TWI414315B - Method of dyeing and re-dyeing hair - Google Patents

Abstract

A method for dyeing and redyeing the hair which comprises the dyeing step of forming inside the hair an oxidation dye polymer which is made from a specific oxidation dye and has specific properties and the redyeing step of treating the resulting hair with a hair-redyeing composition which contains an oxidizing agent and exhibits a pH exceeding 9.6 in application to conduct at least the decomposition of the polymer. According to the method, a satisfactory hair-dyeing power can be exerted in the first hair dyeing, and the hair dyed by the first hair dyeing can be satisfactorily redyed in a bright color or bleached by decomposing the dark-colored oxidation dye polymer formed inside the hair from the oxidation hair dye without conducting the removal of hair dye with a dye-removing agent.

Description

Hair dyeing and re-staining method

The present invention relates to a method of dyeing and re-dying. Some of the technical terms used in the present invention are defined as follows.

"Hair hair dye composition" means a composition comprising at least an oxidative dye and capable of forming an oxidized dye polymer inside the hair by acting on the hair. Direct dyes can sometimes be blended in the hair dye composition to adjust the color tone.

"Oxidized dye polymer" refers to a polymer obtained by polymerization of an oxidative dye under oxidation of an oxidizing agent or air.

"Oxidizing hair dye" is used for dyeing and degrading melanin in hair. The oxidative hair coloring agent is typically a two-part hair dye composition, the first agent comprising an oxidative dye and an alkaline chemical, and the second agent comprising an oxidizing agent such as hydrogen peroxide. The first dose and the second dose are mixed when applied to the hair. Direct dyes can sometimes be blended in oxidative hair dyes to adjust the color tone.

"Falancing agent" is used for the purpose of bleaching hair by degrading melanin in the hair. The bleaching agent differs from the above oxidative hair coloring agent in that the first agent contains an alkaline chemical but does not contain an oxidative dye. The rinse agent is also typically in two dosage forms and the first and second doses are combined when applied to the hair.

A "de-staining agent" differs from an oxidative hair dye or a bleaching agent in that it is used for the purpose of lightening the color of the hair or returning the color of the hair to the original light color by degrading the oxidized dye polymer in the hair. As the decoloring agent, examples include a decoloring agent having a strong oxidative degradation effect in addition to an oxidizing agent and a basic chemical, such as a persulfate, and a mildening agent such as a reducing ketone, a mercaptan or a sulfite. A degrading agent for reducing degradation.

The concept of "heavy dye composition" includes at least oxidative hair dyes and rinsers but does not include the above-described dye removers. The heavy dye composition contains at least an oxidizing agent.

When an acid hair dye is applied to the hair, the acid dye adheres only to the surface of the hair by ionic bonds, so the dyeing effect is semi-permanent and cannot be retained for a long time. Moreover, the melanin pigment in the hair does not degrade, so it is difficult to obtain a dye having a bright hue.

However, when an oxidative hair dye is applied to the hair, it is possible to obtain a dyeing effect which is strong enough to be said to be permanent and to obtain a dye having a bright hue. In other words, first, the hair swells due to the action of alkaline chemicals, and the film covering the surface of the hair is opened. Therefore, the components of the first agent and the second agent are easily penetrated into the inside of the hair. As a result, the active oxygen derived from the oxidizing agent contained in the second agent degrades the melanin pigment in the hair to bleach the hair, and at the same time, the oxidative dye contained in the first agent contacts the oxidizing agent inside the hair to form an oxidation inside the hair. Dye polymer. When the alkaline chemicals are removed by shampooing after the dyeing process is completed, the film of the hair is closed and the oxidized dye polymer is sealed inside the hair.

Therefore, in order to remove the dye from the hair dyed by the oxidative hair dye, it is necessary to degrade the oxidized dye polymer in the interior of the hair. However, it has been conventionally believed that "oxidized dye polymers cannot be degraded with oxidative hair dyes or oxidizing agents contained in bleaching agents" and no exceptions have been known. Therefore, in order to degrade such oxidized dye polymers, it is necessary to use a dye removal treatment using a special treatment agent called a "decolorizer".

On the other hand, as a method of treating the hair dye, for example, a case where all the hair is dyed in a light color to cover the gray hair and a case where the black hair is dyed in a light color is exemplified. The oxidative hair dye to be used in these cases is dyed with an oxidized dye polymer having a light color tone while bleaching the melanin pigment contained in the hair, so that the hair can be dyed in a light color tone.

However, it is hoped that the hair will be dyed in a light shade with an oxidative hair dye after it has been dyed with an oxidative hair dye. In this case, even if the hair dye treatment for obtaining a light color is carried out with an oxidative hair dye capable of forming an oxidized dye polymer having a light color tone, the dye polymer having dark color tone which has been formed in the interior of the hair is Not degradable, so it is difficult to give the hair a bright, light hue. Further, in the case where hair is bleached with a hair bleaching agent after dyeing the hair to a dark color with an oxidative hair dye, there is a problem that the hair cannot be bleached into a bright hue for the same reason. Therefore, in order to obtain good results, it is necessary to carry out a hair dye treatment or a bleaching treatment after the dye removal treatment with the above-mentioned decolorizing agent to obtain a light color tone. The new hair dye treatment or bleaching treatment after the dye removal treatment with the dye remover and the dye removal treatment as described above is particularly complicated. Furthermore, types of depigmenting agents with strong oxidative degradation are difficult to control to achieve a suitable increase in hair brightness and the risk of excessive damage to the hair. In addition, a class of decolorizing agents having a reductive degradation effect has a problem of low dyeing performance.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for dye removal, i.e., degradation of dark colored oxidized dye polymers formed from oxidative hair dyes within the hair without the use of a dye remover.

