JPH07116014B2 - Hair treatment agent and hair treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a process for forming permanent waves on hair or straightening curls such as curly hair and curly hair (in the present specification, "formation process for permanent waves"). And a hair dyeing treatment, and a hair treatment agent comprising a combination of a permanent wave liquid and a metallic hair dyeing agent, and a hair treatment method using the same. Regarding

"Prior art" Along with clothes, jewelry, makeup, etc., hair treatment such as permanent wave and dyeing is an important element of modern fashion. As a fashionable technique for hair, a forming process such as a permanent wave and a hair dyeing process have been widely performed. Also, as the number of people aiming for individual fashion increases, the number of people who perform both permanent wave and hair dyeing treatment also increases, so it can be said that there is a great interest in fashioning hair.

First, a process of forming a permanent wave or the like will be described. Conventional permanent wave liquids usually consist of a combination of a first liquid and a second liquid. The first liquid contains a reducing agent such as thioglycolate or cysteine, and the second liquid contains an oxidizing agent such as bromates, perborates and hydrogen peroxide.

There are roughly two types of methods for forming permanent waves and the like. One is a heating wave method that requires a heating operation, and the other is a cold wave method that is performed at room temperature. The procedure for forming a permanent wave or the like by the cold wave method will be roughly described as follows.

First, the hair is wound on a rod to be shaped into a desired wave shape, and then the first liquid is applied to the hair wound on the rod and left for a required time. Alternatively, the hair may be wrapped around the rod while applying the first liquid. First
The reducing agent in the liquid cleaves the cystine bond of the keratin side chain to remove the restoring force from the hair. After the plasticized hair is washed with water and rinsed, the second
Apply liquid. The oxidizing agent contained in the second liquid has an action of recombining the cleaved cystine bond. Therefore, the hair is fixed in a new state in which waves or the like are formed. When the desired permanent wave or the like is formed in this manner, the rod is removed from the hair, and the hair is washed, rinsed and dried.

The heating wave method is the same as the above-mentioned cold wave method, in which the first liquid is applied to the hair wound around the rod, and then 60
It is a method of heating to an extent not exceeding ℃ to accelerate the chemical reaction. The heating-type wave method requires less amount of main components such as reducing agent and oxidizing agent than the cold-type wave method, but requires a heating device for heating.

On the other hand, the hair dyeing methods are roughly classified into a temporary hair dyeing method and a permanent hair dyeing method that does not fade even with shampoo.

The temporary hair dyeing method is color spray, color crayon,
This is a method of temporarily coating the surface of hair with a hair dye in which a pigment such as color rinse is mixed with a base. Therefore, there is a drawback in that the color is easily removed by shampoo and the hair dyeing effect is lost.

Therefore, in order to obtain a robust hair dyeing effect, a permanent hair dyeing method using a vegetable hair dye, an oxidative hair dye, a metal hair dye or the like is used.

Among the permanent hair dyes, a typical one as a plant hair dye is a solution prepared by boiling down henna leaves or a solution prepared by kneading dry powder with hot water, and adding citric acid or the like to obtain an acidic solution. .
Apply this to hair and pack with a steaming towel to dye the hair. However, since the plant hair dyeing method has a red color tone,
The treatment target is limited to some people. That is, it is difficult to satisfy various tastes for fashionable hair, which is not practical.

At present, the oxidative hair dyeing method and the metallic hair dyeing method are widely used as permanent hair dyeing methods capable of obtaining various color tones. The oxidative hair dye comprises a first liquid containing an aromatic amino compound such as paraphenylenediamine and paratoluenediamine as a main component, and a second liquid containing an oxidizing agent such as hydrogen peroxide as a main component. To the first liquid, amines, polyphenols and the like are added as a correcting agent for changing the color tone, and in addition, ammonia and the like are added to adjust the alkalinity. When the second liquid is subsequently applied after the first liquid is applied to the hair, the oxidizing agent such as hydrogen peroxide in the second liquid is rapidly decomposed by the alkali of the first liquid to generate oxygen. The aromatic amino compound and the correction agent in the first liquid penetrate into the hair while being oxidized by this oxygen to form an oxidative dye.
On the other hand, the melanin pigment in hair is oxidatively decomposed by nascent oxygen. Thus, the keratin dyeing reaction due to the formation of the oxidative dye and the decolorization reaction due to the oxidative decomposition of the melanin pigment occur in parallel, so that the hair can be dyed in various color tones.

