JP6351277B2 - Hair deformation treatment method, hair deformation treatment agent, hair deformation intermediate treatment agent - Google Patents

Description

  The present invention relates to a hair deformation treatment method such as a method for making a hair shape wavy and a method for straightening hair, and a hair deformation treatment agent and a hair deformation intermediate treatment agent used in this method.

  The peptide obtained by hydrolyzing protein is blended in a composition intended for hair. Research and development aimed at improving the effect of such peptides and adding functions have been conducted, and cationized, acylated or silylated peptide derivatives are known. In Patent Documents 1 and 2, as peptide derivatives to be incorporated into hair treatment agents, thioglycolate, mercaptopropionate, thiolactate or thiomalate is used to convert a carboxymethyl disulfide group into a peptide. Introduced modified peptides are disclosed. Patent Documents 1 to 3 describe that the above peptide derivatives can be blended in a pretreatment agent, an intermediate treatment agent, a posttreatment agent, and the like for hair deformation treatment (perm).

JP 2010-132595 A JP 2012-56855 A JP 2006-169202 A

  By the way, the purpose of performing the hair deformation treatment is naturally to make the hair into a desired shape. However, in daily life, the hair shape immediately after treatment usually changes gradually.

  In view of the above circumstances, an object of the present invention is to provide a hair deformation treatment method, a hair deformation treatment agent, and a hair deformation intermediate treatment agent capable of suppressing changes in the shape of the formed hair.

  As a result of intensive studies by the present inventor, in hair deformation treatment, when a combination of a predetermined modified peptide is applied to the hair during the use of the first agent and the second agent, the hair is heated and formed. The present inventors have found that the change in hair shape can be suppressed, and have completed the present invention.

That is, the hair deformation treatment method according to the present invention includes a reduction step of applying a first agent mixed with a reducing agent to the hair and an oxidation step of applying a second agent combined with an oxidizing agent to the hair. In addition, one or two side chain groups having units selected from the structures represented by the following formulas (Ia) to (Ic) and salts of these structures are provided between the reduction step and the oxidation step. It is characterized by comprising an intermediate treatment step in which an intermediate treatment agent containing a modified peptide comprising at least seeds is applied to hair and the hair is heated.
_{-S-S- (CH 2) n} -COOH (Ia)
(In the formula (Ia), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (Ib)
_{-S-S-CH (COOH)} -CH 2 -COOH (Ic)

The treatment agent for hair deformation according to the present invention comprises a first agent in which a reducing agent is blended and a second agent in which an oxidizing agent is blended, and is represented by the above formulas (Ia) to (Ic). A modified peptide comprising one or more side chain groups having a unit selected from a structure selected from these structures and salts of these structures, and hair between the use of the first agent and the use of the second agent And an intermediate treatment agent that is used by heating the hair.
_{-S-S- (CH 2) n} -COOH (Ia)
(In the formula (Ia), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (Ib)
_{-S-S-CH (COOH)} -CH 2 -COOH (Ic)

The intermediate agent for deforming hair according to the present invention is used between the use of the first agent for deforming hair containing a reducing agent and the use of the second agent for deforming hair containing an oxidizing agent. A modified peptide comprising one or more side chain groups having units selected from the structures represented by the following formulas (Ia) to (Ic) and salts of these structures is blended and applied to hair. The hair is used by heating.
_{-S-S- (CH 2) n} -COOH (Ia)
(In the formula (Ia), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (Ib)
_{-S-S-CH (COOH)} -CH 2 -COOH (Ic)

  According to the present invention, a predetermined modified peptide is added to the intermediate treatment agent used between the first agent and the second agent, and then the hair coated with this intermediate treatment agent is heated. Daily changes in the shape of the cut hair are suppressed.

The photograph which image | photographed the dry hair | bristle bundle after the hair deformation process of Example 1, Comparative Examples 1a-1d, and Reference Example 1. FIG. The photograph which image | photographed the dry hair | bristle bundle which wash | cleaned repeatedly after the hair deformation process of Example 1, Comparative Examples 1a-1d, and Reference Example 1. FIG. The photograph which image | photographed the dry hair | bristle bundle which performed the immersion in a hot water after the hair deformation process of Example 2, the comparative example 2, and the reference example 2. FIG. The flowchart which shows the manufacturing method example of the modified | denatured peptide in this invention.

