JP7063998B2 - A multi-step method for dyeing keratin fibers using indigo-producing plant powder and acidic treatments containing specific dyes. - Google Patents

Description

The present invention is (I) a method for dyeing keratin fibers, particularly human keratin fibers such as hair, wherein the fibers are i) indigo-producing plant powder and / or indigo-producing plant dye extract and optionally. At least one step E1 for dyeing the fiber using a cosmetic dye composition A comprising Henna, ii), one or more specific natural dyes iii) and one or more acidic other than Henna and Indigoid. Aqueous cosmetic composition B comprising an agent, wherein the aqueous cosmetic composition B having a pH of less than 7 is used in several steps comprising at least one step E2 to post-treat the fibers. Processed, the composition A is preferably applied first to the keratin fibers; and the composition B is applied to the keratin fibers after the application of the composition A, and (II) indigo and optionally. To promote the stabilization of the color of the fibers dyed with Henna over time (on the day the dyeing method was performed) and to improve the strength, buildup and / or its color persistence. With respect to the use of an acidic aqueous composition B comprising one or more specific natural dyes.

Specifically, the coloring produced using indigo and optionally henna generally progresses over time with respect to color. They have a characteristic yellow / green tint on the date of application (ie, the date of staining). This relatively unattractive "raw" color, which is barely recognized by dye users, changes to the desired color after a few hours (48 hours to 1 week) and over time the color (generally 2 to 2). It may change to purple-red color appearance after 3 weeks. Therefore, at the same time, the integrity of the keratin fibers is preserved, and this coloring is stabilized in order to obtain a beautiful coloring (for example, brown with no yellow / green tone) that hardly changes over time (the color does not change). There is a need to let it.

Two main methods for dyeing human keratin fibers, especially hair, are known.

The first method known as oxidative staining or permanent staining uses one or more oxidative dye precursors, more specifically one or more oxidative bases, optionally in combination with one or more couplers. Including doing.

Usually, the oxidizing base is selected from ortho- or para-phenylenediamine, ortho- or para-aminophenol and heterocyclic compounds. These oxidative bases are colorless or pale compounds and, when combined with oxidation products, can yield colored seeds that remain trapped within the fiber through the process of oxidative condensation.

The shades obtained with these oxidizing bases select these oxidizing bases, in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds. It often fluctuates when combined with one or more couplers.

The variety of molecules used as oxidizing bases and couplers makes it possible to obtain a wide range of colors.

A second dyeing method known as direct dyeing or semi-permanent dyeing involves the application of direct dyes, which are colored and colored molecules that have an affinity for fibers. Given the nature of the molecules used, these molecules tend to rather stay on the surface of the fiber and relatively little penetrate the fiber when compared to the smaller molecules of the oxidative dye precursor. The main advantage of this type of dyeing is that it does not require any oxidants that limit the decomposition of the fibers and that it does not use any dyes with specific reactivity that limit the risk of intolerability.

である。 The first hair dye was a semi-permanent dye. One of the most widely known natural dyes is Indigo (see (Non-Patent Document 1)). Indigo continues to be used in women's aesthetic enhancement to dye hair or nails or to dye cloth (jeans), leather, silk, wool and the like. Indigo [482-89-3] is a natural blue dye whose isomer indirubin is red. Its empirical formula is C ₁₆ H ₁₀ N ₂ O ₂ ; its chemical structure is:

Is.

Depending on the oxidation / peroxidation, isatin may confer indigotin or indirubin (Non-Patent Document 2). The presence of these two isomers is the main cause of the violet color of Indigo, which appears more or less depending on the respective proportions of the two isomers formed in the hair (especially the amount of indirubin). If it increases, from violet to purple).

Indigo is derived from indican and can be prepared from various plants known as indigofera-producing plants such as Indigofera tinctoria, Indigofera tinctoria, and Polygonum tinctorium (Polgygonum tinctorium). Please refer to 3)). These indigo-producing plants are generally chopped into small pieces, soaked in boiling water, heated, fermented, and oxidized outdoors to release purple-blue colored indigo (see Non-Patent Document 4). Indican is the result of hydrolysis of indican (glycosyl precursor) and subsequent oxidation.

The problem is that staining with indigo leaves is difficult due to the variability of staining kinetics in keratin fibers. Moreover, the staining method is unstable. Indigo theoretically gives gray hair a blue tint and a gray-type "cold" color. However, staining methods using indirubin are difficult to control due to competing reactions to the formation of indirubin, including the oxidation step with the formation of a yellow-colored isatin intermediate, and over time, maroon. -Gives a yellow to deep purple hue that complements brown hair.

Therefore, the coloration obtained from the mixture of Indigo and Henna generally progresses over time with respect to color, and on the day of dyeing, the characteristic yellow / green color (relatively little recognized by dye users). It has an unattractive "raw" color), but after a few hours (48 hours to 1 week) it changes to the desired coloration and over time the color (generally a purple-red tone after 2-3 weeks). May change the appearance). Therefore, there is a need to stabilize this coloration in order to obtain a beautiful coloration (eg, brown with no yellow / green tones) that hardly changes over time (color does not change) on the day of application.

To overcome this problem of relatively unattractive coloring and color change on the day of dyeing, undesired shades such as nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethin, xanthene, acridine, azine or triarylmethane direct dyes. It is a known technique to "dope" the dye by adding direct dyes for masking (these dyes are commonly used in direct dyeing) (see, eg, (Patent Document 1)). I want to be). This option has drawbacks for natural product users or proponents of "natural / biological" products in that coloring is carried out partially using synthetic dyes. However, the shades provided on the day of application do not prevent color changes over time (progression of the yellow shades (although masked) that are still present in the fibers to red).

Further, the coloring obtained by using Indigo is not always uniform between the root and the end or between one fiber and another fiber ((Non-Patent Document 5)).

Finally, since the indigo molecule is insoluble in water, when a mixture of indigo and henna, which is water-soluble in itself, is used, this results in a substantial inhomogeneity of color adhesion between the root and the end. (Selectivity) is brought about.

European Patent No. 0806199

Ullmann's Encyclopedia of Industrial Chemistry, "Hair preparation", point 52.3, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; 10.1002 / 14356007. a12 571. pub2 Maugard et al. , 2001 Kirk-Othmer Encyclopedia of Chemical Technology, updated on 17/04/2009, DOI: 10.1002 / 0471238961.0519030150618. a01. pub2 Chem. Rev. 2011,111,2537-2561, pages 2537-2561 The Science of Hair Care, C.I. Bouillon, J.M. Wilkinson, 2nd Ed. , CRC Press, Taylor & Francis Group; Boca Raton, Florida, pages 236-241 (2005)

Therefore, at the same time, while preserving the cosmetic properties of keratin fibers, it is possible to obtain strong, beautiful and natural coloring from the end of application, and especially rapid coloring (the resulting coloring is not beautiful by the user). It is possible to obtain a yellow / green tone that is considered to be), and the color adhesion is improved, it is not so invasive to the hair, and at the same time external factors (light, bad weather, shampoo washing) ), And at the same time strong and / or vivid but persistent and / or uniform, and there is a real need to develop a dyeing method that does not change color (especially red tones) over time. exist.

This goal is achieved by the present invention, wherein one subject is a method for dyeing keratin fibers, particularly human keratin fibers such as hair, wherein the fibers are:
-At least one step E1); dyeing the fibers using a cosmetic dye composition A comprising indigo-producing plant powder and / or extract i) and optionally henna ii);
-One or more natural dyes iii)
-Iii-i) Anthraquinone preferably comprising at least one carboxylic acid functional group, preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D and / or kermesic acid;
-Iii-iii) Betalain, preferably betanin;
-Iii-iii) Cyanidin, delphinidin, pelargonin, malvidin, peonidin and petunidin and mixtures thereof, preferably containing at least three hydroxyl groups, preferably also as anthocyanidins of formula (Vg) (anthocyanids or anthocyanidols). Known);
-Iii-iv) Carthamin;
-Iii-v) Alkanine (also known as Orcanette) and / or naphthoquinone containing at least two hydroxyl groups, preferably at least three hydroxyl groups, preferably selected from sicokin; and -Aqueous cosmetic composition B comprising one or more natural dyes iii); and iv) one or more acidifying agents selected from the mixture, the pH of which is less than 7. At least one step E2) to process the fiber using B)
Processed in several steps, including;
-It is understood that preferably composition A is first applied to the keratin fiber; and composition B is applied to the keratin fiber after the application of composition A;
-This method preferably involves at least one rinsing step and / or one washing step between the staining step using composition A and the treatment step involving the application of composition B.

Therefore, according to a preferred embodiment, the dyeing method according to the invention comprises applying the dye composition A, which comprises indigo-producing plant powder and / or extract and optionally henna, to keratin fibers. An aqueous composition B comprising a first step of staining followed by one or more specific natural dyes as defined above and one or more acidifying agents, the pH of which is less than 7. Including the step of treating with the aqueous composition B, i.e. in the post-treatment.

According to another embodiment, the dyeing method according to the invention is an aqueous composition B comprising one or more specific natural dyes as defined above and one or more acidifying agents. Through the step of treating with an aqueous composition B having a pH of less than 7, and then application of the dye composition A containing indigo-producing plant powder and / or extract and optionally henna to keratin fibers. It involves dyeing the fibers.

The subject matter of the present invention is to promote color stabilization of fibers dyed with indigo and optionally henna over time, and to improve color intensity and / or color adhesion and / or color persistence. Aqueous composition B comprising one or more specific natural dyes iii) as defined above and iv) one or more acidifying agents for the purpose of comprising, wherein the pH is less than 7. It is also the use of the aqueous composition B.

The methods for dyeing keratin fibers according to the present invention have natural staining results without any yellow / green tones and / or strong and vibrant coloring (these are resistant to washing, sweating, sebum and light). And has the advantage of dyeing said fibers, especially human keratin fibers, especially hair, with (and lasting longer without damage to the fibers). Moreover, the coloration obtained using this method is uniform from the root to the end of the fiber (with little color selectivity). The treated keratin fibers exhibit very good cosmetic properties; in particular, their integrity is highly valued and they have an excellent level of luster.

The composition used in accordance with the present invention is a cosmetic composition, i.e., it is cosmetically acceptable and therefore for application to keratin fibers, especially human keratin fibers such as hair. Suitable for use.

