Permanent waving composition

Permanent waving composition containing as active ingredients cysteine and N-acetylcysteine. The composition contains preferably 3-15% cysteine and 0.2-3% N-acetylcysteine. It is possible to avoid the separation of crystals derived from the air-oxidation of cysteine by the composition of the present invention.

The present invention relates to permanent waving composition. Permanent 
waving compositions containing thioglycollic acid were previously known. 
However, the activity of thioglycollic acid on the hair of human is strong 
so that the permanent waving compositions of this type can give rise to 
the allergic reactions on the skin, damage to the hair roots, the 
breaking, falling and discolouring of the hair and other undesired side 
effects. Recently, permanent waving compositions containing cysteine as 
active ingredient have been proposed. Although cysteine possesses a milder 
activity on the hair when compared with the activity of thioglycollic 
acid, the stability of cysteine is more or less doubtful. For example, 
when applied to the hair of users, the crystals derived from cysteine are 
liable to be separated from the permanent waving compositions onto the 
hair and skin owing to the air-oxidation, which results in the lowering of 
operational efficiency and also damage to the skin of the user and artist. 
Another defect of cysteine resides in a poor storage stability. 
Various proposals have been made to overcome the above-mentioned 
difficulties. For example, Japanese PS No. 14934/73 discloses a permanent 
waving composition for the socalled cold permanent waving system, which 
contains cysteine as active ingredient in an amount of 3-15% by weight and 
has a pH of from 7 to 10. The storage stability is improved by addition of 
thioglycollic acid in an amount which is as itself inoperative in 
permanent waving, together with ethylenediamine tetraacetic acid, 
nitrilotriacetic acid or water-soluble salts thereof. Japanese PS No. 
48504/74 discloses a permanent waving composition for the cold permanent 
waving system containing as active ingredients both L- and D-cysteine at a 
ratio of 7:3 to 3:7 by weight and having pH of 7-12, whereby to avoid the 
separation of the crystals derived from air-oxidized L-cysteine. However, 
the results of experiments conducted by us revealed that these processes 
were insufficient to inhibit the separation of the crystals when applied 
to the hair of human. On the other hand, a permanent waving composition 
containing as active ingredient N-alkanoylcysteine such as 
N-acetylcysteine in an amount of 3-20% (preferably 7-10%) by weight 
exhibits an excellent stability and safety of the hair (U.S. Pat. No. 
3,242,052). However, permanent waving composition of this type has the 
disadvantage that the composition is very slippery on the hands of the 
artist and the operational efficiency is considerably lowered when applied 
to the hair tightly rolled. In addition, the composition of this type is 
expensive because N-acetylcysteine is derived from cysteine. 
It has unexpectedly been discovered that permanent waving composition 
containing as active ingredients both cysteine and N-acetylcysteine 
exhibits improved properties without the above-mentioned defects. 
An object of the present invention is to provide a permanent waving 
composition without the above-mentioned defects, which may be produced at 
cheaper costs and which may be used for both the cold system and the heat 
system with excellent results. 
According to the present invention, there is provided a permanent waving 
composition, which comprises cysteine and and N-acetylcysteine as active 
ingredients. 
Permanent waving compositions of the known types contain usually cysteine 
in an amount of about 3-15% cystein [% denotes % (weight/volume) 
hereinafter otherwise specified] when cysteine is used as active 
ingredient. In a preferred embodiment of the present invention, the 
composition contains cysteine in an amount of about 3-15% and 
N-acetylcysteine in an amount of about 0.2-3% of the composition to 
inhibit the separation of the crystals derived from cystein. On the other 
hand, the presence of N-acetylcysteine solely in an amount of not more 
than 3% is inoperative in permanent waving, as is previously known. 
Advantageously, the higher the amount of cysteine is, the more the absolute 
amount of N-acetylcysteine is. It is usually preferred to use 
N-acetylcysteine amounting to more than about 10% by weight of cysteine 
present in the composition according to the present invention. However, 
when the amount of cysteine rises to more than about 10%, it is then 
advantageous to use N-acetylcysteine in an amount of more than about 30% 
by weight of cysteine. In general, the presence of more than about 10% of 
cysteine and more than about 3% of the composition seems to be superfluous 
for practical use because the presence of more than about 3% of the 
composition of N-acetylcysteine is not only liable to cause the 
above-mentioned slipping trouble in use but also expensive without 
additional merit. 
Especially good results may be obtained when the amount of cysteine and 
N-acetylcysteine contained in the composition according to the present 
invention is about 4-10% in total. 