Based on an embodiment of the present invention, the present invention will be described below.
The hair deformation treatment of this embodiment is a method using a first agent containing an oxidizing agent, an intermediate treatment agent containing a predetermined modified peptide, and a second agent containing a reducing agent.

(First agent)
The 1st agent of this embodiment is what a reducing agent was mix | blended with water (A typical thing as the 1st agent of this embodiment is a thing with the compounding quantity of water of 80 mass% or more.) . Moreover, what was suitably selected from the well-known raw material for 1st agents is arbitrarily mix | blended with the 1st agent of this embodiment.

  The reducing agent blended in the first agent of the present embodiment is a known reducing agent having a thiol group, such as thioglycolic acid, thioglycolate (such as ammonium thioglycolate, monoethanolamine thioglycolate), Cysteine (L-cysteine, DL-cysteine, etc.), cysteine salt (hydrochloric acid L-cysteine, hydrochloric acid DL-cysteine, etc.), acetylcysteine (N-acetyl-L-cysteine, etc.), cysteamine, cysteamine salt (cysteamine hydrochloride), Examples include glyceryl thioglycolate, thiolactic acid, thiolactate, and butyrolactone thiol. The blending amount of the reducing agent in the first agent of this embodiment may be set as appropriate, and is, for example, 2% by mass or more and 15% by mass or less.

  What was suitably selected from the well-known raw material for 1st agents is arbitrarily mix | blended with the 1st agent of this embodiment as above-mentioned. The raw materials to be optionally blended include alkali agents, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, polymer compounds, silicones, hydrocarbons, waxes, higher alcohols, polyhydric alcohols, Fatty acids, fats and oils, ester oils, proteins, amino acids, chelating agents, anti-inflammatory agents, preservatives, fragrances and the like.

  When an alkaline agent is blended with the first agent of this embodiment, the reducing power of the reducing agent is increased. The alkali agent may be one or more selected from known alkali agents such as ammonia, amino alcohol (monoethanolamine, triethanolamine, isopropanolamine, 2-amino-2-methyl-1 -Propanol, 2-amino-2-methyl-1,3-propanediol, etc.), basic amino acids (such as arginine), morpholine, carbonates (such as ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate), phosphorus Acid salts (ammonium monohydrogen phosphate, sodium monohydrogen phosphate, etc.) and caustic alkalis (potassium hydroxide, sodium hydroxide).

  The pH of the 1st agent of this embodiment is alkaline below 9.5, for example, and 8.0 or more and 9.2 or less are good. These pH ranges may be adjusted by blending the alkali agent.

  The dosage form at the time of use of the 1st agent of this embodiment is not specifically limited, For example, liquid form, cream form, and foam form (foam form) are mentioned.

(Intermediate treatment agent)
The intermediate treatment agent of this embodiment is obtained by blending a predetermined denatured peptide in water (the blending amount of water is, for example, 90% by mass or more). Moreover, what further mix | blended as a raw material of a well-known intermediate processing agent as an arbitrary raw material is good also as an intermediate processing agent of this embodiment.

  The modified peptide blended in the intermediate treatment agent of the present embodiment includes a main chain formed by peptide bonds of two or more amino acids and a side chain group bonded to the main chain.

  The main chain of the modified peptide is not particularly limited. Examples of this main chain include the same main chain of peptides having cysteine as one of the constituent amino acids. Examples of peptides having cysteine as one of the constituent amino acids include keratin and casein. Keratin is known to have a high cysteine ratio among peptides derived from natural products, and is a raw material from which the modified peptide can be efficiently obtained. From this viewpoint, the main chain of the modified peptide is preferably the same as the main chain of keratin.

The predetermined modified peptide includes one or more side chain groups having units selected from the structures represented by the following formulas (Ia) to (Ic) and salts of these structures.
_{-S-S- (CH 2) n} -COOH (Ia)
(In the formula (Ia), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (Ib)
_{-S-S-CH (COOH)} -CH 2 -COOH (Ic)

The salt having the structure represented by the above (Ia) to (Ic) is an ionic conjugate of a carboxylate anion and a cation. Examples of the unit serving as the cation include ammonium such as NH ₄ and metal atoms such as Na and K.