On the other hand, the metallic dyeing agent is a two-component type (or a pretreatment agent for hair or the like) consisting of a metal salt solution containing a metal compound such as iron or copper as a main component, and a color developing agent that exhibits a color reaction with the metal. It is a three-liquid type drug added. When the metal salt solution is applied to hair,
Metal molecules such as iron bind to keratin and settle on the surface of hair. Then, when the color former is applied, a color reaction occurs with the fixed metal, and the hair is dyed in a predetermined color tone.

[Problems to be solved by the invention] When hair is subjected to both permanent wave forming treatment and permanent hair dyeing treatment in a beauty salon, barber shop, etc., each treatment is performed separately, that is, It is a general method to form a permanent wave or the like on the hair and then to subject the hair to a dyeing treatment, or to apply a hair dyeing treatment and then to form a permanent wave or the like. Therefore, no matter which order the procedures are performed, it takes a lot of time and labor and is very uneconomical.

The oxidative hair dyeing method, which is widely used as a permanent hair dyeing method, has the features of rich color tone and less color loss due to shampoo, but has the drawback of high incidence of allergic dermatitis. Aromatic amino compounds such as para-phenylenediamine and para-toluenediamine, which are the main ingredients, are known to be the most sensitizing allergens used in cosmetics. A high rate of allergic dermatitis occurs when used. Many cases of this have been observed not only in the person to be subjected to hair dyeing but also in the hairdresser who is in charge of the treatment. Moreover, it has been clarified that those who have experienced allergic reaction cause a cross reaction by an aromatic amino compound having a structure similar to that of paraphenylenediamine and paratoluenediamine contained in sulfa drugs, anesthetics and the like. In addition, the first liquid is strongly alkaline and therefore has primary irritation to the skin.
Since the hair dyeing reaction is mainly an oxidative reaction that proceeds under strong alkalinity, hair damage is remarkable. Permanent wave is less likely to be applied because the cystine bond is broken. Further, there are many problems such as fading due to irradiation with ultraviolet rays, acidic shampoo and acidic rinse.

"Means for Solving Problems" The present inventor has made diligent efforts for the purpose of simultaneously performing safe and highly permanent permanent wave forming treatment and hair dyeing treatment in parallel. . As a result, they have invented a hair treatment agent and a hair treatment method using the same as described below.

The hair treatment-requiring agent according to the present invention is a first agent containing a thioglycollate or a mercapto compound of cysteine as a reducing agent, a second agent containing a metal salt of iron or copper, and a second agent contained in the second agent. A third agent containing a compound having a phenolic hydroxyl group, an enol type hydroxyl group or a hydroxyl group similar thereto or a compound having a carboxyl group or a derivative thereof as a color-forming agent that causes a color reaction with a metal salt of iron or copper, and bromic acid as an oxidizing agent. It comprises the first to fourth agents of the fourth agent containing salts, perborates or hydrogen peroxide water.

In the above-mentioned first agent, the thioglycolates refer to thioglycolic acid, ammonium thioglycolate, sodium thioglycolate, potassium thioglycolate and the like. The metal salt of iron or copper in the second agent is iron compounds such as ferrous sulfate, ferric chloride, ferric tetroxide, ferric sesquioxide, and iron oxide yellow, and copper acetate, copper sulfate, glycine. Refers to copper compounds such as copper. Further, the compound having a phenolic hydroxyl group, an enol type hydroxyl group or a hydroxyl group similar thereto or a carboxyl group in the third agent or a derivative thereof is gallic acid, gallic acid esters such as propyl gallate, salicylic acid, sodium salicylate / salicylic acid. Salicylates such as potassium, salicylates such as methyl salicylate and phenyl salicylate, tannic acid and its esters, resorcin, resorcin acetate,
Pyrogallol, catechol, hydroquinone, hematein, hamamelis water, vanillide nonylate, 2-hydroxy-5-nitro-2 ', 4'-diaminoazobenzene-5'
-Sodium sulfonate, phenol, nitrophenol, orthoaminophenol, metaaminophenol,
Sulfuric acid metaaminophenol, sulfuric acid paraaminophenol, sulfuric acid paramethylaminophenol, sulfuric acid orthoaminophenol, parachlorophenol, 2-amino-4-
Nitrophenol-2-amino-5-nitrophenol-3,3'-iminodiphenol-sulfuric acid 2-amino-5-
Phenols such as nitrophenol, 2,4-diaminophenol, paraaminophenol, paramethylaminophenol, orthophenylphenol, pyridoxine hydrochloride, hexachlorophene, hinokitiol, cresol, 5-aminoorthocresol, 5-aminoorthocresol sulfate Cresols such as chlorcresol, chlorxylenol, 1-amino-4-methylaminoanthraquinone, sodium picramate, 1,4-diaminoanthraquinone, 1,5-dihydroxynaphthalene, α-
Naphthol, eugenol, isoeugenol, vanillin, paraphenolsulfonic acid subsalt, 2- (2-hydroxy-5-methylphenyl) benzotriazole, acetoacetic acid esters such as ethyl acetoacetate, ascorbic acid, gluconic acid and salts thereof, Benzoic acid, benzoates such as sodium benzoate and disodium benzoate, benzoates such as amyl benzoate, isobutyl benzoate, pantothenyl benzoate and sucrose benzoate, para-aminobenzoic acid, para-aminobenzoic acid It refers to para-aminobenzoic acid esters such as glyceryl ethyl-para-aminobenzoate and derivatives thereof. The bromates and perborates of the fourth agent are bromates such as potassium bromate and sodium bromate, and perborates such as sodium perborate.