Another object of the present invention is to provide a dyeing method which dyes hair into a dark shade after oxidation with a oxidative hair dye, and which is dyed or rinsed without a dye remover to obtain a bright, light hue.

A further object of the present invention is to provide a method of dyeing and re-dying in which sufficient hair dyeing ability is obtained at the first dyeing, while good dyeing (or bleaching) performance is ensured upon heavy dyeing.

The inventors believe that the key to achieving these goals is to study the degradability of oxidized dye polymers.

Studies have found that when the oxidative dye to be used in the oxidative hair dye composition is limited to a specific type, or if another type of oxidative dye is also blended therein and the blending amount is limited to a given range, oxidative polymerization When the pH is limited to the range of 4.5 to 9.6, an oxidized dye polymer having interesting properties will be formed. The oxidized dye polymer has a dark to black hue and is suitable for dyeing hair to a dark color.

Surprisingly, when using this particular oxidative dye, the polymerization is accelerated by the action of the oxidizing agent and thus forms an oxidized dye polymer in the range of pH 4.5-9.6, but at a pH above 9.6. The polymerization reaction is inhibited and thereby inhibits the formation of the oxidized dye polymer. It is also surprising that in this pH range above 9.6, the oxidized dye polymer exhibits an interesting behavior of degradation under the action of an oxidizing agent.

In the conventional ordinary oxidative hair dye or rinse agent, the pH at the time of preparation by mixing the first agent and the second agent is adjusted to a value of about 10 to 12. That is, the pH range in which the above oxidized dye polymer undergoes a degradation reaction is in the pH range of a conventional oxidative hair dye or a bleaching agent. Therefore, the above respective objects of the present invention can be attained when carrying out the following dyeing and re-dying methods using such oxidized dye polymers.

(First aspect of the invention)

A first aspect of the invention is a method of dyeing and re-dyeing, the method comprising: satisfying a relationship by using a mass ratio comprising the following component (A) to component (C) as an oxidative dye; And 1> And the hair dye composition having a pH in the range of 4.5 to 9.6 at the time of use forms an oxidized dye polymer inside the hair for the hair dyeing step of hair dyeing; and performing at least after the hair dyeing step by causing the oxidizing agent to be used A process for re-dyeing the treatment of a dye-dye polymer having a pH above 9.6 acting on the hair to degrade the oxidized dye polymer: component (A): diamine oxidation dye; component (B): phenol, Is an oxidation dye different from component (A) and has a -R group in the ortho and para positions of the hydroxy substitution position (R is -H, -OH, -CH ₃ , -NH ₂ or -NHCH ₃ , and The two R groups may be the same or different); and the component (C): an oxidative dye different from the components (A) and (B).

In the first aspect and the second aspect described below, "diamine oxidative dye" refers to an ortho position having two substituent sites attached to the phenyl ring and one of the amine groups attached to the other amine group or Substituted benzene on the para position. Also included are those having any substituent other than an amine group attached to any other substitution position of the phenyl ring.

The oxidized dye polymer defined in the first aspect is an oxidized dye polymer obtained by oxidative polymerization of component (A) to component (C) in a pH range of 4.5 to 9.6 which satisfies the above compositional content relationship. . The oxidized dye polymer has a dark to black hue and degrades under the action of an oxidizing agent in a pH range above 9.6. The focus is on the unique nature of the equilibrium between the polymerization and degradation reactions of the oxidized dye polymer as a function of pH conditions.

When the mass ratio of each component of component (A) to component (C) satisfies the relationship: 1>(B)/((B)+(C)) And 1>(A)/((A)+(C)) At the time, it will be advantageous to form the above oxidized dye polymer, but when it does not satisfy these relationships, it will be disadvantageous for the formation of the above oxidized dye polymer.

As described above, the above oxidized dye polymer is an oxidized dye polymer obtained by polymerization of the component (A) to the component (C) and formed using the component (A) and the component (B) as main raw materials. Therefore, the oxidized dye polymer is considered to be a compound different from natural melanin. Furthermore, the oxidized dye polymer is believed to have unique properties resistant to reduction and oxidation.

Therefore, even if the dye removal treatment using the decoloring agent is not performed, the oxidized dye polymer can be degraded when the hair re-dyeing composition containing an oxidizing agent and having a pH higher than 9.6 acts thereon, and thus can be realized Heavy dyeing of hair.

In other words, according to the first aspect, the present invention provides a method for easily obtaining heavy dyeing (bleaching or dyeing) after dyeing using an oxidized dye polymer without dye removal treatment with a dye remover.

It is conventionally known that the component (A) and the component (B) are used as an oxidative dye in the first agent of the oxidative hair dye. However, such an oxidative hair dye generally has a pH higher than 9.6 when the first agent and the second agent are mixed, and therefore it is considered that there is little case in which the oxidized dye polymer of the first aspect of the invention is accidentally formed. It has also been found for the first time that a dye polymer which degrades under the action of an oxidizing agent in a specific pH range without the aid of an oxidizing agent of a decolorizing agent. Furthermore, the oxidized dye polymer degrades in a pH range above 9.6, which is the pH range of conventional oxidative hair dyes. Therefore, ordinary oxidative hair dyes, bleaching agents and the like can be used in the above hair dyeing composition.

(Second aspect of the invention)

A second aspect of the present invention is a method of dyeing and re-dyeing, which comprises using only the following components (A) and (B) as an oxidative dye, and having a pH in the range of 4.5 to 9.6 in use. The hair dye composition forms an oxidized dye polymer inside the hair for the hair dyeing step of hair dyeing; and the hair dyeing composition comprising at least the hair dyeing step after the hair dyeing step by using an oxidizing agent and having a pH of more than 9.6 at the time of use a process of re-dyeing the treatment of degrading the oxidized dye polymer on the hair: component (A): diamine oxidation dye; and component (B): phenol, which is an oxidation dye different from component (A) respectively, and hydroxy-substituted ortho position and the para position with a group -R (R is _{-H, -OH, -CH 3, -NH} 2 or -NHCH _3, and two R groups may be the same or different).

