Hair-dyeing composition and hair-dyeing method using the same

Disclosed is a hair-dyeing composition comprising geraniintannin and a water-soluble iron salt and optionally containing one or more selected from tannic acid, L-cysteine and salts thereof, sodium hydrogen sulfite, sodium sulfite, hydrolyzed product of collagen and resins for hair. The composition may be in the form of either a one-solution-type or a two-solution-type. Also disclosed is a hair-dyeing method using the said composition. The hair dyed with the composition has an almost natural and fast black color.

BACKGROUND ON THE INVENTION 
1. Field of the Invention 
The present invention relates to a hair-dyeing composition which comprises 
geraniintannin and a water-soluble iron salt and which has excellent black 
colorability, dyeability, color tone and color fastness, as well as to a 
hair-dyeing method using the same. 
2. Prior Art 
In general, a so-called gray-hair-dyeing composition for dyeing the gray 
hair of the aged is widely used. The gray-hair-dyeing composition which is 
generally used at present is essentially an oxidizing hair-dyeing 
composition. The hair-dyeing composition of this kind comprises a dye 
intermediate of an aromatic amino compound such as paraphenylenediamine, a 
coupler of a phenol compound such as m-phenylenediamine or m-aminophenol, 
and an oxidizing agent such as hydrogen peroxide or sodium perborate. 
However, such a hair-dyeing composition has a drawback as a substance which 
is directly applied to the skin, as the dye intermediate component in the 
composition causes inflammation of the skin. In addition, the operation 
for dyeing hair with the composition is complicated since plural agents of 
the dye intermediate, coupler and oxidizing agent are to be used. 
In order to overcome inflammation or any similar disorder of the skin by 
the said oxidizing hair-dyeing composition, a non-oxidizing type 
hair-dyeing composition has been proposed, which comprises a water-soluble 
iron salt and gallic acid, tannic aid and pyrogallol. (For example, refer 
to Japanese Patent Kokai Nos. 49-36838, 60-209513 and 51-56119.) 
In addition, a hair-dyeing composition of another type is also known, which 
comprises Japanese gall, nutgall (Turkey gall) extract and ferric chloride 
(Japanese Patent Kokai No. 62-116504). 
The non-oxidizing type hair-dyeing compositions by the prior art have 
defective problems in that the dyeability thereof is poor, the hair 
blackened therewith does not have a glossy and lustrous color tone which 
is intrinsic t black hair and the blackened hair is faded by shampoo and 
is lacking in color fastness. 
SUMMARY OF THE INVENTION 
The object of the present invention is to provide a non-oxidizing type 
hair-dyeing composition which can dye gray hair into black hair having a 
nearly natural color tone and having a high color fastness, as well as a 
hair dyeing method using the said hair-dyeing composition. 
In order to attain the said object, there is provided, in accordance with 
the present invention, a hair-dyeing composition comprising geraniintannin 
and a water-soluble iron salt. As one embodiment of the present invention, 
the composition is a one-solution-type hair-dyeing composition comprising 
geraniintannin and a water-soluble iron salt as a mixture thereof. 
As another embodiment of the present invention, the composition is a 
two-solution-type hair-dyeing composition composed of a 
geraniintannin-containing first solution and a second solution of an 
aqueous water-soluble iron salt solution. 
In accordance with the present invention, there is also provided a 
hair-dyeing method with the said hair-dyeing composition, where the 
geraniintannin-containing first solution is first applied to the hair to 
be blackened and, after the hair is dried, the second solution of the 
aqueous water-soluble iron salt-containing solution is thereafter applied 
to the hair. 
DETAILED DESCRIPTION OF THE INVENTION 
The present inventor has noted the fact that the reaction of a tannin and 
an iron salt yields a black color and he carried out various hair dyeing 
tests for various tannins with such knowledge. As a result, it has been 
found that geraniintannin is superior to any other tannins such as 
catechin-tannin and tannic acid since the former has a higher coloring 
capacity for dyeing a gray hair into a nearly natural black-colored hair 
than the latter, and thus the present invention has been completed. 
In addition, it has also been found that incorporation of one or more 
selected from tannin acid, L-cysteine and salts thereof, sodium hydrogen 
sulfite, sodium sulfite, hydrolyzed product of collagen and resins for 
hair into the hair-dyeing composition of the invention is advantageous for 
increasing the color fastness of the hair as blackened with the 
composition. 