Next, a method for simultaneously performing in parallel a hair forming treatment such as a permanent wave and a hair dyeing treatment using the first to fourth agents will be described. First, while applying or after applying the first agent, the hair is shaped into a desired shape by wrapping it around a rod, etc., and is left on the hair surface for a required time while maintaining the shaped state and then washed with water. And removing the first agent. Next, after applying a second agent containing a metal salt such as iron or copper to the hair and leaving it for a required time,
The second agent remaining on the hair surface is removed by washing with water again. Next, after applying a third agent that exhibits a color reaction with iron or copper contained in the second agent to the hair, subsequently applying a fourth agent containing an oxidizing agent, and leaving it for a required time, By releasing the shaping and holding state of the hair and performing appropriate treatments such as washing and drying, it is possible to obtain hair that has been subjected to the treatment of forming a desired shape and the hair dyeing treatment.

Instead of washing with water after applying the first agent and washing with water after applying the second agent, a method of sucking or wiping off the surplus agent remaining on the hair surface with a sponge or the like may be used.

In the hair treatment method of the present invention, not only the first agent to the fourth agent are sequentially applied to the hair, but also the second agent and the third agent are mixed and applied to the hair, and the hair is allowed to stand for a required time and then washed with water. It is also possible to remove the second agent and the third agent remaining on the hair surface by applying, and then apply the fourth agent, and further mixing the third agent and the fourth agent. It can also be applied to hair.

"Action" The reducing agent in the first agent breaks the cystine bond and makes the hair plastic while it is shaped and held in the desired shape.
At this time, since it also undergoes swelling at the same time, the metal molecules in the second agent to be applied subsequently easily penetrate into the hair. Next, by applying the second agent, metal molecules such as iron or copper are firmly bound to the keratin of the hair. Then, by applying a third agent, a compound having a phenolic hydroxyl group, an enol type hydroxyl group or a hydroxyl group or a carboxyl group similar thereto contained in the third agent, or a derivative thereof or the like (hereinafter, referred to as "hydroxyl group or carboxyl group"). Compounds having)) and the metal molecules described above to form colored molecules, and dye hair with a predetermined color tone. The subsequently applied fourth agent has the action of recombining the cystine bond cleaved by the first agent. Therefore, the hair is fixed in a new cystine-bonded state while maintaining the shape of the hair.
In addition, the fourth agent has an action of oxidizing the colored molecule to make the coloration remarkable, and an action of oxidatively polymerizing compounds having a hydroxyl group or a carboxyl group into the colored molecule to grow the colored molecule. ing. Therefore, by applying the fourth agent, the entire hair can be dyed evenly and deeply, and the fastness of hair dyeing is enhanced. It is considered that the metal molecules are catalytically involved in the above oxidative polymerization reaction.

[Example] A specific example of simultaneously performing the permanent wave forming process and the hair dyeing process according to the present invention will be described below.

