U.S. patent number 3,838,966 [Application Number 05/040,423] was granted by the patent office on 1974-10-01 for permanent but removable hair-coloring system.
This patent grant is currently assigned to The Mennen Company. Invention is credited to Myron Barchas, Magda Ofelia Gutierrez.
United States Patent |
3,838,966 |
Barchas , et al. |
October 1, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
PERMANENT BUT REMOVABLE HAIR-COLORING SYSTEM
Abstract
Hair is colored by treating it with a solution containing a
transition metal compound having a valence less than the maximum
and then oxidizing the compound to an insoluble form. Colors so
imparted and colors imparted to other procedures using transition
metal compounds may be removed by treatment with a reducing agent
or a chelating agent.
Inventors: |
Barchas; Myron (New York,
NY), Gutierrez; Magda Ofelia (Morristown, NJ) |
Assignee: |
The Mennen Company (Morristown,
NJ)
|
Family
ID: |
21910908 |
Appl.
No.: |
05/040,423 |
Filed: |
May 25, 1970 |
Current U.S.
Class: |
8/405; 8/404;
8/429; 8/102; 8/406; 424/62 |
Current CPC
Class: |
A61K
8/19 (20130101); A61Q 5/065 (20130101) |
Current International
Class: |
D06P
1/36 (20060101); D06P 3/04 (20060101); D06P
3/08 (20060101); D06P 1/00 (20060101); D06L
3/10 (20060101); D06L 3/00 (20060101); D06p
001/36 () |
Field of
Search: |
;8/10,11,52,102,111 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lesmes; George F.
Assistant Examiner: Ives; Patricia C.
Attorney, Agent or Firm: Davis, Hoxie, Faithfull and
Hapgood
Claims
What is claimed is:
1. A method for removing color from hair dyed with a coloring
material which is an oxide or a sulfide of a transition metal,
which comprises treating said hair with a solubilizing agent which,
when the coloring material is an oxide, is a reducing agent or a
chelating agent and when the coloring material is a sulfide, is a
chelating agent.
2. The method claimed in claim 1 wherein the solubilizing agent is
thiourea.
3. The method claimed in claim 1 wherein the hair is dyed with an
oxide and the solubilizing agent is a metabisulfite.
4. A method for coloring hair which comprises treating the hair
with an aqueous solution of a transition metal compound in which
the metal is present in less than its highest valence state to
deposit said compound on the hair and oxidizing said compound to an
insoluble compound in which the metal is in a higher valence state,
to impart to the hair a color which is permanent under ordinary
washing conditions.
5. A method of removing the color from hair colored according to
claim 4 which comprises treating the colored hair with a reducing
or chelating agent.
6. The method claimed in claim 4 wherein the transition metal is
manganese, cobalt or iron.
7. The method claimed in claim 4 wherein the oxidizing agent is a
permanganate, persulfate, perborate or periodate.
8. A method of coloring hair which comprises treating the hair with
an aqueous solution of a manganous salt to deposit said manganous
salt thereon, and treating the so treated hair with an aqueous
perborate, persulfate, periodate or permanganate solution to
precipitate an insoluble manganese oxide on the hair.
9. A method of coloring hair which comprises treating the hair with
an aqueous solution of a cobaltous salt to deposit said cobaltous
salt thereon and treating the so treated hair with an aqueous
solution of a perborate, persulfate, periodate or permanganate to
insolubilize said cobaltous salt.
10. A method of coloring hair which comprises treating the hair
with an aqueous solution of a ferrous salt to deposit said salt
thereon and subsequently treating the so treated hair with an
aqueous solution of a perborate, persulfate, periodate or
permanganate to insolubilize said ferrous salt.
11. A method for treating hair which comprises coloring hair by
depositing thereon a coloring material which is a sulfide or an
oxide of a transition metal and subsequently removing the color by
treating the hair with a solubilizing agent which, when the
coloring material is an oxide, is a reducing agent or a chelating
agent, and when the coloring material is a sulfide, is a chelating
agent.
12. The method claimed in claim 11 wherein the transition metal is
manganese, nickel, cobalt or iron.
13. The method claimed in claim 11 wherein the solubilizing agent
is thiourea.
