U.S. patent number RE33,786 [Application Number 07/469,364] was granted by the patent office on 1992-01-07 for hair dyeing process and composition.
This patent grant is currently assigned to Clairol, Inc.. Invention is credited to Michael Hnatchenko, Stanley Pohl.
United States Patent |
RE33,786 |
Pohl , et al. |
January 7, 1992 |
Hair dyeing process and composition
Abstract
A two part oxidation dyeing method for human hair is provided
together with a composition therefor in which both parts are
relatively fluid until mixed, after which the combination becomes
viscous and can be applied to hair.
Inventors: |
Pohl; Stanley (Scarsdale,
NY), Hnatchenko; Michael (Bronx, NY) |
Assignee: |
Clairol, Inc. (New York,
NY)
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Family
ID: |
27042743 |
Appl.
No.: |
07/469,364 |
Filed: |
January 12, 1990 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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841404 |
Mar 19, 1986 |
|
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Reissue of: |
052219 |
May 18, 1987 |
04776855 |
Oct 11, 1988 |
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Current U.S.
Class: |
8/406;
252/186.28; 424/62; 8/407; 8/410 |
Current CPC
Class: |
A61K
8/8152 (20130101); A61Q 5/10 (20130101); A61K
2800/88 (20130101) |
Current International
Class: |
A61K
8/72 (20060101); A61K 8/81 (20060101); A61Q
5/10 (20060101); A61K 007/13 (); A61K
007/135 () |
Field of
Search: |
;8/406,407,410
;252/186.28 ;424/62 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Rohm and Haas Company Brochure, "Acrysol ICS-1 Thickener for Use in
Cosmetics and Toiletry Products", Aug. 1983. .
Witiak, D., "A New High Efficiency Aqueous Thickener", Happi, Feb.
1983, pp. 56-60. .
Witiak, David, "A High Efficiency Aqueous Thickener",
CA98L20):166753W. .
Balsam et al, Cosmetics Science and Technology, 2nd ed., vol. 2,
Wiley Interscience, NY, 1973, p. 681..
|
Primary Examiner: Lieberman; Paul
Assistant Examiner: Skaling; Linda D.
Attorney, Agent or Firm: Simon; M. S.
Parent Case Text
This is continuing application of application Ser. No. 841,404,
filed on Mar. 19, 1986, now abandoned.
Claims
What is claimed is: .[.1. A two part composition for hair treating
when combined, wherein the two parts are intended to be admixed
with each other shortly before use, which comprises
(a) an aqueous first part containing an alkaline material in an
amount sufficient to provide a final pH of about 8 to 12 when
admixed with a second part; and
(b) an aqueous second part containing about 0.04 to 25% by weight
of a polymer of an ester of a C.sub.16 to C.sub.22 carboxylic acid
and a polyalkylene glycol ether of a C.sub.16 to C.sub.22 alcohol
and two or more monomers of C.sub.16 to C.sub.22 carboxylic acid or
their esters, and
1 to 10% by weight of a peroxide at a pH of about 1.5 to 5.5..]. 2.
