KR20140084093A - Dye composition comprising a non-glycosyl iridoid compound and a particular aldehyde or imine, dyeing process and device therefor - Google Patents

Abstract

(식 중, R₁: 수소, (히드록시)메틸, 알데히드, -CO₂R₄ (R₄: 수소, 알킬), -CH₂-글루코오스; R₂: 수소, 히드록실, 글루코오스; R₃: 수소, 히드록실, 알킬옥시; n 은 1 내지 5 범위; R₅: -CO₂R'₆ (R'₆: 수소, 알킬, 양이온));
** 화학식 (i) 및 (ii) 의 하나 이상의 알데히드 또는 이민 화합물, 및 또한 하나 이상의 알데히드 또는 이민 관능기를 포함하는 산화 올리고당 또는 다당류:

(식 중, n 은 0 또는 1; X: O, NR"₁; A: COOH, 임의로 치환된 아릴, 1 또는 2 개의 헤테로원자를 포함하는 양이온성 또는 비양이온성, 포화 또는 불포화 5- 또는 6-원 헤테로사이클, 임의로 치환된, 알킬, 알케닐; A₂: 2가 알킬렌; 알데히드의 경우, 상기 화합물은 아세탈 또는 헤미아세탈 형태일 수 있음).
본 발명의 주제는 또한 상기와 같은 조성물을 사용하는 방법 및 화학식 (I) 및/또는 (II) 의 하나 이상의 화합물 또는 상기를 포함하는 식물 추출물을 함유하는 제 1 구획, 및 화학식 (i) 또는 (ii) 의 하나 이상의 화합물, 하나 이상의 알데히드 또는 이민 관능기를 포함하는 산화 올리고당 또는 다당류를 함유하는 제 2 구획을 포함하는 다중 구획 장치이다.The present invention relates to a composition for human keratin fibers, which comprises in a cosmetically acceptable medium:
A compound of formula (I) and / or formula (II), or a plant extract comprising the compound:

(Wherein, R _1: hydrogen, (hydroxy) methyl, _{aldehyde, -CO 2 R 4 (R 4} : hydrogen, alkyl), -CH ₂ - glucose; R _2: hydrogen, hydroxyl, glucose; R _3: Hydrogen, hydroxyl, alkyloxy, n is in the range of 1 to 5, R _{5 is} -CO ₂ R ' ₆ (R' ₆ : hydrogen, alkyl, cation);
** Formula (i) and (ii) at least one aldehyde or imine of the compound, and also at least one aldehyde or imine oxidation of oligosaccharides or polysaccharides containing the functional group:

(Wherein, n is 0 or 1; X: O, NR "1; A: COOH, optionally substituted aryl, with one or two heteroatoms, cationic or non-cationic containing sex, saturated or unsaturated 5-or 6 A ₂ : divalent alkylene; in the case of an aldehyde, the compound may be in the form of an acetal or hemiacetal).
The subject matter of the present invention also relates to a process for the use of such a composition and to a first compartment containing at least one compound of formula (I) and / or (II) or a plant extract comprising the same, a second compartment containing one or more compounds of ii), an oxidized oligosaccharide comprising at least one aldehyde or an imine functional group or a polysaccharide.

Description

TECHNICAL FIELD [0001] The present invention relates to a dye composition containing a non-glycosyl iodide compound and a specific aldehyde or an imine, a dyeing method using the dye composition,

The present invention relates to a dye composition comprising in a cosmetically acceptable medium at least one compound selected from the group of non-glycosyl iridoids extracted from plants and at least one specific aldehyde or imine compound, To a dyeing process using the same composition.

Recently, there is an increasing interest in natural compounds that can be used as hair dyes.

For example, the patent application EP 440 494 discloses the use of a plant of the genus Rubiaceae, Euphorbiaceae, Valerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, One or more compounds of (seko) iridoid-glycoside or non-glycosyl (seko) iridoid (also known as aglycone), extracted from plants such as the genus Ericaceae, Loganiaceae, A method for dyeing hair using the composition.