14. The method claimed in claim 11 wherein the solubilizing agent
is a metabisulfite.
Description
The art of imparting color to hair is an ancient one whose origin
is lost in antiquity. In addition to natural vegetable dyes such as
henna and synthetic materials such as coal tar dyes, various
metallic compounds have been employed, principally based on lead,
silver or copper, but also including the transition metals,
particularly cobalt, iron, nickel and manganese. See "Cosmetics --
Science and Technology" (1957) pp. 515-524. Prior metal coloring
systems depended for the most part on the formation of metal
sulfides, either by reaction of the dyeing solution with the
keratinous sulfur in the hair itself or with sulfur from some
external source; or on the reduction of the metal from a higher
valence state to a lower state, as for example by the reduction of
a permanganate to manganese dioxide. None of these techniques have
been particularly successful. Moreover there was no practicable
technique for removing the color from the hair once it had been
developed.
The present invention provides a novel method of hair coloring
which will give a wide range of shades permanent to normal washing
but whose coloration is readily removed if desired. The invention
also provides methods of removing hair color applicable to hair
dyed in accordance with the invention and also to hair colored in
more conventional ways.
In accordance with the invention, hair is dyed by contacting it
with a solution of a transition metal compound in which the metal
is in a first valence state less than the maximum, to deposit the
compound on the hair, and then oxidizing the compound to form an
insoluble oxide in which the metal has a higher valence state.
Further, in accordance with the invention, color so imparted to
hair may be removed by treating the hair with a suitable reducing
agent or with a chelating agent. This removal technique, it will be
recognized, may also be used where the original color was imparted
by oxides formed by reduction of transition metal compounds in
accordance with known dyeing techniques; and, if a chelating agent
is used, where the color was imparted by deposition of certain
transition metal sulfides.
The transition metals used for dyeing in accordance with the
invention are those forming water soluble compounds capable of
being oxidized to form an insoluble, colored oxide. Manganese, iron
and cobalt are of principal interest, and of these manganese is
preferred. The form in which the metal is initially applied to the
hair is not important, so long as it is in a lower state of
oxidation. Various salts, e.g., the halides (especially the
chlorides), sulfates, or nitrates may be used, as may stable salts
of organic acids, such as the acetates. Manganese is preferably
used in the form of manganous salts such as manganous sulfate or
chloride. Iron and cobalt are used as the corresponding ferrous or
cobaltous salts.
The conditions under which the metallic compounds are applied to
the hair are capable of considerable variation. Normally the
compounds will be applied as aqueous solutions, 0.26 to 1.05
formal, at moderate temperature, say from about 10.degree. to about
40.degree.C., and at a pH of from about 4 to about 10. Where the
initial metal solution is followed by a separate oxidizing
solution, it will be allowed to remain on the hair for say 5 to 30
minutes before the oxidizing solution is applied, so that the metal
may penetrate into the interior of the hair.
At this point it may be pointed out that dyeing according to the
invention can be carried out using a single solution containing an
alkali metal peroxydisulfate, e.g., sodium peroxydisulfate, as the
oxidizing agent. In this instance a metal salt solution, e.g., a
solution of MnCl.sub.2, is mixed with a solution of peroxydisulfate
just before it is applied to the hair. The efficacy of the
peroxydisulfate as an oxidizing solution depends on its
decomposition according to the reaction
2S.sub.2 O.sub.8 .sup.- + +2H.sub.2 O .fwdarw. 4HSO.sub.4 .sup.-
+O.sub.2
This reaction, however, is relatively slow, permitting the
manganous ions to penetrate the hair filaments before they are
oxidized.
Where a single step technique, as described above, is used, the
solution applied to the hair will normally have a metal compound
concentration of 0.05 to 0.50 gram formula weight (GFW)/liter, a
peroxydisulfate concentration of 0.08 to 0.60 mols/liter and a pH
of between about 8.0 and about 10.0. It may be applied at
temperatures of say about 10.degree. to about 40.degree.C., and is
left in contact with the hair for between about 5 and about 60
minutes.
