Permanent waving and color enhancing composition and method

Simultaneous permanent waving and dyeing of hair fibers is attained by incorporating a silk amino acid and a water soluble or emulsifiable silicone based compound in the permanent waving lotion and intermixing the dyestuff with the oxidizing or neutralizing composition. Preferably, the combined dyeing and neutralizing composition is adjusted to have a pH ranging between about 7 and 9. In this preferred embodiment, the hair is warmed after receiving the combined dyeing and neutralizing composition with said composition preferably being processed on the hair at a temperature ranging between 40.degree. C. and 65.degree. C. In addition, further enhanced coloring and permanent waving is attained by incorporating a lipotropic material into the dye additive composition.

TECHNICAL FIELD This invention relates to products for permanently waving 
hair and, more particularly, to products for permanently waving and 
concurrently coloring or dyeing 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 been realized in a broadly useable 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 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.KSSK+2H.sub.2 O 
One 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. 
Consumers have long sought to have a composition and process which would 
enable both color and permanent waving to be achieved simultaneously. 
However, no prior art system has been able to provide an effective or 
reliable composition which would enable simultaneous coloring 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 consumer's need. 
Prior to the advance detailed in U.S. Pat. No. 5,094,662, no prior art 
system existed for effectively permanently waving and permanently dyeing 
hair simultaneously. In the procedure detailed in this prior art patent, 
the dye must be incorporated in the permanent waving lotion to provide the 
permanent dyeing of the hair. 
Although the teaching of U.S. Pat. No. 5,094,662 is highly effective in 
producing results previously unattainable, there is no teaching or 
suggestion in U.S. Pat. No. 5,094,662 which achieves a long lasting, 
durable semi-permanent dyeing or coloring for hair wherein the dye is 
mixed with the neutralizer. It is this area which the present invention 
has overcome. 
The principal concern that has existed in the prior art is that the typical 
processes used to color hair involve contacting the hair with a mixture of 
dyes and ammonia and hydrogen peroxide. This combination can cause 
irreversible damage to the keratin matrix of the hair fiber. Furthermore, 
in order to be effective, the process requires some mode of swelling of 
the hair to allow for the penetration of the dye. In the case of tint 
impartation, whereby the deposited color is a shade or tone lighter than 
the naturally underlying color, a bleaching of the natural color is 
required. 
Due to the attention that has been given to hair dyeing, the mechanisms 
involved in the action of dye formation are well understood. In addition, 
the damage done to the hair fibers is also well-known. In particular, some 
characteristics of this damage are the dimmunization of the structural 
integrity of the hair fibers, as evidenced by the loss of resiliency and 
increased porosity or capability to uptake water. 
One principal factor which has led prior art investigators to seek 
achieving adequate hair dyeing and permanent waving concurrently is the 
belief that one can capitalize on the increased swelling of the hair which 
occurs during the reduction step of the permanent wave process. By 
contacting the hair with a dyestuff composition at this time, greater dye 
penetration is achieved, as compared to the dye uptake during the typical 
process of applying hair dyes in a separate process. In addition, by 
adding the dyestuff to the neutralizing mixture, it is believed that the 
dyes enter the hair more freely while the hair fibers are in the reduced 
state. 
In spite of the possibility of increased damage to the hair fibers due to 
the combination of a perming lotion with an oxidative dyestuff 
composition, the expected longevity of the dyes in hair and the retention 
of the imparted color were important factors in pursuing this method. The 
following patents are representative of the prior art technology that has 
been developed. 
In European Patent Application 0260,716A and U.S. Pat. No. 5,161,553, the 
use of oxidative dyestuffs is disclosed for being applied to hair in the 
mixture of a neutralizing composition following a permanent wave process. 
In this teaching, the hair is contacted with a permanent wave lotion while 
wrapped about a molding rod, rinsed thoroughly and then saturated with a 
neutralizing composition, typically between 2.2% and 3% hydrogen peroxide. 
After approximately one-half the time required for neutralizing, the hair 
is again contacted with the neutralizing composition, but this time a 
suitable amount of dyestuffs has been added to the composition so as to 
impart color during the final phase of the process. 
Another prior art teaching of using permanent dyestuffs during the 
neutralizing step is found in U.S. Pat. No. 4,630,621. In this patent, a 
broad teaching of dyestuffs is claimed to be useful. However, the examples 
found in the patent focus principally on the use of oxidation dyes. The 
sole illustration of a direct dye merely employs a derivative of an 
anthraquinone, which is typically included in permanent hair dyeing 
compositions only to achieve the blue tones. 
Although this patent suggests that the addition of the dyestuffs to the 
neutralizer attains both an acceptable curl and dye uptake by the hair 
fibers in a uniform manner, we have found the actual results achieved by 
employing the processes of the patent are unacceptable. In our 
experiments, all of which are detailed below, each of the processes 
defined in the examples of U.S. Pat. No. 4,630,621 were repeated. In each 
instance, the resulting dyeing and permanent wave characteristics of the 
hair fibers were significantly weaker than the results attained when the 
dyestuffs are used without the permanent waving solution. 