  The modified peptide is more easily dispersed in the intermediate treatment agent of the present embodiment as the molecular weight is smaller, and the influence on the dispersibility when the pH of the intermediate treatment agent is lowered is small. In this respect, the molecular weight of the modified peptide is preferably 70000 or less, preferably 50000 or less, and more preferably 30000 or less. The molecular weight of the denatured peptide is more favorable for adhesion to the outer surface of the hair as the denatured peptide molecule is larger, preferably 2000 or more, preferably 10000 or more, more preferably 20000 or more, further preferably 30000 or more, and 40000 or more. Even more preferred. Here, regarding the molecular weight of the modified peptide, the molecular weight calculated from the relative distance between the band of the modified peptide and the band of the molecular weight marker by Sodium Dodecyl Sulfate-polyacrylamide gel electrophoresis (SDS-PAGE method) is the molecular weight of the modified peptide. Adopted by assuming that.

  Although the minimum of the said modified | denatured peptide compounding quantity in the intermediate processing agent which concerns on this embodiment is not specifically limited, For example, it is 0.01 mass%, and 0.1 mass% is good. On the other hand, the upper limit of the modified peptide blending amount is preferably 5% by weight, preferably 3% by weight, more preferably 2% by weight, and even more preferably 0.5% by weight, from the viewpoint of suppressing cost increase due to blending in large amounts.

  Next, as an example of a method for producing a modified peptide, a method for producing a modified peptide using keratin as a raw material will be described. The modified peptide production method preferably includes the reduction step (STP1), the oxidizing agent mixing step (STP2), the solid-liquid separation step (STP3), and the recovery step L (STP4) shown in FIG. In the method including all the steps shown in FIG. 4, denatured peptides (denatured peptides dissolved in the liquid part L and denatured peptide contained in the solid part S shown in FIG. 4) are generated in the oxidizing agent mixing step (STP2). Therefore, the modified peptide can be produced without providing the solid-liquid separation step (STP3) and the recovery step L (STP4).

Examples of the keratin as a raw material include wool (merino wool, lincoln wool, etc.), human hair, animal hair , nails and the like containing this as a constituent protein. Among them, it is preferable to use wool as a raw material in order to obtain a modified peptide inexpensively and stably. About raw materials, such as this wool, it is good to process beforehand, combining sterilization, degreasing, washing, cutting, crushing, and drying suitably.

  The reduction step (STP1) is a step of mixing the reducing agent, keratin, and water. In this reduction step (STP1), the disulfide group (—S—S—) of keratin is reduced to a mercapto group (—SH HS—).

  The reducing agent used in the reduction step (STP1) is one or two selected from thioglycolic acid, thioglycolate, mercaptopropionic acid, mercaptopropionic acid, thiolactic acid, thiolactate, thiomalic acid, and thiomalate. More than a seed. Examples of the salt form include sodium salt, potassium salt, ammonium salt and the like. The amount of the predetermined reducing agent used is preferably 0.005 mol or more and 0.02 mol or less based on 1 g of raw materials such as wool. In addition, the amount of the reducing agent used is 0.1 mol based on the volume of the liquid to be treated (including keratin or a keratin-derived treatment product and a reaction system in each step; the same shall apply hereinafter). / L or more and 0.4 mol / L or less.

  The amount of water is not particularly limited. For example, the amount of water is preferably 20 parts by volume or more and 200 parts by volume or less with respect to 1 part by mass of raw materials such as wool.

  The pH of the liquid to be treated in the reduction step (STP1) is preferably 9 or more and 13 or less, and preferably 10 or more and 12 or less. By reducing the pH to 9 or more, keratin can be efficiently reduced, and by reducing the pH to 13 or less, keratin main chain cleavage can be suppressed (the purpose is to promote keratin main chain cleavage). In this case, the pH of the liquid to be treated may be adjusted to exceed 13.) In addition, when adjusting to said pH, it is good to use sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, etc.