Returning to the two-step procedure, after the metal compound
having the metal in a lower valence state has been left in contact
with the hair for a time sufficient for the metal ions to have
penetrated into the core of the hair filaments, an oxidizing
solution is applied. Various oxidizing agents may be used, the
criteria being merely that they be effective to convert the
soluble, lower valence metallic compound to a higher valence state
in a condition under which it becomes insoluble, and not be
injurious to the hair or scalp under the effective oxiziding
conditions.
Among the oxidizing agents which have been found useful are the
permanganates, perborates, persulfates, periodates, perphosphates
and monopersulfates, used alone or in combination, as the alkali
metal salts, or in the case of the periodates, as the acid
(paraperiodic acid, H.sub.5 IO.sub.6). Hydrogen peroxide may also
be used. The conditions of treatment with the oxidizing agent are,
again, subject to considerable variation. In general it will be
used in a concentration of say 0.01 to 0.30 GFW/liter at
temperatures of say 10.degree. to 40.degree.C., and at a pH of say
7.0 to 10.5. The solution will be left in contact with the hair
until the desired shade develops (other things being equal). In
general, contact time will be from 1 to 10 minutes.
It will be understood that the shade of dyeing may be varied by
varying the kinds of metals used and their proportions as well as
by varying the reaction conditions, especially concentration, pH
and contact time.
Both the initial metal solutions and the oxidation or fixation
solutions may contain various auxiliary materials such as buffers,
wetting agents, perfumes and the like.
After the oxidizing solution (or the combined solution) has been
left in contact with the hair for the requisite time, the hair may
be shampooed using any conventional soap or synthetic detergent
composition.
One of the advantages of dyeing in accordance with the invention is
that the color may easily be removed, if desired, even though it is
permanent under normal washing conditions.
The agencies useful for removing color imparted according to the
invention, and as will be explained below, colors imparted by
certain prior art metallic coloring systems, are either reducing
agents or chelating agents.
In the case of reducing agents, the particular agent selected
should be one sufficiently active to convert the oxidized metallic
color compound to a soluble lower valence state. The most
advantageous materials so far found effective are the alkali metal
metabisulfites, e.g., sodium metabisulfite (Na.sub.2 S.sub.2
O.sub.4). Other equivalent reducing agents such as other reducing
salts of the oxy acids based on SO.sub.2, e.g., sodium sulfite
(Na.sub.2 SO.sub.3), sodium thiosulfate (Na.sub.2 S.sub.2 O.sub.3)
and sodium hydrosulfite (Na.sub.2 S.sub.2 O.sub.4) may also be
used.
The reducing agent is employed in a concentration of say 0.05 to
0.5 mols/liter, normally at say 10.degree. to 40.degree.C., and at
a pH of from about 1.5 to about 7. The time of treatment is, of
course, dependent on the other conditions. Normally substantially
all the color can be removed in a matter of say 0.5 to 20
minutes.
Following treatment with the reducing agent, the hair may be washed
in normal manner.
As an alternative to removing color using a reducing agent, color
may be removed from hair dyed in accordance with the present
invention by using a chelating or complexing agent.
It is well known that various organic compounds form water soluble
complexes with transition metal compounds and use may be made of
this principle to remove color derived from transition metals from
hair. A variety of chelating agents may be used, depending on the
metal concerned. Thiourea has been found especially useful, but
other materials in which the donor is sulfur may be used as may
chelating agents in which the donor is nitrogen, e.g., EDTA, or
oxygen, e.g., citric acid.
The conditions under which the chelating agent is used will vary
widely depending on the agent and the metal to be removed. In
general the concentration of agent will range between about 0.1 and
about 1.0 mols/liter. The solution will usually have a pH from say
2.5 to 5.0 and will be applied at temperatures of say 10.degree. to
40.degree. C.. Contact time is determined by the speed of the
particular reaction. Normally an application of say 1 to 15 minutes
will remove substantially all color. However, in certain instances
times of an hour or even longer may be required. Sulfide colors
generally require longer times or higher temperatures than oxide
colors.
