US3399682A

US3399682A - Method of simultaneously permanently dyeing and waving human hair

Info

Publication number: US3399682A
Application number: US300043A
Authority: US
Inventors: Isaji Toshio
Original assignee: Hoyu Shokai KK
Current assignee: Hoyu Shokai KK
Priority date: 1963-08-05
Filing date: 1963-08-05
Publication date: 1968-09-03
Anticipated expiration: 1985-09-03

Description

United States Patent Oifice 3,399,682 METHOD OF SIMULTANEOUSLY PERMANENTLY DYEING AND WAVING HUMAN HAIR Toshio Isaji, Aichi-gun, Aichi-ken, Japan, assignor to Kabushiki Kaisha Hoyu Shokai, Higashi-ku, Nogoyashi, Japan, a joint-stock company of Japan No Drawing. Filed Aug. 5, 1963, Ser. No. 300,043 7 Claims. (Cl. 132-7) This invention relates to a method and a preparation of a safe and harmless substance which can be classified as a hair dye and permanent waving agent which is capable of permanently dyeing keratin, especially human hair, to any desired color tones, simultaneously enabling one to make a permanent wave by winding it around a rod.

It is an object of the present invention to provide a method of attaining such a permanent dyeing of keratin, especially human hair, using non-poisonous coal tar dyes which have not been well utilized for such purpose under ordinary conditions, without causing any injury to the keratin, especially human hair, to be dyed, and obtaining a strong adherence of the dye such as not to be sepa rated easily through rubbing or shampooing.

It is another object of the present invention to provide a method capable of dyeing keratin, especially human hair, permanently as well as making a permanent wave by winding keratin, especially human hair, around a rod at a proper time.

It is another object of the present invention to provide a preparation for permanently dyeing keratin, especially human hair, to any desired color tone safely and easily by a simple process without causing any undesirable consequence derived therefrom.

It is still "another object of the present invention to provide a preparation for dyeing keratin, especially human hair, by winding it around a rod as well as making a permanent wave at a proper time.

Hereinafter this invention will be explained in detail.

This invention is characterized by a process of making a permanent wave by treating keratin to be dyed with a mild alkaline aqueous solution composed of a small quantity of water soluble mercaptans and dyestuffs such as certified coloring agents or a group of dyestuff made of a kind of coal tar dyestutf which is certified as nonpoisonous (especially such metal containing dyestuffs as Neolan dye or Palatine fast dye) or a mixture of these, and winding the said keratin around a rod at a proper time to obtain a permanent wave, thereafter treating the same with an acidic substance so as to strengthen the bond between the dyestuif and keratin, especially human hair, restoring the keratin, especially human hair, back to its normal condition i.e., isoelectric point in a pH range of -6 and also treating the same with an aqueous solution of an oxidizer to strengthen and fix the permanent wave formed on the keratin, especially human hair.

The dyeing method and its preparation contained in this invention have partly been publicized by Morgan in U.S.P. No. 2,776,668. The mercaptans as being used in this invention and U.S.P. No. 2,776,668 are considered to aid the permeation and fixation of the dye into the keratin to be colored by transferring the dye directly into the cell structure of the keratin to be dyed.

However, it is a well known fact that a group of mercaptans consisting of thioglycolic acid, thiosuccinic acid, thiolactic acid and thiophenol, and their derivatives is capable of reducing cystine linkage to cysteine in keratin, and in reality of weakening keratin.

Such functions of mercaptans are influenced especially by the concentration of the mercaptan, as well as the alkalinity of the solution, temperature and treating time; and in cases Where any of such factors exceed tolerance limit, the keratin will be weakened considerably, result- Patented Sept. 3, 1968 ing in undesirable swelling, twisting or softening thereof.

Therefore, needless to say, it becomes necessary to maintain these factors within as mild a condition as possible and at the same time to prevent such disadvantages as described above from happening through ade quate after treatment.

This invention is characterized by the following special features as opposed to the USP. No. 2,776,668 by Morgan.

In accordance with this invention mercaptans having a concentration as low as possible are to be used, and reducing sulfide, urea or thiourea and proteolytic enzyme are to be added as an assistant into aqueous solution of alkaline mercaptans for the purpose of attaining the intended purpose at a low alkalinity, low temperature and in a short treating time.

Alkaline aqueous solutions of reducing sulfide such as ammonium sulfide and sodium sulfide etc. are capable of softening and swelling keratin.