In the second aspect, since the hair dye composition to be used in the hair dyeing step contains only the component (A) and the component (B) as the oxidative dye, it is more preferable to obtain the same effects as the first aspect of the invention.

(The third aspect of the invention)

In a third aspect of the invention, the hair dye composition according to the first aspect or the second aspect is prepared by mixing the first agent and the second agent at the time of use and having a pH in the range of 4.5 to 9.6 when prepared by mixing. Oxidizing hair dye.

The type of the hair dye composition to be used in the hair dyeing step (first step) in the first aspect or the second aspect is not necessarily limited, but is particularly preferably oxidized by a type prepared by mixing the first agent and the second agent at the time of use. Hair dye.

(Fourth aspect of the invention)

In a fourth aspect of the invention, the phenol as the component (B) according to any one of the first aspect to the third aspect, wherein the phenol is a hydrogen which is not substituted at the middle position.

As the component (B), a phenol in which the hydrogen in the meta position is not substituted is particularly preferable. The oxidized dye polymer formed in this case is particularly susceptible to degradation by a degradation composition containing an oxidizing agent and having a pH higher than 9.6.

(Fifth aspect of the invention)

In a fifth aspect of the invention, the component (B) according to any one of the first aspect to the fourth aspect is selected from the group consisting of p-aminophenol, p-methylaminophenol, 2,4-diaminophenol Hydroquinone and its salts.

As component (B), it is particularly preferred to be selected from the group consisting of p-aminophenol, p-methylaminophenol, 2,4-diamino group from the viewpoint of forming an oxidized dye polymer which is highly degradable by the hair re-dyeing composition. A compound of phenol, hydroquinone or a salt thereof.

(Sixth aspect of the invention)

In a sixth aspect of the invention, the hair redyeing composition according to any one of the first aspect to the fifth aspect is any one of the following (1) and (2):

(1) an oxidative hair dye prepared by mixing a first agent and a second agent at the time of use and having a pH higher than 9.6 at the time of preparation by mixing;

(2) A rinse-off agent in a use form prepared by mixing a first agent and a second agent at the time of use and having a pH higher than 9.6 at the time of preparation by mixing.

As the hair redyeing composition defined in the first aspect or the second aspect, a composition dedicated to degrading the oxidized dye polymer can be used, but an oxidative hair dye or a rinse agent can be preferably used.

In the oxidative hair dye or rinse agent "in the form of use prepared by mixing the first agent and the second agent at the time of use", it is also included in the oxidation of the three doses for a given purpose such as hair conditioning or hair styling. Hair dye or rinse agent.

In general, the pH of these compositions is initially adjusted to a value above 9.6, so that it is not necessary to adjust its pH when used as a hair redying composition. In addition, the original purpose of oxidative hair dyes or rinses can be achieved along with the purpose of degrading the oxidized dye polymer.

Embodiments and preferred embodiments of the first to sixth aspects of the invention will be described below.

[dyeing step (first step)]

In the hair dyeing step of the hair dyeing and re-dyeing method according to the present invention, an oxidized dye polymer having unique properties is formed inside the hair using a predetermined hair dye composition.

As the hair dye composition, any of the following two types of hair dye compositions can be used. The first hair dye composition contains the following components (A) to (C) as an oxidative dye, and the mass ratio of the component content satisfies the relationship: 1> with And the pH at the time of use is in the range of 4.5-9.6. The second hair dye composition contains only the following components (A) and (B) as an oxidative dye and the pH at the time of use is in the range of 4.5 to 9.6.

Component (A): Diamine oxidation dye

Component (B): a phenol which is an oxidative dye different from component (A) and has a -R group at the ortho and para positions of the hydroxy substitution position (R is -H, -OH, -CH ₃ , -NH ₂ or -NHCH ₃ , and the two R groups may be the same or different)

Component (C): Oxidation dye different from component (A) and component (B)

As the hair dye composition, in particular, an oxidative hair dye, particularly preferred examples are oxidative hair dyes prepared by mixing the first agent and the second agent at the time of use and having a pH in the range of 4.5 to 9.6 when prepared by mixing. Agent.

[Oxidized hair dye]

The oxidative hair coloring agent is a two-part type comprising or containing the first agent and the second agent as follows, and a third dose form having a third agent having an optional composition in addition to the first agent and the second agent. These first and second agents (or otherwise third agents) are mixed at the time of use and are adjusted such that the pH falls within the range of 4.5 to 9.6 upon mixing.

The first agent contains an alkaline chemical and an oxidative dye consisting of the above component (A) to component (C) or component (A) and component (B).

The basic chemical is not limited, but for example, ammonia water, an alkanolamine (such as ethanolamine or isopropanolamine), an ammonium salt, an organic amine (such as 2-amino-2-methyl-1-propene) may be used. Alcohol, 2-amino-2-methyl-1,3-propanediol or hydrazine), an inorganic base, a basic amino acid, and the like.

The second agent contains at least an oxidizing agent. As the oxidizing agent, hydrogen peroxide is usually used, but other materials selected from various known oxidizing agents such as potassium bromate, sodium bromate and sodium perborate may be used.

As a third agent, an example may be a third agent that is suitable for a given purpose such as hair conditioning or hair styling.

