcohol (e.g., ceteareth-25); 0.1 to 1 wt. % of a
delivery agent, which is a C.sub.1 to C.sub.4 dialkoxy substituted
dianhydrohexitol (e.g., dimethyl isosorbide), 70 to 85 wt. % water,
1 to 3 wt. % of an organic solvent (e.g., ethanol), 0.001 to 0.3
wt. % of a preservative, which is a mixture of methylparaben,
sodium benzoate, and benzyl alcohol, 0.001 to 0.2 wt. % of an
acidulant (e.g., citric acid), 3 to 7 wt. % of a conditioning
agent, which is a monomeric polyol having at least three hydroxyl
groups (e.g., glycerin), and 0.01 to 0.5 wt. % of a fragrance.
[0097] The hair coloring compositions herein can be prepared by any
method known to those of ordinary skill in the art. By way of
example, the hair coloring composition may be prepared by (i)
mixing together all water soluble components in an appropriately
sized vessel with water with optional heating (e.g., 40 to
90.degree. C., preferably 50 to 80.degree. C., more preferably 60
to 70.degree. C.) and stirring until homogenous, (ii) in a separate
vessel, mixing all oil phase ingredients, if any, with optional
heating (e.g., 40 to 100.degree. C., preferably 50 to 90.degree.
C., more preferably 60 to 80.degree. C.) and stirring until
homogeneous, (iii) mixing together the homogenous mixture from (i)
with the homogenous mixture from (ii), if any, with optional
heating (e.g., 40 to 100.degree. C., preferably 50 to 90.degree.
C., more preferably 60 to 80.degree. C.) and stirring to form the
hair coloring composition.
[0098] Alternatively, the hair coloring composition may be prepared
by (i) mixing together all water soluble components except for the
dyestuff component (e.g., the first and second monosaccharides
having 2 to 4 carbon atoms) in an appropriately sized vessel with
water with optional heating (e.g., 40 to 90.degree. C., preferably
50 to 80.degree. C., more preferably 60 to 70.degree. C.) and
stirring until homogenous, (ii) in a separate vessel, mixing all
oil phase ingredients, if any, with optional heating (e.g., 40 to
100.degree. C., preferably 50 to 90.degree. C., more preferably 60
to 80.degree. C.) and stirring until homogeneous, (iii) mixing
together the homogenous mixture from (i) with the homogenous
mixture from (ii), if any, with optional heating (e.g., 40 to
100.degree. C., preferably 50 to 90.degree. C., more preferably 60
to 80.degree. C.) and stirring until a homogenous aqueous
composition or uniform oil in water emulsion is formed, and (iv)
adding the dyestuff component (e.g., the first and second
monosaccharides having 2 to 4 carbon atoms) to the homogenous
aqueous composition or uniform oil in water emulsion, once the
homogenous aqueous composition or uniform oil in water emulsion has
cooled to 40.degree. C. or below, and stirring under conditions
similar to above, to form the hair coloring composition.
[0099] Once cooled, the hair coloring composition produced by
either method may then be packaged, for example in a non-aerosol
foam generating dispenser, for sale and/or distribution.
Properties
[0100] The hair coloring compositions of the present disclosure are
stable for up to 4 years, for example from 24 months to 36 months,
at room temperature or at sub-ambient temperatures without
significant/rapid degradation of the active components or
ingredient precipitation, which is known to sometimes occur with
hair coloring compositions. The hair coloring compositions are thus
suitable for long-term storage, distribution, and storage in
between uses.
[0101] The hair coloring compositions disclosed herein have
acceptable viscosity and surface tension in a liquid state, which
allows for facile processing, workability (e.g., foamability), and
packaging, and provides suitable foam characteristics once
converted into a foam.
