Product for improved permanent waving of hair and simultaneously coloring and permanently waving hair and method therefor

By combining a fluoroscein-based dye with a mercaptan based permanent waving composition and maintaining the pH of the resulting composition between about 2.5 and 4.5, a composition is achieved which simultaneously colors and permanently waves the hair. In addition, even if no coloring or dyeing of the hair is desired, the use of a colorless or complimentary fluoroscein-based dye with the mercaptan based permanent waving composition achieves a composition which imparts a substantially improved curl configuration to the hair as well as substantially longer lasting curls. Preferably, the mercaptan based permanent waving composition employed comprises an ester of either thioglycolic acid, thiolactic acid, or the amide of 2-aminoethanethiol.

TECHNICAL FIELD 
This invention relates to products for permanently waving hair and, more 
particularly, to products for permanently waving hair with substantially 
improved curl retention and, if desired simultaneously coloring the hair. 
BACKGROUND ART 
In view of the unique composition of hair fibers and the numerous changes 
that occur in styles and fashion, both the waving of hair and the dyeing 
of hair have long been of particular interest. In particular, hair color 
alteration by dyeing while permanent waving hair for long-lasting style 
retention have long been sought by many individuals. However, due to the 
composition of hair fiber, either the color or curls are not retained as 
long as desired and the simultaneous permanent waving and dyeing of hair 
fibers has not yet been achieved by any commercially available product. 
In order to best understand the reasons for the inability of the hair fiber 
to retain curls for substantially long time periods or to be 
simultaneously permanently waved and colored, it is important to 
understand that hair is composed of a unique protein material called 
"keratin" and 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. This chemical process typically follows that after 
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--thiol group e.g., --SH. 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+2RSH.revreaction.2KSH+RSSR 
EQU KSSK+RSH.revreaction.KSSR+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 any water soluble disulfide reaction 
products 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, typically hydrogen peroxide, and can be 
illustrated by the following chemical reaction: 
EQU 2 KSH+H.sub.2 O.sub.2 .fwdarw.KSK+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 physical and 
chemical analyses 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; a lessening of the cystine content relative 
to the hair not so processed; or loss of tensile properties. 
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. The recovery of these disulfides is 
the determining factor for the tightness of the curls and overall tensile 
strength. 
One problem typically encountered with the use of mercaptan reducing agents 
for the permanent waving of hair is that one lotion strength is needed for 
virgin hair, while a different lotion strength is needed for damaged or 
hair that had been previously chemically processed and, hence, difficult 
to wave. This problem is further compounded when there is a mixture of 
both damaged as well as normal hair fibers on a head of hair to be 
permanently waved. In particular, with either oxidatively or deposit 
colored dyed hair, the subsequent application of mercaptan reducing agents 
causes a discoloring of the imparted dye in the hair fiber, thereby 
leaving the hair with an undesired or different shade than had previously 
existed before the process. 
Another problem typically found in the prior art occurs when an individual 
wishes to dye hair which had been permanently waved. In these 
circumstances, the dye uptake will usually be uneven from the root to the 
tip of the hair fibers due to the structural alteration caused to the hair 
fiber by the permanent wave process. 
In practice, this problem is often circumvented by waiting for the hair to 
"heal", by allowing for a substantial time interval in which aerial 
oxidation reseals the excessively damaged areas, thereby providing hair 
fibers which are more amenable to dye uptake in a level manner. 
Although the consumer has long sought to have a composition and process 
which would enable both color and permanent waving to be achieved 
simultaneously, no prior art system has been able to provide an effective 
or reliable composition which would enable simultaneous dyeing and 
permanent waving of hair fibers. In fact, even though this need has 
existed in the art for decades, no successful commercial product has been 
attained which satisfies the consumers' need. 
One of the difficulties encountered in providing a prior art composition 
which will achieve this simultaneous dyeing and permanent waving of hair 
fibers is due to the chemical nature of typical prior art dyestuffs. In 
general, oxidative dyestuffs are irreversibly altered in their color upon 
contacting sulfurous materials, such as found in the permanent wave 
compositions. Consequently, oxidative dyestuffs cannot be successfully 
employed with permanent waving compositions. 