Preferably, the composition A is prepared by mixing the indigo-producing plant powder i) and optionally the henna ii) immediately before use with the aqueous composition, preferably in the form of a poultice. Obtained by obtaining the dye composition A.

Preferably, composition A is an aqueous composition.

i) Indigo-producing plant powder and / or extract The dye composition A according to the present invention contains indigo-producing plant powder and / or extract. (For the purposes of the present invention, the term "indigo-producing plant extract" means "dye extract from indigo-producing plants").

Indigo-producing plants include numerous species from the following genera:
－ コマツナギ属（Ｉｎｄｉｇｏｆｅｒａ）、例えばタイワンコマツナギ（Ｉｎｄｉｇｏｆｅｒａ ｔｉｎｃｔｏｒｉａ）、インジゴ・サフルティコサ（Ｉｎｄｉｇｏ ｓｕｆｆｒｕｔｉｃｏｓａ）、インドコマツナギ（Ｉｎｄｉｇｏｆｅｒａ ａｒｔｉｃｕｌａｔａ）、ナタルインディゴ（Ｉｎｄｉｇｏｆｅｒａ ａｒｒｅｃｔａ）、キダチニワフジ（Ｉｎｄｉｇｏｆｅｒａ ｇｅｒａｒｄｉａｎａ）、インディゴフェラ・アルゲンタ（Ｉｎｄｉｇｏｆｅｒａ ａｒｇｅｎｔａ ), Indigofera indica or Indigofera longiracemosa;
-The genus Isatis, such as Woad tinctria;
-Knotweed (Polygonum) or Knotweed (Persicaria), such as eye (Polygonum tinctorium) or eye (Persicaria tinctoria);
-The genus Writia, eg, Writia tinctria;
-The genus Calanthe, such as Calanthe veratrifolia; and-The genus Pink Strobilanthes, such as Pink Strobilanthes.

Preferably, the indigo-producing plant is of the genus Indigofera, more specifically, Indigofera tinctoria, Indigofera sufruticosa, or Indigofera algentea, Indigofera tinctoria. (Indigofera tinctoria).

All or part of the indigofera tinctor (especially leaves for Indigofera tinctoria) can be used.

Sieves of indigo-producing plant powder can be sieved to obtain particles having an upper limit size corresponding to the pores or mesh size of the sieve, specifically 35-80 mesh (US).

According to the particular mode of the invention, the size of the indigo-producing plant powder particles is fine. According to the present invention, more specifically, a particle size of 500 μm or less is intended. Preferentially, this powder consists of fine particles having a size of 50-300 μm, more specifically 10-200 μm, including both ends.

It is understood that the indigo-producing plant particles preferentially have a water content of 0 to 10% by mass with respect to the total mass of the powder.

The indigo-producing plant extract according to the present invention is a product of maceration in a solvent, generally an organic solvent, of all or part of the indigo-producing plant (especially leaves for Indigofera tinctoria).

The Indigo-producing plant powder according to the present invention is a natural product derived from the Indigo-producing plant, which is reduced to fine particles by grinding or other mechanical means.

Preferably, indigo-producing plant powder is used.

According to a particular embodiment of the invention, composition A is in the form of a solid, preferably powdery, preferably anhydrous composition. According to this embodiment, the indigo-producing plant powder is preferably in the range of 10% by mass to 99% by mass, more specifically in the range of 20% by mass to 90% by mass, with respect to the total mass of the composition A. Is preferably present in the composition A in a content in the range of 20% by mass to 80% by mass.

According to another particular embodiment of the invention, preferably the composition A comprises an indigo-producing plant powder and / or extract i) and optionally henna ii) and a water or aqueous composition. It is obtained by mixing immediately before (ie, immediately), preferably in the form of a pack, to obtain a ready-to-use dye composition A.

According to this embodiment, the indigo-producing plant powder and / or extract is preferably in the range of 0.5% by mass to 50% by mass, based on the total mass of the composition A, when the composition A is aqueous. More specifically, it is present in the composition A in a content in the range of 1% by mass to 40% by mass, preferably in the range of 5% by mass to 30% by mass.

According to a particularly preferred embodiment, composition A contains water when ready for use.

Therefore, the composition A is preferably aqueous. The term "ready to use" refers to a composition that can be applied immediately and directly to keratin fibers.

According to a particular embodiment of the invention, the composition A of the invention may also contain one or more surfactants, preferably anionic or nonionic surfactants.

The ready-to-use composition A applied to the keratin fiber according to the method of the present invention comprises a molded or disorganized form of indigo-producing plant powder and / or extract i) and optionally henna ii). , Preferably obtained by mixing with an aqueous composition, preferably water.

Preferably, the ready-to-use composition A applied to the keratin fibers according to the method of the present invention is in the form of a pack.

Preferably, the dye composition A prepared for use is 10% by mass to 99% by mass, more specifically 20% by mass to 98% by mass, and more preferably 20% by mass, based on the mass of the ready-to-use composition A. It contains a water content in the range of 40% by mass to 95% by mass.

To do this, indigo-producing plant powder or extract i), optionally henna ii), and optionally additional compounds (as described above) are provided with an aqueous composition containing water. When mixed, a creamy and pleasingly firm packing agent corresponding to the ready-to-use composition A is obtained. If the indigo-producing plant powder is a molded product, it is ground into an aqueous composition, which is preferentially ground into water.

Henna ii)
The dye composition A) according to the present invention preferably contains henna ii).

According to the present invention, the term "henna" preferably refers to henna plant powders and / or henna vegetable dye extracts from henna plants, such as henna plants (Lawsonia alba) or henna (Lawsonia inermis). Henna plant powders and / or dye extracts specifically include Lawson and / or glucosylated precursors thereof.

Preferably, the henna used according to the present invention is in powder form.

It is understood that "henna powder" and indigo-producing plant powder are different from the extract. Specifically, the extract is the product of maceration in a solvent, generally an organic solvent, whereas the powder according to the invention is reduced to fine particles by grinding or other mechanical means, Henna. Or it is a natural product derived from indigo-producing plants.

The henna used in the present invention is preferably red henna (Lawsonia inermis (alba)). Lawson [83-72-7] (CI Natural Orange 6; CI 75420), also known as isojuglon, is found in henna shrubs (Lawsonia alba, Lawsonia inermis). Preferably, henna is in powder form. Henna powder can be sifted to obtain particles with a pore or mesh size in the sieve, specifically particles having an upper limit size corresponding to 35-80 mesh (US). According to the particular mode of the invention, the size of the henna powder particles is fine. According to the present invention, more specifically, a particle size of 500 μm or less is intended. Preferentially, this powder consists of fine particles having a size of 10-300 μm, more specifically 50-250 μm, including both ends. It is understood that the henna particles preferentially have a water content of 0-10% by mass with respect to the total mass of the powder.

Preferably, the henna particles are derived from henna leaves.

As shown above, according to a particular embodiment of the invention, the composition A is in the form of a solid, preferably powdery, preferably anhydrous composition. According to this embodiment, henna is in the range of 5% by weight to 99% by weight, more specifically 10% by weight to 60% by weight, based on the total weight of composition A, especially when composition A is anhydrous. It is preferably present in the composition A in a content in the range of%, preferably in the range of 15% by mass to 40% by mass.

As previously indicated, according to another particular embodiment of the invention, composition A comprises an indigo-producing plant powder i) and henna ii) (if present) and a water or aqueous composition immediately prior to use. (Ie, immediately) to obtain a ready-to-use dye composition A, preferably in the form of a pack.

According to this embodiment, when the composition A is aqueous, the henna is preferably in the range of 0.1% by mass to 30% by mass, more specifically 0.15, based on the total mass of the composition A. It is present in composition A with a content in the range of% by mass to 20% by mass, preferably in the range of 0.2% by mass to 10% by mass.

Preferably, when the staining method according to the present invention uses henna, the indigo-producing plant powder and / or extract i) and henna i) are 0.1 to 95, preferably 0.5 to 50, and even better. Is present in composition A in an i) / ii) mass ratio in the range of 1-10.

Composition B:
The composition B used according to the present invention is an aqueous composition having a pH of less than 7. Preferably, the pH of composition B is less than 6, preferably less than 5.0. Preferably, the pH of the composition B used according to the present invention is 0.5 to 5, more specifically 0.5 to 4.5, preferably 2 to 4, including both ends.

The composition B according to the invention is preferably from iv) mineral or organic acids such as carboxylic acids such as hydrochloric acid, orthrinic acid, sulfuric acid, acetic acid, α-hydroxycarboxylic acid (AHA) such as citric acid and lactic acid; and mixtures thereof. Contains one or more acidifying agents of choice.

In particular, the pH of composition B can be adjusted to the desired value using an acidifying agent as described above or instead using a standard buffer system.

According to a particular embodiment of the invention, the composition (A) is preferably at least selected from hydrochloric acid, phosphoric acid and sulfuric acid and conjugate salts thereof, particularly mineral acids preferably selected from phosphoric acid and salts thereof. Contains one acid.

Preferably, the composition (B) comprises an inorganic buffer system comprising at least one mineral acid (inorganic acid) and a conjugate base thereof, i.e., an inorganic salt of said inorganic acid. Preferably, the composition (B) is at least phosphoric acid (H ₃ PO ₄ ), particularly potassium dihydrogen phosphate KH ₂ PO ₄ , sodium dihydrogen phosphate NaH ₂ PO ₄ , dipotassium hydrogen phosphate K ₂ HPO ₄ . , Disodium Hydrogen Phosphate Na ₂ HPO ₄ , Potassium Hydrogen Phosphate K ₃ PO ₄ and Sodium Na Phosphate ₃ PO ₄ and an Inorganic Buffer Containing a Mixture with At least One Inorganic Phosphate Selected From The Mixtures thereof. Including liquid system.

The acidifying agent iv) as defined above is preferably 0.001% by mass to 15% by mass with respect to the mass of composition B, and more specifically, 0. It occupies 005% by mass to 10% by mass, and more preferably 0.5% to 5%.

Preferably, the acidifying agent iii) is present in the aqueous composition B at a concentration of 0.1 M to 1 M, for example 0.5 M, including both ends.