[0102] The viscosity of the hair coloring composition (as a liquid
at 25.degree. C.) is typically from about 1 mPas, preferably from
about 2 mPas, more preferably from about 3 mPas, more preferably
from about 5 mPas, even more preferably from about 10 mPas, yet
even more from about 20 mPas, and up to about 300 mPas, preferably
up to about 200 mPas, more preferably up to about 100 mPas, even
more preferably up to about 50 mPas, yet even more preferably up to
about 30 mPas. It is to be noted that the viscosity as referred to
herein refers to a value obtained after rotating the liquid mixture
at 60 rpm for one minute at 25.degree. C. by a B-type rotational
viscometer (model TV-10), manufactured by TOKYO KEIKI INC., with
rotor No. 1 or 2. When the object to be measured has a viscosity of
less than 100 mPas, the viscosity is measured using rotor No. 1,
whereas when it has a viscosity of 100 to 499 mPas, the viscosity
is measured using rotor No. 2. Measurement is made in a thermostat
bath at 25.degree. C. immediately after mixing, and temperature
fluctuations caused by heat of reaction are negligible.
[0103] In preferred embodiments, the hair coloring composition is
foamable and is in the form of a foam when applied. The stability
of foam depends upon an interaction between the foam and an
interface between foams. The foam bursts as a liquid film becomes
thinner from flowing downward due to gravity or as liquid generally
flows due to curvature differences of the foam. If the thickness of
the liquid film is in the range of about 5 to 15 nm, the liquid
film cannot resist the pressure from the inside to burst. In
general, foams generated from aqueous solutions lack repulsive
forces of an electric double layer in a liquid film, have low
stability by hydration, and low resistance against liquid film
thinning due to gravitational/curvature effects, leading to poor
foam stability. However, the addition of one or more surfactants in
an appropriate amount lowers the surface tension thereby
accelerating foam formation, maintaining liquid film thickness for
longer periods of time, and delaying gravitational/curvature
breakdown effects. Thus, the present inventors have discovered that
the hair coloring compositions herein, in addition to providing
desirable hair dyeing results, are also capable of being foamed
into easily-applied and stable foams that resist dripping (i.e.,
conversion back into a liquid state) to aid hair application while
preventing staining of the skin (e.g., the scalp). In preferred
embodiments, the foams generated from the hair coloring
compositions disclosed herein are continuously retained for at
least 1 minute, preferably at least 2 minutes, more preferably at
least 10 minutes, and up to 50 minutes.
Method for Coloring Hair
[0104] The present disclosure provides a method for coloring hair
by applying the hair coloring composition, in one or more
embodiments, onto the hair. In order to achieve an acceptable
amount of coloration, a person who desires such coloration can
apply evenly an effective amount of the hair coloring composition
for an effective application time over an entire treatment area
(e.g., total coverage of gray hair), or to particularly problematic
spots (e.g., gray hair located on the side of the head or
sideburns). Thus, the hair coloring compositions can be applied for
subtle changes in hair color such as gray hair blending, or more
dramatic effects such as total gray hair coverage. Further, the
method herein produces natural looking dyed hair, and after dyeing,
provides excellent fastness to shampooing, irrespective of the kind
of shampoo used for shampooing. In hair coloring applications, the
steadfastness of the color (i.e., the resistance to color fading
after washing) is of greater importance than in skin
coloring/tanning applications, since dyed hair is likely to be
exposed to a greater number of washings per dyeing application when
compared to dyed skin as skin cells are shed and renewed at a
higher rate and thus have a lower life cycle than hair
follicles.
[0105] In a typical method, the hair coloring compositions as
described above are topically applied to wet or dry hair.
Preferably, the hair coloring compositions are applied to freshly
shampooed and dried hair. The hair coloring compositions may be
used as a single treatment to color the hair or applied in a
progressive manner so that the hair color becomes more intense on
subsequent applications until a desired coloration is reached. To
avoid staining of skin, the hair coloring compositions may be
applied with gloves or with a spreading instrument such as a comb
or brush. Preferably, the hair coloring composition is applied
uniformly to each hair fiber, from the root to the end of the hair
fiber.
[0106] The effective application time may range from 1 minute,
preferably from 3 minutes, more preferably from 5 minutes, even
more preferably from 10 minutes, and up to 60 minutes, preferably
up to 50 minutes, more preferably up to 40 minutes, even more
preferably up to 30 minutes, yet even more preferably up to 20
minutes, depending on whether or not heat is applied. Application
times outside of these ranges may also be used to vary the degree
of coloration, as desired.