Alternatively, semi-permanent dyestuffs may be employed and have been used 
to provide a temporary dyeing of the hair. However, such dyestuffs tend to 
be removed from the hair upon washing and rubbing, or by the increased 
porosity of hair resulting from chemical processing. Consequently, their 
incorporation into a permanent waving process does not provide the desired 
consumer result, since they are incapable of providing the permanent hair 
coloring effect desired by the consumer. 
A further problem found with oxidatives or direct dyes is the fact that 
these materials are typically irritants or sensitizers of human skin. 
Consequently, these dyes should be employed either by skilled technicians 
or home users who are extremely careful to apply the dyes explicitly in 
accordance with included directions. 
Although numerous attempts have been made in the prior art to provide a 
combined permanent waving and hair dye product, no prior art product has 
been successful in achieving a universally applicable or a commercially 
acceptable product. 
Representative prior art attempts to meet the commercial demand are found 
in various prior art patents. Those patent includes U.S. Pat. No. 
4,630,621, wherein a common oxidative dyestuff is added to the 
neutralizing composition for subsequent application to the hair after the 
hair has been treated with a permanent wave reducing solution. However, as 
discussed above, such oxidated dyestuffs must be used carefully by skilled 
technicians or individuals who are extremely cautious and careful with the 
dyes, due to the irritation that may result on the skin of the user. 
In U.S. Pat. No. 4,781,724, a process is disclosed for simultaneously 
dyeing and permanently waving white and gray hair. Although this patent 
teaches the incorporation of specific dyestuffs in the permanent wave 
reducing solution, the dyes taught herein are specifically limited to use 
on white and gray hair only. In addition, as will be detailed beloW, the 
operative pH range of the composition incorporating the dyestuffs is 
substantially greater than the operative pH range of the present 
invention. 
Other prior art patents, such as U.S. Pat. No. 3,299,682, U.K. Patent 
1,077,758 and U.S. Pat. No. 4,844,712 teach the use of various dyestuffs. 
However, these patents do not provide any teaching of combining the dye 
with a permanent wave composition for achieving simultaneous hair dyeing 
and permanent waving. 
Furthermore, these prior art patents do not, in any way, teach or suggest a 
permanent waving composition which comprises a pH ranging between 3.0 and 
4.5. In fact, any of these prior art references which discuss permanent 
waving specifically teach away from employing a permanent wave at this 
particular pH range and, instead, teach compositions wherein the pH is 6.0 
or greater. 
Therefore, it is a principal object of the present invention to provide a 
permanent waving composition which is capable of providing substantially 
tighter curls and longer lasting curls than previously attained in prior 
art systems. 
Another object of the present invention is to provide a permanent waving 
composition having the characteristic features described above which is 
also capable of simultaneously dyeing the hair as an integral part of the 
permanent waving process, when desired by the consumer. 
Another object of the present invention is to provide a permanent waving 
composition and process for application thereof having the characteristic 
features described above which is capable of providing optimum results at 
a pH level previously found unsuitable for permanent waving of hair. 
Other and more specific objects will in part be obvious and will in part 
appear hereinafter. 
DISCLOSURE OF THE INVENTION 
By employing the present invention, prior art difficulties and drawbacks 
have been eliminated and tighter, more durable permanent waving results 
are achieved as well as the ability to simultaneously color and 
permanently wave the hair. It has been found that the prior art 
inabilities are completely eliminated by incorporating fluoroscein based 
dyestuffs in a permanent wave composition comprising a mercaptan selected 
from the group consisting of an ester of either thioglycolic acid, 
thiolactic acid, or the amide of 2-aminoethanethiol. Furthermore, the 
resulting composition is maintained at a pH of between about 2.5 and 4.5. 
Depending upon the fluoroscein based dyestuff employed, the hair can be 
simultaneously permanently waved, while also being dyed. If the actual 
dyeing of the hair is not desired, the fluoroscein based dyestuff can 
either be colorless or may employ a complimentary color, which would 
highlight the hair. 