With regard to the oxidative hair dye, it is also preferred to combine ascorbic acid into the first agent and/or the second agent and/or the third agent to have a concentration of ascorbic acid in the mixture of 0.5 to 10% by mass. As used herein, "ascorbic acid" includes various salts of ascorbic acid, various derivatives of ascorbic acid, and ascorbic acid. Ascorbic acid is also used as a reducing agent for oxidative dyes and inhibits the formation of oxidized dye polymers which are easily reduced, and furthermore, oxidized dye polymers having the unique properties of reduction and oxidation of the present invention can be more preferably formed.

The preparation of the oxidative hair dye can be arbitrarily selected from various known preparations. Examples thereof include liquids, emulsions, pastes, gels, pastes, sprays (sprays), and aerosol foams. A particularly preferred example may be an oxidative hair coloring agent in the form of a paste.

In the first or second agent of the oxidative hair dye, in addition to the above various components, the oil component, the solvent, the surfactant, the polymer, the polypeptide, the protein hydrolyzate, the amine group may be optionally blended as needed. Acids, vitamins, metal chelators, perfumes, disinfectant preservatives, anti-inflammatory agents, UV absorbers, propellants, thickeners, colorants, and the like. Further, water may be blended therein as a solvent or dispersion medium for each component of the oxidative hair dye and the concentration of each component may be adjusted.

[Component (A) to Component (C)]

The type of the oxidative dye as the component (A) is not limited as long as it is a diamine oxidative dye as defined above, but examples thereof include p-phenylenediamine, toluene-2,5-diamine, and hydroxymethyl group. - p-phenylenediamine, N,N-bis(?-hydroxyethyl)-p-phenylenediamine and 2-chloro-p-phenylenediamine. The blending amount of the component (A) in the hair dye composition is not particularly limited. However, for example, when the hair dye composition is a two-part oxidative hair dye in which the first agent and the second agent are mixed in a mass ratio of 1:1, the blending amount of the component (A) in the first agent can be adjusted to about 0.1. -3% by mass.

The type of the oxidative dye as the component (B) is not limited as long as it is a phenol and the phenol is an oxidation dye different from the component (A) and has a -R group at the ortho and para positions of the hydroxy substitution position, respectively. The group (R is -H, -OH, -CH ₃ , -NH ₂ or -NHCH ₃ , and the two R groups may be the same or different). However, phenols in which the hydrogen in the meta position is unsubstituted are particularly preferred, and phenols selected from the group consisting of p-aminophenol, p-methylaminophenol, 2,4-diaminophenol, hydroquinone and salts thereof are more particularly preferred.

As the oxidative dye of the component (C), any type of oxidative dye different from the component (A) and the component (B) may be added. Examples thereof may include m-aminophenol, resorcin, 2,4-diaminophenoxyethanol hydrochloride, and 5-amino o-cresol. Other examples thereof may include 4-amino m-cresol and 1-hydroxyethyl-4,5-diaminopyrazole sulfate.

The blending amount of the component (B) or the component (C) in the hair dye composition or the total blending amount thereof is not limited, but for example, when the hair dye composition is the first agent and the second agent is 1: The mass ratio of 1 is mixed while satisfying the above relationship "1>(B)/ In the case of the two-part oxidative hair dye, the total blending amount of the component (B) and the component (C) in the first dose can be adjusted to, for example, about 0.1 to 3% by mass.

Further, the blending amount of the component (C) in the hair dye composition needs to satisfy the relationship with respect to the blending amount of the component (A)" ".

[Heavy Dyeing Step (Step 2)]

In the re-dyeing step of the hair dyeing and re-dying method according to the present invention, a treatment comprising at least a dye polymer which degrades the above oxidation is carried out using a predetermined hair re-dyeing composition. The hair redyed composition contains an oxidizing agent and has a pH above 9.6 at the time of use.

As a hair dyeing composition, preferred examples are the following (1) and (2),

(1) an oxidative hair dye prepared by mixing a first agent and a second agent at the time of use and having a pH higher than 9.6 at the time of preparation by mixing,

(2) A rinse-off agent in a use form prepared by mixing a first agent and a second agent at the time of use and having a pH higher than 9.6 at the time of preparation by mixing.

In the re-dyeing method, the oxidative hair dye described in (1) and the bleaching agent described in (2) are not limited as long as the pH thereof is higher than 9.6, for example, an ordinary commercially available oxidative hair dye and Bleaching agent. As such an oxidative hair dye or rinse, for example, a three-part form which further contains a third agent having any composition suitable for a given purpose such as hair conditioning or hair styling can be used.

That is, the oxidative hair dye described in (1) is substantially the same composition as the oxidative hair dye used in the above first step, but the pH thereof is different and the type of the oxidative dye is not limited. Generally, the oxidative hair coloring agent is also a two-part hair dye composition, the first agent comprising an oxidative dye and a basic chemical, and the second agent comprising an oxidizing agent such as hydrogen peroxide. The first agent and the second agent are mixed while applied to the hair.

The rinse agent described in (2) differs from the above-described oxidative hair dye described in (1) in that the first agent contains a basic chemical but does not contain an oxidative dye. Generally, the rinse is also in two dosage forms and the first and second doses are combined when applied to the hair.

Example

Embodiments of the invention are described below. The technical scope of the present invention is not limited to the following embodiments.

[First Group of Embodiments]

This set of examples evaluates hair dyeing and re-dyeing methods by subjecting the hair to oxidative hair dye treatment and bleaching treatment as described below.

A composition in the form of a paste having any of the compositions of Comparative Example 1 to Comparative Example 10 shown in Examples 1 to 20 and Table 3 shown in Tables 1 and 2 below was prepared in a conventional manner. The first agent of the oxidative hair dye. Further, a second agent in the form of a paste having a composition of a column represented by "Ox6" in Table 4 below is prepared in a conventional manner.