  Although the temperature conditions of a reduction process (STP1) are not specifically limited, 35 degreeC or more and 60 degrees C or less are good, and 40 degreeC or more and 50 degrees C or less are preferable. When the temperature condition is less than 35 ° C., the reduction reaction rate for converting the disulfide group into a mercapto group is lowered, and keratin may not be sufficiently reduced. On the other hand, when it exceeds 60 ° C., the keratin main chain tends to be cleaved. Moreover, the time of the reduction process (STP1) becomes longer as the set temperature is lower, and becomes shorter as the set temperature is higher.

  The oxidizing agent mixing step (STP2) is a step of mixing the processed product (keratin-derived product) that has undergone the reducing step (STP1) and an oxidizing agent to generate a modified peptide. The mixing of the oxidizing agent is performed to promote an oxidation reaction that modifies the mercapto group of the processed product.

  Examples of the oxidizing agent include sodium bromate, potassium bromate, sodium perborate, potassium perborate, hydrogen peroxide, and the like. The oxidizing agent to be used is 1 type, or 2 or more types. The amount of the oxidizing agent used is not particularly limited, but may be 0.001 mol or more and 0.02 mol or less on the basis of 1 g of raw materials such as wool, and the volume of the liquid to be treated in the oxidizing agent mixing step (STP2) As a reference | standard, it is good in it being 0.02 mol / L or more and 1 mol / L or less. It is normal to mix an oxidant with the liquid to be processed containing the processed product that has undergone the reduction step (STP1), and in this mixing, the concentration of the oxidant is locally increased in the liquid to be processed. In order to avoid this, it is preferable to gradually mix an oxidizing agent solution of about 1 mol / L or more and 5 mol / L or less.

  The pH of the liquid to be treated in the oxidizing agent mixing step (STP2) is adjusted according to the progress of this step. The pH at the start of mixing of the oxidizing agent is preferably 9 or more and 13 or less, preferably 10 or more and 12 or less, and more preferably 10 or more and 11 or less. When the pH is 9 or more, the generation efficiency of the modified peptide is good, and when the pH is 13 or less, the cleavage of the main chain of the keratin-derived processed product can be suppressed.

  The pH of the liquid to be treated at the end of the oxidizing agent mixing step (STP2) is not particularly limited, but may be about 7. In order to adjust to this pH, it is good to use 1 type, or 2 or more types selected from the organic acid and the inorganic acid. Examples of the organic acid include citric acid, lactic acid, succinic acid, and acetic acid, and examples of the inorganic acid include hydrochloric acid and phosphoric acid. When mixing the acid with the liquid to be treated, if the pH is locally lowered in the liquid to be treated, the mercapto groups of the treated product may become disulfide groups, so the acid is gradually mixed with the liquid to be treated. It is preferable.

  The temperature condition in the oxidizing agent mixing step (STP2) is preferably 10 ° C. or more and 60 ° C. or less, and preferably 40 ° C. or less. By controlling the temperature within the above range, the production of by-products such as cystine monoxide can be suppressed.

The reaction formula in the oxidizing agent mixing step (STP2) is changed to thioglycolic acid or a salt thereof, mercaptopropionic acid or a salt thereof, thiolactic acid or a salt thereof, or liomalic acid or a salt thereof as a reducing agent in the reduction step (STP1). In the order of the reducing agent, it is as follows.

  The solid-liquid separation step (STP3) is a step of separating the liquid to be processed after the oxidizing agent mixing step (STP2) into the liquid part L and the solid part S. In the solid-liquid separation step (STP3), known solid-liquid separation means such as filtration, centrifugation, squeezing separation, sedimentation separation, and flotation separation can be employed, and desalting by ion exchange, electrodialysis, etc., if necessary. Etc.

  The recovery step L (STP4) is a step of recovering the modified peptide L dispersed and dissolved in the liquid part L obtained in the solid-liquid separation step (STP3) as a solid product. As a method for recovering the solid modified peptide L in the recovery step L (STP4), (1) recovery by freeze-drying the liquid part L, (2) recovery by spray-drying the liquid part L, (3) Examples thereof include recovery of a denatured peptide L precipitate generated by adding an acid such as hydrochloric acid to the liquid part L and lowering the pH of the liquid part L from about 2.5 to about 4.0. About the collect | recovered solid modified | denatured peptide L, washing | cleaning with water or acidic aqueous solution, drying, etc. are performed as needed.

