Oxidizing mixtures for hair care use

By combining an aqueous chlorite solution with an organic or inorganic buffer salt and a divalent metal ion, a stable aqueous chlorite solution is attained for use in substantially improving the durability and resulting visual appearance of permanently waved hair. In addition, the present invention is equally effective as a post treatment for freshly permanently waved hair or as the oxidizer in the permanent waving process. Furthermore, this aqueous chlorite solution can be intermixed with conventional oxidizers to attain the desirable beneficial results.

TECHNICAL FIELD 
This invention relates to permanent waving compositions and, more 
particularly, to novel oxidizing mixtures used in conjunction with 
permanent waving compositions for imparting a permanent wave to the hair. 
BACKGROUND ART 
It is well known that hair is composed of a unique protein material called 
"keratin", which is distinguished by the fact that it contains a very 
significant amount of an amino acid (cystine) which contains the element 
sulfur in addition to the elements nitrogen, oxygen, carbon and hydrogen. 
In the natural synthesis of hair, the element sulfur covalently links 
intra or inter polypeptide chains (K) through two sulfur atoms (S--S) to 
give keratin protein (K--S--S--K). Only by chemical action can this 
covalent linkage be broken. 
In this regard, many prior art compositions have been developed for the 
"cold permanent waving" of hair. Typically, these prior art systems treat 
the hair with a reducing agent which breaks the disulfide (cystine) 
linkage in the hair while the hair is wound around a curling rod. 
In general, permanent hair waving is usually carried out by subjecting the 
hair to reagents containing a free--SH group or thiol. These materials are 
also called mercaptans. In this treatment, the hair usually is either 
wrapped on the rods with water or the lotion containing the thiol, and 
then saturated with thiol lotion. The thiol waving agent acts to break the 
disulfide bonds within the hair fiber forming thiol groups in the hair 
protein and disulfide bonds between two thiol waving agent molecules. The 
chemistry involved in the reaction of the mercaptan with the cystine 
disulfide bonds in the hair fiber is illustrated by the following chemical 
equations: 
EQU KSSK+2KSH.div.2KSH+RSSR 
EQU KSSK+2RSH.div.KSR+KSH 
When a sufficient number of hair disulfide bonds have been broken, the hair 
is realigned to pair previously unpaired hair protein thiol groups 
opposite each other. At this point, the hair is rinsed, removing the 
unreacted thiol waving agent and disulfide reaction product formed from 
it. Then, the hair is saturated with an oxidizing agent, or neutralizer, 
such as hydrogen peroxide or bromate salt, to reform disulfide bonds 
between the newly paired hair protein thiols, thereby giving the hair a 
new configuration or wave, or adding curl to the hair. By rebonding the 
sites of the reduced keratin in their new curled configuration, a 
permanent set which is impervious to water is established. 
Much of the rebonding of the reduced sites is accomplished by the action of 
the chemical oxidizing agent, which is typically hydrogen peroxide and can 
be illustrated by the following chemical reaction: 
EQU 2 KSH+H.sub.2 O.sub.2 .fwdarw.KSSK+2H.sub.2 O. 
In the art of permanent waving, there is much trial and error, with the 
hair being over-processed, in some instances. The characteristics of 
over-processing are raspy feel to the hair or a bleaching of the natural 
underlying color. Structural evaluation of the hair fiber by 
instrumentation usually reveals that the structural integrity of the hair 
is lessened, which is evidenced by either an increase in the amount of 
cysteine and cystic acid or a lessening of the cystine content relative to 
the hair not so processed. 
Some detrimental effect to hair fiber is unavoidable, as the process of 
permanent waving involves controlled bond scission of the disulfide 
linkages within the keratin proteins. Recovery of these disulfides is the 
determining factor for the tightness of the curls and overall tensile 
strength. 
For these reasons, improved oxidizing agents or neutralizers which might be 
more efficient in reforming the disulfide bonds is constantly being 
sought. The typical oxidizing agents used in the art of hair care are 
hydrogen peroxide and the alkali metal and ammoniated salts of bromate, 
persulfate and carbonates. However, these conventional oxidizing agents 
typically exhibit such disadvantages as the bleaching of the hair, skin 
irritation and instability in solution. 