Regardless of whether actual coloring is imparted to the hair fibers, it 
has been found that the combination of a fluoroscein based dyestuff With 
the particular permanent waved composition, when maintained at a pH of 
between about 2.5 and 4.5, provides heretofore unattainable results. In 
particular, the hair is permanently waved with substantially improved curl 
configuration, while also providing curls which are retained for 
substantially longer time periods than ever previously achieved. 
By employing the present invention, it has been found that the hair is 
permanently waved in a tight curl and, when desired, is also colored in a 
level, uniform and controlled fashion. It is believed that the fluoroscein 
based dyestuff acts synergistically in combination with the permanent wave 
solution to promote curl impartation, resulting in substantially improved 
results than ever previously attained. Furthermore, the permanent wave 
composition of this invention operates at a pH of between about 2.5 and 
4.5, a pH range which has typically been incapable of providing acceptable 
results. 
In developing the present invention, it has been found that the fluoroscein 
based dyestuff should comprise only dyestuffs which have been approved by 
the Food and Drug Administration. Consequently, all of the dyestuffs 
employed in the present invention comprise either F,D and C colors 
(suitable for foods, drugs, and cosmetics) or D and C colors (suitable for 
drugs and cosmetics). In addition to employing a fluoroscein based dye, it 
is also required that the permanent wave composition comprise an ester of 
either thioglycolic acid, thiolactic acid, or the amide of 
2-aminoethanethiol. It has been found that only these mercaptans in 
combination with a fluoroscein based dyestuff provides the synergistic 
interaction herein described. 
It has also been discovered that all of the suitable mercaptans in 
accordance with this invention cause the fluoroscein based dyestuff to 
become discolored or colorless when intermixed therewith. In fact, this 
phenomenon has been found to represent a characteristic requisite for a 
composition that is capable of concurrently permanently waving and 
coloring the hair. 
In the preferred composition, the mercaptan comprises an ester of 
thioglycolic acid with the ester being derived from one selected from the 
group consisting of glycerin, glyercol and glycosyl. In addition, it has 
been found that the concentration of the fluoroscein based dyestuff should 
range between 0.0000001 and 8.0% by weight of the total composition, while 
the ester of the thioglycolic acid preferably comprises a concentration 
ranging between 0.0001 and 30% by weight of the total composition. 
The invention accordingly comprises a composition possessing the features, 
proportions, and the relation of constituents, as well as the several 
steps and the relation of one or more of such steps with respect to each 
of the other, all as fully detailed herein, with the scope of the 
invention being indicated in the claims.

BEST MODE FOR CARRYING OUT THE INVENTION 
In order to demonstrate the unique capabilities of the present invention, 
the following examples are provided, detailing various aspects of this 
invention. 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. 
By employing the compositions of this invention, substantially improved 
curl retention and hair strength are attained. In order to show the 
substantial enhancements provided by the present invention, a plurality of 
comparative tests were conducted on hair permanently waved with the 
different compositions formulated in accordance with the present 
invention. The results attained were compared to standard permanent wave 
compositions, in order to demonstrate the efficacy of the present 
invention. In order to provide a useful and instructive comparative 
analysis, various test mixtures were prepared and applied to the hair as 
detailed below. In Table I, the permanent wave composition employed in the 
test mixtures are detailed, while Table II provides the compositions 
employed for the fluoroscein-based dyes and one triphenylmethane based 
dye. 
For purposes of clarity and explanation, the dyes are deatiled using the 
designations adopted by the Cosmetic, Toiletry, and Fragrance Association 
(CTFA), and detailed in the CTFA Cosmetic Ingredient Dictionary, 4th 
Edition, Published 1991. In addition, the color index numbers for each 
specifid dye is also provided. In using the designation F,D & C or D & C, 
it is understood that the designated colors are to be certified according 
to the United States Certification Regulations. 
