JP2006522077A - Composition for dyeing human keratin materials containing a fluorescent dye and a specific sequestering agent, method and use thereof - Google Patents

Abstract

The present invention relates to compositions containing at least one fluorescent dye and at least one particular sequestering agent, as well as methods and apparatus for using these compositions. Similarly, the present invention comprises at least one fluorescent dye for dyeing human keratin materials, in particular artificially dyed or colored hair, and colored skin with a lightening effect, and at least It relates to the use of a composition containing one specific sequestering agent.

Description

  The present invention relates to compositions containing at least one fluorescent dye and at least one specific sequestering agent, and methods and apparatus for using these compositions. In addition, the present invention also provides a human keratin material, particularly keratin fibers such as artificially dyed hair or pigmented hair, and colored skin with lightening effect. For the use of a composition comprising at least one fluorescent dye and at least one specific sequestering agent.

It is common for individuals with colored skin to wish to whiten the skin color and for this purpose to use cosmetic or dermatological compositions containing bleaching agents.
The substances most commonly used as depigmenting agents are hydroquinone and its derivatives, kojic acid and its derivatives, azelaic acid, arbutin and its derivatives alone or in combination with other active agents.
However, these drugs are not without their drawbacks. In particular, in order to obtain a decoloring effect on the skin, it is necessary to use a large amount of these for a long period of time. Furthermore, no immediate effect is observed when applying compositions containing them.
In addition, hydroquinone and its derivatives are used in an amount effective to produce a noticeable decolorizing effect. In particular, hydroquinone is known for its cytotoxicity against melanocytes.
Furthermore, kojic acid and its derivatives are expensive and thus have the disadvantage that they cannot be used in large quantities in products that are widely distributed on the market.
Thus, there is still a need for cosmetic compositions that can provide a brighter, more homogeneous and uniform tone with a natural appearance and have satisfactory transparency after application to the skin.

In the field of hair care, there are mainly two main types of hair dyeing.
The first is semi-permanent or direct dyeing, which is resistant to several shampoos, and can give a more or less obvious color change to the natural color of the hair. Use the dye to make. These dyes are known as direct dyes and can be used in two different ways. Coloring involves applying a composition containing a direct dye (s) directly to keratin fibers, or a composition comprising an oxidative decolorizer, preferably an aqueous hydrogen peroxide solution, and a composition containing the direct dye (s). This can be done by applying a mixture prepared immediately. In that case, such a method is referred to as “lightening direct dyeing”.

  The second is permanent or oxidative dyeing. This is done with an “oxidation” dye precursor, which, in use, is a colorless or weakly colored compound that can be mixed with an oxidant material to yield a colored compound and dye by an oxidative condensation process. One or more oxidation bases and couplers to neutralize or weaken colors with too much red, orange or gold gloss, or vice versa, to highlight these red, orange or gold gloss It is often necessary to combine these direct dyes.

Among the available direct dyes, nitrobenzene direct dyes are not strong enough, and indoamines, quinone dyes and natural dyes have low affinity for keratin fibers and therefore various treatments that the fibers will suffer. In particular, only coloring with insufficient fastness to shampoo can be obtained.
In addition, it is necessary to obtain a lightening effect on human keratin fibers. This lightening is obtained through a process of decoloring the melanin of the hair, usually through an oxidative system generally composed of hydrogen peroxide which may be combined with a peracid salt. This decolorization system has the disadvantage of degrading keratin fibers and impairing their cosmetic properties.

The object of the present invention is to solve the above-mentioned problems, in particular it has good dyeing affinity for keratin substances such as keratin fibers and good resistance to external factors, in particular shampoo, and is further processed. The object is to propose a composition capable of achieving lightening without damaging certain materials, particularly keratin fibers.
Thus, surprisingly and unexpectedly, it has been found that these objectives can be achieved in the presence of certain sequestering agents, in particular by using fluorescent dyes in the orange range. .

  Thus, the first subject of the present invention is that in a cosmetically acceptable medium, at least one fluorescent dye soluble in the medium, and a hydroxycarboxylic acid and polycarboxylic acid, and a monovalent or divalent alkali. Containing at least one complexing agent selected from metals, alkaline earth metals, transition metals, organic amines or ammonium salts thereof, alone or as a mixture; 2- [2- (4-dialkyl as fluorescent agent) Amino) phenylethenyl] -1-alkylpyridinium, wherein the alkyl group of the pyridinium ring represents a methyl or ethyl group, the alkyl group of the benzene ring represents a methyl group, and the counter ion is a halide. It is in.

The second subject of the present invention is
a) applying the composition of the present invention to keratin fibers for a time sufficient to produce the desired color and lightening;
b) Rinse the fiber in some cases,
c) optionally washing the fiber with shampoo, rinsing,
d) drying the fiber or leaving it to dry;
The present invention relates to a method for dyeing human keratin fibers with a lightening effect.
Another subject of the present invention is a cosmetically acceptable medium comprising at least one fluorescent dye soluble in the medium, a hydroxycarboxylic acid and a polycarboxylic acid, and a monovalent or divalent alkali metal, alkaline earth. A human keratin substance having a lightening effect, comprising a composition comprising at least one complexing agent selected from a group of metals, transition metals, organic amines or ammonium salts thereof alone or as a mixture Relates to use for dyeing.

  Multi-compartment for dyeing and lightening keratin fibers comprising at least one compartment containing a composition of the invention and at least one other compartment containing a composition containing at least one oxidizing agent The instrument constitutes the final subject of the present invention.

With the composition of the present invention, it is possible to increase the fluorescence effect and the lightening effect as compared with the case of using a fluorescent dye alone.
Also, better tolerant results are found for washing or shampooing.
However, other features and advantages of the present invention will become more apparent upon reading the following description and examples.
Unless otherwise explained, the limits of the ranges of values given in the specification are included in these ranges.

As mentioned above, the composition of the present invention contains at least one fluorescent dye and at least one specific sequestering agent.
For the purposes of the present invention, the term “fluorescent dye” is a molecule that is colored by itself and thus absorbs light in the visible spectrum, and possibly in the ultraviolet spectrum (wavelength range of 360-760 nanometers), Unlike standard dyes, it means a dye that converts the absorbed energy into longer wavelength fluorescence that is emitted in the visible region of the spectrum.

The fluorescent dyes of the present invention must be distinguished from optical brighteners. Fluorescent whitening agents, also known as brighteners, brighteners, fluorescent brighteners, fluorescent whitening agents, whiteners or fluorescent whiteners, are colorless It is a transparent compound that does not absorb light in the visible region only in the ultraviolet region (200-400 nanometer wavelength range) and converts the absorption energy into longer wavelength fluorescence emitted in the visible region of the spectrum, No staining; the color impression mainly arises from pure blue (only 400-500 nanometer wavelength range) pure fluorescence.
Finally, the fluorescent dye used in the composition is soluble in the medium of the composition. It should be pointed out here that fluorescent dyes are themselves different from fluorescent pigments that are insoluble in the medium of the composition.

In particular, the fluorescent dye used in the present invention and optionally neutralized is at least 0.001 g / l, in particular at least 0.5 g / l, preferably at least 1 g / l at a temperature of 15 to 25 ° C. l, in a more preferred embodiment at least 5 g / l, soluble in the medium of the composition.
Furthermore, in one of the characteristics of the present invention, the composition is a fluorescent dye, wherein the alkyl group of the pyridinium ring represents a methyl or ethyl group, the alkyl group of the benzene ring represents a methyl group, and the counter ion is a halide. Does not contain 2- [2- (4-dialkylamino) phenylethenyl] -1-alkylpyridinium.

In a particular embodiment of the invention, the composition does not contain a compound selected from monocationic heterocyclic fluorescent dyes as azo, azomethine or methine as the fluorescent dye.
The fluorescent dyes preferably used in the present invention are those in the orange region.
Preferably, the fluorescent dyes of the present invention exhibit a maximum reflectance in the wavelength range of 500 to 650 nanometers, preferably in the wavelength range of 550 to 620 nanometers.