In an attempt to eliminate these prior art difficulties and drawbacks 
typically encountered with the oxidizing or neutralizing agents, attention 
has been paid to chlorite, chlorite salts, and aqueous solutions of 
chlorite. 
First, these aqueous solutions tend to decompose to the other equilibrium 
species of hypochlorous acid that is, hypochlorite and chlorine dioxide. 
Both of these chemicals damage the cuticle and other components of hair 
with the net result that the hair takes on the appearance of being 
"damaged", e.g., there may be a raspy feel to the hair and even some 
degree of lightening. Second, and of more serious concern, is that both 
hypochlorite and chlorine dioxide can irritate skin more so than either 
hydrogen peroxide, persulfate, or bromate. 
U.S. Pat. No. 3,265,582 teaches that salts: of chlorate and perchlorate are 
capable of oxidizing hair which had been previously relaxed and so 
imparting a wave to the hair. The solutions so described are aqueous. 
German Patent No. 2,039,358 describes the use of chlorates to affect the 
color formation of standard oxidation dyes to color the hair and by doing 
so establishes that variants of hypochlorous acid in the lower oxidation 
states are indeed applicable to the art of hair care. More recently, U.S. 
Pat. No. 4,776,857 introduced the use of perhalosalts, perchlorates 
included, to affect the in-situ condensation of indole derivatives also 
for the exclusive effect of coloring the hair. Unfortunately, there is the 
severe drawback to use of such oxychlorine salts in that they are 
typically unstable in water and must therefore be mixed immediately prior 
to use and more so, the solutions are irritating to skin. 
In U.S. Pat. No. 2,899,965, the use of specifically aqueous chlorite, 
preferably, derived from sodium chlorite as the oxidizing agent in a 
permanent wave solution, is discussed. However, in addition to describing 
the advantages of chlorite, the undesirable features associated with 
chlorite compositions are also fully discussed. In particular, the 
chlorite solutions were used by working through the hair after unwinding 
from the roller followed by rewrapping. Chlorite compositions can explode 
into flames or cause organic materials to spontaneously combust when 
brought in contact with reductants such as thioglycolic acid, especially 
if the combinations were allowed to dry. In an attempt to overcome these 
extremely detrimental properties, which rendered such chlorite 
inapplicable for commercial use, additives such as urea and sodium lactate 
were disclosed. 
It has been demonstrated that aqueous solutions of chlorite can convert 
mercaptans into disulfides, and hence, in the process of permanent waving, 
thereby neutralize a permanent wave solution to impart a wave to hair 
[see, for example, T. Ruemele in Kosmetic; Vol. #23; pp. 695-696; (1957); 
and K. Plouch and D. Dziewonska: Roc. Chemi Ann. Soc. Chim.; Vol. 41; pp. 
1285-1289; (1967)]. In Kosmetic, the use of aqueous sodium chlorite is 
discussed for permanent waving. In that discussion, the concentration of 
chlorite, which was generated in-situ, is estimated at 4% to 10%. However, 
these earlier experiments suggested that there were several problems 
associated with the use of this material in purely aqueous media. 
In U.S. Pat. No. 2,780,579, the use of chlorite in association with 
ascorbic acid to produce dehydroasorbic acid using sodium chlorite as well 
as other conventional oxidizing compounds is provided. 
Although substantial effort has been expended in developing commercially 
employable oxidizing mixtures or neutralizers, it is clearly apparent that 
prior art systems have failed to develop a chlorite based oxidizing 
mixture which is easy to produce, store and use. Typically, the prior art 
problems detailed in the patents identified above have continued and have 
been incapable of being eliminated, prior to the present invention. 
Therefore, it is a principal object of the present invention to provide a 
chlorite based solution which attains the advantages well known for 
chlorite solutions, without experiencing any of the difficulties and 
drawbacks previously encountered with chlorite solutions. 
Another object of the present invention is to provide a chlorite based 
solution having the characteristic features described above which can be 
formulated inexpensively and used widely without any detrimental effects. 