  As described above, by finishing the treatment in the oxidizing agent mixing step (STP2), a denatured peptide that is highly dispersed and dissolved in the solution to be treated and a denatured peptide that is not dissolved in the same solution are obtained. If these modified peptides are reduced in molecular weight, the dispersibility in water is improved and the solubility is increased. As modes for reducing the molecular weight, (1) a mode in which the solid part S obtained in the solid-liquid separation step (STP3) is hydrolyzed, and (2) a solution in the liquid part L obtained in the solid-liquid separation step (STP3). The modified peptide L is hydrolyzed, (3) the modified peptide L recovered in the recovery step L is hydrolyzed, and (4) the modified peptide L and the solid part S are hydrolyzed together. Can be mentioned. In addition, as a method for reducing the molecular weight by hydrolysis, before the reduction step (STP1), simultaneously with the reduction step (STP1), between the reduction step (STP1) and the oxidizing agent mixing step (STP2), One example is hydrolysis for lowering the molecular weight. Methods for hydrolyzing the modified peptide include those known as peptide hydrolysis, and examples include hydrolysis with an enzyme, hydrolysis with an acid, and hydrolysis with an alkali.

  In order to recover the hydrolyzed modified peptide, the same method as in the recovery step L (STP4) can be employed. However, in the recovery method in which an acid is added so that the pH is about 2.5 to 4.0, the denatured peptide is reduced in molecular weight by hydrolysis, so that it may be difficult or impossible to recover.

  Optional raw materials blended in the intermediate treatment agent of the present embodiment include, for example, surfactants (cationic surfactants, nonionic surfactants, etc.), higher alcohols, lower alcohols, polyhydric alcohols, sugars, ester oils, fats and oils, Fatty acids, hydrocarbons, waxes, silicones, polymer compounds, amino acids, animal and plant extracts, microorganism-derived substances, inorganic compounds, fragrances, preservatives, ultraviolet absorbers and the like.

  The dosage form at the time of using the intermediate treatment agent is not particularly limited, and examples thereof include liquid, cream, foam (foam), and mist. When this dosage form is adjusted to a liquid state, the viscosity after 60 seconds measured at 25 ° C. and a rotor rotational speed of 12 rpm using a B-type viscometer is, for example, 200 mPa · s or less.

  The pH of the intermediate treatment agent of this embodiment is, for example, 5.0 or more and 8.0 or less. In the case where degradation of the dispersibility of the modified peptide becomes a problem when the pH is acidified, for example, one or more surfactants selected from trimethylammonium salts (II) represented by the following formula (II) It is advisable to add an agent and increase the amount until the dispersibility is improved.

[In the above formula (II), R ¹ represents an alkyl group having 12 to 22 carbon atoms, and X represents a halogen atom. ]

(Second agent)
The second agent of the present embodiment is one in which an oxidizing agent is blended in water (typical as the second agent of the present embodiment is a blending amount of water of 80% by mass or more). . Moreover, what was suitably selected from the well-known raw material for 2nd agents is arbitrarily mix | blended with the 2nd agent of this embodiment.

  The oxidizing agent blended in the second agent of the present embodiment is, for example, bromate (sodium bromate, potassium bromate, etc.) or hydrogen peroxide, like the known second agent for permanents.

  When the bromate is blended, the pH of the second agent of the present embodiment is, for example, 5.0 or more and 7.5 or less. The pH of the second agent when hydrogen peroxide is blended is, for example, 2.5 or more and 3.5 or less.

  As described above, the second agent of the present embodiment is arbitrarily blended with materials appropriately selected from known second agent raw materials. Examples of the raw material to be arbitrarily blended include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, polymer compounds, silicones, hydrocarbons, waxes, higher alcohols, polyhydric alcohols, fatty acids. Oils, fats, ester oils, proteins, amino acids, chelating agents, anti-inflammatory agents, preservatives, and perfumes.