Some of the fluorescent dyes of the present invention are compounds known per se.
Examples of fluorescent dyes that can be used include the following families: naphthalimides; cationic or non-cationic coumarins; xanthenodiquinolidines (eg in particular sulforhodamines); azaxanthenes; naphtholactams; azlactones Oxazines; thiazines; dioxazines; fluorescent dyes belonging to a single or mixture of polycationic fluorescent dyes of the azo, azomethine or methine type, preferably the following families: naphthalimides; cationic or non-cationic coumarins Azaxanthenes; naphtholactams; azlactones; oxazines; thiazines; dioxazines; azo, azomethine or methine-type polycationic fluorescent dyes, which are single compounds or mixtures thereof.

を有し、サンド社(Sandoz)から販売されているブリリアントイエローＢ６ＧＬ；
− 次の構造：

を有し、プロラボ社(Prolabo)、アルドリッチ社(Aldrich)又はカルロ・エルバ社(Carlo Erba)から販売されている、ベーシックイエロー２又はオーラミンＯ、
４,４'-(イミドカルボニル)ビス(Ｎ,Ｎ-ジメチルアニリン)モノヒドロクロリド-CAS No.2465-27-2；
を挙げることができる。 As dyes mentioned above, in particular the following dyes:
The following structure:

Brilliant Yellow B6GL sold by Sandoz;
The following structure:

Basic Yellow 2 or Auramine O, sold by Prolabo, Aldrich or Carlo Erba,
4,4 ′-(imidocarbonyl) bis (N, N-dimethylaniline) monohydrochloride-CAS No.2465-27-2;
Can be mentioned.

[上式中：
Ｒ_１及びＲ_２は同一でも異なっていてもよく：
・水素原子；
・少なくとも一のヘテロ原子及び／又は少なくとも一のへテロ原子を有する基が挿入されるか及び／又は置換され、及び／又は少なくとも一のハロゲン原子で置換されていてもよい、１〜１０の炭素原子、好ましくは１〜４の炭素原子を有する直鎖状又は分枝状のアルキル基；
・アリール基が６つの炭素原子を有し、アルキル基が１〜４の炭素原子を有するアリール基又はアリールアルキル基であって；アリール基は少なくとも一のヘテロ原子及び／又は少なくとも一のへテロ原子を有する基が挿入されるか及び／又は置換され、及び／又は少なくとも一のハロゲン原子で置換されていてもよい、１〜４の炭素原子を有する一又は複数の直鎖状又は分枝状のアルキル基で置換されていてもよいもの；
を表し；
・またＲ_１及びＲ_２は結合して、窒素原子と共に複素環を形成していてもよく、また一又は複数の他のヘテロ原子を有していてもよく、ここで、該複素環は、少なくとも一のヘテロ原子及び／又は少なくとも一のへテロ原子を有する基が挿入されるか及び／又は置換され、及び／又は少なくとも一のハロゲン原子で置換されていてもよい、好ましくは１〜４の炭素原子を有する少なくとも一の直鎖状又は分枝状のアルキル基で置換されていてもよいものであり；
・さらにＲ_１又はＲ_２は、窒素原子及び該窒素原子を担持するフェニル基の炭素原子の一つを含む複素環に関与していてもよく；
Ｒ_３及びＲ_４は同一でも異なっていてもよく、水素原子又は１〜４の炭素原子を有するアルキル基を表し；
Ｒ_５は同一でも異なっていてもよく、水素原子、ハロゲン原子又は少なくとも一のヘテロ原子が挿入されていてもよい１〜４の炭素原子を含む直鎖状又は分枝状のアルキル基を表し；
Ｒ_６は同一でも異なっていてもよく、水素原子；ハロゲン原子；少なくとも一のヘテロ原子及び／又は少なくとも一のへテロ原子を担持する基が置換され及び／又は挿入されるか、及び／又は少なくとも一のハロゲン原子が置換されていてもよい、１〜４の炭素原子を含む直鎖状又は分枝状のアルキル基を表し；
Ｘは：
・少なくとも一のヘテロ原子及び／又は少なくとも一のへテロ原子を有する基が挿入されるか及び／又は置換され、及び／又は少なくとも一のハロゲン原子で置換されていてもよい、１〜１４の炭素原子を有する直鎖状又は分枝状のアルキル基又は２〜１４の炭素原子を含むアルケニル基；
・少なくとも一のヘテロ原子で置換されていてもよい、１〜１４の炭素原子を有する少なくとも一の直鎖状又は分枝状のアルキル基で；少なくとも一のヘテロ原子で置換されていてもよい、１〜４の炭素原子を有する少なくとも一の直鎖状又は分枝状のアミノアルキル基で；少なくとも一のハロゲン原子で、置換されていてもよい５-又は６員の複素環基；
・１〜４の炭素原子を含むアルキル基で分離されていてもよい、縮合又は非縮合の芳香族又は二芳香族基で、アリール基が少なくとも一のハロゲン原子で、又は少なくとも一のヘテロ原子及び／又は少なくとも一のへテロ原子を担持する基で置換されるか及び／又は挿入されていてもよい、１〜１０の炭素原子を含む少なくとも一のアルキル基で、置換されていてもよいもの；
・ジカルボニル基；
を表し、
・Ｘ基は一又は複数のカチオン電荷を担持可能であり；
ａは０又は１に等しく；
Ｙ⁻は同一でも異なっていてもよく、有機又は無機アニオンを表し；
ｎは、少なくとも２に等しく、多くとも蛍光化合物中に存在するカチオン電荷の数に等しい整数である]
を有する化合物を挙げることもできる。 And the following formula:

[In the above formula:
R ₁ and R ₂ may be the same or different:
・ Hydrogen atom;
1 to 10 carbons in which a group having at least one heteroatom and / or at least one heteroatom is inserted and / or substituted and / or substituted with at least one halogen atom A linear or branched alkyl group having atoms, preferably 1 to 4 carbon atoms;
An aryl or arylalkyl group in which the aryl group has 6 carbon atoms and the alkyl group has 1 to 4 carbon atoms; the aryl group is at least one heteroatom and / or at least one heteroatom One or more linear or branched having 1 to 4 carbon atoms, which may be inserted and / or substituted and / or substituted with at least one halogen atom Optionally substituted with an alkyl group;
Represents;
R ₁ and R ₂ may be bonded to form a heterocycle with the nitrogen atom, and may have one or more other heteroatoms, where the heterocycle is A group having at least one heteroatom and / or at least one heteroatom may be inserted and / or substituted and / or substituted with at least one halogen atom, preferably 1-4 Are optionally substituted with at least one linear or branched alkyl group having carbon atoms;
-Furthermore, R ₁ or R ₂ may be involved in a heterocycle containing a nitrogen atom and one of the carbon atoms of the phenyl group carrying the nitrogen atom;
R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R ₅ may be the same or different, and represents a linear or branched alkyl group containing 1 to 4 carbon atoms into which a hydrogen atom, a halogen atom or at least one hetero atom may be inserted;
R ₆ may be the same or different, a hydrogen atom; a halogen atom; a group bearing at least one heteroatom and / or at least one heteroatom is substituted and / or inserted and / or at least Represents a linear or branched alkyl group containing 1 to 4 carbon atoms, optionally substituted by one halogen atom;
X is:
1 to 14 carbons in which a group having at least one heteroatom and / or at least one heteroatom is inserted and / or substituted and / or optionally substituted by at least one halogen atom A linear or branched alkyl group having an atom or an alkenyl group containing 2 to 14 carbon atoms;
With at least one linear or branched alkyl group having 1 to 14 carbon atoms, optionally substituted with at least one heteroatom; optionally substituted with at least one heteroatom, At least one linear or branched aminoalkyl group having 1 to 4 carbon atoms; a 5- or 6-membered heterocyclic group optionally substituted with at least one halogen atom;
A fused or non-fused aromatic or diaromatic group, optionally separated by an alkyl group containing 1 to 4 carbon atoms, wherein the aryl group is at least one halogen atom, or at least one heteroatom and Optionally substituted with at least one alkyl group containing 1 to 10 carbon atoms, which may be substituted and / or inserted with a group bearing at least one heteroatom;
・ Dicarbonyl group;
Represents
The X group can carry one or more cationic charges;
a is equal to 0 or 1;
Y ⁻ may be the same or different and represents an organic or inorganic anion;
n is an integer equal to at least 2 and at most equal to the number of cationic charges present in the fluorescent compound]
The compound which has can also be mentioned.