It is not clear why the process taught in U.S. Pat. No. 4,630,621 results 
in a minimal dye uptake. However, we believe that there are several 
explanations as to why the methods taught in this prior art reference fail 
to deliver acceptable results. 
One underlying reason for the failure to obtain intensive coloring may be a 
result of the attempt to impart dyestuffs into the hair fiber in an acidic 
medium. The acid pH of the neutralizer composition causes a rapid decrease 
in hair swelling that could inhibit dye penetration. Consequently, the 
dyestuffs fail to enter the hair fibers and are removed during the final 
rinsing. 
Another reason is that during permanent waving, the hair is wrapped about a 
forming rod under tension. The hair is then secured about this rod with an 
elastic band stretched across the hair bundle, which creates a pressure 
line where the band is contacting the hair. 
Another problem in the prior art is that permanent wave compositions 
typically contain materials which effectively assist the permanent waving 
lotion in wetting the hair. For example, proteinaceous quaternary 
materials, such as are available commercially in the form of Finquat, 
manufactured by Stepan Chemical Co. of Northfield, Ill. and Maypon, 
manufactured by Finetex of Elmwood Park, N.J., give the benefit of a 
conditioned feel to the hair by coating the hair's surface. 
Unfortunately, in the presence of such conditioning and wetting agents, the 
waving lotion inhibits the penetration of such lipophilic materials as 
coal tar derived dyes while in an aqueous medium, such as the peroxide 
derived neutralizing compositions commonly employed. The result is an area 
across at least one section of the hair which does not have an adequate 
amount of dye uptake. This causes a "banding" effect on the hair fibers, 
which is clearly undesirable, as it gives poor color results. 
This "banding" phenomenon may have been anticipated in U.S. Pat. No. 
4,630,621, since the preferred method suggests applying the dye containing 
solution after the waving lotion has been removed. By employing the 
suggested method, the majority of the wetting agents are rinsed off, prior 
to being able to impede the penetration of the dyestuff into the hair. 
It is also apparent that other practitioners in this art discovered the 
phenomenon that conditioning agents affect the dyeing capability when 
performed concurrently with permanent waving. This realization is evident 
from the teaching in U.S. Pat. No. 3,368,941 and 3,399,682, wherein hair 
conditioning materials of the classification of a quaternary amine are 
shown to be useable with specific dyestuffs of certain classes. In U.S. 
Pat. No. 3,368,941, acid and metalized dyestuffs are used as pre-existing 
colored materials. These dyes are attracted to cationic chemicals such as 
those found in quaternary amine conditioners. While not specifically 
taught in this patent, hair dyed with this system has limited durability 
beyond several shampooings. In U.S. Pat. No. 3,399,682, the use of azo 
dyes is shown to deliver results similar to that of the preceding patent. 
Therefore, it is a principal object of the present invention to provide a 
permanent waving composition and method of application which is capable of 
providing permanent waving and hair dyeing concurrently. 
Another object of the present invention is to provide a permanent waving 
and hair dyeing composition and method of application having the 
characteristic features described above which is also capable of providing 
a long lasting durable semi-permanent coloring to the hair. 
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 easy to employ and is capable of 
providing intense color uptake uniformly distributed along the entire 
length of the hair fiber. 
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, the prior art difficulties and 
drawbacks have been eliminated and a composition for simultaneously 
permanently waving and dyeing hair is achieved. Although the mechanism by 
which the present invention operates is not fully understood, the 
compositions and processes detailed herein provide both a remarkable curl 
and uniform, intense color uptake with a durability associated with long 
wearing semi-permanent dyes. 
Although some prior art teachings have asserted the attainment of this 
achievement, it has been found that these prior art methods are incapable 
of providing a uniform, semi-permanent hair dyeing result. However, the 
present invention is capable of eliminating the adverse effects found in 
prior art systems and attains a uniform, long-lasting dyed hair fiber, 
while enabling the hair fibers to be concurrently permanently waved. 
In carrying out the present invention, a permanent waving lotion is first 
applied to the hair in a generally conventional manner. After its 
application and removal, a neutralizing composition is employed, within 
which the desired dye composition is intermixed. In order to attain the 
desired uniform dyeing of the head of hair, while simultaneously 
permanently waving the head of hair, the permanent wave lotion preferably 
comprises one selected from the group consisting of thioglycolate salts 
and esters of thioglycolate salts. 