Natural dye iii) present in composition B:
The composition B used according to the present invention is
-Iii-i) Anthraquinone preferably containing at least one carboxylic acid functional group, preferably selected from carmic acid, laccinic acid and / or kermesic acid;
-Iii-iii) Betalain, preferably betanin;
-Iii-iii) Cyanidin, delphinidin, pelargonin, malvidin, peonidin and petunidin and mixtures thereof, preferably containing at least three hydroxyl groups, preferably also as anthocyanidins of formula (Vg) (anthocyanids or anthocyanidols). Known);
-Iii-iv) Carthamin;
-Iii-v) Naphthoquinone containing at least two hydroxyl groups, preferably at least three hydroxyl groups, preferably selected from alkanine (also known as orcanet) and / or sicokin; and-selected from mixtures thereof. Contains one or more natural dyes iii).

According to a convenient embodiment of the present invention, the natural dye iii) is alizarin, xanthpurpurin, rubiadin, lucidin, mundistin, anthraquinone, purpurin, pseudopurpurin and morindone and mixtures thereof. Preferred from, preferably selected from at least two hydroxyl groups, preferably anthraquinone containing at least three hydroxyl groups, preferably selected from anthragalol, purpurin, pseudopurpurin, morindone and mundistin and mixtures thereof. Will be done.

Preferably, anthraquinone is a dye that absorbs in the red region.

According to a convenient embodiment of the present invention, the natural dye iii) is a compound containing at least one carboxylic acid functional group.

Preferably, according to this embodiment, the natural dye iii) is
-Iii-i) Contains at least one carboxylic acid functional group preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D, pseudopurpurin, mundistin and / or kermesic acid. Anthraquinone;
-Iii-ii) Betalain, preferably betanin; and-preferably selected from mixtures thereof.

According to a convenient embodiment of the present invention, the natural dye iii)
-Iii-iii) Cyanidin, delphinidin, pelargonin, malvidin, peonidin and petunidin and mixtures thereof, preferably containing at least three hydroxyl groups, preferably also as anthocyanidins of formula (Vg) (anthocyanids or anthocyanidols). Known)
Is selected from.

Natural dyes used in accordance with the present invention include compounds that may be naturally present and compounds that are regenerated by chemical (semi) synthesis.

The natural dye according to the present invention may or may not be chloride. These can be in the form of aglycones (unbound sugar) or in the form of glycosylated compounds.

The term "glycosyl group" means a group derived from a monosaccharide or polysaccharide.

The natural dyes according to the invention can be in powder or liquid form. Preferably, the natural dye of the invention can be in powder form.

Preferably, the natural dye used according to the present invention in composition B has an absorption wavelength λ _max of 625 to 750 nm or 300 to 470 nm, and even better, 625 to 750 nm.

Preferably, the dye of the present invention is a dye that absorbs in red, specifically in the absorption wavelength range of 300 to 470 nm or the red-orange purple range of 625 to 750 nm.

（式（Ａ１）中、
・同一であるか又は異なり得るＲ^１及びＲ^８は、水素原子、ヒドロキシル基又はアルキル基、例えばメチルを表し；
・Ｒ^２は、水素原子又はヒドロキシル基、カルボキシル基－Ｃ（Ｏ）ＯＨ若しくはカルボキシレート基－Ｃ（Ｏ）Ｏ^－，Ｑ^＋（ここで、Ｑ^＋は、アルカリ金属又はアルカリ土類金属、例えばカリウム又はカルシウムを表す）を表し；
・Ｒ^３は、ｉ）水素原子、ｉｉ）ヒドロキシル基、又はｉｉｉ）任意選択的に置換されたアリール基、好ましくは、ａ）ヒドロキシル、ｂ）アミノ、ｃ）ヒドロキシル、カルボキシル及び（Ｃ_１～Ｃ_４）アルキルカルボニルアミノから選択される１つ以上の基で任意選択的に置換された（Ｃ_１～Ｃ_６）アルキルから選択される１つ以上の基で任意選択的に置換されたフェニル基を表し；
・Ｒ^４は、水素原子又はヒドロキシル基を表し；
・Ｒ^５は、水素原子又はヒドロキシル、カルボキシル若しくはカルボキシレート基－Ｃ（Ｏ）Ｏ^－，Ｑ^＋（ここで、先に定義された通りである）を表し；
・Ｒ^６は、水素原子、ヒドロキシル基、－Ｏ^－，Ｑ^＋（ここで、Ｑ^＋は、先に定義された通りである）、カルボキシル又はカルボキシレート基－Ｃ（Ｏ）Ｏ^－，Ｑ^＋（ここで、Ｑ^＋は、先に定義された通りである）を表し；
・Ｒ^７は、水素原子、ヒドロキシル基又はグリコシル基、好ましくはグルコースを表す）
のものから好ましくは選択される、少なくとも１つのカルボン酸官能基を含むアントラキノン並びにまたその互変異性及び／又はメソメリー（ｍｅｓｏｍｅｒｉｃ）型、その立体異性体、化粧品的に許容される酸又は塩基とのその付加塩及び水和物などのその溶媒和物である。 In particular, according to the first preferred embodiment of the present invention, the natural dye iii) contains at least one carboxylic acid functional group according to the following formula (A1):

(In formula (A1),
R ¹ and R ⁸ , which may be the same or different, represent a hydrogen atom, a hydroxyl group or an alkyl group, such as methyl;
-R ² is a hydrogen atom or a hydroxyl group, a carboxyl group-C (O) OH or a carboxylate group-C (O) ^O- , Q ⁺ (where Q ⁺ is an alkali metal or an alkaline earth metal, for example. Represents potassium or calcium);
R ³ is i) a hydrogen atom, ii) a hydroxyl group, or iii) an optionally substituted aryl group, preferably a) hydroxyl, b) amino, c) hydroxyl, carboxyl and (C ₁ -C). ₄ ) A phenyl group optionally substituted with one or more groups selected from alkylcarbonylamino (C ₁ to C ₆ ) optionally substituted with one or more groups selected from alkyl. Representation;
-R ⁴ represents a hydrogen atom or a hydroxyl group;
-R ⁵ represents a hydrogen atom or a hydroxyl, carboxyl or carboxylate group-C (O) ^O- , Q ⁺ (here, as defined above);
-R ⁶ is a hydrogen atom, a hydroxyl group, ^-O- , Q ⁺ (where Q ⁺ is as defined above), a carboxyl or carboxylate group-C (O) ^O- , Q ^+. (Here, Q ⁺ is as defined above);
R ⁷ represents a hydrogen atom, a hydroxyl group or a glycosyl group, preferably glucose)
Preferably selected from those of anthraquinone containing at least one carboxylic acid functional group and also its tautomer and / or mesomeric form, its stereoisomer, cosmetically acceptable acid or base. It is a solvate thereof such as its addition salt and hydrate.

（ここで、Ｙは、－ＣＨ（ＮＨ_２）－Ｃ（Ｏ）ＯＨ、－ＣＨ_２－ＯＨ、－ＮＨ－Ｃ（Ｏ）－ＣＨ_３から選択される群を表し；

は、この分子の残部への付着点を表す）
などの（Ｃ_１～Ｃ_４）アルキルカルボニルアミノから選択される１つ以上の基で任意選択的に置換されたフェニル基を表し、
・同一であるか又は異なり得るＲ^５及びＲ^６は、水素原子又はヒドロキシル基、カルボキシル基－Ｃ（Ｏ）ＯＨ若しくはカルボキシレート基－Ｃ（Ｏ）Ｏ^－，Ｑ^＋（ここで、Ｑ^＋は、アルカリ金属又はアルカリ土類金属、例えばカリウム又はカルシウムを表す）を表し；
・Ｒ^７は、水素原子又はヒドロキシル基を表す。 Preferentially, the dyes of the present invention are of formula (A1), especially collectively or separately, in the formula.
R ¹ represents a hydroxyl or (C ₁ to C ₄ ) alkyl group;
R ² , R ⁴ and R ⁸ which may be the same or different represent a hydrogen atom or a hydroxyl group;
R ³ is a hydrogen atom, a hydroxyl group or a hydroxyl, a carboxyl and, for example,

(Here, Y represents a group selected from -CH (NH ₂ ) -C (O) OH, -CH ₂ -OH, -NH-C (O) -CH ₃ ;

Represents the point of attachment of this molecule to the rest)
Represents a phenyl group optionally substituted with one or more groups selected from (C ₁ to C ₄ ) alkylcarbonylaminos such as.
R ⁵ and R ⁶ which may be the same or different are hydrogen atoms or hydroxyl groups, carboxyl groups-C (O) OH or carboxylate groups-C (O) ^O- , Q ⁺ (where Q ⁺ is Represents an alkali metal or alkaline earth metal, eg potassium or calcium);
-R ⁷ represents a hydrogen atom or a hydroxyl group.

According to one embodiment, the dyes of the present invention are of formula (A1), and in particular collectively or separately, in the formula,
R ¹ represents an (C ₁ to C ₄ ) alkyl group;
-R ² represents a carboxyl or carboxylate group-C (O) ^O- , Q ⁺ (where Q ⁺ represents an alkali metal or an alkaline earth metal, such as potassium or calcium);
R ³ and R ⁸ represent hydroxyl groups;
-R ⁴ represents a hydrogen atom or a hydroxyl group, preferably hydrogen;
-R ⁶ represents a hydroxyl group or ^-O- , Q ⁺ (where Q ⁺ is as defined above);
R ⁷ represents a hydrogen atom or a glycosyl group such as glucose.

The natural dye iii) is specifically from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D (also known as flavokermesic acid), pseudopurpurin and mundistin and mixtures thereof; preferably. Is from anthraquinone preferably comprising at least one carboxylic acid functional group, preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C and laccinic acid D, preferably laccinic acid D and / or kermesic acid. Particularly preferably selected.

The structure of these compounds is as follows.

Preferably, the natural dye iii) is selected from carmine acid, laccinic acid D or kermes acid, pseudopurpurin and mundistin and mixtures thereof.

According to a second convenient embodiment of the present invention, the natural dye iii) is selected from betalain, preferably betanin. Betalain is a dye derived from beetroot.