It should be recalled that the term “heteroatom” represents an oxygen or nitrogen atom.
Groups carrying such atoms include, among others, hydroxyl, alkoxy, carbonyl, amino, ammonium, amide (—N—CO—) and carboxyl (—O—CO— or —CO—O—) groups. it can.
With respect to alkenyl groups, they have one or more unsaturated carbon-carbon bonds (—C═C—), preferably only one carbon-carbon double bond.

In this general formula, R ₁ and R ₂ may be the same or different, in particular:
・ Hydrogen atom;
1 to 10 carbon atoms, in particular 1 to 6 carbon atoms, optionally substituted with oxygen atoms, or substituted with at least one hydroxyl, amino or ammonium group, or chlorine or fluorine atoms, Preferably an alkyl group having 1 to 4 carbon atoms;
A benzyl or phenyl group optionally substituted by an alkyl or alkoxy group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms;
Together with the nitrogen atom at least one containing 1-4 carbon atoms, into which nitrogen and / or oxygen atoms and / or groups carrying nitrogen and / or oxygen atoms may be inserted and / or substituted A pyrrolo, pyrrolidino, imidazolino, imidazolo, imidazolium, pyrazolino, piperazino, morpholino, morpholine, pyrazolo or thiazolo type heterocyclic group optionally substituted by a linear or branched alkyl group of
Represents.

With respect to the amino or ammonium groups mentioned above, the groups carried by the nitrogen atom may be the same or different, more particularly a hydrogen atom, a C ₁ -C ₁₀ , preferably a C ₁ -C ₄ alkyl group or an arylalkyl. In particular, aryl groups contain 6 carbon atoms and alkyl groups contain 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
In a preferred embodiment of the invention, the R ₁ and R ₂ groups may be the same or different and are substituted with a hydrogen atom; a linear or branched C ₁ -C ₆ alkyl group; a hydroxyl group. An optional C ₂ -C ₆ alkyl group; a C ₂ -C ₆ alkyl group carrying an amino or ammonium group; a C ₂ -C ₆ chloroalkyl group; an oxygen atom or a group carrying an oxygen atom (eg, an ester) inserted has been C ₂ -C ₆ alkyl group; aromatic groups such as phenyl, benzyl or 4-methylphenyl; heterocyclic group, for example pyrrolo, pyrrolidino, imidazolo, imidazolino, imidazolium, piperazino, Moruhoro, morpholino, pyrazolo or thiazolo group In which at least one C ₁ -C ₆ alkyl or an aromatic group may be substituted.
Preferably, the R ₁ and R ₂ groups may be the same or different and are a hydrogen atom, a linear or branched C ₁ -C ₆ alkyl group such as methyl, ethyl, n-butyl or n-propyl. 2-hydroxyethyl; an alkyltrimethylammonium or alkyltriethylammonium group in which the alkyl group is a linear C ₂ -C ₆ alkyl group; (di) alkylmethylamino or (di) alkylethylamino group , the alkyl group is a linear _{C 1} -C ₆ alkyl _{group; -CH 2 CH 2 Cl ;-( CH} 2) n -OCH 3 , or - n is in _{(CH 2) n -OCH 2 CH} 3 what is an integer of 2 to 6 range; represents a _{-CH 2 CH 2 COOCH 3; -CH} 2 CH 2 -OCOCH 3.

[上式中、Ｒ'は水素原子又はＣ_１-Ｃ_３アルキル基、-ＣＨ_２ＣＨ_２ＯＨ、-ＣＨ_２ＣＨ_２ＯＣＨ_３を表す]
の複素環を形成するように結合した基を表してもよい。 Preferably, the R ₁ and R ₂ groups which may be the same or different and are preferably the same represent a methyl group or an ethyl group.
The R ₁ and R ₂ groups may be the same or different and are pyrrolidino, 3-aminopyrrolidino, 3- (dimethyl) aminopyrrolidino, 3- (trimethyl) aminopyrrolidino, 2,5-dimethylpyrrolo, 1H -Imidazolo, 4-methylpiperazino, 4-benzylpiperazino, morpholine, 3,5- (tert-butyl) -1H-pyrazolo, 1H-pyrazolo or 1H-1,2,4-triazolo type heterocyclic group May be.
The R ₁ and R ₂ groups may be the same or different and are represented by the following formulas (I) and (II):

[In the above formula, R ′ represents a hydrogen atom or a C ₁ -C ₃ alkyl group, —CH ₂ CH ₂ OH, —CH ₂ CH ₂ OCH ₃ ]
A group bonded so as to form a heterocyclic ring may be represented.

In a more particular embodiment of the invention, R ₅ may be the same or different and is a straight chain having 1 to 4 carbon atoms into which a hydrogen atom, a fluorine or chlorine atom, or an oxygen or nitrogen atom may be inserted. Represents a chain or branched alkyl group.
The R ₅ substituent, if other than hydrogen, is advantageously in the 3 and / or 5 position relative to the carbon of the ring carrying the nitrogen atom substituted by the R ₁ and R ₂ groups, preferably It is pointed out that it is in 3rd position relative to carbon.
Advantageously, the R ₅ groups may be the same or different and are a hydrogen atom; a linear or branched C ₁ -C ₄ alkyl group; —O—R ₅₁ where R ₅₁ is a linear C ₁ represent any -C ₄ alkyl group; -R ₅₂ -O-CH ₃ in what _{R 52} represents a linear _{C 2} -C ₃ alkyl _{group; -R 53 -N (R 54)} 2 with _{R 53} is It represents a linear C ₂ -C ₃ alkyl group, and R ₅₄ may be the same or different and represents a hydrogen atom or a methyl group.
Preferably R ₅ may be the same or different and represents hydrogen, methyl or methoxy, more preferably R ₅ represents a hydrogen atom.

In one particular embodiment, the R ₆ groups may be the same or different and are a hydrogen atom; a linear or branched C ₁ -C ₄ alkyl group; —X, where X is a chlorine, bromine or fluorine atom -R ₆₁ -O-R ₆₂ , wherein R ₆₁ represents a linear C ₂ -C ₃ alkyl group and R ₆₂ represents a methyl group; -R ₆₃ -N (R ₆₄ ) ₂ In which R ₆₃ represents a linear C ₂ -C ₃ alkyl group, R ₆₄ may be the same or different and each represents a hydrogen atom or a methyl group; —N (R ₆₅ ) ₂ , R ₆₅ is Which may be the same or different and represents a hydrogen atom or a linear C ₂ -C ₃ alkyl group; —NHCOR ₆₆ , R ₆₆ is a C ₁ -C ₂ alkyl group, C ₁ -C ₂ chloroalkyl group A group represented by the formula: —R ₆₇ —NH ₂ or —R ₆₇ —NH (CH ₃ ) or —R ₆₇ —N (CH ₃ ) ₂ or —R ₆₇ —N ⁺ (CH ₃ ) ₃ or —R ₆₇ —N ⁺ (CH ₂ CH ₃ ) _{3 in} which R ₆₇ represents a C ₁ -C ₂ alkyl group.
It is pointed out that the R ₆ substituent, if other than hydrogen, is preferably in the 2 and / or 4 position relative to the nitrogen atom of the pyridinium ring, more preferably in the 4 position relative to the nitrogen atom. The
In particular, these R ₆ groups may be the same or different and represent a hydrogen atom or a methyl or ethyl group, and R ₆ preferably represents a hydrogen atom.

With respect to the R ₃ and R ₄ groups, these groups may be identical or different and advantageously represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in particular a methyl group. Preferably, R ₃ and R ₄ each represent a hydrogen atom.