In addition, it has been found that in order to enable the permanent wave 
lotion to establish hair fibers which are ready for accepting the direct 
application of the desired dyestuffs, the permanent wave lotion also 
preferably incorporates silk amino acids and a water soluble or 
emulsifiable silicone-based compound. By incorporating these two hair 
enhancing additives into the permanent wave lotion, it has been found that 
the permanent wave lotion acts upon the hair fibers, in a manner which is 
not fully understood, but enables the hair fibers to accept the 
application of the dyestuffs with the neutralizing composition. Throughout 
this specification, chemical compositions are defined by employing, 
wherever possible, the accepted designation as is found in the CTFA 
International Cosmetic Ingredient Dictionary, Fourth Edition, published by 
the Cosmetic, Toiletry, and Fragrance Association, Washington, D.C. By 
employing these universally accepted designations throughout the 
specification, one of ordinary skill in the art will fully understand the 
chemicals stated herein as well as their formulations as provided in the 
CTFA International Cosmetic Ingredient Dictionary. 
In accordance with the present invention, the permanent wave lotion 
incorporates silk amino acids and one or more water soluble or 
emulsifiable silicone based compounds. In the preferred embodiment, the 
water soluble or emulsifiable silicone based compound comprises one or 
more selected from the group consisting of dimethicones and 
amodimethicones. Preferably the silk amino acids employed in the permanent 
wave lotion comprises between about 0.001% and 2.0% by weight of the total 
composition, while the silicone-based compound comprises between about 
0.001% and 5.0% by weight of the final composition. 
Dimethicone is a mixture of fully methylated linear siloxane polymers end 
blocked with trimethylsiloxy units. Empirically, the formula for 
dimethicone is (C.sub.2 H.sub.6 OSi).sub.x C.sub.4 H.sub.12 Si, with the 
following being representative of its general formula: 
##STR1## 
Amodimethicone is a silicone polymer end blocked with amino functional 
groups. Its formula is represented as follows: 
##STR2## 
where x has a value of 4 or more. 
Although one or a combination of these two water soluble or emulsifiable 
silicone based compounds are preferred, other substantially equivalent 
water soluble or emulsifiable silicone based compounds may be employed, 
without departing from the scope of this invention. One such water soluble 
or emulsifiable silicone-based compound comprises dimethicone copolyol, 
which is non-ionic and water soluble, and comprises a polymer of 
dimethylsiloxane with polyoxyethylene and/or polyoxypropylene side chains. 
Another substantially equivalent silicone compound is 
stearoxytrimethylsilane which is an organo-silicone compound having the 
empirical formula of C.sub.21 H.sub.46 OSI. In addition, stearoxy 
dimethicone may be employed, which is a polymer of dimethylpolysiloxane 
end blocked with stearoxy groups. 
Furthermore, the silicone compound employed in the permanent wave lotion 
can be a quaternized silicone compound or a betaine silicone compound. A 
typical quaternized silicone compound is polysiloxane polydimethyl 
dialkylammonium acetate copolymer. The betaine silicone compound is 
typified by polysiloxane polyalkyl betaine copolymer. 
In Table I, the overall formulation is provided for the preferred permanent 
waving lotion of the present invention. As stated therein, up to about 20% 
by weight of the final composition may comprise additives selected to 
provide enhancements to the final composition. Typically, such additives 
comprise one or more selected from the group consisting of alkaline 
agents, penetrating agents, chelating agents, wetting agents, conditioning 
agents and fragrances. In Table II, detailed formulations are provided for 
two alternate permanent waving lotions which employ the teaching of this 
invention. 
TABLE I 
______________________________________ 
Permanent Waving Lotion Composition 
Ingredient Range % by Weight 
______________________________________ 
Reducing Agent 6.0-25.0 
Silk Amino Acids 0.001-2.0 
Water Soluble or Emulsifiable 
0.001-5.0 
Silicone Based Compound 
Additives 0-20 
Deionized Water q.s. to 100% 
______________________________________ 
TABLE II 
______________________________________ 
Preferred Permanent Wave Lotion Formulations 
Formula A Formula B 
Ingredients % by Weight 
% by Weight 
______________________________________ 
Glyceryl Monothioglycolate 
6-25% -- 
Glycerin 2-5% -- 
Ammonium Thioglycolate (as 
-- 6-12% 
T-Acid) 
Diammonium Dithiodiglycolate 
-- 2-6% 
(as DTDG Acid) 
Ammonium Chloride 1-2% -- 
Ammonia 1-5% 2-5% 
Styrene/Acrylate Copolymer 
-- 0.001-3% 
Laureth-23 1-4% 1-4% 
Propylene Glycol 0.001-5% -- 
Silk Amino Acids 0.001-2% 0.001-2% 
Trimethylsilylamodimethicone 
0.001-5% 0.001-5% 
Octoxynol-40 0.001-1% 0.001-1% 
Isolaureth-6 0.001-1% 0.001-1% 
Fragrance 0.5-2% 0.5-2% 
Deionized Water 60-89% 70-89% 
______________________________________ 
Laureth-23 is the polyethylene glycol ether of Lauryl Alcohol (q.v.) that 
conforms to the formula: 
EQU CH.sub.3 (CH.sub.2).sub.10 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.n OH 
where n has an average value of 23. 