According to a third convenient embodiment of the present invention, the natural dye iii) is a cyanidin, cyanidin, delphinidin, pelargonin, malvidin, peonidin, petunidin, aurantidin and luteolinidin and mixtures thereof, heterosides thereof. Anthocyanidins (anthocyanids or anthocyanidols) of the formula (Vg), preferably comprising at least three hydroxyl groups, preferably selected from, for example, dihydroxyanthocyans (or dihydroxyanthocyansides or anthocyanins), oligomers and polymers thereof, such as proanthocyanins. Also known as); preferably anthocyanidins preferably selected from cyanidins, delphinidins, pelargonins, malvidins, peonidins and petunidins and mixtures thereof, especially cassis, blueberries, radishes, grapes, red cabbage, elderberries, black carrots. And selected from black rice extracts.

（式（Ｖｇ）中、
・同一であるか又は異なり得るＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、水素若しくはハロゲン原子又はｉ）ヒドロキシル、ｉｉ）（Ｃ_１～Ｃ_６）アルキル、ｉｉｉ）（Ｃ_１～Ｃ_６）アルコキシ、ｉｖ）（Ｃ_１～Ｃ_６）アルキルチオ、ｖ）カルボキシル、ｖｉ）アルキル若しくはアルコキシカルボニルカルボキシレート、ｖｉｉ）任意選択的に置換されたアミノ、ｖｉｉｉ）任意選択的に置換された直鎖若しくは分枝のアルケニル、ｉｘ）任意選択的に置換されたシクロアルキル、ｘ）任意選択的に置換されたアリール、ｘｉ）１つ以上のケイ素原子を含有する基、ｘｉｉ）（ジ）（（ヒドロキシ）（Ｃ_１～Ｃ_６）アルキル）アミノ、ｘｉｉｉ）グルコシル、ｘｉｖ）Ｒ－Ｚ－Ｃ（Ｘ）－Ｙ－（ここで、Ｒは、水素原子又は特に少なくとも１つのヒドロキシル基で任意選択的に置換された（Ｃ_１～Ｃ_６）アルキル若しくはアリール基、例えば３，４，５－トリヒドロキシフェニルを表し；同一であるか又は異なり得るＹ及びＺは、結合、又は酸素若しくは硫黄原子、又は基－Ｎ（Ｒ’）－（ここで、Ｒ’は、水素原子又は（Ｃ_１～Ｃ_６）アルキル基を表す）を表し、Ｙは、（Ｃ_１～Ｃ_６）アルキレン基も場合により表し；Ｘは、酸素若しくは硫黄原子又はＮ－Ｒ’’（ここで、Ｒ’’は、水素原子又は（Ｃ_１～Ｃ_６）アルキル基を表す）を表す）から選択される基を表し；
・同一であるか又は異なり得るＲ^６及びＲ^８は、水素原子又はヒドロキシル基、（Ｃ_１～Ｃ_６）アルキル基若しくは先に定義された通りの基Ｒ－Ｚ－Ｃ（Ｘ）－Ｙ－から選択される基を表すか；又は
・代わりに、単位（Ｖ）は、クロマン環の４、６又は８位を介してポリフェノールの他の単位と連結されることになる前記ポリフェノールの重合単位を構成する（ここで、Ｒ^１又はＲ^３及びＲ^６は、前記ポリフェノールの他の単位との共有結合を形成する））
のアントシアニジン（アントシアニド又はアントシアニドールとしても公知である）から選択され；
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^８、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４から選択される、式（Ｖｇ）の化合物の少なくとも３つの基は、ヒドロキシル基を表すことが理解され；
式（Ｖｇ）の化合物は、カチオン性であり、且つハロゲン化物などの有機又は無機アニオン性対イオンＡｎ^－と会合される。 According to a convenient embodiment of the present invention, the natural dye iii) contains at least three hydroxyl groups and has the following formula (Vg):

(In the formula (Vg),
• R ¹ , R ² , R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ which may be the same or different are hydrogen or halogen atoms or i) hydroxyl, ii) (C ₁ ). ~ C ₆ ) alkyl, iii) (C ₁ ~ C ₆ ) alkoxy, iv) (C ₁ ~ C ₆ ) alkyl thio, v) carboxyl, vi) alkyl or alkoxycarbonyl carboxylate, vi) optionally substituted Amino, viii) Arbitrarily substituted linear or branched alkenyl, ix) Arbitrarily substituted cycloalkyl, x) Arbitrarily substituted aryl, xi) One or more silicon atoms (Xii) (di) ((hydroxy) (C ₁ to C ₆ ) alkyl) amino, xiii) glucosyl, xiv) RZC (X) -Y- (where R is hydrogen). Represents an (C ₁ -C ₆ ) alkyl or aryl group optionally substituted with an atom or particularly at least one hydroxyl group, such as 3,4,5-trihydroxyphenyl; Y and which may be the same or different. Z represents a bond or an oxygen or sulfur atom, or the group -N (R')-(where R'represents a hydrogen atom or a (C ₁ -C ₆ ) alkyl group) and Y represents (where). C ₁ to C ₆ ) alkylene groups are also optionally represented; X stands for oxygen or sulfur atom or NR'' (where R'' stands for hydrogen atom or (C ₁ to C ₆ ) alkyl group). Represents a group selected from);
R ⁶ and R ⁸ which may be the same or different are hydrogen atoms or hydroxyl groups, (C ₁ to C ₆ ) alkyl groups or groups as previously defined RZC (X) -Y-. Represents a group selected from; or • Alternatively, the unit (V) is a polymerization unit of said polyphenol that will be linked to another unit of polyphenol via the 4, 6 or 8 position of the chroman ring. ^{Consists (} where ^R1 or R3 and R6 form a covalent bond with the other units of the polyphenol))
Selected from anthocyanidins (also known as anthocyanids or anthocyanidols);
At least three groups of the compound of formula (Vg) selected from R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have hydroxyl groups. Understood to represent;
The compound of formula (Vg) is cationic and is associated with an organic or inorganic anionic counterion An ⁻ such as a halide.

Preferably, the groups R1, R6, R14 and R10 represent hydrogen atoms.

Preferably, the group RZC (X) -Y- of the compound of formula (V) represents 3,4,5-trihydroxyphenyl-1-carbonyloxy (-O-gallate). Preferably, the groups R ₁ , R ₂ , R ₃ , R ₄ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are selected from hydrogen atoms and hydroxyl, glycosyloxy and alkoxy groups.

According to a particularly preferred embodiment of the present invention, the natural dye iii) is an anthocyanidin of the formula Vg (wherein the groups R1, R6, R14 and R10 represent hydrogen atoms).

The other groups R2, R3, R4, R8, R13, R12 and R11 contain at least 4 hydroxyl and / or alkoxy functional groups (preferably methoxy), and more preferably at least 5 hydroxyl and / or methoxy functional groups. ..

According to a preferred embodiment of the invention, the natural dye iii) is anthocyanidin of formula Vg selected from the compounds listed in the table below and mixtures thereof.

According to a preferred embodiment of the present invention, the natural dye iii) is anthocyanidin selected from cyanidin, delphinidin, malvidin, peonidin and petunidin, and mixtures thereof.

According to a preferred embodiment of the invention, the natural dye iii) is anthocyanidin selected from delphinidin, malvidin and petunidin and mixtures thereof.

According to a fourth convenient embodiment of the present invention, the natural dye iii) is selected from carthamin.

According to a fifth convenient embodiment of the invention, the natural dye iii) is preferably selected from alkanine (also known as orcanet) and / or sicokin, at least two hydroxyl groups, preferably at least. Selected from naphthoquinones containing 3 hydroxyl groups.

According to a preferred embodiment, the natural dye iii) used according to the present invention is a polyphenol (and / or a polyphenol concentrated extract).

The term "polyphenol" means a compound whose structure contains several hydroxyl functional groups on one or more 6-membered carbon-based aromatic rings.

According to this embodiment, the natural dye iii) used according to the present invention is
-Iii-i) Anthraquinone preferably comprising at least one carboxylic acid functional group, preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D and / or kermesic acid;
-Iii-iii) Betalain, preferably betanin;
-Iii-iii) Also known as anthocyanidins of formula (Vg) (anthocyanids or anthocyanidols) containing at least three hydroxyl groups, preferably selected from cyanidin, delphinidin, pelargonin, malvidin, peonidin and petunidin and mixtures thereof. be);
-Iii-iv) Carthamin; and-a polyphenol selected from the mixture thereof.

According to another convenient embodiment of the present invention, the natural dye iii) is a compound containing at least one carboxylic acid functional group.

Preferably, according to this embodiment, the natural dye iii) is
-Iii-i) Contains at least one carboxylic acid functional group preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D, pseudopurpurin, mundistin and / or kermesic acid. Anthraquinone;
-Iii-ii) Betalain, preferably betanin; and-a mixture thereof.

Preferably, the natural dye iii) is
-Iii-i) Contains at least one carboxylic acid functional group preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D and / or kermesic acid, pseudopurpurin and mundistin. Anthraquinone;
-Selected from betanin.

Preferably, the natural dye iii) is
-Iii-i) Contains at least one carboxylic acid functional group preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D, pseudopurpurin, mundistin and / or kermesic acid. Anthraquinone-iii-iii) betanin; and-selected from a mixture thereof.

Even more preferably, the natural dye iii)
-Iii-i) Contains at least one carboxylic acid functional group preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D, pseudopurpurin, mundistin and / or kermesic acid. Selected from anthraquinone.

In the context of the present invention, the "pure" natural dye iii) is in the range of 0.05% by weight to 25% by weight with respect to the total weight of the dye composition, in particular 0. It is present in the composition B in a total amount in the range of 1% by mass to 10% by mass, preferably in the range of 0.5% by mass to 5% by mass with respect to the total mass of the composition B.

With respect to the extract iii), the content of the contained extract itself in the composition B is preferably 0.1% by mass to 20% by mass, more preferably 0.5, based on the mass of the composition B. It is from mass% to 5% by mass.

Organic solvent:
The compositions A and / or B as defined above can contain one or more organic solvents. Examples of preferred organic solvents are C1 _{- C4} lower alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, hexylene. Glycols and also aromatic alcohols such as benzyl alcohol or phenoxyethanol can be mentioned.

The organic solvent is preferably present in a proportion of about 0.1% by mass to 20% by mass, more preferably about 0.5% by mass to 10% by mass, based on the total mass of the assumed composition. ..

Oils Compositions A and / or B as defined above can contain one or more of the same or different oils.