The values indicating the contents of the respective components in Table 1 are expressed in units of % by mass, and the same applies to Tables 2 to 4, and also to Tables 5 to 7, Table 9, and Table 10 below. In addition, in the components shown in Table 1, the component having "(a)" in front of the component name, the component having "b", and the component having "c" respectively represent the component (A) ), component (B) and component (C). The same applies to Tables 2, 3, 6, and 9. In addition, the components represented by "POE (30) cetyl ether" in the column giving the name of the components in Tables 1 to 3, Table 5 to Table 7 and Table 9 refer to "polyoxyethylene (30) cetyl wax" The component represented by "POE (2) cetyl ether" in the column giving the component name in Table 1 to Table 7 and Table 9 means "polyoxyethylene (2) cetyl ether". In addition, the numerical values shown in the columns represented by "pH after mixing" in each of Examples and Comparative Examples in Tables 1 to 3 represent the first agents of each of the oxidative hair dyes of these Examples and Comparative Examples. Any of the pH values prepared when mixing with the second dose "Ox6", likewise, in Tables 5 to 7 and Table 9, the values shown in the columns represented by "pH after mixing" are indicated by respectively given with The second agent is mixed with the pH at the time of preparation.

Next, the outlines of the respective examples and comparative examples in Tables 1 to 3 are briefly described on the basis of the indexes shown in the top row of Tables 1 to 3. In Examples 1 to 6, the combination of the component (A) to be blended with the component (B) and the blending amount thereof were varied in various ways. In Example 7 to Example 12, the component (A) and the component (B) were blended in the same manner as in Example 1, and the relationship was still satisfied. "and"1>(A)/((A) Any of various types of components (C) are blended in the range of ". In Example 13 to Example 20, by changing the blending amount of ammonia water and ascorbic acid in Example 1, by passing with the second agent The pH at the time of the mixed preparation was varied in various ways in the pH range of 4.5 to 9.6. In Comparative Example 1 to Comparative Example 5, the component (B) in Example 1 was not added or the same amount of the components. (C) Blending instead of component (B) in Example 1. In Comparative Example 6 and Comparative Example 7, component (A) to component (C) were blended to give the quality of each component Ratio dissatisfaction "1>(B)/((B)+(C)) "with" In Comparative Example 8 to Comparative Example 10, by changing the blending amount of ammonia water and ascorbic acid in Example 1, the pH at the time of preparation by mixing with the second agent fell outside the range of 4.5 to 9.6.

The first agent having any of the compositions of Example 1 to Example 20 and Comparative Example 1 to Comparative Example 10 was then mixed with an equal amount of the above second agent "Ox6" to effect preparation, and then the resulting mixture was applied. MBW hair (medium brown hair, as a hair sample) produced by Stuffs Inc. After the hair sample was kept as it is for 20 minutes, it was shampooed and dried. The L*a*b value (L ₁ , a ₁ , b ₁ ) of the MBW hair subjected to such an oxidative hair dye treatment was measured with a colorimeter (CM-508d) manufactured by Minolta Company Ltd. In this regard, the L ₀ , a ₀ and b ₀ values of the untreated hair were also separately measured in advance for the MBW hair subjected to the oxidative hair dye treatment.

The L* value represents brightness (0 to 100), and the higher the L* value, the higher the brightness. The a* value and the b* value each represent a chromaticity (-60 to 60). The higher the a* value, the redder the color, the lower the a* value, the greener the color; the higher the b* value, the yellower the color, b* The lower the value, the bluer the color.

On the other hand, the first agent of the rinse agent in the form of a paste having the composition of Example 21 shown in Table 5 below and prepared in a conventional manner is mixed with an equal amount of the second agent "Ox6" to prepare. Bleaching agent. The resulting bleaching agent was applied to MBW hair one day after the above drying, and the hair was left as it was for 30 minutes, then shampooed and dried. The L ₂ value, the a ₂ value, and the b ₂ value of the MBW hair subjected to such bleaching treatment were also measured in the same manner as above.

Based on the above formula and measurement, the L ₀ value, the a ₀ value, and the b ₀ value of the untreated MBW hair and the MBW after the oxidative hair dye treatment according to each of the above Examples and Comparative Examples were used in the following formula (1). The L ₁ value, a ₁ value and b ₁ value of the hair were calculated for the color difference ΔE ₁ between the untreated hair and the hair treated with the hair dye, and the calculated values are shown in Table 1 to Table 3 for the "dyeing ability ΔE ₁ " line. in. If the value of ΔE ₁ is 25 or higher, the hair dyeing ability of the oxidative hair dye can be evaluated as good.

ΔE ₁ ={(L ₁ -L ₀ ) ² +(a ₁ -a ₀ ) ² +(b ₁ -b ₀ ) ² } ^1/2 (1)

Further, regarding the MBW hair according to each of the above examples and the comparative examples, the L ₁ value, the a ₁ value and the b ₁ value after the treatment with the oxidative hair dye, and the L ₂ value, the a ₂ value and the b after the bleaching treatment. _{The 2-} value calculation calculates the color difference ΔE ₂ between the hair treated with the hair dye and the hair subjected to the bleaching treatment, and the calculated values are shown in the "bleaching property ΔE ₂ " row of Tables 1 to 3. If the value of ΔE ₂ is 4 or higher, the bleaching properties of the rinse can be evaluated as good.

[Evaluation Results of the First Group of Examples]

The evaluation results shown in the "dyeing ability ΔE ₁ " and "bleaching properties ΔE ₂ " rows of Tables 1 to 3 are described below. We have found that even if the combination of the components (A) and (B) to be blended in the oxidative hair dye to be used in the first step and the blending amount thereof are changed in various manners as in Examples 1 to 6, the dyeing is performed. The value of the ability ΔE ₁ is 25 or higher, the hair dyeing ability of the oxidative hair dye is good, and the value of the bleaching property ΔE ₂ is 4 or more, and the bleaching property of the bleaching agent in the second step is good.