The problem with such staining is that they are not particularly strong or that repeated application of the composition over several days or weeks is required to obtain satisfactory staining.

Furthermore, it is difficult to achieve the desired advantage, natural hue. Moreover, it is not uncommon for significant color changes to be observed over time when such a hue is achieved.

Accordingly, the object of the present invention is to overcome the disadvantages described above.

In particular, it has been surprisingly found that by combining the compound with a particular aldehyde or imine compound, using a compound of the non-glycosyl idide type of build-up and derivatives thereof and generally any of the natural extracts containing it , It can be substantially improved.

It was also confirmed that the structure of the treated fiber was not damaged by the coloring according to the present invention.

Accordingly, one subject of the present invention is a cosmetic acceptable medium for dyeing human keratin fibers, comprising:

An optically or geometrically isomer thereof, an inorganic or organic acid salt thereof, a solvate thereof, or a plant extract comprising the compound of formula (I) and / or formula (II)

In formulas (I) and (II):

R ₁ is a hydrogen atom, a methyl radical, a hydroxymethyl radical, an aldehyde group; -CO ₂ R ₄ group, wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl radical; -CH ₂ - represents a glucose;

R ₂ represents a hydrogen atom, a hydroxyl radical or a glucose radical;

R ₃ may be the same or different and represents a hydrogen atom, a hydroxyl radical, or a (C ₁ -C ₄ ) alkyloxy radical; The number of the hydroxyl groups is 2 or less;

N is an integer from 1 to 5;

R ₅ represents a -CO ₂ R ' ₆ group (wherein R' ₆ represents a hydrogen atom or a C ₁ -C ₂ alkyl radical; an alkali metal cation or an ammonium group);

R ₆ represents hydrogen, -CO ₂ R ' ₆ group (wherein R' ₆ represents a hydrogen atom, a C ₁ -C ₂ alkyl radical, an alkali metal cation or an ammonium group)];

** the following formulas (i) and one or more selected from (ii) an aldehyde or imine compound, its optical or geometric isomers thereof, organic or inorganic acid salt, a solvate thereof, and also the oxidation of oligosaccharides comprising at least one aldehyde or imine functional groups Or polysaccharides:

[In the formulas (i) and (ii)

M is an integer of 0 or 1,

X represents an oxygen atom, NR " ₁ , wherein R" ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl radical;

When X represents an oxygen atom, the compound may be of the form:

an additional primary monoalcohol (R ' ₃ OH), wherein R' ₃ is a symmetrical 1,2- or 1,3-diol containing a C ₁ -C ₅ alkyl radical or a C ₂ -C ₃ alkyl chain, Or a form of a 5-or 6-membered cyclic or acyclic acetal,

о A or A ₁ represents an alkyl radical, when n is 0, the form of a hemiacetal obtained by condensation of the hydroxyl groups existing on the A or A _1;

The radicals R ' ₁ and R' ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl radical;

The monovalent radical A and the bivalent radical A ₁ represent a group selected from the following:

* Hydroxycarbonyl group (- CO - OH ):

* At least optionally substituted C ₆ Aryl group :

- a hydroxyl group,

- a C ₁ -C ₄ alkyl radical,

- aryl-ethylenyl radical, wherein the aryl group is C ₆ , optionally substituted by one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals,

-CO-OR ' ₄ or -O-COR' ₄ group (wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical or a phenyl group);

-COOH groups in acidic or chlorinated form,

-OR ' ₅ group (wherein R' ₅ represents a C ₁ -C ₈ alkyl radical optionally substituted with one or more hydroxyl groups), -N ⁺ R " ₆ ammonium group (wherein R" ₆ is the same can be different from each other, it represents a C ₁ -C ₂ alkyl radicals), -SiR _'7 group (wherein, R' is _7, which may be the same or different, represents a C ₁ -C ₂ alkyl radical); Benzyl radicals (-CH ₂ -C ₆ H ₆ ),

According to one particular variation, the two radicals -OR ' ₅ in the ortho position with respect to the C ₆ aryl group may form a 5- or 6-membered heterocycle by two radicals R' ₅ ,