TABLE I 
______________________________________ 
Permanent Wave Compositions 
______________________________________ 
Part A Glycerine monothioglycolate 70% 
32.5% 
in glycerine 
Part B De-ionized water 98.44% 
Ammonium Chloride 1.50% 
Preservative 0.06% 
Part C Glycerin-thiolactic acid ester 
32.5% 
(in 25% - glycerin) 
Part D De-ionized water 88.5% 
Ammonium chloride 1.5% 
Animal protein, cocohydrolyzed 
1.0% 
potassium salt 
Laureth ether 2.0% 
Fragrance 1.0% 
Polystyrene emulsifier 
2.0% 
Ammonium hydroxide (28%) solution 
4.0% 
______________________________________ 
TABLE II 
______________________________________ 
Part E Propylene glycol 76.8% 
D&C Red No. 21 (CI 45380:2) 
20.0% 
Monoethanolamine 3.2% 
Part F De-ionized water 79.8% 
D&C Red No. 22 (CI 45380) 
20.0% 
Preservative 0.2% 
Part G De-ionized water 94.8% 
D&C Red No. 28 (CI 45410) 
5.0% 
Preservative 0.2% 
Part H De-ionized water 79.8% 
D&C Blue No. 1 (CI 42090) 
20.0% 
Preservative 0.2% 
______________________________________ 
In Table III, each of the compositions tested is clearly presented as a 
separate example, with the test results attained for each test sample also 
provided for ease of comparison. In each of the examples provided in Table 
III, about one gram of medium brown hair was crimped at its end with a 
metal staple and wetted with water. Next, the hair was wrapped about a 
styling rod, secured with a rubber band and then saturated with the 
particular composition mixture detailed in Table III. 
The particular mixture was allowed to remain on the hair for about twenty 
minutes under a plastic wrapper, while being warmed with hot water. At the 
end of the required time period, the hair was rinsed with running tap 
water and then saturated with a solution of 2% hydrogen peroxide 
stabilized with 0.2% phosphoric acid. This composition remained on the 
hair for about five minutes and then the hair was thoroughly rinsed with 
tap water. 
The test results provided in Table III provide the degree of curl found for 
each test sample when the hair was dryed as well as after forty-eight hour 
exposure to 90% humidity. For the purpose of this comparative study, the 
results provided represent the degree of curl (C), which is defined by the 
following equation: 
##EQU1## 
where H is the total hair length d is the distance from the hair root to 
the first curl, and 
n is the total number of curls. 
In addition to comparing the curl resiliency for each of the test samples, 
the strength of the resulting hair fibers was also determined for most of 
the test samples. These results are also provided in Table III and were 
determined by using a tensile property determining apparatus such as is 
available from the Instron Corporation, specifically their Model 20/20 
Machine. 
The results provided in Table III represent the amount of change in tensile 
strength of the hair fiber as a comparison before and after the treatment 
of the hair. In order to determine the tensile strength of the resulting 
hair fiber, the force needed to elongate the hair fiber by 10% before 
treatment is determined as well as the force needed to elongated the hair 
fiber by 10% after treatment. The test results provided in Table III 
represent the pre-treatment result minus the post-treatment result divided 
by the pre-treatment result. As is apparent from this analysis, values 
nearest to 1.00 indicate stronger relative tensile properties. 
TABLE III 
______________________________________ 
Composition of 
Degree of Curl Instron 
Ex- Mixture After 48 Hrs 
Force 
ample (Relative Parts) 
pH Dry @ 90% Humidity 
(S) 
______________________________________ 
1 Part A:Part D 
9.2 1.00 1.07 1.00 
2 Part A:Part B 
4.0 1.40 1.53 1.03 
3 Part A:Part B: 
4.7 0.98 1.03 1.05 
0.01 Part E 
4 Part A:Part B: 
4.7 1.00 1.03 1.07 
0.01 Part F 
5 Part A:Part B: 
3.2 0.98 1.03 1.04 
0.005 Part G 
6 Part A:Part B: 
3.7 0.96 0.99 -- 
0.01 Part H 
7 Part B:Part C: 
4.8 1.60 -- 
0.01 Part E 
8 Part B:Part C: 
3.2 1.73 -- 
0.01 Part F 
9 Part B:Part C: 
3.6 1.73 -- 
0.005 Part G 
10 Part A:Part B: 
4.0 1.40 1.50 -- 
0.000001 CI 
Basic Violet 10** 
11 Part A:Part B: 
3.2 1.33 1.56 -- 
0.001 Basic Violet 
10 then, 20 vol. 
peroxide:CI 
Acid Violet 43** 
12 Part A:Part B: 
4.4 1.13 1.37 -- 
0.5% Merquat S* 
13 Part A:Part B: 
4.4 1.43 1.41 -- 
1.0% Merquat S* 
______________________________________ 
*Merquat S is the trade name for a quarternary amine component produced b 
Merck, Inc. 