The term "oil" means a "fat substance" that is liquid at room temperature (25 ° C.) and atmospheric pressure (760 mmHg); the viscosity at 25 ° C. is preferably less than 1200 cps, and even better less than 500 cps (eg, less than 500 cps). Newtonian plateau, determined using an ARG2 rheometer from TA Instruments equipped with a spindle having a cone-plate shape with a diameter of 60 mm and an angle of 2 degrees over a shear stress range of 0.1 Pa to 100 Pa. (Defined from).

The term "fat substance" is an organic that is insoluble in water (less than 5%, preferably less than 1%, even more preferably less than 0.1%) at room temperature (25 ° C.) and atmospheric pressure (760 mmHg). Means a compound. It has at least one hydrocarbon-based chain containing at least 6 carbon atoms or a sequence of at least two siloxane groups within its structure. In addition, fatty substances are generally organic solvents such as chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petrolatum jelly or decamethylcyclo under the temperature and pressure conditions described above. Soluble in pentasiloxane.

The term "non-silicone oil" means an oil that does not contain a silicon (Si) atom, and the term "silicone oil" means an oil that contains at least one silicon atom.

More specifically, the oils are non-silicone oils, especially C ₆ to C ₁₆ hydrocarbons or hydrocarbons containing more than 16 carbon atoms, especially alkanes; animal origin oils; plant origin triglyceride oils; essential oils. Selected from fluoro oils or synthetic origin, glycerides of fatty alcohols; fatty acids and / or fatty alcohol esters (other than triglycerides), fatty acid amides and silicone oils.

Preferably, the oil is not an oxyalkyleneized or glycerolated ether.

Preferably, the oil does not contain any _{C2 -} C3 oxyalkylene units or glycerolated units.

Preferably, the oil is not a fatty acid that gives a water-soluble soap in chloride form.

The oil that can be used as the second component b) in the composition A or B according to the present invention can be silicone.

Silicones are volatile, unmodified or modified with organic groups, having a viscosity of 5 × 10 ^-6 to 2.5 m ² / s, preferably 1 × 10 ^-5 to 1 m ² / s at 25 ° C. Alternatively, it can be a non-volatile cyclic, linear or branched silicone.

Preferably, the silicone is selected from polydialkylsiloxanes, in particular polydimethylsiloxane (PDMS) and organomodified polysiloxanes, which contain at least one functional group selected from poly (oxyalkylene) groups, amino groups and alkoxy groups. ..

Organopolysiloxanes are defined in detail by Walter Noll's Chemistry and Technology of Siloxanes (1968), Academic Press. Organopolysiloxanes can be volatile or non-volatile.

When the organopolysiloxane is volatile, the silicone is more specifically from those having a boiling point of 60 ° C to 260 ° C, and even more specifically.
(I) Selected from cyclic polydialkylsiloxanes containing 3-7, preferably 4-5 silicon atoms. This is, for example, Octamethyl Cyclotetrasiloxane sold under the name Volatile Silicone® 7207 by Union Carbide or Silicone® 70045 V2 by Rhodia, Volatile Silicone® 7158 by Union Carbide. Silicone® 70045 V5 by Decamethylcyclopentasiloxane and Rhodia for sale and mixtures thereof.

を有する、Ｕｎｉｏｎ Ｃａｒｂｉｄｅによって販売されているＶｏｌａｔｉｌｅ Ｓｉｌｉｃｏｎｅ（登録商標）ＦＺ ３１０９などのジメチルシロキサン／メチルアルキルシロキサン型のシクロコポリマーも挙げることができる。 The following formula:

Also mentioned are dimethylsiloxane / methylalkylsiloxane type cyclocopolymers such as Volitele Silicone® FZ 3109 sold by Union Carbide.

Mixtures of cyclic polydialkylsiloxanes and organosilicon compounds, such as mixtures of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and octamethylcyclotetrasiloxane and oxy-1,1'-bis (hexa-2). , 2,2', 2', 3,3'-trimethylsilyloxy) Mixture with neopentane;
(Ii) A linear volatile polydialkylsiloxane containing 2 to 9 silicon atoms and having a viscosity of 5 × ^10-6 m ² / s or less at 25 ° C. can also be mentioned. An example is the decamethyltetrasiloxane sold under the name SH 200, in particular by Toray Silicone. Silicones belonging to this category are described in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. It is also described in a paper published in 27-32, Todd & Byers, "Voltile Silicone Fluids for Cosmetics".

Non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the above organic functional groups and mixtures thereof are preferably used.

More specifically, these silicones are selected from polydialkylsiloxanes, among which polydimethylsiloxanes having a trimethylsilyl terminal group can be mainly mentioned. Silicone viscosities are measured at 25 ° C. according to ASTM Standard 445 Appendix C.

Among these polydialkylsiloxanes, the following commercially available products can be mentioned without limitation:
-47 and 70 047 series of Silver® oils or Mirasil® oils sold by Rhodia, such as 70 047 V 500 000 oils;
-Mirasil® series oils sold by Rhodia;
-200 series oils from Dow Corning, eg DC200 with a viscosity of 60,000 mm ² / s;
-Viscasi® oils from General Electric and certain oils in the SF series from General Electric (SF 96, SF 18).

Polydimethylsiloxane with a dimethylsilanol end group known under the name dimethiconol (CTFA), such as the 48 series oils from Rhodia, can also be mentioned.

Compositions A and / or B as defined above can include one or more oils selected from fatty alcohols, fatty acid amides and fatty acid esters in the form of oils.

For the purposes of the present invention, fatty alcohols, esters and acids are more specifically optionally substituted with one or more hydroxyl groups (particularly 1 to 4), 6 to 30 carbons. It is recalled to have at least one linear or branched saturated or unsaturated hydrocarbon-based group containing an atom. If they are unsaturated, these compounds can contain 1-3 conjugated or unconjugated carbon-carbon double bonds.

More precisely, these compounds are esters of C1 to _C10 alcohols and C6 to _C30 fatty acids, such as RC (O) -OR'(where R is ₁ or ₂ ). Represents a linear or branched C ₆ to C ₃₀ alkyl or linear or branched C ₆ to C ₃₀ alkenyl group containing one unsaturated, where R is a linear or branched C ₁ to C ₁₀ alkyl group. Represents).

Preferentially, R represents a linear C ₁₀ -C ₂₀ alkyl group and R'represents a branched C ₁ -C ₆ alkyl group, such as isopropyl myristate.

According to another convenient variant, component ii) is one or more amides of C ₆ to C ₃₀ fatty acids and primary or secondary, preferably primary C ₁ to C ₁₀ amines, such as formula R'. '-C (O) -N (R _a ) -R''' (where R'' is a straight chain containing one or two unsaturated groups which can be substituted with one or more hydroxyl groups. Or a branched C ₆ to C ₃₀ alkyl or a straight chain or a branched C ₆ to C ₃₀ alkenyl group or (di) (C ₁ to C ₆ ) (alkyl) amino, where R'''is a straight chain. Or represents a C ₁ to C ₁₀ alkyl group of a branch, where Ra represents _a hydrogen atom or an alkyl group as defined for R'''). Preferably, R'' represents a C ₁₄ to C ₂₀ alkenyl group, Ra represents _a hydrogen atom, and R''' represents a (di) (C ₁ to C ₄ ) such as oleylamide propyldimethylamine. (Alkyl) Represents a C ₁ to C ₆ alkyl group optionally substituted with an amino.

C ₆ to C ₁₆ alkanes are linear or branched and optionally cyclic. Examples that can be mentioned include hexane, dodecane and isoparaffin, such as isohexadecane and isodecane. Linear or branched hydrocarbons containing more than 16 carbon atoms are selected from liquid paraffin, petrolatum, liquid petrolatum, polydecene and hydrogenated polyisobutene such as Parleam®, squalene, squalene and mixtures thereof. be able to.

Among the hydrocarbons are purified vegetable perhydrosqualene sold under the name Fitoderm by Cognis; for example, vegetable squalane sold under the name Squalive by Biosynthes.

The following compounds:
-For example, a mixture of C15- _C16 branched alkanes sold by SEPPIC under the name _Emogreen L15;
-For example, a mixture of C ₁₃ to C ₁₅ linear and / or branched alkanes sold by SEPPIC under the name Emosmart L15 can also be mentioned.

Among animal oils, perhydrosqualene can be mentioned.

Among plant or synthetic origin triglycerides, liquid fatty acid triglycerides containing 6-30 carbon atoms, such as heptane or octanoic acid triglycerides, or instead, for example, sunflower oil, corn oil, soybean oil, pumpkin oil, grape. Seed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arala oil, castor oil, avocado oil, capril / capric acid triglyceride, such as those sold by Stearinerie Dubois or registered by Dynamit Nobel. Examples include those sold under the names 810, 812 and 818, jojoba oil and shea butter oil.

Among the fluorooils, perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold by BNFL Fluorochemicals under the names Flutec® PC1 and Flutec® PC3; Perfluoro1 , 2-Dimethylcyclobutane; perfluoroalkanes sold under the names PF 5050® and PF 5060® by 3M, such as dodecafluoropentane and tetradecafluorohexane or Foralkyl (registered by Atchem). Bromoperfluorocutyl sold under the name (trademark); nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholin derivatives sold under the name PF 5052® by 3M, eg 4- (tri). Fluoromethyl) perfluoromorpholin can be mentioned.

Among the essential oils contained in the composition of the present invention, Ullmann's Encyclopedia of Internal Chemistry (“Flavors and Fragrances”, Karl-Georg Fahlbush et al. 14356007. A11_141) can be mentioned.

Preferably, the oil of the present invention is a non-silicone oil. The term "non-silicone oil" means an oil that does not contain a silicon (Si) atom, and the term "silicone oil" means an oil that contains at least one silicon atom.

According to a variant of the invention, the oil is a liquid ester of C ₆ to C ₁₆ alkanes, hydrocarbons, polydecenes, fatty acids and / or fatty alcohols containing more than 16 carbon atoms and liquid fatty alcohols or mixtures thereof. Is selected from.

Even better, the oil is selected from liquid petrolatum, C6 to _C16 alkanes, polydecene and hydrocarbons containing more than ₁₆ carbon atoms.

In this preferred variant, the oil is selected from mineral oils such as liquid petrolatum, squalene and squalene.