[0107] In preferred embodiments, the hair coloring compositions
herein are applied to the hair in the form of a foam. Foam hair
coloring compositions are easy to apply (for both complete coverage
or for targeting problematic spots), and also help prevent unwanted
staining of the skin and scalp that can be problematic with sprays
and other topical forms, for example, by reducing the propensity of
the compositions to drip. Any foaming method known to those of
ordinary skill in the cosmetics arts can be used for foaming the
hair coloring compositions of the present disclosure, but
preferably a non-aerosol foam generating dispenser is used for
discharging the hair coloring compositions as a foam. A non-aerosol
foam generating dispenser is a device which is used to discharge
the hair coloring composition in the form of a foam by mixing it
with air without using a propellant, for example a dispenser
actuated by manual mechanical pumping.
[0108] In preferred embodiments, the method further involves
applying heat to the hair at a dyeing temperature of 30 to
205.degree. C. It has been surprisingly found that heat speeds up
the color development with exemplary effective application times of
less than 20 minutes, preferably less than 10 minutes, more
preferably less than 5 minutes, and produces dyed hair with a
deeper, richer color than colors produced in the absence of applied
heat.
[0109] In some embodiments, heat is applied by use of a hair
dryer/blow dryer, for example, to achieve a dyeing temperature of
from about 30.degree. C., preferably from about 35.degree. C., more
preferably from about 40.degree. C., and up to about 60.degree. C.,
preferably up to about 55.degree. C., more preferably up to about
50.degree. C., even more preferably up to about 45.degree. C.
Therefore, common commercial/household hair dryers/blow dryers may
be used as they would for normal operation for applying heat in the
methods herein. While hair dryers or blow dryers capable of
producing high temperatures (i.e., dyeing temperatures above
60.degree. C.) may also be used, it is often difficult to apply
high heat to hair in this fashion without burning the scalp.
Therefore, in some embodiments, a hair iron (e.g., a straight iron,
a curling iron, etc.) is used to apply high temperatures, that is,
dyeing temperatures of more than 60.degree. C., preferably more
than 70.degree. C., preferably more than 80.degree. C., preferably
more than 90.degree. C., preferably more than 100.degree. C.,
preferably more than 110.degree. C., preferably more than
120.degree. C., preferably more than 130.degree. C., and up to
205.degree. C., preferably up to 200.degree. C., preferably up to
190.degree. C., preferably up to 180.degree. C., preferably up to
170.degree. C., preferably up to 160.degree. C., preferably up to
150.degree. C., preferably up to 140.degree. C. Thus, common
commercial/household hair irons may be used as they would for
normal operation for applying high heat in the methods herein.
[0110] In some embodiments, after application of the hair coloring
composition, and any optional heating, the hair is simply allowed
to dry. In some embodiments, after application of the hair coloring
composition, and after optional application of heat, the hair is
rinsed and/or washed with shampoo to remove the hair coloring
composition. Preferably, the hair coloration fully develops during
the application process and prior to rinsing/washing, particularly
when heat is applied. However, in some instances the color may
continue to develop slightly, even after the hair coloring
composition is removed by rinsing or shampooing.
[0111] Even with the application of high heat, the methods herein
are mild and do not damage keratin fibers during the dyeing
process. To this end, it is preferable that the methods herein do
not require the use of harsh chemicals, such as oxidizing agents,
either together with the hair coloring compositions, or as a
separate application. Oxidizing agents conventionally used for
oxidative dyeing of keratin fibers are, for example, peroxides
(e.g., hydrogen peroxide, benzyl peroxide, urea peroxide, etc.),
bleaching agents (e.g., chlorine dioxide, hypochlorite, etc.),
alkali metal bromates (e.g., sodium bromate), persalts such as
perborates (e.g., sodium perborate) and persulfates (e.g.,
potassium persulfate), peracids (e.g., peracetic acid, pemonoic
acid, nonylamidoperoxycaproic acid (NAPCA)), and oxidase enzymes
such as peroxidases, 2-electron oxidoreductases (e.g., uricases)
and 4-electron oxygenases (e.g., laccases). Preferably, the water
used to wet and/or rinse the hair, either before or after
application of the hair coloring composition, also contains less
than 1 ppm of oxidizing agents (e.g., chlorine dioxide,
hypochlorite, etc.), preferably less than 50 ppb.