First, apply the first agent to the hair wound on the rod, or
While applying the agent to the hair, wrap it around a rod and leave it for 10 to 20 minutes. Then, it is washed with water to remove the first agent remaining on the surfaces of hair and scalp. Next, the second agent is evenly applied to the hair wound on the rod and left for 10 minutes to allow a metal such as iron or copper to penetrate into the hair. Then, it is washed again with water to remove the second agent remaining on the hair surface. Subsequently, the third agent and the fourth agent are sequentially applied to the hair, or the third agent and the fourth agent are mixed and applied immediately before use in order to save processing time. After leaving it for 10 to 15 minutes, remove the rod and wash with water and dry. In this way, the formation of the permanent wave and the dyeing of hair are completed in about 1 hour including the time required for winding the rod (about 20 minutes). However, the treatment time can be appropriately changed according to the condition of the hair of the subject, the desired shape and wave degree of the permanent wave, the degree of hair dyeing, and the like.

Tables 1 to 3 below show the test results of the waviness, the wave holding property, the color tone, and the fading property of the hair obtained by the present invention. For test hair, use 20 cm long white hair or decolorized hair.
A bundle of 50 pieces, shampoo, washed with water and dried was used. As shown in FIG. 1, the wave forming tool used to form a permanent wave is a plate-shaped material in which seven pins A to G are erected in parallel two rows at predetermined intervals. The pins have a diameter of 3 mm and the spacing between the pins is A.
22.5 mm between B, BC,…, BF, 20.0 m between AC and CE and between BD, DF and FG
m. The test method is to fix one end (hair root side) of a hair bundle that has been washed with water and lightly moistened to the pin A of the wave forming tool as shown in FIG. 2, and staggered across the pins B to F and G. Then, the wave forming tool is erected so that the pin A is on the upper side and the pin G is on the lower side, and the weight is hung on the lower end of the hair bundle to apply a load of 100 g. After fixing the hair bundle to the pin G in the stretched state, the load is removed, the wave forming tool is made horizontal, and hair treatment is performed.

As for the hair treatment method, the first agent is evenly applied to the hair bundle with a dropper, left for 10 minutes, and then washed with water for 30 seconds. Next, the second agent is applied in the same manner as the first agent, left for 10 minutes, and then washed with water for 30 seconds. Then, apply the mixture of the third agent and the fourth agent in a ratio of 2: 1 in the same manner as the first agent, leave it for 15 minutes, remove the hair bundle from the wave forming tool, wash with water for 30 seconds, and wipe with a cotton cloth. Dry on.

The wave degree in each table is obtained by the following equation.

However, X: the length of the hair fixed between the pins CDE Y: the distance between the pins CE Z: The distance between the points where the hair bundle was in contact with the pins C and E when removed from the wave former (3rd (See the figure.) In addition, the wave holding property is the detergent solution (0.5% lauryl sulfate triethanolamine aqueous solution) of the hair bundle that has been treated as above.
After soaking in 1 minute for 10 minutes, soak in 10 beakers with purified water, wash, and dry with a hand dryer. Repeat 5 times (however, 5 times on a cotton cloth without using a hand dryer. Air-dry), measure the value of Z in the above formula to determine the wave degree before and after the treatment,
It is calculated by the following formula.

The wave retention test is a considerably severe test for hair, which is equivalent to repeating the washing of hair, which is usually performed in daily life, five times in succession.

The judgment of the color tone is carried out by visual evaluation of a hair bundle that has been subjected to the first hair treatment under a 500 W daylight color spotlight by five judges.

Then, the fading is judged by performing the same visual evaluation as the above-mentioned color tone judgment on the hair bundle subjected to the detergent treatment of the wave retention test, and judging the presence or absence of the fading by comparing with the hair bundle before the detergent treatment. Is.

The first to fourth agents used in the test are all aqueous solutions prepared with purified water, and the composition other than the main agent is as follows. (All units are% by weight) 1st agent Ethanol 10.0% Fatty acid diethanolamide 1.2% Amphoteric surfactant 12.0% 2nd agent Nonionic surfactant 10.0% 3rd agent Ethanol 45.0% 4th agent Purified water only [ Test 1] Test 1 demonstrates that according to the present invention, a permanent wave forming treatment and a hair dyeing treatment can be simultaneously performed on hair, and at the same time, a metal salt and a third agent are added to the second agent. It was confirmed that hair with various color tones and wave degrees can be obtained by changing the type of the coloring agent used. The time required for this hair treatment was about 40 minutes.

The test results are shown in Table 1.

In Comparative Example C-1, the second agent and the third agent were omitted. That is, only the permanent wave forming treatment was performed and the hair dyeing treatment was not performed.