The pH of the composition in use is adjusted to 7.0-10.0 (preferably about 
7.2 when used for the cold permanent waving). For this purpose, it is 
conventional to use for example ammonia, ethylenediamine, ethanolamine, 
diethanolamine, triethanolamine, piepridine, caustic soda and like. It is 
also conventional to add to the composition a suitable chelating agent 
(e.g. ethylenediamine tetraacetic acid, nitrilotriacetic acid, sodium 
gluconate, sodium tripolyphosphate ans like as a buffer. If desired, it is 
also possible to add suitable wetting agents (e.g. cetylalcohol), 
emulsifiers (e.g. glycerine, polyethylene glycol, higher alcohol esters, 
higher fatty acid esters and like), effect-promoting agents (e.g. urea), 
thickners, hair nutrients, colouring agents, perfumes and like in 
convnetional manner. The permanent waving composition according to the 
present invention may be used for the cold permanent waving and heat 
permanent waving in conventional manner. The pH of the composition may be 
adjusted, depending upon the types and purposes of the operations. 
Cysteine and N-acetylcysteine used for the present invention may be 
selected from the free L-, D-, DL-forms and a mixture thereof, although it 
is also possible to use inorganic salts thereof. 
When the composition according to the present invention is preserved in a 
bottle, it is advantageous to substitute the air in the bottle with 
nitrogen gas. In this case, the storage stability is at least equal to the 
storage stabilities of the permanent waving compositions of the known 
types. 
Particular advantages achieved according to the present invention are 
exemplified as follows. It is possible to avoid the separation of the 
crystals derived from cysteine on the skin and hair, which is liable to 
cause various undesired side effects such as allergic reactions. On the 
other hand, conventional permanent waving composition containing 
N-acetylcysteine as active ingredient has the inherent disadvantage that 
the hair applied with the composition is considerably slippery and can 
hardly held tightly by the hands of artist, resulting in the lowering of 
operational efficiency. Although the composition according to the present 
invention also contains N-acetylcysteine, the amount thereof is so small 
and thus it is possible to avoid the slipping trouble completely. 
D-cysteine contained in the composition of the known type is derived from 
L-cysteine and also N-acetylcysteine is derived from cysteine, and the 
costs thereof are expensive. According to the present invention, it is not 
necessary to use both L-cysteine and D-cysteine at a certain ratio and the 
amount of N-acetylcysteine is small, which make the cost cheaper.

The following example including comparative data illustrates the invention. 
EXAMPLE 
(A) Preparation of test samples: 
Each sample shown in Table 1 was prepared in the following manner. Cysteine 
and N-acetylcysteine were dissolved in pure water (20 ml) at room 
temperature in nitrogen atmosphere. Each solution was adjusted to a pH of 
7.0 with addition of ammonia and was then added with sodium 
ethylenediamine tetraacetic acid (0.05 g) as a buffer. By adding pure 
water, the solution was made up to 100 ml, and the pH was adjusted to 9.2 
(for the cold system) with addition of monoethanolamine. The samples 
prepared in this manner are shown in Table 1 and may be divided into the 
following groups: (i) (A) + (B) = 7.0 g; (ii) (A) = 7.0 g and (iii) 
comparative samples. This was because the examples described in the prior 
art literatures referred to above use various permanent waving 
compositions containing active ingredients at a concentration around 7% 
which may accordingly be deemed as a middle value of practically used 
concentrations. 
TABLE 1 
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Samples (unit -gram) 
(A) 
Cysteine (B) N-acetyl 
Sample No. 
L- D- cysteine B/A (%) 
(A) + (B) 
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1 10.0 -- -- -- -- 
2 10.0 -- 3.0 30.0 13.0 
3 7.0 -- -- -- 
4 3.5 3.5 -- -- -- 
5 6.8 -- 0.2 2.9 7.0 
6 6.65 -- 0.35 5.2 7.0 
7 6.3 -- 0.7 11.1 7.0 
8 3.15 3.15 0.7 11.1 7.0 
9 5.6 -- 1.4 25.0 7.0 
10 5.38 -- 1.62 30.0 7.0 
11 4.9 -- 2.1 42.0 7.0 
12 4.2 -- 2.8 66.7 7.0 
13 3.5 -- 3.5 100.0 7.0 
14 3.15 -- 3.85 122.0 7.0 
15 7.0 -- 7.0 100.0 14.0 
16 7.0 -- 4.0 57.0 11.0 
17 7.0 -- 3.0 42.0 10.0 
18 7.0 -- 1.75 25.0 8.75 
19 7.0 -- 0.78 11.1 7.78 
20 7.0 -- 0.37 5.3 7.37 
21 -- -- 3.0 -- -- 
22 -- -- 1.5 -- -- 
23 3.6 -- 2.4 66.7 7.0 
24 3.5 -- 1.5 42.9 5.0 
25 2.1 -- 0.9 42.8 3.0 
26 7.0 -- 0.7** -- -- 
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**thioglycollic acid 
(B) Test on the separation of the crystals on the skin: 
Each sample (0.5 ml) was dropwise applied to the crotches between the 
fingers of the left and right hands (each 2 crotches at each hand) of each 
person of a test panel consisting of 20 persons. The test sample was 
applied to the same positions daily 4 times i.e. at 9, 11, 13 and 15 
o'clock and the hands were allowed to stand without any after-treatment 
except being washed with water and soap at 12 and 17 o'clock every day. 