**Colour Index number of dyestuff 
A review of the test results provided in Table III clearly demonstrates 
that the inclusion of a fluoroscein-based dye in the permanent wave 
composition substantially improves the curl retention characteristics of 
the resulting permanent waved hair, as well as improving the structural 
integrity of the hair over hair reduced at an alkaline pH. In particular, 
where Xanthene and anthraquinone dyes were employed in the relaxing 
solution, the structural integrity of the resulting hair was not enhanced, 
as was provided by the fluoroscein-based dye stuffs. 
In Table IV, examples of the range of colors attainable by employing the 
present invention are provided, along with the resistance to color change 
attained by the composition of this invention after repeated shampooing or 
exposure to sunlight. Table IV clearly shows the increased durability of 
the dye when incorporated into the relaxing solution of the present 
invention as opposed to prior art conventional methods. 
In Table IV, the hair samples were prepared and permanent waved as detailed 
above in reference to Table III. The information provided in Table IV 
represents the chromicity values, L, A, and B for the same hair sample 
before and after seven shampoo, rinse and dry cycles, as well as after 
exposure to ten hours of simulated sunlight. Except where noted, medium 
brown hair was used. All of the measurements were taken employing a 
Spectrogard II system available from Pacific Instruments. 
TABLE IV 
__________________________________________________________________________ 
Composition of Chromicity Values: .sub.-- L, .sub.-- A, .sub.-- B 
Mixture After After 10 Hrs 
Example 
(Relative Parts) 
Color 
Initial 
Shampooing 
Shampooing 
__________________________________________________________________________ 
14 Part A:Part B: 
Light 
L = 21.84 
L = 21.45 
L = 20.36 
0.01 part F 
Auburn 
a = 11.66 
a = 11.62 
a = 14.28 
b = 10.07 
b = 10.39 
b = 9.31 
15 Part A:Part B: 
Auburn 
L = 21.25 
L = 20.99 
L = 21.48 
0.01 Part E a = 12.08 
a = 11.49 
a = 12.69 
b = 9.65 
b = 9.43 
b = 9.49 
16 Part A:Part B: 
Dark L = 21.18 
L = 20.64 
L = 22.28 
0.01 Part G 
Auburn 
a = 9.11 
a = 9.68 
a = 8.70 
b = 6.71 
b = 7.93 
b = 8.59 
17 Part A:Part B: 
Blue/ 
L = 15.33 
L = 15.75 
L = 16.28 
0.01 Part D 
Brown 
a = 2.15 
a = 2.21 
a = 2.38 
b = 3.31 
b = 3.29 
b = 3.23 
18 Part A:Part B: 
Blue/ 
L = 39.90 
L = 41.55 
L = 43.15 
0.01 part D on 
Grey a = -2.00 
a = -3.24 
a = -3.65 
blended grey hair 
b = 0.32 
b = 0.31 
b = 0.30 
19 Part A:Part B: 
Pink L = 41.70 
L = 41.27 
L = 41.65 
0.01 Part F on 
a = 49.44 
a = 49.25 
a = 49.33 
White Hair b = 27.44 
b = 27.05 
b = 26.93 
20 Part B: 0.01 
Light 
L = 55.00 
L = 78.26 
L = 56.92 
on White Hair 
Pink a = 20.76 
a = 8.72 
a = 13.70 
b = 3.14 
b = 6.55 
b = 5.36 
__________________________________________________________________________ 
Chromicity values of .sub.-- L = total reflectance of 0 = black, 100 = 
white; a = (+) for red; (-) for green; -b = (+) yellow, (-) for blue as 
determined by the average of triplicate measurements performed on a 
Spectrogard II system available from Pacific Instruments. 
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 the composition detailed herein, as 
well as in carrying out the above process 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 to be understood that the following claims are intended to coverall 
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 are intended to include compatible 
mixtures of such ingredients wherever the sense permits.