We have found that even if component (C) is blended in addition to component (A) and component (B), as in Example 7 to Example 12, when the content of each component falls within the satisfaction relationship " "with" In the range of 0.6", the hair dyeing ability of the oxidative hair dye obtained in the same manner as above and the bleaching property of the bleaching agent are good.

Further, we have found that even when the pH of the oxidative hair dye is changed in various manners as in Example 13 to Example 20 by the preparation of the mixture, the hair dyeing ability of the oxidative hair dye obtained in the same manner as above and the bleaching of the bleaching agent are obtained. The nature is good.

On the other hand, we found that in Comparative Example 1 to Comparative Example 10 in which component (B) was not added or component (B) was replaced by component (C), and component (A) thereof was (C) Blend but does not satisfy the relationship "1>(B)/((B)+(C)) "with" In Comparative Example 6 and Comparative Example 7, the hair dyeing ability ΔE ₁ was 25 or higher, and the hair dyeing ability of the oxidative hair dye was good, but the value of the bleaching property ΔE ₂ was significantly lower than 4, and the bleaching agent was The bleaching properties are significantly lower.

In addition, we found that in the comparative example 8 in which the component (A) to the component (C) were blended in the oxidative hair dye in an advantageous mass ratio but the pH value fell below 4.5 to 9.6 at the time of preparation by mixing In Comparative Example 10, the value of the bleaching property ΔE ₂ was higher than 4, and the bleaching property of the bleaching agent was good, but as a problem before the bleaching property, the hair dyeing ability ΔE ₁ was less than 25, and the dyeing ability of the oxidative hair dye was difference.

[Second set of embodiments]

In the same manner as above, the content of the aqueous ammonia in the first agent of the bleaching agent (the composition according to Example 21) used in the bleaching treatment and the pH value in the preparation by mixing with the second agent are in the same manner as above. Example 1 of the first set of examples above evaluates the method of dyeing and re-dying in the case of oxidative hair dye treatment and bleaching treatment of hair in various ways.

That is, the first agent of the oxidative hair dye according to the above Example 1 was mixed with an equivalent amount of the second agent "Ox6" in exactly the same manner as in the first group of examples to prepare. The resulting oxidative hair dye was then applied to MBW hair, the hair was left as it was for 20 minutes, then shampooed and dried, and the L*a*b value (L ₁ , a ₁ , b ₁ ) was determined.

When the MBW hair after one day from the drying was subjected to the bleaching treatment, in addition to the first agent of the rinse agent of Example 21, it was also prepared in the form of a paste having Example 22 to Example 25 as shown in Table 5. And the first agent of the rinse agent of any of Comparative Example 11 and Comparative Example 12. Each of these first agents is mixed with an equal amount of the second agent "Ox6" to prepare a rinse. The prepared bleaching agent was applied to the above MBW hair to effect bleaching treatment, and the bleaching property ΔE _{2 was} calculated in exactly the same manner as in the first group of examples. The results are shown in the "bleaching properties ΔE ₂ " row of Table 3. If the value of ΔE ₂ is 4 or higher, the bleaching properties of the rinse can be evaluated as good.

[Evaluation results of the second group of examples]

We have found that when the pH of the rinse agent to be used in the second step is changed in various ways under the condition that the hair has been dyed with the oxidative hair dye according to the above Example 1, if the pH of the rinse agent is higher than 9.6, From Example 21 to Example 25, the value of ΔE ₂ is 4 or higher, and the bleaching property of the bleaching agent is good, if the pH of the bleaching agent is 9.6 or lower, as in Comparative Example 11 and Comparative Example 12 Then, the value of ΔE ₂ is less than 4, and the bleaching property of the bleaching agent is poor.

[Third Group of Embodiments]

This group of examples evaluates the case where the effect of the present invention is effectively exhibited in actual use, that is, the case where the hair is first dyed with a dark color and then dyed with a light color. At this time, as a control, the natural black hair containing the natural melanin pigment was dyed in a light color in the same manner. In general, the color when hair dye is treated with hair is represented by the color produced by the degradation of melanin and the color of the oxidized dye polymer. Therefore, it is also preferred to obtain not only a light color but also a color similar to the case where the black hair is subjected to the treatment of the hair dye in the case where the hair is subjected to the hair re-dyeing treatment after it is dyed into a dark color.

Namely, a first agent of an oxidative hair dye in the form of a paste having any of the compositions of Example 26 and Comparative Example 13 shown in Table 6 below was prepared. These first agents of the resulting oxidative hair dye have a composition capable of dyeing hair to a dark color, but Comparative Example 13 differs from Example 26 in that it contains component (C) and component (A) and component ( B) that the mass ratio of the content of each component falls within the range " "and"1>(A)/((A)+ "Beyond."

Each of these first agents of the oxidative hair coloring agent was mixed with an equal amount of the second agent "Ox6" in exactly the same manner as in the first group of examples to prepare an oxidative hair dye, and the resulting oxidative hair dye was applied to MBW hair. The hair was then left as it was for 20 minutes, then shampooed and dried. This program is the first step in the treatment of oxidative hair dyes.

On the other hand, the first agent of the oxidative hair dye in the form of a paste having any of the compositions shown in "C1" and "C2" in Table 7 was prepared in a conventional manner. The composition of these first agents of the oxidative hair dye is a conventional composition that dyes the hair to a light color, C1 provides a light color based on yellow, and C2 provides a light color based on pink. Each of these first agents is mixed with an equal amount of the second agent "Ox6" to prepare an oxidative hair dye. Each of the thus obtained oxidative hair dyes was then applied to each of the MBW hair samples which were treated by the above oxidative hair dye and dried one day after drying, and black hair (as a hair sample) produced by Beaulax Co., Ltd. The hair was then left as it was for 30 minutes, then shampooed and dried. This program is the second step in the treatment of oxidative hair dyes.