  The dosage form at the time of use of the 2nd agent of this embodiment is not specifically limited, For example, liquid form, cream form, and foam form (foam form) are mentioned.

(Hair deformation treatment method)
The hair deformation treatment method of the present embodiment is used to form a hair shape such as a wave shape or a straight line shape, similarly to a known permanent wave treatment or a known hair straightening. In the method, the first agent and the second agent are used, and the intermediate treatment agent is used between these agents.

  The first agent of the present embodiment is used by applying to the hair in the same manner as the known first agent for permanent wave or first agent for straightening hair, and then the hair with water before using the intermediate treatment agent. Is preferably washed. Here, as a known permanent wave, there are a cold-type permanent wave that gives a wave to hair at room temperature, a warm-type permanent wave that gives a wave to hair under heating, and the like. In addition, as known curly hair straightening, cold curly hair straightening that straightens straight hair at room temperature, warm hair straightening straightening and straightening hair under heating, for high-temperature hair styling For example, warming hair straightening using an iron.

  The intermediate treatment agent of this embodiment is applied to hair and used, and the hair after application is heated. If a cationic contact step for contacting the hair with the cationic compound disclosed in JP 2010-155823 A is provided before application of the intermediate treatment agent after using the first agent, the modified peptide adheres to the hair. It becomes easy.

  The heating of the hair is preferably performed until the hair is dried by a heating device such as a commercially available dryer, a rod having a heat generating function, or a hair iron. The temperature at the time of heating is preferably a temperature at which the hair can be dried. For example, the set temperature of the heat generating part of the heating device is 80 ° C. or higher and 180 ° C. or lower.

  The second agent of this embodiment may be used in the same manner as the known permanent wave second agent or second hair straightening agent. Here, the known permanent wave and curly hair straightening are a cold permanent wave, a warming permanent wave, a cold curly hair straightening, a warming curly hair straightening and the like, as described above.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

(Intermediate treatment agent)
The intermediate treatment agent used in Examples and Comparative Examples was a transparent solution in which a modified peptide having a side chain group (n = 1) represented by the above formula (Ia) was dispersed. This solution was prepared according to the following reduction process, oxidant mixing process, solid-liquid separation process, recovery process, and hydrolysis process.

Reduction process:
Merino wool, washed with neutral detergent and dried, was cut to about 5 mm. 5.0 parts by weight of this wool, 15.4 parts by weight of 30% by weight sodium thioglycolate aqueous solution and 8.5 parts by weight of 6 mol / L sodium hydroxide aqueous solution were mixed, and water was further mixed to give a total amount of 150 parts by weight, pH 11 A liquid to be treated was prepared. This liquid to be treated was stirred at 45 ° C. for 1 hour. Subsequently, water was further mixed to make the total amount 200 parts by mass, left under conditions of 45 ° C. for 2 hours, and then naturally cooled until the liquid temperature reached room temperature.

Oxidant mixing process:
While stirring the liquid to be treated after the reduction step, 178 parts by mass of an aqueous solution containing 15.26 parts by mass of 35% by mass hydrogen peroxide was mixed with the liquid over about 30 minutes while stirring (peroxidation). The pH of the liquid to be treated increases with the mixing of the hydrogen water, but the increase was adjusted to a range of pH 10 to 11 by mixing an aqueous solution of about 20% by mass acetic acid. Then, about 20 mass% acetic acid aqueous solution was mixed gradually, and it adjusted so that the pH of a to-be-processed liquid might become 11-7 gradually.

Solid-liquid separation process:
By filtering the liquid obtained in the oxidizing agent mixing step, the liquid part (filtrate) and the solid part were separated.

Hydrolysis process:
The solid part obtained in the solid-liquid separation step was added to 100 parts by mass of water and then left overnight. Next, 0.05 part by mass of the enzyme (“NEP” manufactured by Toyobo Co., Ltd.) was added, followed by heating at 60 ° C. for 1 hour. Thereafter, the temperature in the solution to which the enzyme was added was 80 ° C., and the temperature was maintained for 30 minutes. And the liquid obtained by allowing it to cool naturally at room temperature and filtering was made into the intermediate processing agent used by the Example and the comparative example.