Accordingly, the present invention provides a hair-dyeing composition 
comprising geraniintannin and a water-soluble iron salt; a hair-dyeing 
composition additionally containing one of more selected from tannic acid, 
L-cysteine and salts thereof, sodium hydrogen sulfite, sodium sulfite, 
hydrolyzed product of collagen and resins for hair, in addition to 
geraniintannin and water-soluble iron salt; a one-solution-type 
hair-dyeing composition comprising geraniintannin and a water-soluble iron 
salt as a mixture; a two-solution-type hair-dyeing composition composed of 
a geraniintannin-containing solution and an aqueous water-soluble iron 
salt solution; and a hair-dyeing method with the said hair-dyeing 
composition where the first solution of the geraniintannin-containing 
solution is first applied to a hair and, after dried, the second solution 
of the aqueous water-soluble iron salt solution is then applied to the 
hair. 
In general, it is said that tannins have an astringent effect to the skin 
and mucosa. Because of the effect, tannins have widely been utilized as a 
tanning agent, an antidiarrheal and an antiinflammatory agent from the 
past. Geraniintannin is well known as the main ingredient of a herb 
cranesbill (Geranium nepalense var. thunberqii). Geraniintannin is known 
as a tannin which does not taste bitter, although it has a strong biding 
capacity with proteins. It is said that geraniintannin is a tannin which 
hardly stimulates the skin and mucosa. 
Geraniintannin is derived form a herb cranesbill. A powdered form of the 
herb is extracted with a mixed solvent of ether/water (3/1), and the ether 
layer is harvested. This is concentrated under reduced pressure and 
ethanol is added thereto. The resulting mixture is discolored, filtered 
and further concentrated under reduced pressure. The concentrated liquid 
is dried to obtain a powder. The powder thus obtained contains 
geraniintannin in an amount of about 90%. 
As the water-soluble iron salt for use in the present invention may be any 
iron salt which is soluble in water and may react with a tannin to be 
colored in black, for example, ferric chloride, ferrous chloride, ferric 
sulfite or ferric phosphate. Among these, ferric chloride is preferred. 
The hair-dyeing composition of the present invention comprises the 
above-mentioned geraniintannin and water-soluble iron salt. The 
composition may be in any form of one-solution-type and two-solution-type 
compositions, which may properly be selected in accordance with the use of 
the composition. 
In the case of a one-solution-type composition, it is an aqueous solution 
containing the said geraniintannin in an amount of from 0.1 to 10.0% by 
weight, preferably from 1.0 to 5.0% by weight, and the said water-soluble 
iron salt in an amount of from 0.01 to 5.0% by weight, preferably from 1.0 
to 3.0% by weight. A polyhydric alcohol such as propylene glycol or 
glycerin or ethanol is added to the said aqueous solution to form a 
liquid, emulsion or cream, which may directly be applied to a gray hair to 
blacken the same. Alternatively, it may be incorporated into shampoo or 
rinse. 
In the case of a two-solution-type composition, a polyhydric alcohol such 
as propylene glycol or glycerin or ethanol is added to an aqueous solution 
containing the above-mentioned geraniintannin in an amount of from 0.1 to 
10.0% by weight, preferably from 1.0 to 5.0% by weight, to form a first 
solution. 
One the other hand, ethanol is added to an aqueous solution containing the 
above-mentioned water-soluble iron salt in an amount of from 0.1 to 10% by 
weight, preferably from 2.0 to 5.0% by weight, to form a second solution. 
Addition of one or more selected from tannic acid, L-cystein and salts 
thereof, sodium hydrogen sulfite, sodium sulfite, hydrolyzed product of 
collagen and resins for hair to the hair-dyeing compositions of the 
present invention is advantageous, since the hair blackened with the 
resulting composition may have an elevated color fastness even after 
repeated hair-shampooing. The resins for hair include, for example, a 
copolymer of ethoxyethyl acrylate and hydroxyethyl acrylate, a cationated 
cellulose, etc. 
The amount of the said additives to be added to the composition of the 
invention is from 0.1 to 5.0% by weight, preferably from 0.5 to 3.0% by 
weight. They may be added to the mixture of geraniintannin and 
water-soluble iron salt for the one-solution-type composition, or may be 
added to the geraniintannin-containing solution for the two-solution-type 
composition. 
In the case of the two-solution-type composition, the first solution is 
first applied to hair and kept as it is until the solution becomes dried, 
or the hair is dried with a drier, and the second solution is then applied 
to the hair.

Next, the following examples illustrate some embodiments of the hair-dyeing 
composition of the present invention and the hair-dyeing method using the 
composition, which, however, do not whatsoever restrict the scope of the 
present invention. 
EXAMPLE 1 
Two-solution-type Composition: 
1.0% of geraniintannin, 1.0% of tannin acid, 5.0% of propylene glycol, 5.0% 
of ethanol (95%), 1.2% of carboxyvinyl polymer, 0.5% of L-cysteine 
hydrochloride and 86.3% of pure water were mixed to form a first solution. 