Another object of the present invention is to provide a chlorite based 
solution having the characteristic features described above which can be 
employed as a neutralizer or an oxidizer in the permanent waving of hair. 
Another object of the present invention is to provide a chlorite based 
solution having the characteristic features described above which can be 
used as an additive to commercially available oxidizers or neutralizers. 
A further object of the present invention is to provide a chlorite based 
solution having the characteristic features described above which can be 
employed as a post treatment for permanently waved hair. 
Other and more specific objects will in part be obvious and will in part 
appear hereinafter.

DETAILED DESCRIPTION 
In order to overcome the prior art difficulties and drawbacks previously 
encountered with employing chlorite as the oxidizing mixture or 
neutralizer in a permanent waving procedure, it has been found that an 
aqueous solution of chlorite can be successfully stabilized by combining 
therewith a divalent metal ion and an organic or inorganic buffer salt. 
In the preferred embodiment, the chlorite comprises an alkali metal, 
ammonium, or organo ammonium chlorite salt, with sodium chlorite being 
preferred. In addition, the buffer salts comprise the alkali metal salts 
of citric acid, tartaric acid, ethylene tetra-acetoxylamine or 
acetylacetone. Finally, the divalent metal ion preferably comprises one 
selected from the group consisting of zinc, copper, magnesium, and 
manganese. 
In order to obtain a stable solution, it has been found that the aqueous 
chlorite solution of the present invention preferably comprises between 
about 0.001% and 10.0% by weight of the divalent metal ion, between about 
0.01% and 20.0% by weight of the organic or inorganic buffer salt, and 
between about 0.001% and 8.0% by weight of the alkali metal, ammonium or 
organo ammonium chlorite salt. More particularly, it has been found that a 
stable aqueous chlorite solution is obtained by employing between about 
0.4% and 6.0% by weight of sodium chlorite, between about 1.2% and 12.0% 
by weight of the divalent metal ion, and between about 1.2% and 12.0% by 
weight of the organic or inorganic buffer salt. The resulting composition 
is preferably diluted in water at a ratio ranging between 1 and 30. 
In the preferred formulations, sodium chlorite is employed as the chlorite 
salt and tribasic sodium citrate is preferably employed as the buffer 
salt. In addition, the divalent metal ion is provided by incorporating at 
least one water soluble salt of a divalent metal ion selected from the 
group consisting of magnesium sulfate, magnesium chloride, copper sulfate, 
copper chloride, magnesium chloride hexahydrate, zinc chloride hydrate, 
zinc sulfate, and zinc chloride. 
It has also been found that the chlorite composition of the present 
invention has a half-wave oxidation potential of 0.65 eV whereas the 
chemicals typically used in the prior art, eg. bromates and hydrogen 
peroxide possess half wave-oxidation potentials above 1.2 eV. While this 
phenomenon cannot be directly correlated with specific reactivity to only 
those components within the hair that are reformed during the so-called 
neutralization step, it has been found that the recovery of disulfide 
structures in the hair is vastly better than the recovery typically 
achieved when hydrogen peroxide is employed; examples are detailed below. 
Furthermore, by employing the chlorite solution of the present invention, a 
stable, aqueous oxidizing mixture is attained which can be maintained at a 
neutral pH range by the use of the desired buffers either alone, or in 
combination, with materials such as ascorbic acid or bromate, typically 
employed in various hair care applications. The resulting solutions remain 
exceptionally stable and perform exceptionally well as the oxidizing 
mixture or neutralizer. 
In the compositions employing ascorbic acid, it has been found that the 
chlorite composition transforms the ascorbic acid to dehydroascorbic acid 
which then acts as the oxidizing component. Although U.S. Pat. No. 
2,780,597, discussed above, reveals the reaction of hydrogen peroxide 
with ascorbic acid to get dehydroascorbic acid for use as a permanent 
waving neutralizer, various disadvantages have been realized in using 
hydrogen peroxide to oxidize the ascorbic acid. In particular, the 
ascorbic acid solid must be added to the peroxide solution and then mixed 
thoroughly prior to use and, even then, conversion to dehydroascorbic acid 
by the hydrogen peroxide has been found to be only moderately efficient. 