The permanent wave lotion of this invention is applied to the hair using 
generally conventional procedures. In this regard, the hair is first wound 
on rods or rollers, followed by the application of the permanent waving 
lotion to the hair on the rods. The lotion is then allowed to remain on 
the hair for between about 5 and 30 minutes. Once the desired processing 
time has been reached, the lotion is removed by rinsing and towel 
blotting. 
In addition to employing the wave lotion composition detailed above, the 
preferred embodiment of the present invention has overcome the prior art 
difficulties by combining the dyestuffs with the neutralization 
composition, while maintaining the composition at an alkaline pH. Although 
any alkaline pH level is effective, the preferred pH of the 
dye/neutralizer composition ranges between 7 and 9. By referring to Table 
III, the overall formulation for the preferred dye/neutralizer composition 
is provided. 
TABLE III 
______________________________________ 
Dye/Neutralizer Formulation 
Ingredient Range (% by Weight) 
______________________________________ 
Dyestuff 0.01-5 
Hydrogen Peroxide 1.0-3.0 
Alkali to Adjust pH to Range Between 
7.0 and 9.0 
Additives 0-20 
Deionized Water q.s. to 100% 
______________________________________ 
A further unique aspect of the present invention is the additional 
discovery that the application of heat to the hair during the neutralizing 
process provides substantially enhanced, beneficial results. This 
discovery is believed to be particularly unique, since no prior art 
references teaches or suggests the application of heat to the hair during 
these procedures. 
In the present invention, it has been found that the hair should be warmed 
while the dye/neutralizer composition is saturated on the hair. In 
addition, it has been found that the optimum benefit is realized when the 
hair is warmed to between about 40.degree. C. and 65.degree. C. By 
employing this warming process, both the penetration and levelness of the 
dyes about the hair fibers are maximized. 
In the preferred embodiment, a dye additive composition is prepared and 
intermixed with the neutralizing composition prior to use. The principal 
ingredient in this composition is the particular dye or combination of 
dyes selected to attain the desired coloring. Although not intended as an 
exhaustive testing of all of the dyes employable in this invention, Table 
IV identifies the principal dyestuffs which have been found to be 
effectively employable using the teaching of the present invention. 
TABLE IV 
______________________________________ 
Dyestuffs 
______________________________________ 
HC Blue No. 2 
HC Red No. 3 Disperse Black 9 
HC Blue No. 4 
HC Yellow No. 2 
Disperse Blue 1 
HC Blue No. 5 
HC Yellow No. 3 
Disperse Blue 3 
HC Orange No. 1 
HC Yellow No. 4 
Disperse Violet 1 
HC Red No. 1 
HC Yellow No. 5 
Disperse Violet 4 
Acid Orange No. 3 
______________________________________ 
It has also been discovered that the present invention is able to achieve 
further efficacious results by incorporating a lipotropic material into 
the dye additive composition. Due to its cationic nature, the lipotropic 
material is extremely substantive to hair. It possesses excellent 
spreading properties on hair to help improve color evenness, in addition 
to imparting lustre and improving manageability. Preferably, the 
lipotropic material employed in the composition comprises a chemical 
structure capable of delivering a lipophilic material in an aqueous medium 
to a lipid environment, such as the direct dyes used in the application of 
the neutralizing composition to hair fibers. 
In the preferred embodiment of the present invention, the lipotropic 
materials comprise the derivatives of vegetable derived amino acids 
substituted with one or more moieties selected from the group consisting 
of lauryl-, stearoyl-, and cocoyl-methylamine. In addition, it has been 
found that the lipotropic materials perform most efficaciously when 
incorporated into the dye additive composition at a concentration ranging 
between about 0.001% and 2.5% by weight. 
By referring to Table V, the preferred formulation for the dye additive is 
provided. In addition, in Table VI, formulations for two alternate 
preferred neutralizer compositions are detailed. As shown in Table VI, the 
preferred neutralizer composition incorporates a silk amino acid and a 
water soluble or emulsifiable silicone based compound in addition to a 
generally conventional neutralizer formulation. Although not mandatory, 
the incorporation of a silk amino acid and a water soluble or emulsifiable 
silicone compound into the neutralizer has been found to provide a further 
enhanced beneficial result to the simultaneous permanent waving and 
coloring of the hair in accordance with this invention. 