5.0% of ferric chloride, 40.0% of ethanol and 55.0% of pure water were 
mixed to form a second solution. (The "percentage" is all by weight.) 
EXAMPLE 2 
One-solution-type Composition: 
1.0% of geraniintannin, 1.0% of tannic acid, 5.0% of propylene glycol, 
30.0% of ethanol, 1.0% of ferric chloride, 0.5% of sodium hydrogen sulfite 
and 61.5% of pure water were mixed to form a hair dyeing composition. (The 
"percentage" is all by weight.) 
EXAMPLE 3 
Hair-dyeing method with the Hair-dyeing Composition of the Invention: 
The two-soluble-type composition prepared in Example 1 was used for dyeing 
a gray hair. A proper amount of the first solution was applied to the 
necessary part of the gray hair to be blackened with a comb. During 
application of the composition to the hair, the hair was dried with a 
drier. Then the hair was kept as it was for a while, and thereafter the 
second solution was lightly sprayed over the hair, whereupon the hair was 
colored in a dark black and the hair was combed to complete the 
hair-dyeing. 
EXPERIMENTAL EXAMPLE 1 
Comparative Test for Coloration and Color Tone Using Various Tannins and 
Iron Salts: 
(a) Samples: 
(1) Solution comprising 1.0% of geraniintannin, 10.0% of propylene glycol, 
10.0% of ethanol and 79.0% of pure water. 
(2) Solution comprising 1.0% of catechin-tannin, 10.0% of propylene glycol, 
10.0% of ethanol and 79.0% of pure water. 
(3) Solution comprising 0.6% of geraniintannin, 0.4% of tannic acid, 10.0% 
of propylene glycol, 10.0% of ethanol and 79.0% of pure water. 
(The "percentage" is all by weight.) 
(b) Test Method: 
1 ml of each of Samples (1) to (3) and 1 ml of aqueous solution of 0.1M 
ferric chloride or ferrous chloride were mixed, and the color of the 
resulting mixture was observed with the naked eye immediately after 
preparation of the mixture and one day after the said preparation. 
(c) Test Result: 
The results are shown in Table 1. 
TABLE 1 
______________________________________ 
Sample Fresh One-day Stored 
______________________________________ 
(1) & Ferric Chloride 
Black (A) Somewhat Greenish 
Black (B) 
(2) & Ferric Chloride 
Black (B) Blackish Brown 
(3) & Ferric Chloride 
Dark Black (A) 
Dark Black (A) 
(1) & Ferrous Chloride 
Greenish Black (C) 
Black (B) 
(2) & Ferrous Chloride 
Green (D) Blackish Green (B) 
(3) & Ferrous Chloride 
Black (A) Black (A) 
______________________________________ 
Note: 
A . . . Excellent 
B . . . Very Good 
C . . . Good 
D . . . Somewhat Good 
From the results shown in Table 1, it noted that geraniintannin is better 
than catechin-tannin as the former had a higher reactivity and gave a 
darker black color than the latter in the coloration test (in vitro) using 
a tannin-containing solution and an iron salt solution. Addition of the 
tannic acid to geraniintannin resulted in increase of the black density of 
the color formed. 
EXPERIMENTAL EXAMPLE 2 
Comparative Test for Coloration and Color Tone Using Various L-cysteine 
Hydrochloride-containing Tannins and Iron Salts: 
(a) Samples: 
(1) Solution comprising 1.0% of geraniintannin, 0.5% of L-cysteine 
hydrochloride, 10.0% of propylene glycol, 10.0% of ethanol and 78.5% of 
pure water. 
(2) Solution comprising 1.0% of geraniintannin, 0.05% of L-cysteine 
hydrochloride, 10.0% of propylene glycol, 10.0% of ethanol and 78.95% of 
pure water. 
(3) Solution comprising 1.0% of tannic acid, 0.5% of L-cysteine 
hydrochloride, 10.0% of propylene glycol, 10.0% of ethanol and 78.5% of 
pure water. 
(4) Solution comprising 1.0% of tannic acid, 0.05% of L-cysteine 
hydrochloride, 10.0% of propylene glycol, 10.0% of ethanol and 78.95% of 
pure water. 
(5) Solution comprising 1.0% of catechin-tannin, 0.5% of L-cysteine 
hydrochloride, 10.0% of propylene glycol, 10.0% of ethanol and 78.5% of 
pure water. 
(6) Solution comprising 1.0% of catechin-tannin, 0.05% of L-cysteine 
hydrochloride, 10.0% of propylene glycol, 10.0% of ethanol and 78.95% of 
pure water. (The "percentage" is all by weight.) 