The test samples were prepared every day newly. The same procedures were 
repeated for one week to observe the changes occured at the crotches. When 
it was found that a specific sample was liable to cause a heavy allergic 
effect in the course of the test, then the test was no longer continued. 
The results are as follows. 
No. 1 
White crystals were found at the crotches between the fingers of all 
persons on the first day and could not removed even when washed with water 
and soap. The test was discontinued. 
No. 2 
A slight separation of the crystals was found on 2 persons on the 5th day 
and on all persons on the 6th day. After this, a remarkable tendency to 
increase was not found. However, the test was not continued further. 
No. 3 
An almost similar result to that of No. 1. 
No. 4 
A similar result to that of No. 1 was found on the 2nd day. The test was 
not continued further. 
Nos. 5 and 6 
White crystals were found on 4 persons on the 2nd day and on all persons on 
the 3rd day. The degree of the separation was lower than the degrees 
observed in Test Nos. 3 and 4. However the test was not continued further. 
No. 7 
A slight separation of the crystals was found on 2 persons on the 3rd day 
and a similar result to that of No. 5 was found on all persons on the 4th 
day. The test was discontinued. 
No. 8 
A slight separation of the crystals was found on 3 persons on the 5th day 
and on all persons on the 6th day. The test was discontinued. 
No. 9 
An analogous tendnecy to that of No. 8 was found. A slight separation of 
the crystals was observed on all persons on the 6th day, and after this no 
remarkable change was observed. The test was completed. 
No. 10 
A similar tendency to that of No. 9 was observed. 
Nos. 11-17 and 21-.congruent. 
The separation of the crystals and the occurrence of erythema were not 
found until the completion of the tests. 
No. 18 
A similar tendency to that of No. 9 was found. 
No. 19 
A similar tendency to that of No. 7 was found. 
No. 20 
A similar tendency to that of No. 6 was found. 
No. 26 
White crystals were separated on several persons on the first day and on 
almost all persons on the 2nd day, and the test was discontinued. The 
result was similar to that in No. 1. 
From these results, it has been confirmed that the separation of the 
crystals is liable to increase according to the increase in the absolute 
amount of cysteine in the composition and/or the decrease in the ratio of 
N-acetylcysteine to cysteine (B/A in Table 1) and that the degree of the 
separation onto the skin is liable to rise according to the increase of 
the period of time, in which the skin was placed in contact with cysteine. 
(C) Test on cold permanent waving 
In taking into account of the above-mentioned results, the samples shown in 
Table 2 were used for cold permanent waving test carried out in a usual 
manner which was obvious for average artists. Namely, each sample and 
sodium bromate solution (5%) were respectively used as the first and 
second solutions for convnetional two step cold permanent waving system. 
The results were evaluated and shown in Table 2 by using the following 
remarks. 
(A) Waving condition and luster of the hair after the treatment: +++ (very 
good), ++ (good), + (normal) and .+-. (poor or no good) 
(B) Slipping trouble: + (no trouble), .+-. (light trouble), -- (middle 
trouble) and --(heavy trouble). 
Other results than those shown in Table 2 were at least equal to those 
obtained from conventional cold permanent waving compositions. 
TABLE 2 
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Sample Waving 
No. B/A (%) (A) + (B) condition 
Luster 
Slipping 
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2 30.0 13.0 ++ +++ .+-. 
7 11.1 7.0 ++ +++ + 
8 11.1 7.0 +++ +++ + 
9 25.0 7.0 +++ +++ + 
12 66.7 7.0 +++ +++ + 
13 100.0 7.0 ++ +++ - 
14 122.0 7.0 ++ +++ - - 
15 100.0 14.0 ++ +++ - - 
16 57.0 11.0 ++ +++ - - 
17 42.0 10.0 +++ +++ - - 
18 25.0 8.75 +++ +++ .+-. 
19 11.1 7.78 +++ +++ + 
20 5.3 7.37 ++ +++ + 
21 -- -- .+-. + - 
22 -- -- .+-. + .+-. 
23 66.7 7.0 +++ +++ + 
24 42.0 5.0 ++ +++ + 
25 42.8 3.0 + ++ + 
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