TABLE V 
______________________________________ 
Preferred Dye Additive Formulation 
Material WT. % 
______________________________________ 
Dyes (selected from Table IV) 
0.01-5 
Ethanolamine 0-1 
Ethoxydiglycol 0-2 
Glycoproteins 0-2 
Hydroxyethylcellulose 0-2 
Lauryloleylmethylamine 
0.001-2.5 
Soy Amino Acids (Lipotrope) 
PEG-8 Hydrogenated Tallow Amine 
0-5 
Tetrasodium EDTA 0-1 
Fragrance 0-2 
Deionized Water 78-99 
______________________________________ 
TABLE VI 
______________________________________ 
Preferred Neutralizer Formulations 
Formula A Formula B 
Material % by Weight 
% by Weight 
______________________________________ 
Sodium Lauryl Sulfate 
0-2 0-2 
Cetearyl Alcohol 0-2 0-2 
Ceteth-20 0-2 0-2 
Mineral Oil 0-2 
Hydrogen Peroxide 1-3 1-3 
Disodium Phosphate 
0-2 0-2 
Phosporic Acid 0-2 0-2 
Olealkonium Chloride 
0-2 0-2 
Silk Amino Acids 0.001-2 
Trimethylsilylamodiumethicone 
0.001-5 
Octoxynol-40 0-1 
Isolaureth-6 0-1 
Dimethicone 0.001-3 
Cyclomethicone 0.001-3 
Propylene 0-5 0-5 
Methyl Paraben 0-2 0-2 
Fragrance 0-2 0-2 
Deionized Water 65-98 68-98 
______________________________________ 
Ceteth-20 is the polyethylene glycol ether of Cetyl Alcohol (q.v.) that 
conforms to the formula: 
EQU CH.sub.3 (CH.sub.2).sub.14 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.n OH 
where n has an average value of 20. 
Octoxynol-40 is the ethoxylated alkyl phenol that conforms generally to the 
formula: 
EQU C.sub.8 H.sub.17 C.sub.6 H.sub.1 (OCH.sub.2 CH.sub.2).sub.n OH 
where n has an average value of 40. 
Isolaureth-6 is the polyethylene glycol other of branched chain aliphatic 
12 carbon alcohols. It conforms generally to the formula: 
EQU C.sub.12 H.sub.25 (OCH.sub.2 CH.sub.2).sub.n OH 
where n has an average value of 6. 
Any of the silicone compounds detailed above may be employed in the 
neutralizer. Similarly, as detailed above, one or more selected from the 
group consisting of dimethicones and amodimethicones is preferred. 
Using the formulation detailed above, the dye additive mixture and the 
neutralizer mixture are combined to form a dye and neutralizing 
composition for application to the hair. In accordance with the preferred 
process of the present invention, once the permanent wave lotion has been 
removed from the hair fibers, a portion of the dyeing and neutralizing 
composition is applied to the hair wound on the rods. After allowing a 
processing time of between about 3 minutes and 5 minutes, the rods are 
removed from the hair fibers. Then, the remaining dyeing and neutralizing 
composition is applied to the hair fibers, and allowed to remain on the 
hair for between about 5 minutes and 15 minutes. 
As detailed above, in the preferred application process, heat is applied to 
the hair after the application of the dyeing and neutralizing mixture to 
the rod-free hair. Although the hair can be heated for between about 2 
minutes and 15 minutes, it has been found that the hair should be heated 
for substantially the entire processing time of the dyeing and 
neutralizing mixture on the rod-free hair. Once this processing time has 
been completed, the hair is allowed to cool for between 1 and 2 minutes. 
Then, the dyeing and neutralizing mixture is rinsed from the hair. 
By employing the permanent wave lotion and dyeing and neutralizing 
composition of this invention, the prior art difficulties are virtually 
eliminated and resilient, permanently waved hair fibers are produced along 
with uniform, intense, durable simultaneously coloring being imparted 
thereto. 
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 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 
and prove the efficacy of the formulations and processes detailed herein, 
the following examples are provided. Although these examples are intended 
as a teaching of the best mode for carrying out the present invention, the 
examples are not intended to limit, in any manner, the breadth of this 
discovery. 
By employing the permanent waving and hair dyeing compositions of this 
invention, as well as the application methods detailed herein, hair fibers 
are simultaneously permanently waved and dyed in a manner which attains 
both long lasting curl retention and improved dye retention. Unless 
otherwise stated, the methods defined above were employed in conducting 
the following tests. Furthermore, in order to provide repeatable, 
objective, quantitative measurements of the hair coloring and durability 
achieved by the present invention, a colorimeter was employed, with the 
dyed hair samples being tested for color permanency, durability and 
washability. 
A colorimeter measures the intensity of lightness, hues and tones of the 
hair, as delineated in the C.I.E. Scale for color measurements. In these 
measurements, the chromaticity values of "L", "a", and "b", are employed, 
wherein "L" equals the total reflectance of the hair fiber, with black 
equal to a value of zero and white equal to a value of one hundred. In 
addition, "a" equals a positive value for red and a negative value for 
green while "b" equals a positive value for yellow and a negative value 
for blue. For consistency, all measurements were taken employing a 
Spectroguard II system from Pacific Scientific Instruments, or a 
Chromameter CR-300 from Minolta. 
In order to further quantify the measurements taken and compare the results 
achieved in the present invention with the results achieved in the prior 
art, the following equation was employed. In this equation AE is employed 
to quantitatively represent the overall color change or resulting color 
effect. 
##EQU1## 
where c=value of control, and 
t=measurement of test samples using the present invention. 