It will be understood that while it is particularly advantageous to
use the removal techniques described above in conjunction with the
dyeing procedures described and claimed herein, since it is much
easier to select the particular removal reagent and conditions with
relation to a specific dyeing procedure, the removal techniques
themselves represent a separate aspect of the present invention and
are capable of being used to remove transition metal oxide or
sulfide coloring materials regardless of how they have been
applied. Thus, for example, cobalt or nickel salts may be applied
to the hair from aqueous solution, and fixed by treatment with a
dithionite (hyposulfite) solution. Again, potassium permanganate
may be applied to the hair and reduced by the use of sodium sulfide
or pyrogallol, to give a color which may be removed either by
reduction using metabisulfite, or by a thiourea complexing
solution.
The invention is described by the following specific examples which
are, of course, only illustrative and are not intended to restrict
the invention as it is defined in the claims:
EXAMPLE I
A first solution was prepared containing:
Ingredient Wt. % ______________________________________ MnCl.sub.2
20 NH.sub.4 Cl 20 H.sub.2 O 60 100
______________________________________
and adjusted to pH 8 with NaOH. Human hair was treated with this
solution for 30 minutes at room temperature (70.degree.F.) and
rinsed with water. It was then treated with an aqueous solution
containing 2.1 percent sodium perborate at a pH of 10.2-10.4 for 10
minutes, again at room temperature. After shampooing, the hair had
a warm dark brown color.
Varying the pH of the second solution from 10.2 to 2.5 whilst
holding the first solution at pH 8 gave a range of colors from dark
warm brown through medium and light warm brown to medium and light
ash blond. Maintaining the pH of the second solution at 10.2 and
varying the pH of the first from 2.5 to 8 with NaOH or NH.sub.4 OH
gave a range of colors from dark warm brown to light reddish
brown.
The procedure just described may be varied in other ways to give
varying results. For example, by varying the times of exposure,
different shades of brown are obtainable as indicated in the table
below:
Contact Time (minutes) ______________________________________
Solution 1 5 10 15 20 25 30 35 Solution 2 35 30 25 20 15 10 5 Color
LB MB MB MB DB DB DB ______________________________________
Where LB is light brown; MD is medium brown and DB is dark
brown.
The role of the ammonium chloride in solution 1 is to permit the
manganese to be retained in solution after the solution is rendered
alkaline. The mechanism appears to be a complex formation.
EXAMPLE II
A first solution having the following composition was prepared:
Ingredient Weight % ______________________________________
MnSo.sub.4.sup.. H.sub.2 O 28 H.sub.2 O 62 Na lauryl sulfate 10
100.0% ______________________________________
The pH of the solution was brought to 6.5 by the addition of NaOH.
Human hair was treated with the solution at room temperature for
seven minutes and then rinsed with water. Then a second solution,
freshly prepared, and containing
Ingredient Weight % ______________________________________ Standard
KMnO.sub.4 Solution containing 0.44% (wt.) KMnO.sub.4 25 H.sub.2 O
57.5 Aqueous solution containing 28% by weight ammonium lauryl
sulfate 17.5 100.0% ______________________________________
was used to treat the hair for a total contact time of 35 minutes.
The hair was then washed with a standard commercial shampoo. It had
a very dark warm brown color.
Increasing the permanganate concentration up to twice that
specified, gives darker colors ranging to warm blacks.
The presence of ammonium lauryl sulfate in the oxidizing solution
increases color intensity. This was not noted with such related
surfactants as sodium lauryl sulfate or triethanol amine lauryl
sulfate (or with ammonium sulfate) and its rationale is not known.
It is important, however, when using ammonium lauryl sulfate to mix
the oxidizing solution just before using since the oxidant is
inactivated by the surfactant within about 50 minutes.
EXAMPLE III
A solution was prepared containing
Ingredient Proportion (Wt.%) ______________________________________
MnCl.sub.2 15 sodium perborate 2 water + IN HCl to pH 4.5 balance
______________________________________
This was applied to human hair for five minutes at pH 4.5 The hair
was rinsed with water and then an aqueous solution of 0.4%
KMnO.sub.4 was applied for about 35 minutes at a pH of A black
color was obtained.
If the permanganate was kept at a pH of less than 7 only brown
shades are obtained, unless an extremely porous type of hair was
treated. Variations in the pH of the manganous solution from 1.0 to
5.7 did not affect the final color.