  The concentration of the modified peptide in the intermediate treatment agent used in Examples and Comparative Examples was 0.3% by mass. Further, in the SDS-PAGE method, a band of a denatured peptide was observed in a molecular weight range of 6500 or less.

Example 1
As Example 1 for forming a hair bundle in a wave shape, a hair bundle (weight 0.2 g, length 23 cm) was prepared, and hair deformation treatment was performed by a reduction process, an intermediate treatment process, and an oxidation process.

Reduction process:
In the reduction step, about 3 ml of the first agent (thioglycolic acid 5.5% by mass and dithiodiglycolic acid 1.0% by mass are blended in the hair bundle wound around the rod having a diameter of 12 mm, monoethanolamine, (Aqueous solution adjusted to pH 9.0 with ammonium hydrogen carbonate and aqueous ammonia) was applied, and then allowed to stand at room temperature for 15 minutes. Thereafter, the hair bundle was immersed in water for 3 minutes.

Intermediate processing steps:
In the intermediate treatment step following the reduction step, a 0.1% by mass aqueous solution of a dimethyldiallylammonium chloride / acrylamide copolymer prepared using “Merquat 550” manufactured by Nalco was applied to the hair bundle and towel-dried. Next, about 3 ml of intermediate treatment agent containing the above modified peptide was applied to the hair bundle and left at 40 ° C. for 10 minutes. Thereafter, the hair bundle was heated and dried with a commercially available hair dryer.

Oxidation process:
In the oxidation step following the intermediate treatment step, about 3 ml of the second agent (8.0% by mass of sodium bromate and 1.0% by mass of sodium monohydrogen phosphate is blended in the hair bundle, and the pH is 6.2 using phosphoric acid. The liquid prepared in the above was applied, and then allowed to stand at room temperature for 10 minutes. Thereafter, the hair bundle was immersed in water for 5 minutes.

(Comparative Examples 1a to 1d, Reference Example 1)
In the hair deformation treatments in Comparative Examples 1a to 1d and Reference Example 1, a part of the intermediate treatment process in Example 1 was changed. In Comparative Example 1a, heat drying was omitted from the application of the intermediate treatment agent in Example 1. In Comparative Example 1b, the intermediate treating agent in Example 1 was replaced with water, and heat drying was omitted. In Comparative Example 1c, the heat drying in Example 1 was omitted. In Comparative Example 1d, the intermediate treating agent in Example 1 was replaced with water. In Reference Example 1, the intermediate treating agent in Example 1 was replaced with a 0.3% by mass hydrolyzed keratin solution (solution prepared by mixing “Promois WK-L” manufactured by Seiwa Kasei Co., Ltd. and water).

The differences in the intermediate treatment steps of Example 1, Comparative Examples 1a to 1d and Reference Example 1 are shown in Table 1 below for reference.

  The hair bundle subjected to the hair deformation treatment of Example 1, Comparative Examples 1a to 1d and Reference Example 1 was removed from the rod, washed with water, fixed at one end, and observed in the shape when naturally dried. The hair bundle after this observation is washed with an aqueous polyoxyethylene lauryl ether sulfate triethanolamine solution (“Typol NLET-236” manufactured by Taiko Yushi Kagaku Kogyo Co., Ltd.), washed with water, and dried with a hair dryer. After repeating 5 times, the hair bundle was observed as described above.

  FIG. 1 is a photograph taken during observation of the hair bundle before washing, and FIG. 2 is a photograph taken during observation of the hair bundle after washing. As shown in FIG. 2, the wave shape of the hair bundle subjected to the hair deformation treatment of Example 1 is superior to Comparative Examples 1a to 1d.

(Example 2)
As Example 2, a hair bundle (weight 1.5 g, length of about 30 cm) was prepared, and the hair bundle was straightened by performing hair deformation treatment by a reduction process, an intermediate treatment process, and an oxidation process.

Reduction process:
In the reduction process, about 2 ml of the first agent (8.5% by mass of thioglycolic acid and 2.5% by mass of dithiodiglycolic acid is blended in the hair bundle, and monoethanolamine, ammonium hydrogen carbonate, and aqueous ammonia are used. The aqueous solution adjusted to pH 8.5) was applied and allowed to stand at room temperature for 30 minutes. Thereafter, the hair bundle was immersed in water for 3 minutes.