The composition according to claim .[.1.]. .Iadd.10
.Iaddend.wherein .[.said polymer is acrylates/steareth 20
methacrylate copolymer and.]. said
peroxide is hydrogen peroxide. 3. The two part hair treating
composition according to claim 2 wherein the first part further
contains a
tinctorially effective amount of an oxidation hair dye
intermediate. 4. The composition according to claim 2 wherein said
second part is combined just prior to mixing with said first part
from two sub-parts, one containing the acrylate/steareth 20
methacrylate copolymer and the other
the hydrogen peroxide. 5. The composition according to claim 3
wherein the first part further contains an amount of a solvent
sufficient to solubilize the hair dye intermediate up to about 20%;
said solvent selected from the group consisting of hexylene glycol,
propylene glycol, diethylene glycolmonoethyl ether and mixtures of
two or more thereof, and said second part further contains 0 to
about 0.2% phenacetin, and 0 to
about 0.1% EDTA. 6. The composition according to claim 2 wherein
said first part contains 2% hexylene glycol, 4%
diethyleneglycolmonoethyl ether, 5.77% ammonia (28%) 2.84% ammonium
chloride, 2% sodium lauryl
sulfate (30%), and 0.2% sodium chloride. 7. The composition
according to claim 2 wherein said second part contains 10%
acrylates/steareth-20 methacrylate copolymer, 12.3% hydrogen
peroxide (50%), and 0.04% phenacetin and 0.02% EDTA. .[.8. A method
for oxidation dyeing of human hair comprising admixing an aqueous
lotion containing a tinctorially effective amount of an oxidation
hair dye intermediate, and an alkaline material in an amount
sufficient to provide a final pH of about 8 to 12 when admixed with
an aqueous developer; and an aqueous developer containing about
0.04 to 25% by weight of a polymer of an ester of a C.sub.16 to
C.sub.22 carboxylic acid and a polyalkylene glycol ester of a
C.sub.16 to C.sub.22 alcohol and two or more monomers consisting of
C.sub.16 to C.sub.22 carboxylic acid or their esters, and 1 to 10%
by weight of a peroxide at a pH of about 1.5 to 5.5; the lotion and
the developer being thin emulsions which upon said admixing thicken
to produce a thickened emulsion; then applying the thickened
emulsion to the hair for a period of time sufficient for the dyeing
process to take place..]. .[.9. The method according to claim 8
wherein the aqueous developer contains an aqueous emulsion of
hydrogen peroxide and acrylates/steareth-20
methacrylate copolymer..]. .Iadd.10. A two part composition for
hair treating when combined, wherein the two parts are intended to
be admixed with each other shortly before use, which comprises:
(a) an aqueous first part containing an alkaline material in an
amount sufficient to provide a final pH of about 8 to 12 when
admixed with a second part, and
(b) an aqueous second part containing about 0.04 to 25% by weight
of a copolymer of an acrylates/steareth 20 methacrylate and about 1
to 10% by
weight of a peroxide at a pH of about 1.5 to 5.5. .Iaddend.
.Iadd.11. A method for oxidation dyeing of human hair comprising
admixing an aqueous lotion containing a tinctorially effective
amount of an oxidation hair dye intermediate, and an alkaline
material in an amount sufficient to provide a final pH of about 8
to 12 when admixed with an aqueous developer; and an aqueous
developer containing about 0.04 to 25% by weight of a copolymer of
an acrylates/steareth 20 methacrylate and about 1 to 10% by weight
of a peroxide at a pH of about 1.5 to 5.5; the lotion and the
developer being thin emulsions which upon said admixing thicken to
produce a thickened emulsion; then applying the thickened emulsion
to the hair for a period of time sufficient for the dyeing process
to take place. .Iaddend.
Description
BACKGROUND OF THE INVENTION
In dyeing of human hair with direct dyes as distinguished from
oxidation dyes, the resultant final color is a combination of the
natural hair color plus the color added by the dye. Where oxidation
dyes are utilized and the hair is to be dyed a shade that is
lighter than the shade of the person's hair, the dyeing procedure
first eliminates the natural shade of the hair through bleaching
with an oxidizing agent such as alkaline hydrogen peroxide. Then
the desired shade is obtained on the hair by contacting it with the
oxidation dye. Colored polymeric compounds of high molecular weight
are produced on the hair by the action of atmospheric oxygen or by
oxidizing agents such as hydrogen peroxide. It is also possible to
simultaneously bleach and color the hair. In such cases hair is
concurrently bleached by alkaline hydrogen peroxide as dyestuff
penetrates into the hair and is oxidized to produce the desired
color.
When oxidation dyes are used in the dyeing of human hair, the
procedure usually involves the use of a two part system. One part
is the lotion formulation which contains a variety of ingredients
including the oxidation dye precursor chemicals which when mixed
with the second part, the developer formulation, prior to
application to the human head, causes the formation of the desired
colored dyes. The developer usually contains an oxidizing agent
such as hydrogen peroxide or a peroxide precursor. If sufficient
peroxide is used, some of the natural melanin pigment of the hair
may be destroyed first and the colored dyestuffs formed by
oxidative coupling of the precursors in the first part, penetrate
into the hair to give it the desired color. Such systems will
generally contain 50% or more of organic solvents and surfactants,
and require relatively high levels of dye to produce the desired
color.