EXAMPLE IV
Human hair was treated with a solution containing
Ingredient Weight % ______________________________________
MnCl.sub.2 15 C.Cl.sub.2 5 water balance
______________________________________
at a pH of .about. 5.0, at room temperature, for about 15 minutes.
After rinsing, the hair was treated with 0.4% KMnO.sub.4 for about
5 minutes. The color was brown but much less warm (less red) than
was observed when the cobalt was omitted.
EXAMPLE V
The procedure of Example I was repeated, but the first solution was
a simple 10 percent aqueous solution of MnCl.sub.2. Treatment with
this was at pH 4.7 for 30 minutes at room temperature. The
oxidizing solution was an aqueous solution containing 2.1 percent
sodium perborate at pH 10.2, and room temperature. After a contact
time of 5 minutes, the hair assumed a medium ash brown color.
Decreasing the perborate concentration gave lighter colors with a
medium ash brown at 1 percent, light ash brown at 0.05 percent and
ash blond at 0.25 percent. The colors from these perborate
treatements tended, in general, to be more drab than similar
treatments using permanganate.
EXAMPLE VI
A solution was prepared containing
Ingredient Weight % ______________________________________
CoCl.sub.2.sup.. 6H.sub.2 O 25 NaBO.sub.3.sup.. 4H.sub.2 O 4 water
balance ______________________________________
with sufficient 0.5 N HCl to give a pH of 1.6. Three bleached human
hair swatches (Nos. 1, 2 and 3) were treated for 45, 10 and 20
minutes respectively and rinsed with water. They were then treated
with a 0.44% KMnO.sub.4 solution for 10, 10 and 20 minutes
respectively, shampooed and examined. Swatch No. 1, was dark brown;
No. 2, very dark brown and No. 3, black.
When a 1 percent alkaline potassium persulfate solution pH 10.5 is
substituted for the permanganate solution a reddish brown to red
color is obtained, which can be adjusted by adjusting the pH of the
cobalt from 2.5 to 11.0. Adding 1 percent potassium persulfate and
10 percent urea to the cobaltous solution results in an intense red
color.
EXAMPLES VII - XVI
These examples are grouped together to illustrate the range of
colors which are obtainable in accordance with the invention. In
all cases the dyeings were performed on dark brown hair which had
first been bleached to the pale yellow stage. In all cases the hair
was treated with solution 1, as specified in the table below, for
the specified time, rinsed with water and then treated with
solution 2 for the time specified. Following this it was washed
with a commercial shampoo and dried.
In general, Examples VII - X gave ash colors, while Examples XI -
XVI gave warm colors. The intensity of the colors seems
proportional to the porosity of the hair, which is increased by
bleaching. Lighter colors should therefore be expected when
treating hair bleached to a lesser extent. Black may still be
obtained under these circumstances by increasing the proportion of
perborate in solution 1.
Solution 1 VII VIII IX X XI XII XIII XIV XV XVI BLACK
__________________________________________________________________________
% % % % % % % % % % MnCl.sub.2.sup.. 4H.sub.2 O 19 6 10 10 -- 10 6
6 6 6 28 NH.sub.4 Cl 19 13 -- -- -- -- 13 13 13 13 -- H.sub.2 O +
1N NaOh 62 81 -- -- -- -- 81 81 81 81 -- H.sub.2 O -- -- 90 90 90
90 -- -- -- -- --
__________________________________________________________________________
FeSO.sub.4.sup.. 7H.sub.2 O -- -- -- -- 10 -- -- -- -- -- --
NaBO.sub.3.sup.. 4H.sub.2 O -- -- -- -- -- -- -- -- -- -- 1.5
H.sub.2 O + 1N HCl -- -- -- -- -- -- -- -- -- -- 70.5 pH, Soln. 1
7.9 7.9 5.0 5.0 3.5 5.0 7.9 7.9 7.9 7.9 1-5.7
__________________________________________________________________________
Time in Soln. 1, min. 30 30 15 30 30 15 30 30 30 30 5
__________________________________________________________________________
Solution 2 NaBO.sub.3.sup.. 4H.sub.2 O 3 -- 0.5 -- -- -- -- -- --
-- -- H.sub.2 O + 1N.sup.2 HCl 97 -- -- -- -- -- -- -- -- -- --