Intermediate processing steps:
In the intermediate treatment step following the reduction step, a 0.1% by mass aqueous solution of a dimethyldiallylammonium chloride / acrylamide copolymer prepared using “Merquat 550” manufactured by Nalco was applied to the hair bundle and towel-dried. Next, about 3 ml of intermediate treatment agent containing the above modified peptide was applied to the hair bundle and left at 40 ° C. for 10 minutes. Thereafter, the hair bundle was heated and dried with a commercially available hair dryer. Thereafter, the hair bundle was treated with a curling iron for straightening hair at a temperature setting of 180 ° C. so as to extend the hair bundle.

Oxidation process:
In the oxidation process following the intermediate treatment process, about 3 ml of the second agent (an aqueous solution containing 1.5% by mass of hydrogen peroxide and adjusted to pH 3.0 using sodium monohydrogen phosphate and phosphoric acid) And then left at room temperature for 5 minutes. Thereafter, the hair bundle was immersed in water for 5 minutes.

(Comparative Example 2, Reference Example 2)
In the hair deformation treatment of Comparative Example 2, the application of the intermediate treatment agent in Example 2 was omitted. In the hair deformation treatment of Reference Example 2, the intermediate treatment agent in Example 2 was replaced with a 0.3 mass% hydrolyzed keratin solution (solution prepared by mixing “Promois WK-L” manufactured by Seiwa Kasei Co., Ltd. and water). It was.

Differences in the intermediate treatment steps of Example 2, Comparative Example 2, and Reference Example 2 are shown in Table 2 below for reference.

  The hair bundles subjected to the hair deformation treatment of Example 2, Comparative Example 2, and Reference Example 2 were immersed in hot water at 80 ° C. for 20 minutes, and then fixed at one end and observed for natural drying.

  FIG. 3 is a photograph of a hair bundle that was naturally dried after being immersed in the hot water. As shown in FIG. 3, the hair bundle that has been subjected to the hair deformation treatment of Example 2 is better than that of Comparative Example 2, and thus is excellent in maintaining a straight hair straightening shape.

Claims (3)

A hair deformation treatment method used for permanent wave treatment comprising a reduction step of applying a first agent containing a reducing agent to hair and an oxidation step of applying a second agent containing an oxidizing agent to hair. ,
Modification with one or more side chain groups having units selected from the structures represented by the following formulas (Ia) to (Ic) and salts of these structures between the reduction step and the oxidation step A hair deformation treatment method used for permanent wave treatment, comprising an intermediate treatment step of applying an intermediate treatment agent containing a peptide to hair and heating the hair.
_{-S-S- (CH 2) n} -COOH (Ia)
(In the formula (Ia), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (Ib)
_{-S-S-CH (COOH)} -CH 2 -COOH (Ic) A hair deformation treatment agent used for permanent wave treatment comprising a first agent containing a reducing agent and a second agent containing an oxidizing agent,
A modified peptide comprising one or more side chain groups having units selected from the structures represented by the following formulas (Ia) to (Ic) and salts of these structures; and the use of the first agent; An agent for treating hair deformation used for permanent wave treatment, comprising an intermediate treatment agent that is applied to hair during use of the second agent and is used by heating the hair.
_{-S-S- (CH 2) n} -COOH (Ia)
(In the formula (Ia), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (Ib)
_{-S-S-CH (COOH)} -CH 2 -COOH (Ic) An intermediate treatment agent for permanent wave used between the use of the first agent for permanent wave containing a reducing agent and the use of the second agent for permanent wave containing an oxidizing agent,
A modified peptide comprising one or more side chain groups having units selected from the structures represented by the following formulas (Ia) to (Ic) and salts of these structures is blended, applied to the hair, and the hair An intermediate treatment agent for permanent waves , characterized by being heated.
_{-S-S- (CH 2) n} -COOH (Ia)
(In the formula (Ia), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (Ib)
_{-S-S-CH (COOH)} -CH 2 -COOH (Ic)