However, by employing the chlorite solutions of the present invention, 
essentially 100% conversion of ascorbic acid to its dehydro form is 
realized. 
By employing the aqueous chlorite solution of the present invention, stable 
solutions are obtained which perform excellently as oxidants in the 
practice of permanently waving hair. Furthermore, if desired, these 
mixtures can be admixed with carbohydrates to affect a highly durable, 
reconstruction of the hair after contact with the usual mercaptan species, 
employed for hair relaxation. In this way, a highly effective and 
substantially improved permanent wave composition is attained. 
BEST MODE FOR CARRYING OUT THE INVENTION 
In order to substantiate the versatility of the present invention, the 
following examples are presented detailing the various aspects of this 
invention and the ability for chlorite solutions of the present invention 
to be employed in the art of hair cosmetics, in general, and in the art of 
permanent waving, in particular. These examples are intended as a teaching 
of the best mode for carrying out the present invention and are not 
intended to limit, in any manner, the breadth of this discovery. 
Chlorite Solutions as a Post Treatment 
We have found that by employing the chlorite solutions of the present 
invention to freshly permanent waved hair, substantially improved curl 
retention is realized. As detailed in the following illustrative examples, 
a longer lasting, tighter curl was attained when the chlorite containing 
solutions of the present invention were employed as a post permanent 
waving treatment. 
In order to prove the curl retaining efficacy of the present invention, a 
tress of brown hair of approximately 0.1 to 3 grams with a total length of 
15 centimeters was wetted with water and wrapped about a small plastic 
permanent wave rod. The hair was then thoroughly wetted with a typical 
permanent wave reducing solution, such as detailed in Table I. 
TABLE I 
______________________________________ 
Glycerol-monothioglycolate 
280 g 
(5% solution) 
Ammonium hydroxide 40 g 
Diammonium-dithiodiglycolate 
30 g 
Water 850 g 
______________________________________ 
The hair was then placed in a plastic wrapper and warmed to 50.degree. C. 
for twenty minutes, followed by copious rinsing with tap water. Next, the 
wrapped hair was wetted with 2% H.sub.2 O.sub.2 at pH 4, the pH being 
obtained by the additional phosphoric acid to a solution of 50% H.sub.2 
O.sub.2 suitably diluted with deionized water. After a period of five 
minutes, the hair was then wetted with the chlorite solution "A" detailed 
in Table II. 
TABLE II 
______________________________________ 
Solutions 
Ingredients (grams) 
A B C D E 
______________________________________ 
Sodium Chlorite 4 4 4 5 5 
Tribasic Sodium Citrate 
18 18 18 18 18 
Magnesium Chloride 
7 
Magnesium Sulfate 7 
Zinc Chloride Hydrate 7 
Copper Sulfate 6 
Magnesium Chloride Hydrate 6 
Urea 50 
Hydroxyethyl Cellulose 1 
Water 1,000 1,000 1,000 
1,000 
1,000 
______________________________________ 
After thorough rinsing, the hair was free of the typical odor associated 
with the thio component of the permanent wave solution. In addition, after 
drying and subsequent shampooing, the hair had a fresh odor. 
The resulting curl was compared to an identically curled hair sample which 
had not been post treated with the chlorite solution of this invention. It 
was found that the curl having the chlorite solution post treatment was 
tighter and was retained for a substantially longer time period as 
detailed below. 
After six separate cycles of hand shampooing, rinsing and air drying, the 
permanent waved hair that was post treated with solution "A" of Table II 
retained its degree of curl longer than the hair sample which did not have 
the post treatment. 
In order to further corroborate the efficacy of the present invention, 
chlorite solutions "B", "C", "D" and "E" detailed in Table II were 
individually prepared and applied to a brown hair sample as detailed above 
in reference to solution "A". All of the steps detailed above were carried 
out equally for each of these other solutions and compared to the hair 
sample to which no post treatment application was made. 
In each of the samples treated with one of the chlorite solutions detailed 
in Table II, substantially improved curl retention was attained, even 
after six separate cycles of hand shampooing, rinsing, and air drying. As 
was clearly evident from the results observed, each of the chlorite 
solutions of this invention substantially improve the appearance, 
permanence and durability of permanently waved hair. 