As mentioned above, X is:
Linear or branched, in which at least one heteroatom, at least one group bearing at least one heteroatom is inserted and / or substituted, and / or at least one halogen atom may be substituted An alkyl group having 1 to 14 carbon atoms or an alkenyl group having 2 to 14 carbon atoms;
At least one halogen atom; at least one linear or branched aminoalkyl group having 1 to 4 carbon atoms, optionally substituted with at least one heteroatom, 1 to 14 carbon atoms A 5- or 6-membered heterocyclic group optionally substituted with at least one linear or branched alkyl group having;
A condensed or non-condensed aromatic or diaromatic group which may be separated by an alkyl group having 1 to 4 carbon atoms, wherein the aryl group (s) is at least one heteroatom and / or at least one At least one alkyl group having from 1 to 10 carbon atoms, which may be substituted and / or inserted with a group bearing a telo atom, or at least one halogen atom;
・ Dicarbonyl group;
Represents.
It is further shown that the X group may carry one or more cationic charges.

Thus, X may represent a linear or branched alkyl group having 1 to 14 carbon atoms, or an alkenyl group having 2 to 14 carbon atoms, and one or more oxygen and / or nitrogen atoms And / or may be substituted and / or inserted with one or more groups bearing at least one heteroatom and / or may be substituted with a fluorine or chlorine atom.
Such groups are in particular hydroxyl, alkoxy (especially with R groups of the C ₁ -C ₄ alkyl type), amino, ammonium, amide, carbonyl and carboxyl groups (—COO— or —O—CO—), in particular Mention may be made of those having an alkyloxy type group.
It should be noted that the nitrogen atom, if present, may be in quaternized form or non-quaternized form. In this case, the other two groups or the other two groups carried by the quaternized or non-quaternized nitrogen atom are the same or different and are a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably May be methyl.

  In other variations, the X group is 1 to 10 carbon atoms, preferably 1 to 4 carbons, optionally substituted with a halogen atom or a group having at least one heteroatom (preferably a hydroxyl group). At least one linear or branched aminoalkyl group having atoms; at least one straight chain having 1 to 14 carbon atoms, in particular 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, or It represents an imidazolo, pyrazolo, triazino or pyridino type 5- or 6-membered heterocyclic group which may be substituted with a branched alkyl group. It should be noted that the amino group is preferably attached to the heterocycle.

  In other possible embodiments, the X group is an aromatic group (especially one having 6 carbon atoms) or a condensed or non-condensed diaromatic group (especially one having 10-12 carbon atoms), Represents an alkyl group having 4 carbon atoms, the aryl group (s) being a group having at least one oxygen and / or nitrogen atom and / or at least one heteroatom (e.g. carbonyl, Substituted with at least one alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and / or at least one halogen atom, optionally having a carboxyl, amide, amino or ammonium group) Represents what may have been.

The aromatic group, preferably the phenyl group, is bonded to the CR ₃ R ₄ group via a bond in the 1,2; 1,3 or 1,4 position, preferably in the 1,3 and 1,4 positions. It should be noted. When the phenyl group bonded via a bond at the 1,4-position carries one or two substituents, this or these substituent (s) are preferably attached to one of the CR ₃ R ₄ groups. On the other hand, it is located in the 1st and 4th positions. If the phenyl group bonded via a bond in the 1,3 position carries one or two substituent (s), this or these substituent (s) are preferably CR ₃ R ₄ groups It is located in the 1st or 3rd position with respect to one of the above.
When the group is diaromatic, it is preferably non-condensed and is a single bond (ie each carbon of the two rings) or an alkyl group, preferably of the CH ₂ or C (CH ₃ ) ₂ type. It has two separable phenyl groups. Preferably, the aromatic ring carries no substituent. It should be noted that the diaromatic group is bonded to the CR ₃ R ₄ group via a bond at the 4,4 ′ position.

Examples of suitable X groups are in particular straight-chain or branched alkyl groups having 1 to 13 carbon atoms, such as methylene, ethylene, propylene, isopropylene, n-butylene, pentylene and hexylene; 2-hydroxy propylene and 2-hydroxy -n- _{butylene; -CH 2 CH 2 OCH 2 CH} 2 -, 1,6- dideoxy -d- ^{_{mannitol, -CH 2 N + (CH 3}} ) 2 CH 2 -, - CH 2 CH 2 ^{_{N + (CH 3) 2 -}} (CH 2) 6 N + (CH 3) 2 -CH 2 CH 2 -, CO-CO-, 3,3- dimethyl-pentylene, 2-acetoxyethyl, butylene 1,2 A group bearing at least one heteroatom (eg, hydroxyl, amino, ammonium, carbonyl or carboxyl) and / or one or more nitrogen and / or oxygen atoms, such as 1,3,4-tetraol. A substituted or inserted C ₁ -C ₁₃ alkylene group; —CH═CH—; 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 2,6-fluorobenzene, 4,4 '-Biphenylene, 1,3- (5-methylbenzene), 1,2-bis (2-methoxy) benzene, bis (4-phenyl) methane, methyl 3,4-benzoate and 1,4-bis (amidomethyl) ) Aromatic or diaromatic groups substituted with one or more halogen atoms, one or more groups bearing at least one heteroatom, and / or one or more alkyl groups, such as phenyl; And, for example, pyridine, or derivatives such as 2,6-bispyridine, imidazole, imidazolium or triazine.

In certain embodiments of the invention, X represents a linear or branched C ₁ -C ₁₃ alkyl group; —CH ₂ CH (OH) CH ₂ —; —CH ₂ CH (Cl) CH ₂ —; _{-CH 2 CH 2 -OCOCH 2 -;} - CH 2 CH 2 COOCH 2 -; Ra represents a linear _{C 2} -C ₆ alkyl group, Rb represents a linear _{C 1} -C ₂ alkyl group -Ra-O-Rb-; Rc represents a _{C 2} -C ₉ alkyl group, Rd represents a hydrogen atom or a _{C 1} -C ₂ alkyl group, Re is -Rc-N representing a _{C 1} -C ₆ alkyl group (Rd) -Re-; Rf represents a linear _{C 2} -C ₉ alkyl group, Rg is preferably identical, _{C 1} -C ₂ alkyl group, Rh is a linear _{C 1} - —Rf—N ⁺ (Rg) ₂ —Rh— representing —C ₆ alkyl group; —CO—CO— is represented.

[上式中、Ｒｉ及びＲｊは同一でも異なっていてもよく、直鎖状のＣ_１-Ｃ_６アルキル基を表す]
の二価の基等の、１〜１４の炭素原子、特に１〜１０の炭素原子、好ましくは１〜４の炭素原子を有する少なくとも一のアルキル基で置換されていてもよいイミダゾール基をさらに表し得る。
同様に、Ｘは次の：

二価のトリアジンベース基からも選択され得る。
他の可能な態様では、Ｘは次の：

二価の芳香族基を表してもよい。 X is the following formula:

[In the above formula, Ri and Rj may be the same or different and each represents a linear C ₁ -C ₆ alkyl group]
And further represents an imidazole group optionally substituted with at least one alkyl group having 1 to 14 carbon atoms, particularly 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, such as a divalent group of obtain.
Similarly, X is:

It can also be selected from divalent triazine base groups.
In other possible embodiments, X is:

It may represent a divalent aromatic group.

The general formula for these fluorescent compounds, Y ^- represents an organic or inorganic anion. Several anions Y ^- if there is, these anions may be the same or different.
Inorganic anions are not intended to be limited to these, but anions derived from halogen atoms, such as chlorides, preferably iodides, sulfates or bisulfates, nitrates, phosphates, phosphorus Mention may be made of oxyhydrogen, dihydrogen phosphate, carbonates and bicarbonates.
The organic-derived anion includes a saturated or unsaturated aromatic or non-aromatic monocarboxylic acid or polycarboxylic acid, sulfonic acid or sulfuric acid which may be substituted with a halogen atom or at least one hydroxyl or amino group Anions derived from the salts of Non-limiting examples suitable for use include acetates, hydroxyacetates, aminoacetates, (tri) chloroacetates, benzoxyacetates, propionates, and derivatives bearing chlorine atoms, fumarate , Oxalates, acrylates, malonates, succinates, lactates, tartrates, glycolates, citrates, benzoates and derivatives bearing a methyl or amino group, alkyl sulfates, tosylates, benzenesulfonate And toluene sulfonates.
Preferably, the anions Y may be the same or different and are selected from chloride, sulfate, methosulfate and etosulphate.