Example 1 
The tests performed in this example were designed to show the benefit 
attained by incorporating silk amino acids and a water soluble or 
emulsifiable silicone compounds in the permanent wave lotion prior to the 
application of the dye and by heating the hair during the dye application 
step. In these tests, tresses of hair were processed using an acid 
permanent waving lotion into which silk amino acids and a silicone blend 
of dimethicone and amodimethicone were added, as detailed above. As a 
control or baseline comparison, an acid permanent waving lotion without 
the silk amino acid and the blend of dimethicone and amodimethicone was 
applied to separate tresses of hair. 
In these tests, the acid permanent waving lotion employed as the control 
was the "Quantum" permanent wave lotion which is manufactured by Helene 
Curtis Corporation of Chicago, Ill. 
The permanent wave lotions were applied and removed following identical 
conventional procedures. Then, a dye/neutralizing composition was prepared 
and applied to the tresses of hair. In each instance, a composition 
consisting of a blend of direct dyes, totaling between about 0.5% and 15% 
by weight and selected from Table IV to give the desired natural brown 
shade, was added to the conventional neutralizer at a ratio of one part 
color composition to four parts neutralizer. This resulted in a total dye 
concentration of between about 0.1% to 3% by weight. 
Once prepared, a portion of the color/neutralizer mixture was applied to 
the hair tresses wound on the rods. After five minutes of exposure, the 
rods were removed and the remaining color/neutralizer mixture was applied 
to the shaft and ends of the hair fibers. Once the application of the 
mixture was completed, the tresses of hair were processed with heat at 
about 45.degree. C. for ten minutes, while the color/neutralizer mixture 
remained on the hair. Thereafter, the tresses of hair were allowed to cool 
for one minute and then rinsed. 
Observations of the permanently waved and dyed hair tresses showed that the 
hair tresses which were heated and treated with the permanent wave 
composition incorporating the silicone blend and the silk amino acids 
achieved an increased dye uptake over the hair tresses treated in the 
identical manner, but without the silk amino acids and the silicone blend. 
After the initial observations, the hair tresses were exposed to three 
separate cycles of shampooing and drying, and then re-evaluated. These 
observations show that the hair tresses treated with the silicone blend 
and the silk amino acids attained both improved initial color deposit and 
color durability over the hair tresses not treated with the additives to 
the permanent wave lotion. All of the test results obtained from this 
example are detailed in Table VI. 
TABLE VI 
______________________________________ 
Efficacy of Additives in the Waving Lotion 
Chromaticity Values 
L a b .DELTA.E 
______________________________________ 
Quantum by Helene Curtis 
After Permanent Waving and Dyeing 
31.64 4.23 15.88 
After Three Shampoo/Drying Cycles 
38.12 3.56 19.33 
7.37 
Modified Permanent Waving Lotion 
(Containing Additives) 
After Permanent Waving and Dyeing 
30.04 6.22 15.00 
After Three Shampoo/Drying Cycles 
32.68 5.59 17.12 
3.44 
______________________________________ 
EXAMPLES 2-3 
In order to prove the ability of the present invention to overcome the 
drawbacks encountered in the prior art, tresses of hair were processed in 
accordance with the teachings of Examples I and II of U.S. Pat. No. 
4,630,621. In conducting these tests, the acid perm employed was ACCLAIM 
which is manufactured and distributed by Zotos International of Darien, 
Conn. In addition, the processing time employed for the permanent waving 
lotion was twenty-five minutes. 
The dye employed was Miss Clairol Shade 45 R-Light Auburn, which is 
manufactured by Clairol of New York, N.Y. Four percent by weight of this 
dye mixture was added to the neutralizer and the color/neutralizer mixture 
was applied in the manner detailed in Example I of U.S. Pat. No. 
4,630,621. In accordance with that process, the dye/neutralizer mixture 
was applied to the hair on the rods and allowed to remain for five 
minutes. The rods were then removed, and the product was worked through 
the hair and processed for an additional five minutes before rinsing. 
After completion of this process, observations showed that very little 
color was deposited on the hair tresses. In addition, uneven coverage was 
found from root to end. This poor color performance is evident in Table 
VII, wherein the overall test results are provided. 
TABLE VII 
______________________________________ 
Dye Uptake Using Prior Art Method 
Chromaticity Values 
L a b 
______________________________________ 
White Hair (Standard) 
74.12 -1.48 18.19 
Process of Examples I and II of 
64.49 6.43 20.39 
U.S. Pat. No. 4,6320,621 - 
at hair root 
Process of Examples I and II of 
66.79 4.49 18.92 
U.S. Pat. No. 4,630,621 - 
at hair shaft 
Process of Examples I and II of 
67.15 3.93 19.97 
U.S. Pat. No. 4,630,621 - 
at hair end 
Process of Examples I and II of 
66.14 4.95 19.76 
U.S. Pat. No. 4,630,621 - 
overall average 
______________________________________ 
A plurality of hair tresses were tested using the process defined in 
Example III of U.S. Pat. No. 4,630,621. In addition, the same procedure 
was followed along with certain modifications, detailed herein, in order 
to compare the results of the present invention with this prior art 
teaching. 