It is well known that urea and thiourea destroy the hydrogen bond of keratin, especially human hair, and it is possible to obtain a stronger permanent wave by adding urea into ammonia-alkalic solution of thioglycolic acid when compared with cases where no such urea is added therein. These substances can make a permanent wave on keratin, especially human hair, even when used alone, although it may take a longer time and a higher room temperature. Thus, it can be recognized that the addition of reducing sulfide and urea or thiourea into aqueous solutions of alkaline mercaptans aids the transfer of coal tar dyes into keratin, especially human hair, and furthermore is effective in obtaining a stronger permanent wave.

Although a proteolytic enzyme also has a permanent wave effect on keratin, especially human hair, such effect is only noticeable after a considerably long time.

However, when used together with mercaptans, it can act effectively on keratin, causing the keratin to swell and soften, at the same time making possible the permeation of mercaptans resulting in much improvement in permanent wave effect, i.e., by addition of a proteolytic enzyme a decrease in the concentration of mercaptans becomes possible. Proteinase such as pepsin, papain, phytin etc. can be cited as effective proteolytic enzymes.

These are suitable for the purpose in consideration of the fact that the enzyme action can be restrained by the use of oxidizer in the after treatment.

Through the addition of one or more of reducing sulfides, urea or thiourea and the proteolytic enzymes, it becomes possible to obtain a more reliable hair dyeing effect aswell as permanent wave effect using lower concentration of mercaptans, lower alkalinity and shorter treating time, compared with the cases where mercaptans are used alone, and furthermore it becomes possible to reduce any damaging effect on keratin, especially human hair.

Among coal tar dyestuffs, especially those which are represented by:

(CI. 14885) Acid Black 54 (Commercial name: Neolan Gray N)chr0mium complex derived from (l-a'mino- 6-nitro-2-naphthol-4 sulfonic -acid- 1-naphthol-8-sulfonic acid) (01. 18810) Acid Red 186 (Commercial name: Neolan Pink B)chromium complex derived from (l-amino- 2-naphthol-4-sulfonic acid- 3-methyl-l-(m sulfophenyl)-5-pyrazolone) (CI. 15711) Acid Black 52 (Commercial name: Neolan Black WA)-chromium complex derived from l-amino-6-nitro-2-naphthol-4-sulfonic acid 2-naphthol) (CI. 14880) Acid Black 158 (Commercial name: Palatine Fast Blue GGN)chromium complex derived from (1-amino-2-naphthol-4-sulfonic acid- 1-naphthol- 8-sulfonic acid) 3 (CI. 16260) Acid Violet 56 (Commercialname: Palatine Fast Violet RNA)-chrornium complex derived from (5-chloro-6-anisidine G-acid) which, being metal containing dyestuffs, either Neolan dye or Palatine fast dye, having composition as chromium complex salt of O-O-dioxyazo compound generally having one or more sulfonic acid radicals are different from other common acidic mordant dyes in that chrome is already combined with an individual molecule of dye as a complex compound, the said chrome being considered to combine with S of cysteine linkage resulted from the reduction of cystine linkage. At the same time a complex combination is formed between the chrome and the basic radical (amino radical) in the keratin. Furthermore, the sulfonic acid radical combines also with the amino radical in the keratin, therefore it is considered to form an exceedingly strong combination when compared with the other dyes.

As described above, it is the characteristic feature of the present invention to select and use such a metal containing dye of a kind of Neolan dye or Palatine fast dye which is a chrome complex of O-O-dioxy-azo compound having one or two sulfonic acid radicals. Through the use of such dyestuffs, durability and resistivity against the rubbing or shampooing are much improved. Furthermore, when the keratin, especially human hair, is treated, after dyeing, with a diluted aqueous solution of organic acid substance such as tartaric acid, citric acid or acetic acid, it neutralizes the alkali remaining therein and terminates the dyeing action. On the other hand, the dye which has penetrated in and combined with keratin, especially human hair, forms a still stronger salt forming combination through the change of the liquid nature, which intensifies the resistance thereof still more against the rubbing or shampooing. The isoelectric point of keratin, especially human hair, is in a pH range of 5-6, keratin being said to be the strongest near this range and the luster thereof is excellent.

This is accomplished by changing the liquid nature of the keratin, which has been previously treated with an alkaline mercaptan solution, by such acidic treatment to transfer the pH to the acidic side, whereby it recovers its strength, and injury thereof may be prevented.

Such acid treatment is also to be included in the claims of this invention.