According to another most particularly preferred mode of the invention, the oil is selected from naturally occurring oils, more specifically plant origin oils, preferentially jojoba oil, babas oil, sunflower oil, olive oil, palm. Oil, Brazilian nut oil, Marla oil, Corn oil, Argan oil, Soybean oil, pumpkin oil, Grapeseed oil, Amani oil, Sesame oil, Hazelnut oil, Anzu oil, Macadamia oil, Arara oil, Coriander oil , Almond oil, castor oil, avocado oil, shea butter oil, and rapeseed oil, borage oil, evening primrose oil, pomegranate oil, mango oil, palm oil, cottonseed oil and coconut kernel oil and mixtures thereof.

More specifically, compositions A and / or B contain one or more oils of plant origin, preferably selected from avocado oil, olive oil, palm oil, palm kernel oil, argan oil and sunflower oil. Can; more preferentially, the oil of the invention is selected from coconut kernel oil and mixtures thereof.

According to a preferred embodiment, the compositions A and / or B are from C ₆ to C ₁₆ hydrocarbons or hydrocarbons containing more than 16 carbon atoms, especially alkanes; preferably:
-C ₆ to C ₁₆ hydrocarbons preferably selected from hexanes, dodecanes, isoparaffins such as isohexadecanes and isodecanes and mixtures thereof (the latter being linear, branched and optionally cyclic);
-A straight chain containing more than 16 carbon atoms, preferably selected from liquid paraffin, petrolatum, liquid petrolatum, polydecene and hydrogenated polyisobutene, such as Parleam®, hemisqualan, squalene and squalene and mixtures thereof. Alternatively, it can contain one or more oils selected from branched hydrocarbons; and mixtures thereof.

The composition A and / or B used in the method of the present invention is 1% by mass to 80% by mass including both ends, more specifically 2% by mass to 50% by mass, based on the total mass of the composition. %, Preferably 3% by weight to 40% by weight, more preferably 2% by weight to 25% by weight, preferably one or more oils.

Auxiliary agent:
The compositions A and / or B used in the methods of the invention are various auxiliary agents conventionally used in hair dye compositions, such as anionic, cationic, amphoteric or nonionic surfactants, inorganics. Or organic thickeners, especially anionic, cationic, nonionic and amphoteric polymer-associative thickeners, antioxidants, penetrants, metal ion sequestering agents, fragrances, buffers, dispersants, conditioning agents, for example. Inorganic or organic thickeners such as ceramides, film-forming agents, preservatives, opalescent agents and clay can also be included.

The above adjuvants are generally 0.01% by weight to 40% by weight, preferably 0.1% to 20% by weight, based on the expected weight of the composition, respectively. Exists in quantity.

Needless to say, those skilled in the art will ensure that the favorable properties inherently associated with the compositions or packs useful in the dyeing process according to the invention are not adversely affected or substantially freed by the expected additions. , This or these optional additional compounds will be carefully selected.

Additional dyes:
The composition A and / or B used in the dyeing method of the present invention is one other than the indigo-producing plant powder and / or the extract i) and the henna ii) and the natural dye iii) as described above. These additional direct dyes, especially synthetic dyes or dyes of natural origin, can also be included.

Synthetic direct dyes are preferably selected from those conventionally used in direct dyeing, in which all commonly used aromatic and / or non-aromatic dyes such as neutral, acidic or cationic. Nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes, neutral, acidic or cationic quinones, especially anthraquinone direct dyes, azines, triarylmethanes or indamine direct dyes, methins, styryl , Porphyrin, metalloporphyrin, phthalocyanine, methine, cyanine and fluorescent dyes.

Preferentially, natural substantive dyes other than indigo i) and henna ii) are condensed, gall oak or elagtannin, naphthoquinone (juglone, lawson), anthraquinone (emodin, alizarin, etc.), isatin, curcumin, spinulosin, polyphenols. , For example flavonoids, isoflavonoids, pterocarpanes, neoflavons or orthane and the like.

These natural dyes can be added in the form of defined compounds, extracts or plant parts. The defined compound from an extract or plant moiety is preferably in the form of a powder, particularly a fine powder in which the particles have the same size as the indigo-producing plant powder as previously defined.

Natural or synthetic direct dyes other than the Indigo-producing plant powders i) and henna i) used in the methods of the invention, if present, specifically 0. It occupies 001% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass with respect to the total mass of the assumed composition.

Preferably, the compositions of the invention do not contain any synthetic direct dyes, i.e. non-naturally occurring dyes.

の化合物から選択される１種以上の追加の天然染料又はその混合物を含むことができる。 Conveniently, composition B has the following formula (a) or (b):

Can include one or more additional natural dyes selected from the compounds of the above, or mixtures thereof.

Such compounds include, for example, Monascus purpureus species (also known as M. albidus, M. anka), Monascus araneosus, and M. major. ), Monascus rubiginosus (M. rubiginosus) and Monascus bini (M. vini)) are extracted from the mold.

The composition A used in the method of the present invention can also contain one or more oxidizing bases and / or one or more couplers conventionally used for dyeing keratin fibers.

Among the oxidizing bases, para-phenylenediamine, bis (phenyl) alkylenediamine, para-aminophenol, bis-para-aminophenol, ortho-aminophenol, heterocyclic compound bases and their addition salts can be mentioned. can.

Among these couplers, meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene-based couplers and heterocyclic compound couplers and their addition salts can be specifically mentioned.

The oxidizing bases present in the composition, if present, are generally present in an amount of 0.001% to 10% by weight of the total mass of the dye composition, respectively.

Preferably, the dyeing method of the present invention does not use any oxidative dye.

PH of composition A ready for use
According to a particular embodiment of the invention, the pH of the aqueous composition containing component i) and optionally ii), preferably the ready-to-use composition A after mixing with water, is 2-9. It is preferably in the range of 3 to 7, and even better, in the range of 4 to 6.5.

The pH of the ready-to-use composition A can be adjusted to the desired value using the acidic or alkaline agents commonly used in dyeing keratin fibers or by using a standard buffer system instead. ..

Among the acidic agents that can be used in the compositions of the invention are mineral or organic acids such as hydrochloric acid, ortholic acid or sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid and sulfonic acid. Yes; the acid is preferably an organic acid such as citric acid.

Surfactants According to certain embodiments, the dyeing method uses one or more surfactants. Preferably, the surfactant is selected from anionic and nonionic surfactants.

Dyeing Method According to the Invention The dyeing method according to the invention comprises two different compositions A and B used in two different steps E1) and E2) through its application to keratin fibers.

According to the preferred method according to the invention, composition A is first applied to the keratin fibers; and composition B is applied to the keratin fibers after application of composition A; this method is dyeing with composition A. It preferably comprises at least one rinsing step and / or washing step between the step and the treatment step involving the application of composition B.

Preferably, the staining method according to the invention comprises the following steps:
-The first step is to use indigo-producing plant powder and / or extract i) and optionally henna ii), in the form of a previously defined pack containing water, in particular, prior to it. Includes preparing composition A as defined;
-Then, the ready-to-use composition A as defined above is applied to the keratin fibers, preferably in the range of preferably at least 10 minutes, preferentially in the range of 10 to 12 hours, and even better in the range of 15 to 75 minutes. , And even better, leave on the fibers for a time in the range of 15-60 minutes;
-The fiber is then treated with an aqueous composition B having a pH of less than 7 containing one or more natural dyes iii) selected from the following:
-Iii-i) At least one carboxylic acid functional group preferably selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D, pseudopurpurin, mundistin and / or kermesic acid is preferred. Contains anthraquinone;
-Iii-iii) Betalain, preferably betanin;
-Iii-iii) Cyanidin, delphinidin, pelargonin, malvidin, peonidin and petunidin and mixtures thereof, preferably containing at least three hydroxyl groups, preferably also as anthocyanidins of formula (Vg) (anthocyanids or anthocyanidols). Known);
-Iii-iv) Carthamin;
-Iii-v) naphthoquinone containing at least two hydroxyl groups, preferably at least three hydroxyl groups, preferably selected from alkanine (also known as orcanet) and / or sicokin; and-a mixture thereof; and iv. ) One or more acidifying agents.

Preferably, between the steps of applying the ready-to-use composition A and the step of applying the composition B, the keratin fibers are rinsed with water until the pack is no longer visible and / or in the presence of a hair wash. Wash with; preferably, according to this third step, rinse the fibers with water without washing with a hair wash;
-Preferably, if this rinsing and / or washing step is performed, at the end of the step, the keratin fibers can then be dried or kept wet, preferably kept wet. ..

According to another embodiment of the method according to the invention, the composition B as defined above is first applied to the keratin fibers; then the composition A ready for use as defined above is. , Applied to keratin fibers, preferably left on the fibers as previously defined. According to this embodiment, the fibers are also sooted as previously described.

Preferably, at the end of the dyeing method according to the invention, the keratin fibers are washed and / or sooted.

The ready-to-use composition A preferably contains water and is in the form of a pack; which is one or more oils and / or optionally mixed with an indigo-producing plant powder i) and optionally henna ii). Alternatively, one or more organic solvents and cosmetic additives can also be included.

According to another embodiment of the invention, indigo-producing plant powder i) and optionally henna and water at temperatures below 100 ° C, particularly 25 ° C to 70 ° C, and even better 25 ° C to 50 ° C. The composition, preferably mixed with water or ground in it.

Preferably, the temperature of application of the composition A is in the range of room temperature (15 ° C to 25 ° C) to 50 ° C, more specifically 25 ° C to 40 ° C.

After applying the pack agent according to the present invention, the hair head is heat-treated by heating at a temperature in the range of 30 ° C to 150 ° C, more preferably 30 ° C to 60 ° C. Can be done. In practice, this operation can be performed using a hair styling hood, a hair dryer, a dispenser or any other standard heating device.

Specific embodiments of the present invention relate to dyeing methods performed at room temperature (25 ° C.).

Evaluation of coloration obtained on keratin fibers can be performed visually or using a spectrophotometer in the CIE L ^* a ^* b ^* system, eg, a Minolta CM 3600 spectrocolorimeter (D65 light source, angle 10 °, positive reflection). Can be carried out using light included).

In this L ^* a ^* b ^* system, L ^* represents the brightness of the color, a ^* indicates the green / red axis, and b ^* indicates the blue / yellow axis. The smaller the value of L ^* , the darker the color and the stronger the coloring.

The smaller the value of a ^* , the stronger the greenishness of the color, and the larger the value of a ^* , the stronger the redness of the color.

The smaller the value of b ^* , the stronger the bluish color, and the larger the value of b ^* , the stronger the yellowish color.