[0112] When one or more monosaccharides having 2 to 4 carbon atoms
are employed as the dyestuff in the hair coloring composition, a
two-component application system or "kit" is also envisioned which
includes 1) the hair coloring composition comprising the
monosaccharide(s) having 2 to 4 carbon atoms as discussed above,
and 2) an amino acid composition configured to drive the Maillard
reaction to increase the speed of color formation and/or to produce
certain color tones in reaction with the monosaccharide from the
first component. These two components may be part of an application
kit and stored in separate containers.
[0113] The amino acid composition may comprise any amino acid, but
preferably includes one or more natural amino acids (i.e., 21
proteinogenic .alpha.-amino acids), most preferably one or more of
serine, glycine, alanine, and glutamic acid. In preferred
embodiments, the amount of amino acid(s) in the second component
applied to the hair is at least 10 wt. %, preferably at least 20
wt. %, preferably at least 30 wt. %, preferably at least 40 wt. %,
more preferably at least 50 wt. %, even more preferably at least 60
wt. %, yet even more preferably at least 70 wt. %, yet even more
preferably at least 80 wt. %, and up to 100 wt. %, based on the
total weight of monosaccharide(s) having 2 to 4 carbon atoms
applied to the hair from the first component. The type of amino
acid and the amount of amino acid present in the amino acid
composition may be adjusted to vary the color produced.
[0114] In addition to the amino acid(s), the amino acid composition
may include water and optionally a surfactant, a delivery agent, an
organic solvent, a preservative, an acidulant, a conditioning
agent, a fragrance, and/or any other various ingredients disclosed
herein in amounts similar to that of the hair coloring composition.
In preferred embodiments, like the hair coloring composition, the
amino acid composition is an aqueous mixture capable of being
foamed for ease of application.
[0115] To use the two-component application system, the amino acid
composition may be mixed with the hair coloring composition of the
disclosure at the time of use and the combined mixture may then be
immediately applied to the hair. Alternatively, the amino acid
composition is not premixed with the hair coloring composition.
Instead, the two components are applied sequentially without
intermediate rinsing, whereby the hair coloring composition is
applied first followed by application of the amino acid composition
(or vice versa, that is, the amino acid composition is applied
first followed by application of the hair coloring composition).
Following application of both the hair coloring composition and the
amino acid composition, heat may then be applied at a dyeing
temperature of 30 to 205.degree. C. to speed the color formation
and produce a deeper, richer color as discussed previously.
[0116] The examples below are intended to further illustrate
radiation curable inkjet inks and surface roughness properties and
are not intended to limit the scope of the claims.
EXAMPLES
Example 1
Example Hair Coloring Composition
TABLE-US-00001 [0117] RM in Finished INCI Name Product % wt./wt.
Water 73.418 Glycerin 5.00 Methylparaben 0.20 Sodium Benzoate 0.001
Ceteareth-25 0.40 Citric Acid 0.02 Decyl Glucoside (55%) 0.75
Dimethyl Isosorbide 0.25 Fragrance 0.20 Water 11.00 Erythrulose
(80%) 0.01 Dihydroxyacetone 6.25 Alcohol Denat. 2.50 Benzyl Alcohol
0.001 INCI = International Nomenclature of Cosmetic Ingredients RM
= raw material
[0118] To prepare the hair coloring composition of Example 1, water
and glycerin are added to a large vessel and heated to 75.degree.
C. Additional water soluble ingredients are added and mixed until
homogenous. The mixture is cooled to 40.degree. C. In a separate
vessel dihydroxyacetone and erythrulose are mixed until clear. This
premix is added to the large vessel and mixed for 15 minutes.
[0119] Where a numerical limit or range is stated herein, the
endpoints are included. Also, all values and subranges within a
numerical limit or range are specifically included as if explicitly
written out.
[0120] As used herein the words "a" and "an" and the like carry the
meaning of "one or more."
[0121] Obviously, numerous modifications and variations of the
present invention are possible in light of the above teachings. It
is therefore to be understood that, within the scope of the
appended claims, the invention may be practiced otherwise than as
specifically described herein.
[0122] All patents and other references mentioned above are
incorporated in full herein by this reference, the same as if set
forth at length.
* * * * *