Furthermore, when keratin which is dyed with a mild aqueous solution of an oxidizer such as hydrogen peroxide or potassium bromate etc. and thereafter is wound around a rod is treated, it is effective in strengthening the permanent Waves to restore cysteine to cystine through oxidation of the keratin which has previously been reduced by mercaptans and is also effective in the forming, stressing and fixing of colors in combination with the above mentioned acid treatment. Such treatment with an oxidizer is also to be included in the characteristic features of the present invention.

According to this invention, an aqueous solution of one or more mercaptans selected from a group consisting of thioglycolic acid, thiosuccinic acid, thiolactic acid and their derivatives is used, as thioglycolic acid, the amount of the said mercaptan being equivalent to a concentration of 1-7 weight percent of the solution.

However, for the treatment of keratin, especially human hair, pertaining to this invention, a concentration equivalent to 3-5 weight percent of the solution as thioglycolic acid, is most adequate.

This invention uses, as an assistant, one or more substances selected from the group consisting of reducing sulfide and urea or thiourea, having an amount equivalent to a concentration of 1-5 weight percent of the solution and an enzyme selected from proteolytic enzyme proteinase, having an amount equivalent to 0.1-1 weight percent of the solution.

This invention is to be applied at normal temperature although the most adequate range is 2025 C.

.In this invention, the pH of the dyeing solution is adjusted within a range of 8-9.6, but the most adequate range of pH for treating keratin, especially human hair, is 9.0-9.5.

To obtain the above pH value, inorganic alkali and organic alkali may be used, but generally concentrated ammonia water and monoethanolamine are considered to be adequate.

The process of this invention takes about -60 minutes, and for keratin, especially human hair, 40-50 minutes will be most appropriate.

Each of the above factors, i.e., the concentration of mercaptans, temperature, pH of the solution, and treating time, must be carefully controlled, since excess of one or two of these factors can cause undesirable swelling, twisting or softening to keratin, especially human hair, and can bring about unrecoverable injury.

In order to prevent injury to the keratin, it is necessary, when even one of the factors has exceeded the applicable range as described heretofore, to limit one or two of the other factors at a lower range.

The coal tar dyes to be used in this invention have a concentration of 0.5-5 weight percent of the solution.

Acidic aqueous solution to be used in the after treatment is a diluted aqueous solution of an organic acid such an tartaric acid, citric acid or acetic acid, pH of the said aqueous solution being adjusted within a range of 3-4. Furthermore, as to the aqueous solution of the oxidizer to be used in the after treatment, 1% hydrogen peroxide solution or 3% aqueous solution of potassium bromate is suitable, each treating time being 10-30 minutes.

When a certified coloring agent or a coal tar dyestuff which has been certified as non-poisonous co-exists with the mercaptans, they change gradually, mercaptans also are decomposed, with the result that its effective concentration will be reduced. It is desirable, therefore, to keep the alkaline mercaptan solution and the coal tar dyestuif separate and to mix them together at the time of use.

The coal tar dye can be used in the form of a solution containing surface active agents such assodium alkylbenzenesulfonate or alkylolamide and polyhydric alcohols like propylene glycol and glycerine, and a solvent such as isopropyl alcohol, said additional substances being used with an object of promoting permeability, level dyeing, dispersibility, and adhesiveness, or otherwise can be used as a completely dry powder.

The following are examples of the actual application of this invention.

Example 1 Weight Solution A: percent FD & C Blue No. 1 1 FD & C Orange No. 1 0.6 FD & C Red No. 2 0.4 Sodium alkylbenzenesulfonate Alkylolamide 10 Oleic acid 10 Propylene glycol 13 Isopropyl alcohol 30 Total 100.0

Solution B:

Thioglycolic acid 3 Monoethanolamine 5.25 Thiourea 5 Papain 0.5 Sodium carboxymethylcellulose 0.5 Perfume 1.0 Water 84.75

Total 100.0

The above solutions A and B were mixed in the ratio of 1:2 at the time just before the use (pH=9.4), and was applied onto colorless hair. This hair was, after 5 minutes, wound around a rod.

After having been kept in the position for 25 minutes, the hair was rinsed with water in the state of having been kept still around the rod, then 3% aqueous solution of potassium bromate was applied thereon, and after minutes the hair was removed from the rod, shampooed and then was rinsed finally with an aqueous solution of tartaric acid (pH=3.5).

The hair was dyed a brownish color and thus a stronger permanent wave was obtained.

Example 2 Solution A: Weight percent D & C violet No. 1 2

Castor oil sodium sulfate ester 15 Alkylolamide Isopropylalcohol 15 Propylene glycol Oleic acid 18 Total 100.0

Solution B:

Ammonium thioglycolate 5 Ammonia water 1.5 Urea 3 Pepsin 1 Sodium carboxymethylcellulose 0.5 Perfume 1 Water 88 Total 100.0

The solutions A and B were mixed in the ratio of 1:2 at the time directly before the use (pH=9.2). This mixture was applied onto a colorless human hair.