(b) Test Method: 
1 ml of each of Samples (1) to (6) and 1 ml of aqueous solution of 0.1M 
ferric chloride were mixed, and the color of the resulting mixture was 
observed with the naked eye immediately to 30 minutes after preparation of 
the mixture and two days after the said preparation. 
(c) Test Result: 
The results are shown in Table 2. 
TABLE 2 
______________________________________ 
Fresh to 30-minute 
Sample Stored 2-day Stored 
______________________________________ 
(1) Dark Black (A) Dark Blackish Green (A) 
(2) Black(A) Dark Green(D) 
(3) Black(B) Blackish Brown (A) 
(4) Somewhat Greenish 
Dark Green (D) 
Black (B) 
(5) Black Olive Brown 
Dark Reddish Brown (B) 
maroon (B) 
(6) Blackish Brown Olive 
Reddish Wine (B) 
Brown 
______________________________________ 
Note: 
A, B, C, D . . . Same as those in Table 1. 
Addition of 0.5% of L-cysteine hydrochloride to 1% of tannin prevents 
formation of a precipiate from tannin and iron salt, whereby the 
composition may be stabilized and the color-absorbability to hair is 
improved. 
EXPERIMENTAL EXAMPLE 3 
DDY Mouse Hair-Dyeing Test Using Various Tannins and Iron Salts: 
(a) Samples: 
A liquid comprising 5.0% of ethanol, 5.0% of propylene glycol and 0.8% of 
carboxyvinyl polymer was used as a base material. To the base material, 
2.0% of geraniintannin was added to form Sample (1), 2.0% of 
catechin-tannin was added to form Sample (2). 2.0% of tannic acid was 
added to form Sample (3), and 1.0% of geraniintannin and 1.0% of tannic 
acid were added to form Sample (4). To each sample was added pure water, 
and the resulting mixture was gelled with potassium carbonate. The gel was 
subjected to the following hair-dyeing test. 
(b) Test Method: 
1 ml of each of Samples (1) to (4) was applied to the hair of the back of a 
DDY mouse (male 7 to 1-week age). After left as it was for about 5 
minutes, the hair was dried with a drier. Next, about 1 ml of aqueous 5.0% 
ferric chloride solution was applied to the same part of the back, and the 
coloration and hue (colorability) as well as the color of the dyed hair 
(dyeability) were observed with the naked eye. (The "percentage" is all 
bye weight.) 
(c) Test Result: 
The test results are shown in Table 3. 
TABLE 3 
______________________________________ 
Coloration, Hue 
Sample (Colorability) Color of Dyed Hair 
______________________________________ 
(1) Black (A) Grayish Black (B) 
(2) Greenish Black (B) 
Light Gray (D) 
(3) Blueish Black (B) 
Grayish Black (C) 
(4) Dark Black (A) Black (A) 
______________________________________ 
Note: 
A, B, C, D . . . Same as those in Table 1. 
From the results shown in Table 3, it is noted that geraniintannin had a 
good dyeability, and the hair was dyed best in black by the use of the 
combination of geraniintannin and tannic acid. The dyeability was improved 
by drying the hair after the tannin-containing solution was applied to the 
hair. 
EXPERIMENTAL EXAMPLE 4 
Color Fastness Test: 
About 1 ml of a solution (first solution) comprising 0.1% of 
geraniintannin, 1.0% of tannic acid, 5.0% of ethanol, 5.0% of propylene 
glycol, 5.0% of L-cysteine hydrochloride and 87.5% of pure water was 
applied to the gray hair of the back of a DDY mouse (male, 7 to 10-week 
age). After left as it was for about 5 minutes, the hair was dried with a 
hot air from a drier, and about 1 ml of aqueous 5% ferric chloride 
solution (second solution) was applied to the hair, which was then colored 
in a greenish dark black. (The "percentage" is all by weight.) 
After thus dyed, the hair was washed with tepid water. The thus washed hair 
was observed to be colored dark black. Next, the thus dyed hair was 
shampooed and the hair was observed to remain black. 
From the said result, it is noted that the hair-dyeing composition 
comprising geraniintannin and ferric chloride may dye the hair in a fast 
black color and the thus dyed hair is not faded but can keep the 
originally dyed color even after washing with a tepid water or after 
shampooing. 
The present invention provides a safe non-oxidizing hair-dyeing composition 
which does not damage the skin. When dyed with the composition, the hair 
may be colored in a nearly natural black color, and the thus dyed hair is 
not faded even after shampooing. The present invention also provides a 
hair-dyeing method with the said hair-dyeing composition. The hair dyed by 
the method using the hair-dyeing composition of this invention may be 
colored in a fast black color. The present invention is therefore an 
extremely useful invention. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.