In performing these tests, an auburn semi-permanent color was added to the 
neutralizer at a ratio of one part color to two parts neutralizer. In 
accordance with the teaching of Example III of U.S. Pat. No. 4,630,621, 
the neutralizer, without the color added, was first applied to the hair 
while wound on rods. Then, the color/neutralizing mixture was applied. 
After allowing the color/neutralizer mixture to remain on the hair for 
five minutes, the rods were removed and the product was worked through the 
hair. After an additional five minutes, the hair was rinsed. 
Observations of the hair tresses produced by employing this procedure, 
without any modification, showed a weak dyeing of the hair with the color 
being deposited unevenly along the hair fibers. In particular, the ends 
were lighter than the hair roots and shafts. The chromaticity values 
obtained are shown in Table VIII. 
In order to test the efficacy of the present invention over this prior art 
teaching, hair samples were dyed using the procedure detailed above, as 
defined in Example III of U.S. Pat. No. 4,630,621, along with some 
modifications. In this modified test procedure, the color/neutralizer 
mixture was applied to the hair while wound on the rods, without a 
pre-application of the colorless neutralizer. After five minutes, the rods 
were removed, and the color/neutralizer mixture was worked through the 
hair. In addition, the hair tresses were processed with heat after the 
color/neutralizer mixture had been worked through the hair following the 
removal of the rods. In applying the heat, a plastic bag was placed over 
the hair and heat was applied for five minutes at a temperature of about 
45.degree. C. After this heat application, the hair was allowed to cool to 
room temperature, for about one minute, and was then rinsed. 
Observations of the auburn hair fibers resulting from this modified process 
showed substantially improved dye uptake, with a more even coloring 
resulting along the entire length of hair from its root to its end. The 
chromaticity values obtained using this modified process are shown in 
Table VIII. 
In order to test the durability of the resulting dye on both the prior art 
process and the modified process, the hair tresses were subjected to two 
shampoo and drying cycles, directly after the application of the permanent 
waving lotion and dye/formulation. Observations after the shampoo/drying 
cycles showed more color was retained in the hair employing the modified 
process than was retained by the hair fibers processed in accordance with 
the procedure of Example III of U.S. Pat. No. 4,630,621. The test results 
from these procedures are detailed in Table VIII. 
TABLE VIII 
______________________________________ 
Efficacy of Modified Process and Using Heat 
Chromaticity Values 
L a b .DELTA.E 
______________________________________ 
After Permanent Waving and Dyeing 
U.S. Pat. No. 4,630,621 (Example III) 
38.40 26.24 22.95 
Modified Process and Heat 
28.18 24.65 28.33 
11.37 
After Permanent Waving and Dyeing 
and Two Shampoo/Dry Cycles 
U.S. Pat. No. 4,630,621 (Example III) 
47.62 23.22 25.61 
Modified Process and Heat 
36.15 23.48 22.69 
11.83 
______________________________________ 
As shown by the test results detailed in Table VIII, applying the 
neutralizer before applying the color/neutralizer mixture, as taught by 
U.S. Pat. No. 4,630,621, resulted in reduced dye penetration or deposit. 
However, by employing the modified process of the present invention and 
heating the hair while the dye remained on the hair fibers, dye uptake was 
improved as well as wearability and permanency of the color. 
EXAMPLE 4 
In order to further confirm the efficacy of the present invention and the 
substantially improved results attained by employing the teaching of this 
invention, further comparative experiments were conducted. In these tests, 
tresses of hair were tested following the process detailed in Example III 
of U.S. Pat. No. 4,630,621 as well as using a modification to that process 
as taught herein. In all tests, an acid perm and a natural brown dye were 
used, with the dye being added to the neutralizer in a ratio of 1:4. 
The control test samples were permanently waved and dyed using the teaching 
found in Example III of U.S. Pat. No. 4,630,621. This procedure, with the 
prior art control samples, is fully detailed above in Example 2. In order 
to compare the teaching of the present invention with the prior art 
control samples, the following modifications were made. Firstly, the acid 
perm was modified by incorporating therein 0.001-2% by weight of silk 
amino acids and 0.001%-5% by weight of a silicone blend of dimethicones 
and amodimethicones. 
In addition to employing silk amino acids and the silicone blend in the 
permanent wave lotion, the experimental hair tresses were neutralized 
using the modified process in accordance with this invention. In this 
modified process, no pre-application of the neutralizer was made. Instead, 
the color/neutralizer mixture was applied to natural white hair, purchased 
from DeMeo Brothers in New York. The hair was wound on the rods and 
allowed to stand for five minutes. Thereafter, the color/neutralizer 
mixture was applied to the natural white hair after the rods were removed 
and allowed to stand for an additional ten minutes. Furthermore, during 
this ten minutes, heat was applied to the hair at about 45.degree. C. 
Once the tresses of hair were permanently waved and dyed, observations of 
the hair tresses were made. The hair fibers employed in the prior art 
process exhibited significantly less dye uptake than the hair fibers 
resulting from the modified procedure and formulations of this invention. 