After 10 minutes, the hair was wound around a rod and 25 minutes thereafter was washed with water, and 1% hydrogen peroxide solution was applied thereon. The hair was removed from the rod 20 minutes later, followed by a water washing and after-treatment with aqueous solution of acetic acid (pH=3.8). Thus, the hair was dyed in light purple color having permanent wave thereon.

What is claimed is:

1. A method for the permanent dyeing and waving of human hair comprising treating said hair with an aqueous solution containing about 1-7 percent by weight of a water-soluble mercapto compound selected from the group consisting of thioglycolic acid, thiosuccinic acid, thiolactic acid, and thiophenol, and about 0.5 to 5 percent by weight of a chromium complex of a O-O' dioxyazo compound having at least one sulfonic acid radical. wherein said chromium complex is selected from the group consisting of a chromium complex derived from (l-amino- 6-nitro-2-naphthol-4-sulfonic acid- 1-naphthol-8-sulfonic acid), the chromium complex derived from (l-amin0-2- naphthol-4-sulfonic acid 3-n1ethyl-2- (m-sulfophenyl) -5- pyrazolone), the chromium complex derived from (1- amino 6 nitro-2-naphthol-4-sulfonic acid 2-naphthol), the chromuim complex derived from (l-amino-Z-naphthol-4-sulfonic acid 1-naphthol-8-sulfonic acid), the chromium complex derived from (5-chloro-6-anisidine G-acid).

2. The method of claim 1 wherein said mercapto compound is thiosuccinic acid.

3. The method of claim 1 wherein said solution also contains from 0.1 to 1 percent by weight of a proteinase.

4. The method of claim 1 wherein said solution also contains from 1 to 5% by weight of an agent selected from the group consisting of ammonia sulfide, sodium sulfide, thiourea and urea.

5. The method of claim 1 wherein said human hair is treated with a solution of oxidizer selected from the group consisting of hydrogen peroxide and potassium bromate subsequent to said treatment with said aqueous solution.

6. The method of claim 5 wherein said solution of oxidizer also contains an acidic material selected from the group consisting of tartaric acid, citric acid and acetic acid.

7. The method of claim 5 wherein said solution of oxidizer has a pH of 3 to 4.

References Cited UNITED STATES PATENTS OTHER REFERENCES Merck Index, 5th Edition, Merck and Co., Rahway, NJ. 1940, pp. 593-596.

ALBERT T. MEYERS, Primary Examiner. V. C. CLARKE, Assistant Examiner.

Claims

1. A METHOD FOR THE PERMANENT DYEING AND WAVING OF HUMAN HAIR COMPRISING TREATING SAID HAIR WITH AN AQUEOUS SOLUTION CONTAINING ABOUT 1-7 PERCENT BY WEIGHT OF A WATER-SOLUBLE MERCAPTO COMPOUND SELECTED FROM THE GROUP CONSISTING OF THIOGLYCOLIC ACID, THIOSUCCINIC ACID, THIOLACTIC ACID, AND THIOPHENOL, AND ABOUT 0.5 TO 5 PERCENT BY WEIGHT OF A CHROMIUM COMPLEX OF A O-O'' DIOXYAZO COMPOUND HAVING AT LEAST ONE SULFONIC ACID RADICAL, WHEREIN SAID CHROMIUM COMPLEX IS SELECTED FROM THE GROUP CONSISTING OF A CHROMIUM COMPLEX DERIVED FROM (1-AMINO6-NITRO-2-NAPHTHOL-4-SULFONIC ACID-->1-NAPTHTHOL-8-SULFONIC ACID), THE CHROMIUM COMPLEX DERIVED FROM (1-AMINO-2NAPHTHOL-4-SULFONIC ACID-->3-METHYL-2-(M-SULFOPHENYL)-5-PYRAZOLONE), THE CHROMIUM COMPLEX DERIVED FROM (1AMINO-6-NITRO-2-NAPTHTHOL-4-SULFONIC ACID<--2NAPHTHOL), THE CHROMUIM COMPLEX DERIVED FROM (1-AMINO-2-NAPHTHOL-4-SULFONIC ACID-->1-NAPHTHOL-8-SULFONIC ACID), THE CHROMIUM COMPLEX DERIVED FROM (5-CHLORO-6-ANISDINE--> G-ACID).