--N (R ' ₈ ) ₂ group wherein R' ₈ may be the same or different and is a hydroxyl group, a carboxyl group (-COOH) in acid or chloride form, or a sulfone group in acid or chloride form (-SO ₃ H) as an optionally substituted C ₁ -C ₆ represents an alkyl radical, the radicals R _'8 together with the nitrogen atom containing them, optionally O, N and NR' ₉ (wherein, R _'9 is C search the heterocycle is optionally substituted with a hydroxyl group),; ₁ -C ₂ alkyl refers to the radical) or a saturated or unsaturated 5-or 6-membered heterocycle comprising another hetero atom can form and is selected from

- -COR _'10 group (where, R' ₁₀ represents an optionally substituted 6-membered hydrocarbon ring fused to a C ₆ aryl substituted with one or more C ₁ -C ₂ alkyl radical),

- -SR _'11 group (where, R' ₁₁ represents a C ₁ -C ₂ alkyl radical),

- a halogen atom, preferably selected from chlorine and bromine,

- -O-SO ₂ -C ₆ H ₆ group,

- -SO ₃ H group,

- O, N and NR _'12 , wherein R' ₁₂ represents a C ₁ -C ₂ alkyl group optionally fused to a saturated or unsaturated, aromatic or nonaromatic 5- or 6-membered ring, An unsaturated cationic or non-cationic 5- or 6-membered heterocycle comprising a heteroatom, wherein one of said heteroatoms may be contained within two rings, said heterocycle or fused ring containing one or more C ₁ -C ₂ Which may be substituted by an alkoxy radical,

- the aryl group O, N and NR _'13 (wherein, R' ₁₃ is C ₁ -C ₄ represents an alkyl radical), 1 or 2 cyclic 5-or 6-membered heterocycloalkyl containing heteroatoms selected from the groups Optionally fused, said heterocycle optionally fused to a C ₆ aryl group,

The aryl group is optionally fused to a C ₆ aryl group optionally substituted with one or more C ₁ -C ₂ alkoxy groups;

* Preferably from O, N and NR _'14 (wherein, R' ₁₄ represents a hydrogen atom, (R _{'15) 2} NCO- or (R' ₁₅₎ CO-NH- group (wherein R _'15 are the same or different and can be, it represents a C ₁ -C ₂ alkyl radical) in an optionally substituted C ₆ aryl radical or represents a C ₁ -C ₆ alkyl radical), comprising one or two identical or different heteroatoms selected from cationic or non cationic, saturated or unsaturated, aromatic or non-aromatic 5-or 6-membered heterocyclic group;

Said heterocyclic group is optionally fused to a 6-membered aryl group itself optionally substituted with one or more C ₁ -C ₂ alkyl, C ₁ -C ₄ alkoxy or phenoxy groups;

Said heterocyclic group is optionally substituted at least one of:

a hydroxyl group,

a C ₁ -C ₂ alkyl radical optionally substituted with a hydroxyl radical;

о amino radical -N (R _{'16) 2} (wherein, R' ₁₆ is the same as or may be different and represents a C ₁ -C ₄ alkyl radical optionally substituted by a hydroxyl group, the radicals R _'16 is this together with the nitrogen atom-containing, and optionally O, N and NR _'17 (wherein, R' ₁₇ is C ₁ -C ₂ alkyl refers to the radical) or other heteroatoms, saturated or unsaturated 5-or 6-containing selected from Lt; RTI ID = 0.0 > heterocyclic < / RTI &

о one or more COOH, R _'18 CONH- group (wherein, R' ₁₈ is C ₁ -C ₂ alkyl radical represents a) an optionally substituted C ₆ aryl radicals (wherein the C ₆ aryl radical to the nitrogen atom of the heterocyclic group And when the aryl radical is unsubstituted by the radicals mentioned above, the carbon atom is replaced by a hydrogen atom;

* Linear or branched C _One - C ₁₀ Alkyl Radical, Or one or more conjugated or non-conjugated carbon-carbon double bondsC ₂ - C ₁₀ Alkenyl Radical Wherein said alkyl or alkenyl radical is optionally substituted with one or more hydroxyl groups;

A _divalent radical A ₂ represents a linear C ₁ -C ₁₀ alkylene chain connecting two radicals A ₁ through a carbon, oxygen or nitrogen atom;

If appropriate, the compounds of formulas (i) and (ii) comprise a cosmetically acceptable anion or a mixture of anions An, which ensures the electrical neutrality of the formulation.