による（ΔＥ^＊）によって定義される。 The color adhesion on the hair corresponds to the amount of change in the fixed coloring of the hair before and after treatment or dyeing, and the following formula:

Is defined by (ΔE ^* ).

In this equation, L ^* , a ^* and b ^* represent the values measured for hair fixation after dyeing, and L ₀ ^* , a ₀ ^* and b ₀ ^* are the fixation of undyed hair. Represents the value measured against. The larger ΔE ^* , the better the color adhesion.

によって算出される。 The stability of coloring of keratin fibers over time, especially after 9 days, was also evaluated by measuring the color coordinates of the keratin fibers and comparing them with the color coordinates immediately after the dyeing method according to the present invention was carried out. The color difference ΔE ^* between the color at T0 and the color after 9 days represents the stability of the hair color, and the following formula:

Calculated by.

In this equation, L ₀ ^* , a ₀ ^* and b ₀ ^* represent the colorimetric coordinates measured for hair fixation at T0 immediately after performing the method, L _3s ^* , a _3s ^* and b. _3s ^* represents the colorimetric coordinates 9 days after the method was carried out. The smaller the ΔE ^* stab, the more stable the coloring.

In particular, in the context of the present invention, coloring with a ΔE ^* of less than 2 9 days after staining is considered stable over time.

Therefore, in connection with the present invention, it is required to obtain a value of b ^* as small as possible and / or a value of a ^* as high as possible immediately after the dyeing method. At the same time as obtaining these results, it is required to have efficient color adhesion (large color adhesion value) and coloring that is stable over time.

Dyeing Example Example 1:
The following compositions were prepared. The proportions are shown based on mass with respect to 100 g of composition.

1. 1. Dyeing Steps The following dye compositions are prepared by mixing the natural dye powder with water at 50 ° C. to make the following packs during use.

The listed components i) and ii) are dissolved or dispersed in 50 ° C. water in a bowl in the relative amounts listed in the table above. Homogenize the whole with a spoon or spatula.

The resulting pack is very creamy and is applied to natural hair fixatives containing 90% white hair at a ratio of 10 g composition per 1 g fixative. The fixative is covered with cellophane and left at 33 ° C. for 60 minutes.

At the end of the standing time, the fixative is rinsed and washed with Ultra Doux chamomile shampoo, then squeezed to drain.

2. 2. Neutralization Post-Treatment Step The following post-treatment compositions were prepared.

Then, at the end of the dyeing step, the composition is applied at a rate of 5 g per gram of hair, covered with cellophane and left on the hair at 40 ° C. for 15 minutes, in comparison to which the standard fixation is after any. No processing is received.

Then, at the end of the standing time, all fixatives are rinsed and washed with Ultra Doux chamomile shampoo and then dried.

Colorimetric Results Fixed colors were evaluated in the CIE L ^* a ^* b ^* system using a Minolta CM 3600 spectrocolorimeter (including D65 light source, angle 10 °, specular light).

In this L ^* a ^* b ^* system, L ^* represents the color intensity, a ^* represents the green / red axis, and b ^* represents the blue / yellow axis.

による（ΔＥ^＊）によって定義される。 The color adhesion corresponds to the amount of change in the fixed coloring of the hair before and after the method is carried out, and the following formula:

Is defined by (ΔE ^* ).

In this equation, L ^* , a ^* and b ^* represent the values measured for hair fixation after dyeing, and L ₀ ^* , a ₀ ^* and b ₀ ^* are the fixation of undyed hair. Represents the value measured against. The larger ΔE ^* , the better the color adhesion.

Colorimetric measurements were performed immediately after the method was performed (T0) and then 9 days later (T9D).

によって算出される。 The color difference ΔE between the color at T0 and the color after 3 weeks represents the stability of the hair color, and the following formula:

Calculated by.

In this equation, L ₀ ^* , a ₀ ^* and b ₀ ^* represent the colorimetric coordinates measured for hair fixation at T0 immediately after performing the method, L _9D ^* , a _9D ^* and b. _9D ^* represents the colorimetric coordinates 9 days after the method was performed.

Δb represents the amount of change between b ₀ and b _3s .

We have observed that the coloration obtained by the method according to the invention, including post-treatment with compositions B2 and B3, does not have a yellow / green shade.

Specifically, the staining method according to the present invention including post-treatment with compositions B2 and B3 is the same as the comparative control treatment of the present invention without post-treatment or with post-treatment composition B1 (Comparative Controls 1 and 2). In contrast, it makes it possible to counteract the unattractive yellow / green on the day of staining.

this is,
-For hair dyed without post-treatment or with post-treatment B1 (Comparative Controls 1 and 2) for hair treated in post-treatment with compositions B2 and B3 (method of the invention). It is supported by a significantly higher value of a ^* (less green, and therefore more red).
-Furthermore, the method according to the invention comprising the post-treatment compositions according to the invention (compositions B2 and B3) makes it possible to obtain a coloration showing better color adhesion (higher DE).
-Furthermore, with the hair dyed (Comparative Controls 1 and 2) with or without post-treatment or with post-treatment B1 for the coloring obtained using the post-treatment compositions B2 and B3 (method of the present invention). A significantly lower b ^* value (less yellow) when compared is also obtained.
-Furthermore, the coloring obtained using the method of the present invention) requires a certain amount of time to obtain a beautiful color (brown), in contrast to the coloring without post-treatment (Comparative Control 1). It is stable over time (low DE T0 / T9D value).

In conclusion, the post-treatments of the present invention (compositions B2 and B3) show better color adhesion (higher DE) and more beautiful brown (higher red or lower yellow component) from the end of the dyeing method. Allows you to get coloring. These colors are more stable over time (low _ΔET9-T0 ).

→ Therefore, the method of the present invention promotes the color development using henna and indigo to obtain the final dyeing result from the date of application, and avoids unattractive intermediate tones while at the same time providing better color adhesion. Allows you to get.

Example 2
1. 1. Dyeing Steps: The following dye compositions were prepared by mixing natural dye powders with water at 50 ° C. at the time of use to make the following packs.

This mixture is applied to the fixation of permed Caucasian hair (PWW) containing 90% white hair at a bath ratio of 10 g of composition per 1 g of fixative. Cover this fixative with cellophane and leave at 33 ° C. for 60 minutes.

At the end of the standing time, the fixative is rinsed and washed with Ultra Doux chamomile shampoo, then squeezed to drain.

2. 2. Neutralization Post-Staining The following post-treatment compositions were prepared.

Then, at the end of the dyeing step, each of the post-treatment compositions was applied to a pre-stained fixation with composition C2 at a rate of 5 g per gram of hair, covered with cellophane and fixed at 33 ° C. for 15 minutes. No post-treatment composition was applied to the fixation of the reference stained with composition C2, which was left on top.

Then, at the end of the standing time, all fixatives are rinsed and washed with Ultra Doux chamomile shampoo and then dried.

result:
Fixation was evaluated visually and in the CIELab system as described above.

We have observed the following:
-If no post-treatment is applied, the pack will make the hair look unattractive, golden-green. Over time, the coloration changes and the green tone disappears, but the coloration retains an unattractive shade.
-Basic post-treatment with the dye (comparative control composition B4) partially counteracts the green color of the tint, but the shade remains unattractive.
-The acidic post-treatment of the present invention with the carmine acid dye (Composition B5) according to the present invention is in contrast to the comparative dyeing method (without post-treatment or with alkaline post-treatment with dye), in contrast to the color. It enhances color in terms of adhesion and strength, and makes it possible to counteract unattractive green / golden tones.

These findings are in particular for hair treated with composition C2 followed by post-treatment with composition B5 (the method of the invention), with or without post-treatment or with alkaline post-treatment C. This is supported by colorimetric measurements with significantly lower b ^* values (less yellow) for the dyed hair (Comparative Controls 1 and 2).

In addition, the measured colorimetric values are significantly higher DE ^* values (better color adhesion) and lower L ^* values (stronger coloring) for post-treatment with composition B5 according to the invention. Is shown.

Color change over time:
Visual evaluation: After 3 weeks, in the case of Comparative Methods 1 and 2, the present inventors observed that the coloring changed with time and that the green component of the coloring in particular disappeared. On the other hand, in the case of dyeing via the method according to the present invention, the color is more stable than in the case of the comparison method.

Colorimetric evaluation of changes in coloration:
DE T3 weeks / T0 and Db ^* T3 weeks / T0 values calculated using the same formula as described above, but using colorimetric values measured 3 weeks after the staining method was performed. bottom.

This is supported by colorimetric measurements with lower values of yellow / blue component (Db ^* ) changes and also lower color changes (DE ^* ) for treatment with the compositions of the present invention.

→ Therefore, the dyeing method according to the present invention makes it possible to stabilize the coloring from the date of application, in a beautiful method (less yellow / green), and more efficiently than via the comparative method.

Example 3
1. 1. Dyeing Steps: The following dye compositions were prepared by mixing natural dye powders with water at 50 ° C. at the time of use to make the following packs.

This pack is applied to a permed hair (PWW) fixative containing 90% white hair at a bath ratio of 10 g per 1 g fixative. Cover this fixative with cellophane and leave at 33 ° C. for 45 minutes.

At the end of the standing time, the fixative is rinsed and washed with Ultra Doux chamomile shampoo, then squeezed to drain.

2. 2. Neutralization Post-Treatment Step The following post-treatment compositions were prepared.

Then, at the end of the dyeing step, each of the post-treatment compositions B6-B9 is applied to the pre-stained fixation with composition C3 at a rate of 5 g per gram of hair and covered with cellophane at 40 ° C. for 15 The post-treatment composition was not applied to the fixation of the reference stained with the composition C3, which was left on the fixation for a minute.

Then, at the end of the leaving time, all fixatives are rinsed, squeezed to drain, and then dried.

result:
Fixed colors were evaluated in the CIE L ^* a ^* b ^* system using a Minolta CM 3600 spectrocolorimeter (including D65 light source, angle 10 °, specular light).

In this L ^* a ^* b ^* system, L ^* represents the color intensity, a ^* represents the green / red axis, and b ^* represents the blue / yellow axis.

による（ΔＥ^＊）によって定義される。 The color adhesion corresponds to the amount of change in the fixed coloring of the hair before and after the method is carried out, and the following formula:

Is defined by (ΔE ^* ).