In preparing each of the solutions detailed in Table II, it was found to be 
most expeditious to prepare the stable chlorite solution by adding 18 grams 
of the tribasic sodium citrate to one liter of deionized water and stirring 
until completely dissolved. Then, the appropriate amount of the desired 
metal ion salt is added in order to form the particular solution desired. 
Finally, the desired amount of sodium chlorite is added, resulting in a 
clear solution. In addition, it was also found that all the solutions 
detailed in Table II remained stable over several months at temperatures 
ranging between 0.degree. and 60.degree. C. 
It is interesting to note that prior art patents, such as U.S. Pat. No. 
4,861,514, teach that chlorite compositions may be thickened with various 
cellulose derived gels or gums in order to intentionally form chlorine 
dioxide. However, we have found that the addition of the metal ion salt 
effectively prevents the formation of the chlorine dioxide. 
The discovery of the present invention enables stable chlorite solutions to 
be formed while also incorporating between about 0.001% and 10% xanthan gum 
or gelatin derived thickeners. Suitable gelatin derived thickeners include 
hydroxyethyl cellulose material, and hydroxypropyl methyl cellulose. 
In Table III, the stability of various alternate solutions formed using the 
present invention is shown. Each of the entries in Table III was prepared 
and diluted 100 to 1 with water. Then, each solution was individually 
measured for its optical density at 357 mm using a commercial 
ultra-violet, visible spectrophotometer. The wave length selected 
corresponds to the absorption maximum for chlorine dioxide. Therefore, low 
optical densities at this wave length reflect the stability of the 
solution, corresponding to the prevention of the formation of chlorine 
dioxide and the presence of chlorite. 
TABLE III 
______________________________________ 
Example 
Composition pH T = 60 Min. 
T = 24 Hrs. 
______________________________________ 
1 0.5% NaClO.sub.2 
11 0.123 0.121 
2 1.8% Citrate 
8 0.096 0.096 
0.6% MgCl.sub.2 
0.5% NaClO.sub.2 
5.0% Urea 
3 Example 2 plus 
8 0.105 0.105 
0.8% 
hydroxyethyl 
cellulose 
4 Example 2 plus 
8 0.082 0.105 
0.5% Xanthan 
5 1.8% Citrate 
5.5 0.022 0.026 
0.5% NaClO.sub.2 
0.8% ZnCl.sub.2 
______________________________________ 
It has also been discovered that by employing any one of the solutions 
detailed in Table II, the tensile properties of the treated hair is 
substantially increased over the tensile properties resulting from the 
test sample having no post treatment. In order to effectively measure the 
tensile strength of the hair, an Instron Apparatus Model 1120 was used 
with each of the samples detailed above and the resistance forces for each 
of the hair fibers was determined at 20% elongation under aqueous immersion 
conditions. The results attained from this elongation test are shown in 
Table IV. 
TABLE IV 
______________________________________ 
Post Treatment Force Ratio for 
M/mg Cysteine 
Composition 20% Elongation 
Hair 
______________________________________ 
No post treatment 
0.786 561.6 
Solution A of Table II 
0.869 653.4 
Solution B of Table II 
0.885 874.0 
Solution C of Table II 
0.900 819.2 
______________________________________ 
In Table IV, the values presented represent the initial reading (prior to 
treatment) minus the final reading (after treatment) divided by the 
initial reading. As a result, values closest to 1.000 indicate stronger 
relative tensile properties. 
It has also been found that hair treated with the chlorite solution of the 
present invention also has the specific amino acids content which reflects 
less damage having been done to the hair. Typically, the term "less damage" 
is used to reflect the amount of cystic acid present after cosmetic 
treatments, as this amino acid arises from the destruction within the 
keratin of the disulfides, primarily formed by cystine. The application of 
oxidated agents to the hair following the relaxation process (chemical 
reduction) does not always result in the reforming of the disulfide bond, 
leading instead to hair fibers with markedly reduced structural integrity. 
The hair under these circumstances is such that the surface feels rough and 
weakened, as shown in Table IV. 