Another subject of the present invention is a method of staining human keratin fibers, wherein such compositions are used.

A final subject of the present invention is a pharmaceutical composition comprising a first compartment containing at least one compound of formula (I) and / or (II) or a plant extract comprising the same and at least one compound of formula (i) or (ii) A second compartment containing an oxidized oligosaccharide or polysaccharide comprising an aldehyde or an imine functional group.

The composition according to the invention makes it possible to obtain a variety of shampoo-fast coloring without damaging the hair.

Other features and advantages of the present invention will become more apparent from the following detailed description and examples.

It should be noted that, unless stated otherwise, the limits of the range of values set forth in the detailed description are included within that range.

The human keratin fiber treated through the method according to the invention is preferably hair.

In the following text, the terms "at least one" and "one or more" are considered synonymous.

The inorganic acid salts are more particularly hydrochlorides (hydrochlorides), hydrobromides, sulfates and phosphates; Organic acid salts are more particularly citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates and acetates.

Solvates are more particularly hydrates.

The compounds of formulas (I) and ( II ) Or a plant extract containing the same

As indicated above, the composition comprises, in a cosmetically acceptable medium, one or more compounds of the above-mentioned formula (I) and / or formula (II), or a plant extract comprising the same.

The compounds used in the process according to the invention, and in particular the compounds of formula (I) and / or (II), are characterized in that they have (on an alpha carbon atom with respect to the endocyclic oxygen atom) It should be noted that, unless containing a sugar unit on an oxygen atom, it is referred to as a non-glycosyl.

Preferably, R ₁ is a hydrogen atom, a methyl radical, a hydroxymethyl radical, an aldehyde group; A hydroxycarbonyl radical, a methoxycarbonyl group or an ethoxycarbonyl group.

Preferably, R ₂ represents a hydrogen atom or a hydroxyl radical.

Preferably, R ₃ may be the same or different and represents a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group or an n-butyloxy group.

Preferably, R ₅ represents a hydroxycarbonyl radical, a methoxycarbonyl radical or an ethoxycarbonyl radical.

Preferably, R ₆ represents hydrogen, a hydroxycarbonyl radical, a methoxycarbonyl radical or an ethoxycarbonyl radical.

According to a particularly advantageous embodiment of the invention, the compounds of formula (I) and / or formula (II) are selected from genipin (R ₁ represents methoxycarbonyl group) and / or geniposic acid or (Wherein R ₁ represents a carboxylic acid in an acidic or chlorinated form) and / or genipic acid (R ₅ represents a hydroxycarbonyl radical and R ₆ represents a hydrogen atom) and / or a salt thereof Genipinic acid (R ₅ represents a hydroxycarbonyl radical and R ₆ represents a methoxycarbonyl radical).

The compounds of formula (I) and / or formula (II) are generally found in plant extracts derived from the following plants: Veronica persica ); Genipa americana ) ; Apodytes Dimidiata ); Randia canthioides ); Tarenna attenuata and preferably Genipa < RTI ID = 0.0 > americana ).

It should be noted that the term "extract" means juice or powder obtained from one or more of the following: starting from natural plant material, isolating, enriching and optionally concentrating, and optionally drying the vegetable part of the plant.

These compounds of formula (I) and / or formula (II) are especially extracted from plants in a manner known per se.

In particular the procedure described in international patent application WO 2005/105 020.

Thus, in the case of an aerial part, it is washed, if desired, ground optionally in a frozen form, or minced at room temperature and then macerated in a suitable solvent, in particular ethanol or water, , Concentrated and optionally dried.

In the case of more specific fruids, it is optionally frozen and rinsed with water to remove any impurities present. It may optionally be sterilized using a solution comprising ethanol and chlorine.