As can be seen from Table 1, various color tones can be obtained by changing the type of compounds having a hydroxyl group or a carboxyl group to be blended in the third agent. In the test, propyl gallate, resorcin, catechol, and hinokitiol were used as a compound having a phenolic hydroxyl group or a hydroxyl group similar thereto, and ethyl acetoacetate was used as a compound having an enol type hydroxyl group, and as a compound having a carboxyl group. Benzoic acid and calcium gluconate were used. Note that salicylic acid is a compound having both a phenolic hydroxyl group and a carboxyl group.

Further, the compounds having a hydroxyl group or a carboxyl group do not have to be limited to one kind. Rather, a variety of colors can be obtained by freely combining several types. (See Trial Nos. 2-1 and 2) Further, as shown in Trial No. 3-1, it is also possible to change the kind of the metal salt to impart different color to the hair.

By the way, as compared with the control example (C-1), all the examples of the present invention are excellent in the wave degree and the wave holding property. In particular, it can be seen that even if a severe wave holding property test is performed, a sufficient wave degree is held. This is due to the action of the compounds having a hydroxyl group or a carboxyl group mixed in the third agent, and seems to assist the cystine bond cleavage action of the reducing agent.

[Test 2] Test 2 affects the wave degree and the wave holding property,
It is a test in which the concentration and kind of the reducing agent of the first agent and the kind of the oxidizing agent of the third agent were changed. The results are shown in Table 2. In the tests of Comparative Example C-2, Trial No. 5-1 and Trial No. 6-3 in Table 2, the standing time after application of the first agent was 20 minutes.

[Test 3] Tests 1 and 2 are test results obtained by carrying out the present invention on gray hair or bleached hair, but Test 3 proves that the effect of the present invention can be obtained also on ordinary black hair. Is. The results are shown in Table 3. In the test, the standing time after coating the first agent and the standing time after mixing and coating the third agent and the fourth agent were each 20 minutes.

As is clear from Table 2, by changing the types of reducing agent and oxidizing agent, it is of course possible to obtain hairs having different wave degrees and wave holding properties.
It is possible to dye hair in different color tones without changing the types of the metal salt and the color former. This is probably because the reaction that cleaves and restores the cystine bond of keratin is involved in the coloring reaction of the metal salt. The present invention can dye not only gray hair but also natural hair as shown in Table 3.

The present invention, as shown in the above table, has a high wave degree,
Wave retention, various color tones, and fading resistance can be imparted to hair, but in addition, depending on the type of compound having a hydroxyl group or a carboxyl group to be added to the third agent,
Exhibits various additional effects. For example, hinokitiol has a hair nourishing action, pyridoxine hydrochloride has a skin conditioning action, resorcin has a bactericidal action, paraphenolsulfonic acid subsalt has an astringent action, and propyl gallate has an antioxidant action. As a result, quality stabilization and various pharmacological effects can be imparted.

Also, if the pH of the first agent is adjusted to be alkaline, the permanent wave can be made stronger, and if the pH of the second agent and the third agent are adjusted to be weakly acidic, the treatment will be performed under mild conditions. can do.

In the above-mentioned test example, the third agent and the fourth agent were mixed and applied in the hair treatment, but it is of course possible to apply the third agent and the fourth agent in order, and the second agent and the third agent. You may apply the 4th agent after apply | coating the liquid mixture with an agent, leaving it to stand, and washing with water.

The method of the present invention can be applied not only to the formation of permanent waves but also to straightening curly hair (curly hair, curly hair) (so-called straight perm). In this case, the hair may be spread and fixed on the plate while applying the first agent, and the same treatment may be performed.

Further, the formation of the permanent wave or the like according to the present invention may be performed by the cold wave method or the heating wave method. Further, it is also applicable to apply only hair dye without forming a permanent wave or the like.

"Effects of the Invention" The effects of the present invention will be described below.

A permanent wave forming process or a desired shape forming process such as curly straightening and a hair dyeing process can be simultaneously performed in parallel. Therefore, it is possible to easily perform the forming treatment such as the permanent wave and the hair dyeing, which have required a lot of trouble and time since they have been separately performed in sequence, within a much shortened time. .

Since a metallic hair dye is used as the hair dye, it is possible to perform a durable and highly permanent hair dyeing treatment, and furthermore, there is no sensitizing property or primary irritation to the human body, which is excellent in safety.

By changing the composition of the hair treatment agent, it is possible to obtain a wide variety of color tones, and it is possible to apply not only to hair dyeing, but also to hair treatment such as blonde hair, red hair, and brown hair, as well as black hair treatment. In addition, since the degree of wave can be freely changed, it is possible to satisfy various requests for fashionable hair.