[上式中、Ｒ_１、Ｒ_２及びＲ_６は上述した同様の意味を有する]
の対応するアルデヒドと接触させる。 Finally, the integer n is at least equal to 2 and at most equal to the number of cationic charges present in the fluorescent compound.
Preferably, the fluorescent compounds described in detail are symmetrical compounds.
These compounds are reacted in the first step with α-picoline with a reagent having two leaving groups which can be selected from a group of the tolylsulfonyl or methylsulfonyl type, or a halogen atom, preferably bromine, optionally chlorine. Can be synthesized.
This first step may be performed in the presence of a non-essential solvent such as dimethylformamide.
The number of moles of α-picoline is generally in the range of 2 per mole of reagent having a leaving group.
In addition, the reaction is usually done at the reflux temperature of the solvent and / or reagent if present.
The product derived in this first step is then represented by the following formula:

[Wherein R ₁ , R ₂ and R ₆ have the same meaning as described above]
Contact with the corresponding aldehyde.

In this case, the reaction may be carried out in the presence of a suitable solvent, preferably at the reflux point.
It should be noted that the R ₁ and R ₂ groups of the aldehyde have the meanings indicated in the general formula detailed above.
Alternatively, aldehydes in which the groups represent hydrogen atoms can be used, and replacement of these hydrogen atoms with the appropriate groups described in the general formula can be performed according to standard methods when the second step is completed. .
Reference is made in particular to the synthesis method described in US Pat. No. 4,256,458.

  The fluorescent dye (s) present in the composition according to the invention are advantageously from 0.01% to 20% by weight, in particular from 0.05% to 10% by weight, preferably from the total weight of the composition 0.1 wt% to 5 wt%.

As noted above, the composition comprises at least one complex selected from hydroxycarboxylic acids, polycarboxylic acids, and alkali metals, alkaline earth metals, transition metals, organic amines or ammonium salts thereof, alone or as a mixture. It further contains an agent.
Examples of monovalent cations that may be mentioned include alkali metal, such as sodium or potassium cations.
Mention may also be made of monovalent cations derived from organic amines, for example primary, secondary or tertiary amines, or alkanolamines. The amines may be the same or different and contain one or more groups of linear or branched C1-C20 alkyl type, which may have heteroatoms such as oxygen. Also suitable are cations derived from quaternary ammonium which correspond to the definitions given above and in particular have four groups which may be identical or different.

  Examples of divalent cations that may be mentioned are divalent cations of alkaline earth metals such as calcium or magnesium, or transition metals (metals with incomplete d subshells), especially in the acid value state II For example, divalent cobalt, iron, manganese, zinc or copper cations.

In particular, the hydroxycarboxylic acid type sequestering agent corresponds to the following formula (A): R— (CHOH) ₄ —CO ₂ X, where R is CH ₂ OH or CO ₂ X Represents a group, and X represents hydrogen or a monovalent or divalent cation. This formula includes all enantiomers and diastereoisomers of these compounds.

Regarding polycarboxylic acid type sequestering agents, they correspond in particular to the following formula (B): RN (Y) (CH (R ′) CO ₂ X), where Y is Represents hydrogen or a CH (R ′) CO ₂ X group; R is hydrogen, or (a) —CH (CO ₂ X) (CH ₂ ) _n CO ₂ X, (b) — (CH ₂ ) _n OH, c) -CH (R '') CO 2 X, (d) - (CH 2) n - N- (COR '') - CH 2 CO 2 X, (e) - (CH 2) n -N (CH ₂ CO ₂ X) CH ₂ CO ₂ X, and (f) — (CH ₂ ) _n NH—CH (CO ₂ X) CH ₂ CO ₂ X, wherein R ′ is a hydrogen atom or CH ₂ Represents a CO ₂ X group; R ″ represents a linear or branched C ₁ -C ₃₀ or cyclic C ₃ -C ₃₀ alkyl group, n is an integer of 1 to 5, and X is hydrogen Represents an atom or a monovalent or divalent cation described in formula (A).
In one particular embodiment, n is equal to 2.

Among the sequestering agents that can be used, in particular:
Formula (A): Gluconic acid, mucoic acid (or galactaric acid), glucaric acid, mannaric acid, their salts, and mixtures thereof;
Formula (B):
R represents a hydrogen atom, R ′ represents a —CH ₂ —CO ₂ X group, or R represents a —CH (CO ₂ X) — (CH ₂ ) ₂ —CO ₂ X group, and R ′ represents A compound having four carboxylic acid or salt functional groups when representing a hydrogen atom;
R represents —CH (CH ₃ ) —CO ₂ X and R ′ represents a hydrogen atom, or R represents a — (CH ₂ ) ₂ —N (COR ″) — CH ₂ —CO ₂ X group. And when R ′ represents a hydrogen atom, a compound having three carboxylic acid or salt functional groups;
Is appropriate.
Methylglycine diacetic acid, N-lauroylethylenediamine-N, N ′, N′-triacetic acid, iminodisuccinic acid, N, N-dicarboxymethyl-L-glutamic acid, ethylenediamine-N, N′-disuccinic acid, and Their salts and mixtures are preferred examples of compounds of formula (B).

It should be noted that the term “mixture” means a mixture of several acids, several salts of acids or mixtures of several acid salts, or a mixture of an acid and one or more of its salts. It is.
Preferably, the polycarboxylic acid used is of the formula (B), wherein R represents a hydrogen atom or a group selected from the groups (a) to (d) and (f).
The content of sequestering agent is advantageously between 0.0001% and 20% by weight relative to the weight of the composition, in particular between 0.001% and 10% by weight, preferably relative to the weight of the composition. 0.01 to 5% by weight based on the weight of the product.

Cosmetically acceptable media generally consist of water or a mixture of one or more common organic solvents and water.
Suitable organic solvents for use include in particular alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers such as ethylene glycol monomethyl ether, monoethyl ether or monobutyl ether, propylene glycol and Mention may be made of the ethers such as propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers such as diethylene glycol monoethyl ether or monobutyl ether, or polyols such as glycerol. Polyethylene glycols and polypropylene glycols and mixtures of all these compounds can be used as solvents.
The general solvents mentioned above, if present, are generally 1% to 40% by weight, more preferably 5% to 30% by weight, based on the total weight of the composition.

[ここで、Ｗは、Ｃ_１-Ｃ_６アルキル基又はヒドロキシル基で置換されていてもよいプロピレン残基であり；Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は同一でも異なっていてもよく、水素原子、又はＣ_１-Ｃ_６アルキル又はＣ_１-Ｃ_６ヒドロキシアルキル基を表す]
の化合物が含まれる。 The pH of the composition of the present invention is generally about 3-12, preferably about 5-11.
It can be adjusted to the desired value using acidifying or basifying agents.
Examples of acidifying agents that may be mentioned include inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, or acetic acid.
Examples of basifying agents that may be mentioned include, for example, aqueous ammonia, alkaline carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and their derivatives, sodium hydroxide, potassium hydroxide, and The following formula (C):

Wherein W is a propylene residue optionally substituted with a C ₁ -C ₆ alkyl group or a hydroxyl group; R ₁ , R ₂ , R ₃ and R ₄ may be the same or different; Represents a hydrogen atom, or a C ₁ -C ₆ alkyl or C ₁ -C ₆ hydroxyalkyl group]
These compounds are included.

In addition, the composition of the present invention comprises various conventionally used adjuvants such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, hair dyes, polymers, Inorganic thickeners, antioxidants, penetrants, perfumes, buffers, dispersants, conditioners such as cations, silicones, film formers, preservatives, and stabilizers may also be included.
If one or more surfactants are present, preferably of nonionic, anionic or amphoteric type, their content is 0.01% to 30% by weight relative to the weight of the composition .
Of course, those skilled in the art will note that this or these advantages are not adversely affected or substantially unaffected by the considered additions to the advantageous properties inherent in the compositions of the present invention. Any additional compound (s) will be selected.