In this equation, L ^* , a ^* and b ^* represent the values measured for hair fixation after dyeing, and L0 ^* , a0 ^* and b0 ^* are for undyed hair fixation. Represents the value to be measured. The larger the ΔE ^* value, the better the color adhesion.

Regardless of which family of natural dyes are used, the fixation treated by the method according to the invention has better color adhesion (more) than the fixation treated by the method without post-treatment (Comparative Control 1). It was found to have a high dE ^* value) and a stronger color (lower L ^* value).

In addition, the measured colorimetric values are poorly aesthetically pleasing green / gold reflections when fixed, treated by the method with post-treatment according to the invention, as compared to the method without post-treatment (Comparative Control 1). (Small yellow component b ^* ) is shown.

Claims (33)

A method for dyeing keratin fibers , wherein the fibers are
-At least one step E1); dyeing the fibers using a cosmetic dye composition A comprising indigo-producing plant powder and / or indigo-producing vegetable dye extract i ) ;
-One or more natural dyes iii)
○ iii-i ) Anthraquinone ;
○ iii-iii) Betalain;
○ iii-iii ) Anthocyanidins (also known as anthocyanids or anthocyanidols);
○ iii-iv) Carthamin;
○ iii-v ) naphthoquinone containing at least two hydroxyl groups ; and ○ one or more natural dyes iii) selected from a mixture thereof.
iv) At least one step E2) in which the fibers are treated with an aqueous cosmetic composition B comprising one or more acidifying agents and having a pH of less than 7.
A method that is processed in several steps, including. The indigo-producing plant is a species of the following genera:
-Indigofera ;
-Isatis ;
-Knotweed (Polygonum) or Knotweed (Persicaria );
-The genus Writia ;
-The genus Calanthe ; and-The genus Pink Strobilanthes
The method according to claim 1, which is selected from . The method according to claim 1 or 2, wherein the indigo-producing plant belongs to the genus Indigofera. Claims 1 to 3, wherein the composition A contains an indigo-producing plant powder having a content in the range of 10% by mass to 99% by mass with respect to the total mass of the composition A when the composition A is anhydrous. The method described in any one of the items. The method according to any one of claims 1 to 4, wherein the composition A contains henna ii). The method according to claim 5 , wherein the henna is a red henna. When the composition A is anhydrous, the composition A used in the method contains henna having a content in the range of 1 % by mass to 90 % by mass with respect to the total mass of the composition A. The method according to claim 5 or 6, characterized in that. The method according to any one of claims 1 to 3, 5 and 6, wherein the composition A contains water. One of claims 1 to 8, wherein the composition A contains an indigo-producing plant powder and / or an extract having a content in the range of 0.5% by mass to 50% by mass, and the composition A contains water. The method described in paragraph 1. The composition A used in the method comprises henna having a content in the range of 0.1% by mass to 30% by mass with respect to the total mass of the composition A, and the composition A contains water. 5. The method according to any one of claims 5, 6, 8 and 9. The invention according to any one of claims 5 to 10, wherein the components i) and ii) are present in the composition A in an i / ii) mass ratio in the range of 0.1 to 95. Method. The dyeing method according to any one of claims 1 to 11, wherein the composition A contains one or more kinds of organic solvents. The organic solvent is C ₁ ~ C ₄ Lower alkanols, ethanol and isopropanol; polyols and polyol ethers, 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and hexylene glycol, and aromatic alcohols, benzyl alcohols or phenoxyethanols, and the like. 12. The staining method according to claim 12, which is selected from the mixture. The method according to any one of claims 1 to 13 , wherein the pH of the composition A is in the range of 2 to 9 . The method according to any one of claims 1 to 14 , wherein the composition B has a pH of less than 6. The method according to any one of claims 1 to 15 , wherein the composition B has a pH of 0.5 to 5 including both ends. The method according to any one of claims 1 to 16 , wherein the composition B contains at least one acidifying agent selected from organic and inorganic acids. The acidifying agent according to any one of claims 1 to 17 , wherein the acidifying agent is selected from a carboxylic acid selected from hydrochloric acid, orthophosphoric acid, sulfuric acid, acetic acid and citric acid; and a mixture thereof. Method. The method according to any one of claims 1 to 18 , wherein the acidifying agent occupies 0.001 % by mass to 10% by mass with respect to the mass of the composition B. The method according to any one of claims 1 to 19 , wherein the natural dye of the composition B has an absorption wavelength λ _max of 625 to 750 nm or 300 to 470 nm. Any one of claims 1 to 20 , wherein the natural dye of the composition B is present in a content of 0.05% by mass to 25% by mass with respect to the total mass of the composition B. The method described in. The natural dye iii) of the composition B is
-Iii-i ) Anthraquinone containing at least one carboxylic acid functional group;
-Iii-ii) Betalain;
-Iii-iii ) Anthocyanidins (also known as anthocyanids or anthocyanidols);
The method according to any one of claims 1 to 21 , characterized in that it is a polyphenol selected from an iii-iv) carthamin; and-a mixture thereof. The natural dye iii) of the composition B is
-Iii - i) Anthraquinone selected from carmic acid, laccinic acid A, laccinic acid B, laccinic acid C, laccinic acid D, pseudopurpurin, mundistin and / or kermesic acid;
-Iii-iii ) Betanin ;
iii-iv) The method according to any one of claims 1 to 22 , characterized in that it is selected from carthamin. The natural dye iii) of the composition B has the following formula (A1):

(In formula (A1),
R ¹ and R ⁸ which may be the same or different represent a hydrogen atom, a hydroxyl group or an alkyl group ;
-R ² is a hydrogen atom or a hydroxyl group, a carboxyl group-C (O) OH or a carboxylate group-C (O) ^O- , Q ⁺ (where Q ⁺ is an alkali metal or an alkaline earth metal. Represents);
R ³ represents i) a hydrogen atom, ii) a hydroxyl group, or iii) an optionally substituted aryl group ;
-R ⁴ represents a hydrogen atom or a hydroxyl group;
-R ⁵ represents a hydrogen atom or a hydroxyl, carboxyl or carboxylate group-C (O) O-, Q + (here, as defined above);
-R ⁶ is a hydrogen atom, a hydroxyl group, ^-O- , Q ⁺ (where Q ⁺ is as defined above), a carboxyl or carboxylate group-C (O) ^O- , Q ^+. (Here, Q ⁺ is as defined above);
-R ⁷ represents a hydrogen atom, a hydroxyl group or a glycosyl group ;
^-However , at ^least one of ^R2 , R5 and / or R6 has a carboxyl group-C (O) OH or a carboxylate group-C (O) ^O- , Q ⁺ (where Q ⁺ is. , Representing alkali metal or alkaline earth metal )
Anthraquinone containing at least one carboxylic acid functional group and also its tautomeric and / or mesomeric form, its stereoisomer, its addition salt with a cosmetically acceptable acid or base and its additions, selected from those of the above. The method according to any one of claims 1 to 23 , which is selected from the solvates of the above. The method according to any one of claims 1 to 24 , wherein the natural dye iii) of the composition B is selected from anthraquinone containing at least one carboxylic acid functional group. The method according to any one of claims 1 to 23 , wherein the natural dye of the composition B is selected from betalain . The natural dye of composition B comprises at least three hydroxyl groups according to the following formula (Vg):

(In the formula (Vg),
• R ¹ , R ² , R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ which may be the same or different are hydrogen or halogen atoms or i) hydroxyl, ii) (C ₁ ). ~ C ₆ ) alkyl, iii) (C ₁ to C ₆ ) alkoxy, iv) (C ₁ to C ₆ ) alkyl thio, v) carboxyl, vi) alkyl or alkoxycarbonyl carboxylate, vii ) optionally substituted amino , Viii ) Linear or branched alkenyl which may be substituted, ix) Cycloalkyl which may be substituted, x) Aryl which may be substituted, xi) Group containing one or more silicon atoms. , Xii) (di) ((hydroxy) (C ₁ to C ₆ ) alkyl) amino, xiii) glucosyl, xiv) R-Z-C (X) -Y- (where R is a hydrogen atom or station _May be converted (C _1-6 ) to represent an alkyl or aryl group ; Y and Z, which may be the same or different, may be a bond, or an oxygen or sulfur atom, or a group -N (R')-(here. In, R'represents a hydrogen atom or (C ₁ to C ₆ ) alkyl group), Y represents (C ₁ to C ₆ ) alkylene group in some cases; X represents an oxygen or sulfur atom or N. -Represents a group selected from R'' (where R'' represents a hydrogen atom or (C ₁ to C ₆ ) alkyl group);
R ⁶ and R ⁸ which may be the same or different are hydrogen atoms or hydroxyl groups, (C ₁ to C ₆ ) alkyl groups or groups as previously defined RZC (X) -Y-. Represents a group selected from; or • Alternatively, the formula (Vg) comprises the polymerization unit of said polyphenol that will be linked to another unit of polyphenol via the 4, 6 or 8 position of the chroman ring. ^{Consists (} where ^R1 or R3 and R6 form a covalent bond of the polyphenol with the other unit)).
Selected from anthocyanidins (also known as anthocyanids or anthocyanidols);
At least three groups of the compound of formula (Vg) selected from R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydroxyl groups. It is understood to represent the group;
The method according to any one of claims 1 to 22 , wherein the compound of the formula (Vg) is cationic and is associated with an organic or inorganic anionic counterion An ⁻ . The method according to any one of claims 1 to 22 and 27 , wherein the natural dye iii) is selected from cyanidin, delphinidin, pelargonin, malvidin, peonidin and petunidin and anthocyanidins selected from mixtures thereof. The dyeing method according to any one of claims 1 to 23 , wherein the natural dye iii) is selected from Carthamin. One of claims 1-29 , wherein the composition A is first applied to the keratin fiber; and composition B is applied to the keratin fiber after the application of the composition A. The dyeing method described in 1. 13 . The dyeing method according to item 1. Includes one or more acidifying agents iv) according to any one of claims 1 to 31 and one or more natural dyes iii) according to any one of claims 1 to 31 . In order to promote the stabilization of the color of the fiber dyed with the dye composition A containing the indigo-producing plant powder and / or the extract in the use of the aqueous composition B having a pH of less than 7. And / or use to improve color intensity and / or color adhesion and / or color persistence. 32. The use according to claim 32, wherein the dye composition A comprises henna.