In summary, the present invention provides a hair-treating agent and a hair-treating method that have extremely great practical value.

[Brief description of drawings]

FIG. 1 is a perspective view showing a wave forming tool used for the test of the present invention, and FIG. 2 is a front view showing a situation in which a hair bundle is attached to the wave forming tool. FIG. 3 is a diagram for explaining the location of the hair bundle for measuring the wave degree.

Claims (4)

[Claims] 1. The first listed in (1) to (4) below.
An agent for treating hair, comprising a combination of an agent, a second agent, a third agent and a fourth agent. (1) First agent containing thioglycolates or mercapto compounds of cysteine as a reducing agent (2) Second agent containing iron or copper metal salt (3) Iron contained in the second agent or A third agent containing a compound having a phenolic hydroxyl group, an enol type hydroxyl group or a hydroxyl group similar thereto, or a compound having a carboxyl group or a derivative thereof as a color developing agent that causes a color reaction with a metal salt of copper (4) Bromine as an oxidizing agent Fourth agent containing acid salt, perborate or hydrogen peroxide solution 2. A hair treatment method for simultaneously performing formation treatment of permanent wave and the like and hair dyeing treatment on the hair in parallel, which is characterized by comprising steps A to E listed below. . A. A step of shaping the hair into a desired shape while applying or after applying the first agent containing thioglycolates or mercapto compounds of cysteine as a reducing agent. After that, the first agent remaining on the hair surface is removed by washing with water or wiping, and then the second agent containing a metal salt of iron or copper is applied to the hair. C. After leaving for a desired time, washing with water or wiping The second agent remaining on the hair surface is removed with a phenolic hydroxyl group, an enol type hydroxyl group or a hydroxyl group similar to these as a color-forming agent that causes a color reaction with the metal salt of iron or copper contained in the second agent. A step of applying a third agent containing a compound having a compound having a carboxyl group or a compound having a carboxyl group or a derivative thereof to the hair D. Subsequently, a bromate as an oxidizing agent, a peroxide After the fourth agent containing c acid salts or hydrogen peroxide was left Step E. required time to be applied to the hair, releasing the shaping holding state of the hair,
Steps to apply appropriate treatments such as hair washing and drying 3. A hair treatment method for simultaneously forming hair such as a permanent wave and a hair dyeing treatment in parallel, which comprises the steps A to D listed below. . A. A step of shaping the hair into a desired shape while applying or after applying the first agent containing thioglycolates or mercapto compounds of cysteine as a reducing agent. Then, after removing the first agent remaining on the hair surface by washing with water or wiping, a second agent containing a metal salt of iron or copper,
It contains a compound having a phenolic hydroxyl group, an enol type hydroxyl group or a hydroxyl group similar thereto or a compound having a carboxyl group or a derivative thereof as a color-forming agent that causes a color reaction with the metal salt of iron or copper contained in the second agent. Step of mixing with a third agent and applying it to the hair C. After standing for a required time, the second agent and the third agent remaining on the hair surface are removed by washing with water or wiping, and then the oxidizing agent Step 4 of applying a fourth agent containing bromates, perborates or hydrogen peroxide solution to the hair D. After leaving it for the required time, releasing the hair from the shape-holding state, washing, drying and other appropriate treatments Process of applying 4. A hair treatment method for simultaneously performing, in parallel, a forming treatment such as a permanent wave and a hair dyeing treatment on the hair, comprising the steps A to D listed below. . A. A step of shaping the hair into a desired shape while applying or after applying the first agent containing thioglycolates or mercapto compounds of cysteine as a reducing agent. After that, the first agent remaining on the surface of the hair is removed by washing with water or wiping, and then the second agent containing a metal salt of iron or copper is applied to the hair. C. Leave for the required time, and then wash with water or wiping After removing the second agent remaining on the hair surface by means of a phenolic hydroxyl group, an enol type hydroxyl group or a hydroxyl group similar thereto as a color developing agent that causes a color reaction with the metal salt of iron or copper contained in the second agent. A third agent containing a compound having a compound or a compound having a carboxyl group or a derivative thereof,
Step of mixing with a fourth agent containing bromates, perborates or hydrogen peroxide as an oxidant and applying to the hair D. After leaving for a required time, the shape-holding state of the hair is released. Steps for applying appropriate treatments such as hair washing, drying, etc.