The compositions of the present invention can be in various forms, such as liquids, shampoos, creams or gels, or any other suitable form.
In one particularly preferred form of the invention, the composition is in the form of a light-dyed shampoo containing a cosmetically acceptable aqueous medium.

  The composition of the present invention may further contain at least one oxidizing agent. This agent is selected from, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborate and persulphate, and enzymes such as peroxidase and two- or four-electron oxidoreductases Can be done. The use of hydrogen peroxide or an enzyme is particularly preferred.

The subject of the invention is also a cosmetically acceptable medium, at least one fluorescent dye soluble in the medium, and a hydroxycarboxylic acid and polycarboxylic acid, and a monovalent or divalent alkali metal, alkaline earth In order to dye human keratin materials with a lightening effect in a composition comprising at least one complexing agent selected from metals, transition metals, organic amines or ammonium salts thereof alone or as a mixture Is in use.
In this use, the fluorescent compounds are the following families: naphthalimides; cationic or non-cationic coumarins; xanthenodiquinolidines (eg, especially sulforhodamines); azaxanthenes; naphtholactams; azlactones; Oxazines; thiazines; dioxazines; may be selected from fluorescent dyes belonging to azo, azomethine or methine type monocationic or polycationic fluorescent dyes alone or in mixtures.

[上式中、Ｒはメチル又はエチル基を表し；Ｒ'はメチル基を表し、Ｘ⁻は塩化物、ヨウ化物、スルファート、メトスルファート、アセタート又はペルクロラート等のアニオンを表す]
の化合物を使用することもできる。この種の化合物の例としては、Ｒがエチル基を表し、Ｒ'がメチル基を表し、Ｘ⁻がヨウ化物を表す、ユビケム社(Ubichem)から販売されている光過敏性染料ＮＫ-５５７を挙げることができる。 Compounds which can be mentioned in particular include the compounds of the formulas F1, F2 and F3 already detailed above.
Similarly, the following structure (F4):

[In the above formula, R represents a methyl or ethyl group; R ′ represents a methyl group, and X ⁻ represents an anion such as chloride, iodide, sulfate, methosulfate, acetate or perchlorate]
These compounds can also be used. Examples of this type of compound include the photosensitizing dye NK-557 sold by Ubichem, where R represents an ethyl group, R ′ represents a methyl group and X ⁻ represents an iodide. Can be mentioned.

All of the above is valid with respect to the nature and content of the various additives present in the composition and will not be repeated in this part.
In the context of the present invention, the term “human keratin substance” means skin, hair, nails, eyelashes and eyebrows, in particular colored skin, and artificially dyed or colored hair.
For the purposes of the present invention, the term “colored skin” means skin with a lightness L ^* measured by the CIE L ^* a ^* b ^* system of 45 or less, preferably 40 or less, where L ^* = 0 is equivalent to black and L ^* = 100 is equivalent to white. The skin types corresponding to this lightness are African skin, African American skin, Spanish American skin, Indian skin and North African skin.
For the purposes of the present invention, the expression “artificially dyed or colored hair” means hair whose tone height is 6 (dark blonde) or less, preferably 4 (chestnut brown) or less. .

The lightening of the hair is evaluated by the “tone height” that characterizes the degree or level of lightening. The concept of “tone” is based on the classification of natural tones, where one tone separates each tone from the tone just before or after it. This definition and classification of natural tones is well known to hair styling professionals and published in Charles Zviak 1988, Masson, pp. 215 and 278, "Sciences des Traitements capillaires [Hair treatment sciences]" Has been.
The tone height ranges from 1 (black) to 10 (light blond), one unit corresponds to one tone; the higher the number, the brighter the tone.

Thus, another subject of the invention is the following process:
a) applying the composition of the present invention to keratin fibers for a time sufficient to achieve the desired coloration and lightening;
b) optionally rinsing the fibers;
c) optionally washing and rinsing the fibers with shampoo,
d) the fiber is dried or left to dry,
The present invention relates to a method for dyeing human keratin fibers with a lightening effect.

The subject of the invention is also a method for coloring colored skin with a lightening effect, wherein the composition as described above is applied to the skin and then the skin is dried or left to dry. Preferably, this composition is not used in the presence of an oxidizing agent.
All of the above with respect to the various components of the composition is valid and referenced herein.
In particular, the method according to the invention is suitable for treating human keratin fibers, in particular artificially dyed or colored hair, or colored skin.
In particular, fibers that can be advantageously treated with the method of the invention have a tone height of 6 (dark blond) or less, preferably 4 (chestnut brown) or less.
Furthermore, the colored skin that can be treated according to the present invention has a lightness L ^* of 45 or less, preferably 40 or less, as measured by the CIE L ^* a ^* b ^* system.

In the first embodiment of the present invention, the dyeing method with the lightening effect of the fiber is carried out using a composition containing no oxidizing agent.
In the second embodiment of the present invention, the dyeing method with the lightening effect of the fibers is carried out using a composition containing an oxidizing agent.

In a first variant of these dyeing methods according to the invention, at least one composition as described above is applied to the fibers, in particular the hair, for a time sufficient to achieve the desired coloring and lightening, and then the fibers are applied. Rinse, possibly with shampoo, rinse again and dry.
A second variant of these dyeing methods according to the invention applies at least one composition as described above to the fibers, in particular the hair, without a final rinse.
In a third variant of the dyeing method according to the invention, the dyeing method comprises on the one hand a composition according to the invention and on the other hand at least one oxidizing agent in a cosmetically acceptable medium. The composition comprises a preliminary step consisting of storing them separately and then mixing them at the time of use, and then applying this mixture to the keratin fibers, especially the hair, for a time sufficient to achieve the desired coloration and then The fibers are rinsed, optionally washed with shampoo, rinsed again and dried.

The time required to color the fibers, in particular the hair, and to obtain a lightening effect is about 5 to 60 minutes, in particular about 5 to about 40 minutes.
The temperature required for coloring and obtaining a lightening effect is generally room temperature (15-25 ° C.) to 80 ° C., in particular 15-40 ° C.

  Another subject of the invention is a keratin comprising at least one compartment containing a composition of the invention and at least one other compartment containing a composition containing at least one oxidizing agent. In multi-compartments for dyeing fibers, in particular hair, with a lightening effect. This multi-compartment tool may be provided with means capable of applying a desired mixture to the fibers, for example, a multi-compartment tool described in French Patent No. 2586913.

It should be noted that if the composition of the present invention is used for the treatment of keratin fibers, such as chestnut brown hair, the following results can be achieved with the composition:
Measure the reflectance of hair when emitting visible light in the wavelength range of 400-700 nanometers, and reflect the reflectance curve as a function of wavelength between the hair treated with the composition of the invention and the untreated hair. In the wavelength range of 500-700 nanometers, the reflectance curve corresponding to the treated hair was found to be higher than that corresponding to the untreated hair.
This means that in the wavelength range of 500 to 700 nanometers, preferably 540 to 700 nanometers, the reflectance curve corresponding to the treated hair is at least one higher than the reflectance curve corresponding to the untreated hair. Means that a range exists. The term “higher” means a difference of at least 0.05%, preferably at least 0.1% of reflectivity.
However, in the wavelength range of 500 to 700 nanometers, preferably 540 to 700 nanometers, the reflectance curve corresponding to the treated fiber overlaps with or below the reflectance curve corresponding to the untreated fiber. Suggests that one or more ranges are present.
Preferably, the wavelength at which the difference between the reflectance curve of the treated hair and that of the untreated hair is maximized is in the wavelength range of 500 to 650 nanometers, preferably in the wavelength range of 550 to 620 nanometers. is there.

In addition, preferably, the composition of the present invention has a variable b ^{* of} 6 or more as measured by the CIE L ^* a ^* b ^* system, and the ratio of absolute values of b ^* / a ^* is Hair and skin can be lightened to a color tone greater than 1.2 according to the selection test described.