In practice surfactants are normally used to thicken the hair dye
compositions to a more viscous consistency which will prevent the
composition from running off the hair during use. The surfactants
are dissolved in organic solvents. When the aqueous developer is
added to the lotion, the water dilutes the organic solvents and the
surfactants come out of solution and will thicken the
composition.
It is also known from patents to use certain polymers in the
developer to provide viscous solutions of hydrogen peroxide,
however a number of well known cosmetic thickeners are not stable
in hydrogen peroxide solutions. Furthermore, thickening of the
solution is desirable only after the lotion and developer parts
have been mixed together.
U.S. Pat. No. 4,130,501 discloses the use of various Carbopol
resins for preparing thickened hydrogen peroxide formulations.
These formulations were found to be stable when the solutions were
made alkaline with sodium hydroxide. However, then are stable in
storage only as thickened alkaline gels and are applied in that
form.
U.K. patent No. 827,331 discloses the use of certain polymers,
including copolymers of methacrylic acid, as thickeners for
hydrogen peroxide in bleaching of hair. The formulations in the
patent are described as thick gels over a pH range of 3 to 8 and
are applied to hair in the thick condition. A thickened peroxide
composition, such as is described in this reference would not be
useful for oxidation dyes because it would be difficult to mix with
the dye solution.
U.S. Pat. No. 4,313,932 discloses a dry, powder composition for
admixture with water to provide a hair bleaching composition. The
reference also discloses use of certain acrylic polymers to thicken
peroxide formulations after water is added. The thickener used in
this reference is part of the powder composition which is added to
the peroxide immediately before use. Stability of the thickener to
peroxide during storage is not a consideration as the product is a
dry powder.
Several conditions are important for the procedures using oxidation
dyes to work properly. First and foremost, stability of the
formulations is imperative, particularly if the product is to be
packaged and marketed. Secondly, mixing of the two parts should be
quick and easy. Thirdly, after mixing, the resultant thickened
solution should have the properties of being easily applied to the
head and thick enough to remain on the hair until the dyeing
process is complete and removal can take place.
Accordingly, it is an object of the present invention to provide a
stable, oxidation dye formulation. It is a further object of the
present invention to provide a two part dye composition which can
be readily mixed and easily applied to the hair. It is still a
further object of the present invention to provide an oxidation dye
composition which is thick enough to remain on the hair until the
dyeing process is complete. It is yet another object of this
present invention to provide a two part dye composition containing
substantially lower amounts of solvents, surfactants and dye than
has generally been heretofore employed.
SUMMARY OF THE INVENTION
The present invention involves the use of a unique polymer for
thickening hair treatment formulations. This material forms a
stable fluid emulsion when maintained in aqueous solution or added
to hydrogen peroxide. The formulation does not thicken until
addition of an alkaline dye lotion immediately before application
to the hair. Where a peroxide solution is employed, it is very
important that the peroxide solution remain in a thin, fluid
emulsion until mixed with the dye lotion to enable easy pouring and
mixing. It has now been discovered that .[.polymers of an ester of
a C.sub.16 to C.sub.22 carboxylic acid and a polyalkylene glycol
ether of a C.sub.16 to C.sub.22 alcohol and two or more monomers of
C.sub.16 to C.sub.22 carboxylic acids or their esters are
surprisingly stable to hydrogen peroxide and form thin emulsions
therewith. Of these compounds it is most preferred to employ
acrylates/steareth 20 methacrylate copolymer, [the nomenclature of
the Cosmetic, Toiletry and Fragrance Association (CFTA), Cosmetic
Ingredient Dictionary, Third Edtion Supplement, 1985] such as sold
by Rohm & Haas, Philadelphia, Pa. as a cosmetic thickener under
the trade name Acrysol-ICS. It was discovered.]. that .Iadd.Acrysol
ICS is most stable to hydrogen peroxide and forms a thin emulsion
therewith at a neutral or acid pH. .Iaddend.Acrysol ICS is most
surprisingly stable to hydrogen peroxide and forms a thin emulsion
therewith at neutral or acid pH. .Iadd.Acrysol ICS is sold by Rohm
& Haas, Philadelphia, Pa. .Iaddend.This copolymer is a polymer
of an ester of methacrylic acid steareth 20 and two or more
monomers consisting of acrylic acid, methacrylic acid or their
simple esters. When a solution of Acrysol ICS is treated with an
aqueous ammonia solution, having an alkaline pH in the range range
normally associated with oxidation dyeing, and containing dyestuff
precursors, the resulting mixture has a thickened viscosity which
is suitable for hair dyeing. Very highly aqueous dye systems are
very desirable.