The test results attained from these experiments are provided in Table IX. 
In addition, the test results attained after shampooing and drying the 
hair tresses three times after perming and drying are also provided in 
Table IX. 
TABLE IX 
______________________________________ 
Efficacy of Present Invention 
Chromaticity Values 
L a b .DELTA.E 
______________________________________ 
After Permanent Waving and Dyeing 
U.S. Pat. No. 4,630,621 (Example III) 
46.43 5.10 17.57 
Modified Process and Heat 
30.04 6.22 15.00 
17.16 
After Permanent Waving and Dyeing 
and Two Shampoo/Dry Cycles 
U.S. Pat. No. 4,630,621 (Example III) 
51.53 4.18 18.46 
Modified Process and Heat 
32.68 5.59 17.12 
18.95 
______________________________________ 
As is evident from these test results, the hair tresses processed with the 
modified methods and formulations of the present invention resulted in 
hair fibers exhibiting substantially improved dye uptake. In addition, 
these hair fibers possessed substantially improved or prolonged color 
wearability, as is evident from the results exhibited after three separate 
shampoo and dry cycles. 
EXAMPLE 5 
In this series of tests, two different hair dye formulations, namely golden 
brown and auburn, were evaluated, both with and without the application of 
heat. By employing these tests, the dye uptake achieved by using heat was 
determined for totally different hair dye formulations. The hair tresses 
processed with heat were exposed to heating at a temperature ranging 
between about 40.degree. C. and 50.degree. C. Furthermore, after 
observation of the results, the hair tresses were exposed to three 
separate and independent shampoo and drying cycles and then evaluated 
again to determine the wearability or durability of the color. 
In all of these tests, the color was added to the neutralizer in a ratio of 
1:4. In addition, all of the tests were conducted using the modified 
procedure detailed above in Example 4. In this procedure, the 
color/neutralizing mixture, was applied to the hair fibers when wound on 
curling rods and allowed to stand for five minutes. Then, the rods were 
removed and the hair was processed for an additional ten minutes either at 
room temperature, or with exposure to heat. The test results obtained are 
detailed below in Table X. 
TABLE X 
______________________________________ 
Chromaticity 
Values 
L a b .DELTA. 
______________________________________ 
GOLDEN BROWN 
After Permanent Waving and Dyeing 
At Room Temperature 39.25 7.59 18.01 
With Heat 29.48 7.51 15.54 
10.07 
After Three Shampoo/Drying Cycles 
At Room Temperature 40.91 6.80 18.09 
With Heat 33.74 6.93 18.71 
7.19 
AUBURN 
After Permanent Waving and Dyeing 
At Room Temperature 36.09 24.69 22.50 
With Heat 32.08 25.11 21.45 
4.16 
After Three Shampoo/Drying Cycles 
At Room Temperature 39.44 22.98 23.62 
With Heat 36.53 23.47 23.88 
2.96 
______________________________________ 
As is evident from the results detailed in Table X, significantly greater 
color uptake was obtained on the hair fibers processed with heat, 
regardless of which shade of dye was employed. In addition, the color 
durability or retention for the hair fibers processed with heat was 
substantially greater with both hair dye colors, as compared to the 
application of the hair dye at room temperature. As is evident from these 
results, the application of heat during the neutralizing step produces 
substantially improved results. 
As is now evident from a review of all of the foregoing examples, 
substantially improved concurrent hair dyeing and permanent waving results 
are obtained by employing the procedures and formulations of this 
invention, while the prior art difficulties and drawbacks have been 
substantially eliminated. Furthermore, both improved color uptake and 
color durability are realized. 
Based upon the foregoing teaching, optimum dye uptake and durability are 
obtained by incorporating silk amino acids and a silicone blend into the 
permanent wave lotion, while also maintaining the color/neutralizing 
mixture at an alkaline pH. Furthermore, heat is preferably applied to the 
hair during the final color/neutralizer application. 
A further critically important process step discovered in the present 
invention, which distinguishes the present invention over prior art 
teachings, is the application of the color/neutralizer mixture directly to 
the reduced hair, without first applying the neutralizer without any dye 
to the hair fibers. As is evident from the test results obtained, the 
application of the color-free neutralizer prior to the color/neutralizer 
mixture causes the dye penetration to be inhibited, thereby reducing the 
dye uptake. However, by applying the color/neutralizer mixture directly to 
the reduced hair, substantially improved coloring is achieved, as well as 
substantially improved color durability. 
Finally, it has also been found that additional beneficial results are 
obtained by incorporating a lipotropic material into the dye additive of 
the dye/neutralizer mixture. In addition, the incorporation of silk amino 
acids and water soluble or emulsifiable silicones in the neutralizer of 
the dye/neutralizing mixture provides additional enhancements. 
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 compositions 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 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 are intended to include compatible 
mixtures of such ingredients whenever the sense permits.