Selection test The composition is applied to chestnut brown keratin fibers, especially the hair, at a rate of 10 grams of composition per gram of chestnut brown fibers. Spread the composition to spread throughout the fiber. The composition is allowed to act for 20 minutes at room temperature (20-25 ° C.). The fiber is then rinsed with water and washed with a lauryl ether sulfate based shampoo. Then dry. Next, the spectral colorimetric characteristics of the fiber are measured and the L ^* a ^* b ^* coordinates are determined.
In the CIE L ^* a ^* b ^* system, a ^* and b ^* indicate two color axes: a ^* indicates the green / red color axis (+ a ^* is red, -a ^* is green), b ^{* Indicates} the blue / yellow color axis (+ b ^* is yellow and -b ^* is blue); the values of a ^* and b ^* close to zero correspond to the shade of gray.

９３ｇの２-ピコリンを、１１０℃のジメチルホルムアミドにおいて５時間、１２０ｇの１,６-ジブロモヘキサンと反応させる。
沈殿した生成物を回収し、濾過する。
上述にて得られた１０９ｇの生成物をメタノールに溶解させ、８２．８２ｇのｐ-ジメチルアミノベンズアルデヒドを、ピロリジンの存在下、２つの部分に添加する。
ついで、混合物を３０分間放置する。
沈殿した形態の生成物を回収する。
質量分光分析：２６６
元素分析：Ｃ:６２．４３％；Ｈ:６．４０％；Ｂｒ:２３．０７％；Ｎ:８．０９％
式は次の通りである：Ｃ_３６Ｈ_４４Ｎ_４・２Ｂｒ The following examples are intended to illustrate the invention and are not intended to limit its scope.
Example Fluorescent Compound

93 g of 2-picoline are reacted with 120 g of 1,6-dibromohexane in dimethylformamide at 110 ° C. for 5 hours.
The precipitated product is collected and filtered.
109 g of the product obtained above are dissolved in methanol and 82.82 g of p-dimethylaminobenzaldehyde are added in two parts in the presence of pyrrolidine.
The mixture is then left for 30 minutes.
The product in precipitated form is recovered.
Mass spectrometric analysis: 266
Elemental analysis: C: 62.43%; H: 6.40%; Br: 23.07%; N: 8.09%
The formula is as follows: C ₃₆ H ₄₄ N ₄ · 2Br

染色
各組成物を２０分の放置時間、天然のチェスナットブラウンの毛髪(トーン高さ４)の束に適用する。
ついで毛髪の束をすすぎ、フードにて３０分乾燥させる。
毛髪の束に、顕著な明色化効果が観察された。 Composition

Dyeing Each composition is applied to a bundle of natural chestnut brown hair (tone height 4) for 20 minutes standing time.
The hair bundle is then rinsed and dried in a hood for 30 minutes.
A significant lightening effect was observed on the hair bundle.

Claims (27)

  In a cosmetically acceptable medium, at least one fluorescent dye soluble in the medium, hydroxycarboxylic acid and polycarboxylic acid, and monovalent or divalent alkali metal, alkaline earth metal, transition metal, organic And at least one complexing agent selected from amines or ammonium salts, alone or as a mixture; 2- [2- (4-dialkylamino) phenylethenyl] -1-alkylpyridinium as a fluorescent agent And the alkyl group of the pyridinium ring represents a methyl or ethyl group, the alkyl group of the benzene ring represents a methyl group, and the counter ion is a halide.   Composition according to claim 1, characterized in that the fluorescent dye exhibits a maximum reflectance in the wavelength range of 500 to 650 nanometers, preferably in the wavelength range of 550 to 620 nanometers.   Fluorescent dyes are in the following families: naphthalimides; cationic or non-cationic coumarins; xanthenodiquinolidines; azaxanthenes; naphthactams; azlactones; oxazines; 3. Composition according to claim 1 or 2, characterized in that it is selected from fluorescent compounds belonging to azomethine or methine-type polycationic fluorescent dyes alone or as a mixture. The fluorescent compound has the formula:

[In the above formula:
R ₁ and R ₂ may be the same or different:
・ Hydrogen atom;
1 to 10 carbons in which a group having at least one heteroatom and / or at least one heteroatom is inserted and / or substituted and / or substituted with at least one halogen atom A linear or branched alkyl group having atoms, preferably 1 to 4 carbon atoms;
An aryl or arylalkyl group in which the aryl group has 6 carbon atoms and the alkyl group has 1 to 4 carbon atoms; the aryl group is at least one heteroatom and / or at least one heteroatom One or more linear or branched having 1 to 4 carbon atoms, which may be inserted and / or substituted and / or substituted with at least one halogen atom Optionally substituted with an alkyl group;
Represents;
R ₁ and R ₂ may be bonded to form a heterocycle with the nitrogen atom, and may have one or more other heteroatoms, where the heterocycle is A group having at least one heteroatom and / or at least one heteroatom may be inserted and / or substituted and / or substituted with at least one halogen atom, preferably 1-4 Are optionally substituted with at least one linear or branched alkyl group having carbon atoms;
-Furthermore, R ₁ or R ₂ may be involved in a heterocycle containing a nitrogen atom and one of the carbon atoms of the phenyl group carrying the nitrogen atom;
R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R ₅ may be the same or different, and represents a linear or branched alkyl group containing 1 to 4 carbon atoms into which a hydrogen atom, a halogen atom or at least one hetero atom may be inserted;
R ₆ may be the same or different, a hydrogen atom; a halogen atom; a group bearing at least one heteroatom and / or at least one heteroatom is substituted and / or inserted and / or at least Represents a linear or branched alkyl group containing 1 to 4 carbon atoms, optionally substituted by one halogen atom;
X is:
1 to 14 carbons in which a group having at least one heteroatom and / or at least one heteroatom is inserted and / or substituted and / or optionally substituted by at least one halogen atom A linear or branched alkyl group having an atom or an alkenyl group containing 2 to 14 carbon atoms;
With at least one linear or branched alkyl group having 1 to 14 carbon atoms, optionally substituted with at least one heteroatom; optionally substituted with at least one heteroatom, At least one linear or branched aminoalkyl group having 1 to 4 carbon atoms; a 5- or 6-membered heterocyclic group optionally substituted with at least one halogen atom;
A fused or non-fused aromatic or diaromatic group, optionally separated by an alkyl group containing 1 to 4 carbon atoms, wherein the aryl group is at least one halogen atom, or at least one heteroatom and Optionally substituted with at least one alkyl group containing 1 to 10 carbon atoms, which may be substituted and / or inserted with a group bearing at least one heteroatom;
・ Dicarbonyl group;
Represents
The X group can carry one or more cationic charges;
a is equal to 0 or 1;
Y ⁻ may be the same or different and represents an organic or inorganic anion;
n is an integer equal to at least 2 and at most equal to the number of cationic charges present in the fluorescent compound]
The composition according to any one of claims 1 to 3, wherein the composition has the following.   The fluorescent dye is present in a weight concentration of 0.01% to 20% by weight, in particular 0.05% to 10% by weight, preferably 0.1% to 5% by weight, relative to the total weight of the composition A composition according to any one of claims 1 to 4, characterized in that A hydroxycarboxylic acid type sequestering agent corresponds to the following formula (A): R— (CHOH) ₄ —CO ₂ X, wherein R represents a CH ₂ OH or CO ₂ X group. The composition according to any one of claims 1 to 5, characterized in that X represents hydrogen or a monovalent or divalent cation.   The composition according to any one of claims 1 to 6, characterized in that the sequestering agent is selected from gluconic acid, mucous acid, glucaric acid, and mannalic acid, and salts and mixtures thereof. . The polycarboxylic acid type sequestering agent corresponds to the following formula (B): RN (Y) (CH (R ′) CO ₂ X), wherein Y is a hydrogen atom or CH (R ′) represents a CO ₂ X group; R represents a hydrogen atom, or (a) —CH (CO ₂ X) — (CH ₂ ) _n CO ₂ X, (b) — (CH ₂ ) _n OH, (c _{) -CH (R '') CO} 2 X, (d) - (CH 2) n -N (COR '') - CH 2 CO 2 X, (e) - (CH 2) n -N (CH 2 CO _{2 X) CH 2 CO 2 X} , and _{(f) - (CH 2)} n NH-CH (CO 2 X) CH 2 CO 2 represent the X groups, further wherein R 'is a hydrogen atom or _CH 2 CO ₂ Represents an X group; R ″ represents a linear or branched C ₁ -C ₃₀ or cyclic C ₃ -C ₃₀ alkyl group, n is an integer from 1 to 5, preferably equal to 2, X represents a hydrogen atom or a monovalent or divalent cation, 1 to composition according to any one of 5. Sequestering agent,
R represents a hydrogen atom, R ′ represents a —CH ₂ —CO ₂ X group, or R represents a —CH (CO ₂ X) — (CH ₂ ) ₂ —CO ₂ X group, and R ′ represents A compound having four carboxylic acid or carboxylate functional groups when representing a hydrogen atom;
R represents a —CH (CH ₃ ) —CO ₂ X group and R ′ represents a hydrogen atom, or R represents a — (CH ₂ ) ₂ —N (COR ″) — CH ₂ —CO ₂ X group. And when R ′ represents a hydrogen atom, a compound having three carboxylic acid or carboxylate functional groups;
9. Composition according to claim 8, characterized in that it is selected from   The sequestering agent is methyl glycine diacetic acid, N-lauroylethylenediamine-N, N ′, N′-triacetic acid, iminodisuccinic acid, N, N-dicarboxymethyl-L-glutamic acid, ethylenediamine-N, N ′ 10. Composition according to claim 8 or 9, characterized in that it is selected from disuccinic acid and their salts and mixtures.   The content of the sequestering agent is 0.0001% to 20% by weight relative to the weight of the composition, in particular 0.001% to 10% by weight relative to the weight of the composition, preferably the weight of the composition. The composition according to any one of claims 1 to 10, wherein the content is 0.01% by weight to 5% by weight.   12. Composition according to any one of the preceding claims, characterized in that it contains at least one nonionic, anionic or amphoteric surfactant.   The composition according to claim 12, wherein the content of the surfactant is 0.01 wt% to 30 wt% with respect to the total weight of the composition.   A composition comprising the composition according to any one of claims 1 to 13 and at least one oxidizing agent.   The oxidizing agent is hydrogen peroxide, urea peroxide, alkali metal bromate, persalts such as perborate and persulphate, and enzymes such as peroxidases and two- or four-electron oxidoreductases, preferably 15. Composition according to claim 14, characterized in that it is selected from hydrogen peroxide. In a method for dyeing human keratin fibers with a lightening effect,
a) applying the composition according to any one of claims 1 to 15 to human keratin fibers for a time sufficient to achieve the desired coloration and lightening;
b) Rinse the fiber in some cases,
c) In some cases, the fibers are washed with a shampoo, rinsed,
d) the fiber is dried or left to dry,
Performing the process.   A composition according to any one of claims 1 to 13 on the one hand and a composition comprising at least one oxidizing agent in a cosmetically acceptable medium on the other hand are stored separately and then used. Sometimes comprising a preliminary step consisting of mixing them, and then applying the mixture to the fibers for a time sufficient to obtain the desired coloration, and then rinsing the fibers, possibly shampooing and rinsing again The method according to claim 16, wherein the method is dried.   18. A method according to claim 16 or 17, characterized in that the composition is applied to hair having a tone height of 6 or less, preferably 4 or less.   The method according to claim 16, wherein the human keratin fibers are artificially dyed or colored.   In a method for coloring colored skin with a lightening effect, the composition according to any one of claims 1 to 13 is applied to the skin, and then the skin is dried or left to dry. A method characterized by:   Dyeing keratin fibers, comprising at least one compartment containing the composition according to any one of claims 1 to 13 and at least one other compartment containing a composition comprising at least one oxidizing agent. And multi-compartment tools for lightening.   In a cosmetically acceptable medium, at least one fluorescent dye soluble in the medium, a hydroxycarboxylic acid and a polycarboxylic acid, and a monovalent or divalent alkali metal, alkaline earth metal, transition metal, organic thereof Use of a composition comprising at least one complexing agent selected from amines or ammonium salts, alone or as a mixture, for dyeing human keratin fibers with a lightening effect.   Use according to claim 22, characterized in that the fluorescent dye exhibits a maximum reflectance in the wavelength range of 500 to 650 nanometers, preferably in the wavelength range of 550 to 620 nanometers.   Fluorescent dyes are in the following families: naphthalimides; cationic or non-cationic coumarins; xanthenodiquinolidines; azaxanthenes; naphthactams; azlactones; oxazines; 24. Use according to claim 22 or 23, characterized in that it is selected alone or as a mixture from fluorescent compounds belonging to azomethine or methine-type monocationic or polycationic fluorescent dyes. The fluorescent dye has the following structure:

[In the above formula:
R ₁ and R ₂ may be the same or different:
・ Hydrogen atom;
1 to 10 carbons in which a group having at least one heteroatom and / or at least one heteroatom is inserted and / or substituted and / or substituted with at least one halogen atom A linear or branched alkyl group having atoms, preferably 1 to 4 carbon atoms;
An aryl or arylalkyl group in which the aryl group has 6 carbon atoms and the alkyl group has 1 to 4 carbon atoms; the aryl group is at least one heteroatom and / or at least one heteroatom One or more linear or branched having 1 to 4 carbon atoms, which may be inserted and / or substituted and / or substituted with at least one halogen atom Optionally substituted with an alkyl group;
Represents;
R ₁ and R ₂ may be bonded to form a heterocycle with the nitrogen atom, and may have one or more other heteroatoms, where the heterocycle is A group having at least one heteroatom and / or at least one heteroatom may be inserted and / or substituted and / or substituted with at least one halogen atom, preferably 1-4 Are optionally substituted with at least one linear or branched alkyl group having carbon atoms;
-Furthermore, R ₁ or R ₂ may be involved in a heterocycle containing a nitrogen atom and one of the carbon atoms of the phenyl group carrying the nitrogen atom;
R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R ₅ may be the same or different, and represents a linear or branched alkyl group containing 1 to 4 carbon atoms into which a hydrogen atom, a halogen atom or at least one hetero atom may be inserted;
R ₆ may be the same or different, a hydrogen atom; a halogen atom; a group bearing at least one heteroatom and / or at least one heteroatom is substituted and / or inserted and / or at least Represents a linear or branched alkyl group containing 1 to 4 carbon atoms, optionally substituted by one halogen atom;
X is:
1 to 14 carbons in which a group having at least one heteroatom and / or at least one heteroatom is inserted and / or substituted and / or optionally substituted by at least one halogen atom A linear or branched alkyl group having an atom or an alkenyl group containing 2 to 14 carbon atoms;
With at least one linear or branched alkyl group having 1 to 14 carbon atoms, optionally substituted with at least one heteroatom; optionally substituted with at least one heteroatom, At least one linear or branched aminoalkyl group having 1 to 4 carbon atoms; a 5- or 6-membered heterocyclic group optionally substituted with at least one halogen atom;
A fused or non-fused aromatic or diaromatic group, optionally separated by an alkyl group containing 1 to 4 carbon atoms, wherein the aryl group is at least one halogen atom, or at least one heteroatom and Optionally substituted with at least one alkyl group containing 1 to 10 carbon atoms, which may be substituted and / or inserted with a group bearing at least one heteroatom;
・ Dicarbonyl group;
Represents
The X group can carry one or more cationic charges;
a is equal to 0 or 1;
Y ⁻ may be the same or different and represents an organic or inorganic anion;
n is at least equal to 2 and at most the following fluorescent compounds:

(Wherein R represents a methyl or ethyl group; R ′ represents a methyl group, and X ⁻ represents a chloride, iodide, sulfate, methosulfate, acetate, or perchlorate type anion). Is an integer equal to the number of cationic charges]
25. Use according to any one of claims 22 to 24, characterized in that it is selected from the group consisting of dyes having   26. Use according to any one of claims 22 to 25, characterized in that the keratin substance is artificially dyed or colored keratin fibres, in particular hair, or colored skin.   27. Use according to claim 26, characterized in that the hair has a tone height of 6 or less, preferably 4 or less.