DESCRIPTION OF THE INVENTION
The use of Acrysol-ICS is a key ingredient of the developer part of
this invention when used in oxidative hair dye compositions. It is
described as forming a thin emulsion at neutral or acid pH which
thickens or neutralization above pH 7. Acrysol-ICS when added to
hydrogen peroxide is suprisingly stable. When a solution of
hydrogen peroxide containing at least 3% active Acrysol-ICS is
brought to a pH which is within the alkaline pH range used in hair
dyeing, by the addition of an alkalizer such as ammonia or
alkanolamine, the resulting mixture has a thickened viscosity which
is suitable for dyeing purposes. No organic surfactant or solvent
need be present, although in practice some small amounts of
surfactants or solvents would probably be needed to help dissolve
the dyes and provide foaming and conditioning. Very highly aqueous
oxidation dye systems are very desirable. The oxidation hair dye
bases of the present invention whose compositions are given below
contain only about 5% organic solvents and surfactants as compared
with 50% or more in current products. There are a number of
advantages of such high water content dye systems. Aside from the
obvious cost saving, it was found that dyeing is much more
efficient when solvents and surfactants are kept to a minimum;
about one half as much dye is needed to produce the same shade as
in current products. Also, it is likely that there will be less
skin and scalp staining by dye in a more highly aqueous system,
partly because the low concentration of surfactants washes away
less of the protective oil in the skin. Furthermore, the thickened
solution is quite thixotropic, spreading easily into the hair but
showing excellent "stay-put" quality when the shear is removed.
Adding of about 1% based on the hair dye composition of an aqueous
solution of Acryol-ICS to the developer prior to mixing the lotion
and the developer, enables the tailoring of the viscosity of the
ultimate hair dyeing composition. Thus, for example, a hair dresser
can add Acrysol-ICS to a more fluid hair dye composition suitable
for use by a consumer and thus make it sufficiently viscous e.g.
for root dyeing that is known to require a condsiderbly more
viscous dye composition.
Although developer formulations containing Acrysol-ICS and hydrogen
peroxide are surprisingly stable, it is sometimes advantageous to
add known stabilizers for peroxide to the formulations to
counteract the effect of impurities which could catalyze peroxide
decomposition. Examples of substances which are known to stabilize
hydrogen peroxide are phenacetin, EDTA and other substances which
complex heavy metal ions such as are disclosed in U.S. Pat. Nos.
3,378,444 and 3,632,295.
Typical preferred compositions prepared in accordance with the
present invention will contain a lotion part (Part A) having a pH
of about 8 to 12 and containing the oxidation hair dye intermediate
or intermediates, and a developer part (Part B), the latter
containing from about 0.04% to about 25% by weight of Acrysol-ICS
and 1% to 10% of hydrogen peroxide maintained at a pH of about 1.5
to 5.5. If desired, the primary components of Part B, i.e., the
Acrysol-ICS and the hydrogen peroxide can be maintained separately
and combined just prior to mixing Part B with Part A, such as when
the tailoring of the viscosity of the hair dye composition is
carried out.
In addition to dyes, the lotion (Part A) can contain 0 to 20%
hexylene glycol or propylene glycol which acts as a solvent, 0 to
20% Carbitol [2-(2-ethoxyethoxy)ethanol ethanol, or diethylene
glycolmonoethylether] which acts as a solvent, 0 to 10% ammonia
(28%) which acts as an alkalizer-thickener, 0 to 10% ammonium
chloride which acts as a pH control and provides a buffering
effect, 0 to 10% sodium lauryl sulfate (30%) which acts as a
surfactant and 0 to 10% sodium chloride which assists in viscosity
control, with the remainder being water.