It has been found that by employing the chlorite solution of the present 
invention as a post treatment, this damage is substantially reduced. In 
Table IV, the results achieved by employing the chlorite solution of this 
invention is shown with the substantially reduced damage being represented 
as the ratio of the value of the cysteine to the cystine. In the data 
provided, a value of 1,000 indicates no damage has been caused. 
Consequently, the closer the resulting value is to 1,000, the less was the 
oxidating damage to the hair. As clearly shown in Table IV, the hair fibers 
having the post treatment application of the chlorite solution of this 
invention have attained a ratio substantially closer to 1,000 than is the 
value attained for the hair fibers which were untreated with a chlorite 
solution. 
Chlorite Solution as a Neutralizer 
In addition to employing the chlorite solution of the present invention as 
a post treatment, it has also been found that the chlorite solutions can 
be employed either individually as the neutralizer or in combination with 
conventional neutralizers presently being employed in permanently waving 
hair. In order to prove the efficacy of the present invention, various 
samples of brown, blended gray and white hair were permanently waved. Each 
sample comprised a tress of hair of approximately 0.1 to 3 grams having an 
overall length of 15 centimeters. The hair samples were relaxed using 
conventional permanent waving solutions incorporating either an ammonium 
thioglycolate, a glyceryl monothioglycolate or a monoethanolamine 
thioglycolate. To confirm these results, permanent waving formulations, as 
shown in Table V, were found to provide excellent results at imparting hair 
relaxation. 
TABLE V 
______________________________________ 
Alkaline Permanent Wave Composition 
Ammonium Thioglycolate (100%) 
15% 
Detergent as required 
Fragrance as required 
Ammonium Hydroxide 5.0% 
Water deionized q.s. to 100% 
Acid Permanent Wave Composition 
Glyceryl Monothioglycolate (100%) 
15% 
Ammonium Hydroxide 5% 
Detergent as required 
Fragrance as required 
Water deionized q.s. to 100% 
______________________________________ 
After the application of the permanent wave solution, the hair samples were 
rinsed with tap water, followed by the application of the desired 
neutralizer. For purposes of comparison, some of the samples were treated 
with a conventional neutralizer composition containing hydrogen peroxide, 
such as Zotos International's Vitoxide, and with a neutralizer composition 
comprising sodium bromate, such as Zotos International's Design Freedom 
Bromate Neutralizer. With these samples serving as the control, other 
samples were treated with either the chlorite solutions defined in Table 
II as the neutralizer, the chlorite solutions of Table II in combination 
with ascorbic acid, or the chlorite solutions in combination with hydrogen 
peroxide or sodium bromate. 
The results of these tests are detailed in Table VI, wherein the 
effectiveness of each neutralizing solution was evaluated after the hair 
fibers were permanently waved, as well as after six hand shampooings, 24 
hour exposure to 100% humidity, and 10 hours of exposure to artificial 
sunlight. For the purpose of this comparative study, most of the results 
are given as the curl resiliency or total degree of curl which is defined 
by the following equation: 
##EQU1## 
where H.sub.L is the total hair length d is the distance from the root of 
the first curl, and 
n is the total number of curls 
For this comparison, all of the determinations were made while the hair 
fibers were in the water wetted state. 
In regard to determining the total change in hair color after ten hours 
exposure to artificial sunlight, these tests were conducted by employing a 
Weather-O-Meter Instrument Model 620. The results shown in Table VI, 
represent the change or the difference in light intensity of reflection of 
the hair between the initial reading and the final reading. In such 
measurements, a "+" indicates hair lightening, and a "-" indicates hair 
darkening. The data was determined using a Spectroguard Model 662. 
In all of the test results provided in Table VI, the value presented 
represents the average obtained from numerous test samples conducted under 
the particular test conditions. 