Thus, a total of 6 sets of dried hair samples were obtained as follows: Group 1: Hair coloring samples containing the first dose of "C1" in the second step of treatment with black hair and oxidative hair dye; Group 2: Black The hair powder and the oxidative hair dye treatment in the second step containing the first dose of "C2" oxidative hair dye obtained from the hair; Group 3: the first treatment with the first agent of Example 26 for the peroxide hair dye treatment of MBW hair and A hair dye obtained by the first dose of "C1" oxidative hair dye in the second step of the oxidative hair dye treatment; Group 4: MBW hair and oxidative hair dye treated with the first agent of Example 26 for the peroxide dyeing agent A sample obtained by the first dose of "C2" oxidative hair dye in the second step of the treatment; Group 5: MBW hair and oxidative hair dye treated with the first agent of Comparative Example 13 for the treatment of the peroxide dye The second step of the treatment was carried out with the first dose of "C1" oxidative hair dye; the group 6: treated with the MBW hair and oxidative hair dye treated with the first agent of Comparative Example 13 for the peroxide dye treatment In the second step, the first dose of "C2" oxidative hair dye is obtained.

The L*a*b* values of the six sets of samples were measured, and the bleaching properties ΔL, the redness difference Δa, and the yellowness difference Δb were calculated from these measurement results, respectively. These parameters are defined as follows.

That is to say, the brightness of the untreated black hair in the case of black hair and the brightness of the MBW hair after the first step of the oxidative hair dye treatment in the case of MBW hair are respectively defined as the brightness "L ₁ ", which is oxidized. The brightness of the black hair after the second step of the hair dye treatment and the brightness of the MBW hair were respectively defined as "L ₂ ", ΔL = L _{2 -} L ₁ .

In addition, the redness of untreated black hair in the case of black hair and the redness of MBW hair after the first step of treatment with oxidative hair dye in the case of MBW hair are defined as redness "a ₁ ", respectively. The redness of the black hair after the second step of the oxidative hair dye treatment and the redness of the MBW hair were defined as "a ₂ ", Δa = a ₂ - a _{1 , respectively} .

In addition, the yellowness of untreated black hair in the case of black hair and the yellowness of MBW hair after the first step of treatment with oxidative hair dye in the case of MBW hair are defined as yellowness "b ₁ ", respectively. The yellowness of the black hair after the second step of the oxidative hair dye treatment and the yellowness of the MBW hair were defined as "b ₂ ", Δb = b ₂ - b _{1 , respectively} .

The calculation results of the bleaching properties ΔL, the redness difference Δa, and the yellowness difference Δb of the above six sets of hair samples are shown in Table 8. In Table 8, "black hair", "Example 26" and "Comparative Example 13" are used for the type of the zone distribution sample or the type of the first step of the oxidative hair dye treatment for the hair sample, "C1+Ox6 "and "C2+Ox6" are used to distinguish the type of the second step of the oxidative hair dye treatment performed on the hair sample.

[Evaluation results of the third group of examples]

As is apparent from the results shown in Table 8, in Example 26, regardless of the type of the second step of the oxidative hair dye treatment, "C1 + Ox6" or "C2+Ox6", the corresponding evaluation of ΔL, Δa, and Δb The results were all very close to those of the "black hair" shown in Table 8, and it was found that a color similar to the case where the black hair was subjected to the hair dye treatment was obtained. On the other hand, in the case of Comparative Example 13, the corresponding evaluation results of ΔL, Δa, and Δb differ greatly from the case of "black hair" shown in Table 8, and it was found that the obtained color and black hair were subjected to hair dye treatment. The situation is very different.

[Fourth Group of Embodiments]

This set of examples shows that the oxidized dye polymer formed in the hair dyeing step (first step) of the present invention has an oxidized dye polymer which is close to melanin and which is formed in the hair dyeing step which is not part of the hair dyeing step of the present invention. Does not have the property of being close to melanin. If the oxidized dye polymer formed in the first step exhibits similar degradability to melanin, it can be considered that in the second step (re-dyeing step) after the hair is dyed dark in the first step, Only the color of the hair becomes light, and the adjustment of the brightness when re-dying is similar to that of the black hair. Therefore, it is also expected to easily adjust the brightness.

Namely, the first agent of the oxidative hair dye in the form of a paste having any of the compositions of Example 27 and Comparative Example 14 shown in Table 9 below was prepared in a conventional manner. These first agents of the oxidative hair dye have a composition capable of dyeing the hair to a dark color, but Comparative Example 14 differs from Example 27 in that it contains the component (C) and the component (A) and the component (B). So that the mass ratio of the content of each component falls within the range" "and"1>(A)/ "Beyond."

Each of the first agents of the oxidative hair coloring agent was mixed with an equal amount of the second agent "Ox6" in exactly the same manner as in the first group of examples to prepare an oxidative hair dye. Then, the white hair (as a hair sample) produced by Beaulax Co., Ltd. was subjected to an oxidative hair dye in which each of the thus obtained oxidative hair dyes was applied to the white hair, and the white hair was left as it was for 50 minutes, followed by shampooing. And dry.

On the other hand, a second agent in the form of a paste having the composition represented by "Ox2" shown in the above Table 4 was prepared in a conventional manner. Further, the first agent in the form of a powder and the second agent in the form of a gel of the reducing and decolorizing agent of the composition shown in the "R1" column of Table 10 below were also prepared in a conventional manner. Unlike the above-mentioned bleaching agents, the "reducing decoloring agent" preparation is characterized in that it does not degrade melanin and only degrades the oxidized dye polymer.