In addition to the Acrysol-ICS and the hydrogen peroxide, the
developer (Part B) can contain 0 to 0.2% phenacetin which acts as a
stabilizer and 0 to 0.1% ethylene diamine tetraacetic acid (EDTA)
which acts as a stabilizer, with the remainder being water. All
percentages set forth in this specification, unless otherwise
indicated, expressed are percent by weight.
A most preferred composition contains in Part A, in addition to
dyes, 2% hexylene glycol, 4% Carbitol, 5.77% ammonia (28%), 2.84%
ammonium chloride, 2% sodium lauryl sulfate (30%), 0.2% sodium
chloride, made up to 100% with water. Part B of such preferred
composition contains 10% Acrysol-ICS, 12.3% hydrogen peroxide (50%)
and 0.04 phenacetin and 0.02% EDTA made up to 100% with water.
EXAMPLES 1-24
The six formulations of the lotion (Part A) were mixed in all
possible combinations with the four formulations of the developer
(Part B).
The following lotion formulations (Part A) are prepared:
______________________________________ 1 2 3 4 5 6
______________________________________ p-phenylenediamine 0.3 0.4
0.05 -- 0.5 0.5 bishydroxylethyl- 0.05 -- 0.05 -- -- -- ppd sulfate
p-aminophenol 0.1 0.2 -- 0.4 -- -- resorcinol 0.4 0.5 -- 0.2 0.5
0.5 1-naphthol 0.05 -- 0.05 0.05 0.01 0.01 sodium sulfite 0.1 0.1
0.1 0.1 0.1 0.1 bentone LT 0.4 -- -- 0.2 -- -- propylene glycol 3.0
-- 3.0 0.5 2.0 -- hexylene glycol -- -- -- -- -- 2.0 carbitol 4.0
-- 2.0 3.0 2.0 4.0 ammonia (28%) 6.0 4.0 6.0 2.0 -- 5.77 ammonium
chloride 3.0 3.0 1.5 2.0 2.0 2.84 sodium lauryl -- -- 4.0 -- -- 2.0
sulfate sodium chloride -- 3.0 -- -- -- 0.2 ethanolamine -- -- --
-- 6.0 -- ethanolamine hydro- -- -- -- -- 4.0 -- chloride fragance
-- -- -- -- -- 0.1 water (to 100%)
______________________________________
The following developer formulation (Part B) are prepared:
______________________________________ A B C D
______________________________________ Acrysol ICS-1 12.0 10.0 6.0
10.0 hydrogen peroxide (50%) 12.3 10.0 12.0 12.3 phenacetin -- 0.04
-- 0.02 EDTA -- 0.02 0.02 -- water (to 100%)
______________________________________
All combinations of Part A and Part B are mixed (Examples 1-24) and
applied to human hair. The viscosities of these formulations after
mixing are all in the range of 2000-12000 cps. The hair is dyed to
varying shades of blonde or brown except for combinations
containing lotion #2 which tones hair to a blue-violet hue.
Viscosity measurements, made with a Haake Rotovisco Apparatus on
one of the above combinations (Part A, #6 mixed with Part B, #2)
illustrate the thixothropy exhibited by the system. Results are
shown below:
______________________________________ Shear Rate/ Viscosity Shear
Stress sec cps Dynes/sq cm ______________________________________
8.5 4372.2 162.0 16.9 2662.0 450.2 25.4 1838.0 466.3 50.7 982.4
498.5 76.1 718.3 546.7 152.2 422.5 643.2 228.3 309.9 707.5 456.7
172.5 787.9 685.0 145.5 997.0 1370.0 82.2 1125.6 1370.0 79.8 1093.4
685.0 138.5 948.7 456.7 186.6 852.2 228.3 316.9 723.6 152.2 433.1
659.3 76.1 802.8 611.0 50.7 1077.5 546.7 25.4 1901.4 482.4 16.9
2757.0 466.3 8.5 4753.5 402.0
______________________________________
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