NaBO.sub.3 saturated soln. -- 100 -- 100 100 -- 100 100 100 100 --
H.sub.2 O -- -- 99.5 -- -- 99 -- -- -- -- 99.6
__________________________________________________________________________
KMnO.sub.4 -- -- -- -- -- -- -- -- -- -- 0.4 HsIO.sub.6 -- -- -- --
-- 1 -- -- -- -- -- pH, Soln. 2 5.0 7.2 10.1 10.1 10.1 2.0 7.4
7.6-7.8 8.0-8.2 9.0-10.5 10.5 Time in soln. 2, min 10 10 10 5 5 5
10 10 10 10 35
__________________________________________________________________________
Color Blond Med. Lt. Med. Red- Red Lt Med. Dark Very Black Blond
Brown Brown dish Brown Brown Brown Dark Blond Brown
__________________________________________________________________________
EXAMPLE XVII
A solution was prepared containing, weight percent,
Ingredient Weight % ______________________________________
MnSO.sub.4.sup.. H.sub.2 O 1.6 NH.sub.4 NO.sub.3 7.0 K.sub.2
S.sub.2 O.sub.8 10.6 ammonium lauryl sulfate (28-30%) 13.3 NH.sub.4
OH (28-30%) 2.5 water 65.0
______________________________________
It had a pH of about 9.0. The solution was immediately applied to
bleached human hair for 60 minutes at room temperature, following
which the hair was washed with a commercial shampoo and dried. It
had a warm black color.
EXAMPLE XVIII
Hair dyed in accordance with Example XVI was treated with a 1.0
percent aqueous solution of sodium metabisulfite (Na.sub.2 S.sub.2
O.sub.5) for 5 minutes at room temperature and pH 4.4 and then
rinsed with water. The hair samples had the bleached color which
they showed before dyeing.
EXAMPLE XIX
Hair dyed in accordance with Example VI was treated with an aqueous
solution of sodium metabisulfite at room temperature and pH 4.4 for
5 minutes. Again the hair was restored to its original color.
EXAMPLE XX
A solution was prepared having the following composition:
Ingredient Weight % ______________________________________ 1.
Thiourea 8.0 2. Lactic acid 16.0 3. Sodium lauryl sulfate (28-30%)
50.0 4. Water 26.0 100.0 ______________________________________
Hair dyed according to Examples VI, XI and XVI were treated with
the above solution for 5 minutes (15 min. for Example XI) at pH
2.5. The color was completely removed in each case.
EXAMPLE XXI
Human hair was treated with a 10 percent solution of nickel acetate
(alkalized to pH 9.8 with 28% NH.sub.4 OH) at room temperature for
50 minutes. It was then rinsed with water and treated for 10
minutes with a 10 percent sodium dithionite solution at pH 5.7. A
black color resulted from the precipitation of nickel sulfide in
the hair. If the pH of the nickel solution is left at 918 and that
of the dithionite is increased to 9.0 a medium brown is obtained.
Varying the pH of the nickel in either direction also gives a
brown.
Hair treated in accordance with this example was then treated with
the thiourea solution of Example XX for 15 minutes at room
temperature, with complete removal of color. The same result was
obtained in 3 min. at 40.degree.C.
The foregoing examples illustrate that in accordance with the
invention hair may be dyed with a wide range of permanent colors,
and these colors, as well as colors more conventionally obtained,
may be readily removed with simple and inexpensive reagents.
In the examples in which the color is formed by the oxidation of a
manganous salt, the color is understood to be due to the formation
of manganese dioxide. Similarly where cobaltous or ferrous salts
are oxidized the color apparently results from the formation of one
or more oxides in which the metal, or some of it, has a valence
greater than two.
In all the examples, except where otherwise specified, the
treatments were carried out at approximately room temperature
(20.degree.C.), though the temperatures of the solutions themselves
may have been somewhat greater in certain cases due to heat of
reaction.
The hair treated in the examples, unless otherwise specified, had
been bleached with H.sub.2 O.sub.2 to remove natural color, before
dyeing.
* * * * *