Then, 4 sets of the above-mentioned hair samples (treated hair) which were treated with an oxidative hair dye and dried one day after drying, and untreated black hair (untreated black hair, produced by Beaulax Co., Ltd.) were used as hair samples. Three of the groups were subjected to the following bleaching treatment (oxidative bleaching treatment), and the remaining one was subjected to the following reduction dyeing agent treatment.

In the rinse treatment, with respect to the above-mentioned treated hair and untreated black hair, the application in Group 1 was carried out by mixing the first agent of the rinse agent of the above Example 21 with an equal amount of the second dose "Ox6". The rinse agent, the group 2 was applied by mixing the first agent of the rinse agent of the above control example 12 with the equal amount of the second dose "Ox6", and the application of the group 3 was carried out by mixing as described above. The first dose of the rinse agent of Example 21 was prepared with an equal amount of the second dose "Ox2". In any of Groups 1 to 3, after applying the rinse, the hair was left as it was for 30 minutes, then shampooed and dried. In the treatment of the reductive dyeing agent, the first and second compositions having the composition shown in "R1" of Table 10 were mixed at a mass ratio of 1:10 to the treated hair and the untreated black hair. A reducing decolorizer prepared by the agent. The hair was then left as it was for 30 minutes, then shampooed and dried.

The L*a*b* value of the hair sample is determined after any of these various treatments and the bleaching power ΔE _{2 is} calculated, and ΔE ₂ is the above-mentioned bleaching treatment or reducing decolorizing agent for the above-mentioned treated hair or untreated black hair. The color difference before and after the processing was processed, and the results are shown in the "ΔE ₂ " row of Table 11.

[Evaluation results of the fourth group of examples]

As is apparent from the results shown in Table 11, in Example 27, the evaluation results of ΔE ₂ were the same as those in Table 11 for all three types of undulating treatment and one type of reductive dye treatment in the second step. The results of the "black hair" situation are very close, and it has been found that the control of hair brightness depending on the type of dye remover can be performed in the same manner as in the case of "black hair". On the other hand, in the case of Comparative Example 14, the evaluation result of ΔE ₂ differs greatly from the result of the "black hair" case for all of the above various kinds of the bleaching treatment and the reduction hair dye removal, and it is found that it is difficult to adjust the brightness. .

At this point, the appearance darkness in Table 11 (see Concentrated L" is substantially equivalent between Example 27 and Comparative Example 14, and "appearance darkness L" refers to the L value of the black hair and the hair dye after the corresponding hair dye treatment, and the ease of obtaining a light color for equal comparison, The hair is dyed as dark as possible as close to the black hair.

Industrial applicability

According to the present invention, there is provided a method in which, in the method of obtaining a hair dyeing ability at the time of dyeing hair, the oxidative dye polymer having a dark color tone formed by the oxidative hair dye is internally degraded. The dye removal treatment is carried out without using a desizing agent, and the hair dye treatment or bleaching treatment is advantageously carried out to obtain a light color.

Claims (6)

A method of dyeing and re-dyeing, the method comprising: satisfying a relationship by using a mass ratio of the component (A) to the component (C) as an oxidative dye and a component content: And 1> And the hair dye composition having a pH in the range of 4.5 to 9.6 at the time of use forms an oxidized dye polymer inside the hair for the hair dyeing step of hair dyeing; and performing at least after the hair dyeing step by causing the oxidizing agent to be used A process for re-dyeing the treatment of a dye-dye polymer having a pH above 9.6 acting on the hair to degrade the oxidized dye polymer: component (A): diamine oxidation dye; component (B): phenol, Is an oxidation dye different from component (A) and has a -R group in the ortho and para positions of the hydroxy substitution position (R is -H, -OH, -CH ₃ , -NH ₂ or -NHCH ₃ , and The two R groups may be the same or different); and the component (C): an oxidative dye different from the components (A) and (B). A method of dyeing and re-dyeing, comprising: by using a hair dye composition having only the following components (A) and (B) as an oxidative dye and having a pH in the range of 4.5 to 9.6 at the time of use Forming an oxidized dye polymer inside the hair is a hair dyeing step of hair dyeing; and degrading the hair dyeing composition comprising at least the oxidizing agent and having a pH above 9.6 after application to the hair after the hair dyeing step Re-dyeing step of treatment of oxidized dye polymer: component (A): diamine oxidative dye; and component (B): phenol, which is an oxidative dye different from component (A) and is substituted at the hydroxy group, respectively ortho and para position with a group -R (R is _{-H, -OH, -CH 3, -NH} 2 or -NHCH _3, and two R groups may be the same or different). A hair dyeing and re-dying method according to claim 1 or 2, wherein the hair dye composition is prepared by mixing a first agent and a second agent at the time of use and having a pH in the range of 4.5 to 9.6 when prepared by mixing An oxidative hair dye, wherein the first agent contains an oxidative dye and an alkaline chemical, and the second agent contains an oxidizing agent. A method of dyeing and re-dying according to claim 1 or 2, wherein the phenol as the component (B) is a phenol whose hydrogen is not substituted at the middle position. The method of dyeing and re-dying according to claim 1 or 2, wherein component (B) is selected from the group consisting of p-aminophenol, p-methylaminophenol, 2,4-diaminophenol, hydroquinone and salts thereof . The hair dyeing and re-dying method according to claim 1 or 2, wherein the hair re-dyeing composition is any one of the following (1) and (2): (1) by mixing the first agent at the time of use. An oxidative hair dye prepared in a form of use with a second agent and having a pH above 9.6 when prepared by mixing, wherein the first agent contains an oxidative dye and a basic chemical, and the second agent contains an oxidizing agent; and (2) Mixing the first agent containing basic chemicals with A second dose of oxidizing agent is prepared and used in the form of a bleaching agent having a pH above 9.6 when prepared by mixing.