TABLE VI 
______________________________________ 
Neutralizer 
Chlorite- 
Permanent Wave Ascorbic 
Composition H.sub.2 O.sub.2 
BrO.sub.3 
Chlorite 
Acid 
______________________________________ 
A. Degree of Curl - Brown Hair Permanently Waved 
Glycerolmonothioglycolate 
1.65 3.1 2.4 1.9 
Thioglycolic Acid 
1.8 3.0 2.7 2.3 
Monoethanolamine 
3.2 2.6 1.9 2.6 
Thioglycolate 
B. Degree of Curl - After 24 Hours at 100% Humidity 
Glycerolmonothioglycolate 
2.1 2.7 1.9 2.2 
Thioglycolic Acid 
2.2 2.8 2.1 2.0 
Monoethanolamine 
2.7 2.4 2.0 2.2 
Thioglycolate 
C. Degree of Curl - After 6 Hand Shampooings 
Glycerolmonothioglycolate 
1.9 1.8 1.95 
Thioglycolic Acid 
2.1 1.9 1.8 
Monoethanolamine 
2.2 1.8 1.97 -- 
Thioglycolate 
D. Change in Hair Color - Exposure to Artificial Sunlight 
Glycerolmonothioglycolate 
+0.03 0.00 -0.02 
Thioglycolic Acid 
+0.02 -0.03 0.00 
Thioglycolic Acid 
+0.03 -0.01 -0.01 
Dithiodiammonium 
Thioglycolate 
______________________________________ 
As is apparent from the foregoing test results, the chlorite solutions of 
the present invention, when employed as a neutralizer, provides results at 
least as good as or better than typical neutralizers presently being 
employed in the permanent waving of hair. In addition, the chlorite 
solutions of the present invention are equally effective either 
independently or in combination with ascorbic acid. 
In Table VII, the tensile strength is given for brown hair relaxed with 14% 
aqueous glycerol monothioglycolate at pH 8, followed by neutralization with 
the particular oxidant composition defined. As with one of the previous 
tables, the tensile strength is determined by finding the force needed to 
elongate the hair fiber by 20% before treatment, subtracting from this 
value the 20% elongation value resulting after treatment and dividing the 
remainder by the initial value. As a result, values nearest to 1.000 
indicate stronger relative tensile properties. 
TABLE VII 
______________________________________ 
Relative Force at 20% 
Test Neutralizer Elongation 
______________________________________ 
1 2% H.sub.2 O.sub.2 
0.805 
2 0.6% ClO.sub.2 0.885 
1.8% Citrate 
0.8% MgCl.sub.2 
3 0.6% ClO.sub.2 0.862 
1.8 Citrate 
0.8% MgCl.sub.2 
2.0% Ascorbic Acid 
4 10% BrO.sub.3 0.785 
5 1:1 ratio of 2% H.sub.2 O.sub.2 and 
0.857 
solution in test 2 
6 1:1 ratio of 10% BrO.sub.3 and 
0.825 
solution in test 2 
______________________________________ 
In order to provide a chlorite solution incorporating ascorbic acid, 100 
milliliters of any of the solutions defined in Table II is combined with 2 
grams of ascorbic acid for dissolution therein. In this simple, 
straight-forward manner, an effective combination of the chlorite solution 
and ascorbic acid is attained. 
If desired, the following alternative process can be employed in order to 
attain a combined ascorbic acid-chlorite solution incorporating hair 
conditioners to further condition the hair during the neutralization step 
of the process. In this formulation, 2 grams of ascorbic acid are 
dissolved in a separate container in 4 to 25 grams of propylene or 
ethylene glycol containing between 0.01 and 3 grams of water. In addition, 
between about 0.001% and 2% of conditioners are added to the solution. 
Although various conditioners can be employed, the preferred conditioners 
include ascorbyl palmitate, alkyldimethylsiloxanes, cyclomethicones, and 
dimethicone copolyols. 
The resulting mixture is then added to any of the chlorite solutions 
defined in Table II at a dilution of one part of the ascorbic acid mixture 
to between about 30 to 100 parts of the chlorite solution. The resulting 
mixture is then shaken until thoroughly mixed prior to application to the 
hair. 
As is particularly apparent from the results provided in Table VII, the 
commonly used neutralizer, sodium bromate, may also be mixed with the 
chlorite containing solutions of the present invention to effect the 
neutralization step in a permanent waving process. By employing this 
combination, it has been found that not only did the hair develop a 
durable curl, equal to that observed with the bromate alone, but the 
resulting curl was more durable to such cosmetic after treatments as 
shampooing and combing. It was also observed that the mal-odor associated 
with using monoethanolamine thioglycolate was effectively eliminated. 
One formulation for attaining a bromate and chlorite solution in accordance 
with this invention is to dissolve between about 4 and 24 g of an alkali 
metal, an ammonium, or phosphonium salt of bromate in water or water and 
an alcohol having a carbon length of between C.sub.2 and C.sub.10 and a 
hydroxylic content of between 1 and 15. Additionally, it is desirable to 
also mix urea into the solution at sufficient concentration to maintain a 
bromate:urea ratio of between 0.5 and 2. Finally, any one of the chlorite 
solutions detailed in Table II is mixed therewith at a volume to volume 
ratio of between 0.5 and 2, immediately prior to use. 
Concentrated Chlorite Solutions and Buffering Mediums 
Depending upon the final concentration, a 0.1% to 20% by weight solution of 
sodium chlorite has a pH ranging between 9.9 and 11.2. When kept free from 
oxygen and light, the solutions are moderately stable, however, the high 
degree of alkalanity could be deleterious to the hair. In addition, when 
attempts have been made to lower the pH of the solution, so as to be more 
equivalent to the pH commonly employed with both peroxide and bromate 
containing neutralizing compositions, the immediate degradation of the 
chlorite to chlorine and chlorine dioxide gases was found to occur. 
However, it has now been found that solutions of sodium chlorite can be 
maintained independently in an amber, opaque, or completely pigmented 
bottle for extended time periods with complete stability provided the 
concentration of sodium chlorite ranges between 0.01% and 20% by weight. 
When needed for application to the hair, these solutions can be mixed 
immediately prior to use with the remaining components defined in Table II 
in order to attain the previously described stable 
chlorite/citrate/divalent metal ion composition of the present invention 
for use at a pH of 4.5 to 7.5. In this way, long term, safe storage of the 
chlorite solutions of this invention are assured and a highly effective 
hair application is realized. 
In Table VIII, Table IX and Table X, three alternate formulations are 
provided for attaining a stable, two-part, sodium chlorite composition 
which can be maintained for extended time periods and intermixed prior to 
use to attain the desired sodium chlorite solution for use in accordance 
with the present invention. 
TABLE VIII 
______________________________________ 
% (By Weight) 
______________________________________ 
Part A 
Sodium Citrate 6.0% 
Zinc Chloride 2.0% 
Urea 2.0% 
Cellulose Gum 0.2% 
Water q.s. to 100% 
Part B 
Sodium Chlorite (5% solution) 
1.0% 
______________________________________ 
TABLE IX 
______________________________________ 
% (By Weight) 
______________________________________ 
Part A 
Sodium Citrate 6.0% 
Zinc Chloride 2.0% 
Magnesium Chloride 1.0% 
Urea 2.0% 
Cellulose Gum 0.2% 
Water q.s. to 100% 
Part B 
Sodium Chlorite (20% solution) 
4.0% 
______________________________________ 
TABLE X 
______________________________________ 
% (By Weight) 
______________________________________ 
Part A 
Sodium Citrate 6.0% 
Magnesium Citrate 3.0% 
Zinc Chloride 2.0% 
Urea 2.0% 
Cellulose Gum 0.2% 
Water q.s. to 100% 
Part B 
Sodium Chlorite (10% solution) 
24.0% 
______________________________________ 
It will thus be seen that the objects set forth above, among those made 
apparent from the preceding description are efficiently attained and, 
since certain changes may be made in carrying out the above process and in 
the composition set forth without departing from the scope of the 
invention, it is intended that all matter contained in the above 
description shall be interpreted as illustrative and not in a limiting 
sense. 
It is also to be understood that the following claims are intended to cover 
all of the generic and specific features of the invention herein described 
and all statements of the scope of the invention which, as a matter of 
language, might be said to fall therebetween. 
Particularly, it is to be understood that in said claims, ingredients or 
compounds recited in the singular and intended to include compatible 
mixtures of such ingredients wherever the sense permits.