For practical extraction, the fruit is defrosted and, if desired, compressed, for example using a particularly suitable hydraulic press. The juice thus recovered is filtered and degassed in the presence of nitrogen. This operation increases the amount of dissolved gas to prevent oxidation of the zenith pin or its derivative.

The juice is then stored in a hermetically sealed packaging container.

Thereafter, if appropriate, the recovered juice is concentrated and dried.

According to a preferred embodiment of the present invention, the extract used is < RTI ID = 0.0 > Genipa < / RTI > americana . In this case, the extract was obtained from Genipa americana ) of less ripe fruit. The first step in the preparation of the extract consists of first freezing the fruit and then freezing the frozen fruit at a temperature of, for example, -20 캜 to -200 캜. Thus, a fine and uniform powder is collected.

In carrying out the above operation, the active agent (s) of formula (I) and / or (II) are extracted using, for example, water. The extract is then concentrated and optionally dried.

The content of the compound of formula (I) and / or the compound of formula (II) in the dry extract ranges from 0.01% to 30% by weight.

The content of the compound of the formula (I) and / or the compound of the formula (II) in the composition is 0.001 to 20% by weight, in proportion to the weight of the composition.

Additional dyes

The dye composition may also contain, in addition to the above-mentioned compounds of formula (I) and / or formula (II), additional dyes.

Of these additional dyes, mention may be made of natural or synthetic direct dyes, oxidation dyes having bases optionally combined with couplers, and also combinations thereof.

The direct dyes are, for example, neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinones and in particular anthraquinone dyes, Dyes, triarylmethane direct dyes, indoline amine direct dyes and natural direct dyes.

Among the above natural direct dyes, it is possible to use any one of lawsones, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, Anthragallol protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, chlorophyll, chlorophyllin, Orcein, hematin, hematoxylin, brazilin, brazileine, safflower pigments (e.g. carthamine), flavonoids (e. G. (Including, for example, morin, apigenidines and sandalwood), anthocyanins (such as apigeninidin), carnenoids, tannins, sorghum and cochineal carmine or mixtures thereof have. Extracts or decoctions containing such natural dyes and especially henna based poultices or extracts may also be used.

Among the above oxidation bases, mention may be made of para-phenylenediamine, bis (phenyl) alkylenediamine, para-aminophenol, bis-para-aminophenol, ortho-aminophenol and heterocyclic bases, and addition salts thereof .

Among these linking groups, mention may be made in particular of meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene linking and heterocyclic linking groups, and addition salts thereof.

The oxidizing base (s) present in the dye composition are each present in an amount of from 0.001% to 10% by weight and preferably from 0.005% to 6% by weight, generally proportional to the total weight of the dye composition.

The coupler (s) are each present in an amount of from 0.001% to 10% by weight and preferably from 0.005% to 6% by weight, generally proportional to the total weight of the dye composition.

In general, the addition salts of oxidizing bases and linking groups that can be used in the context of the present invention include, in particular, addition salts with acids such as hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, Benzene sulfonates, phosphates and acetates.

Aldehyde / imine compound

As indicated above, the composition also comprises at least one aldehyde or imine compound selected from the above-mentioned formulas (i) and (ii), and also oxidized oligosaccharides or polysaccharides comprising at least one aldehyde or imine functional group.

According to the first variant of the present invention, the compounds of formulas (i) and (ii) are compounds in which X represents an oxygen atom.

Compound (i) and (ii) is also an additional primary monoalcohol (R _'3 OH) (wherein, R' ₃ is symmetrical containing ₃ alkyl chain C ₁ -C ₅ alkyl radical or a C ₂ -C 1, 2-or 1,3-diol) of 5-or 6-membered cyclic or bicyclic acetals.

The compounds may also be in the A or A ₁ represents a case of an alkyl radical, n is 0, A or in the form of a hemiacetal obtained by condensation of the hydroxyl groups present on the A _1.

It should be noted that the electrical neutrality of the formulas (i) and (ii) is confirmed by a mixture of organic or inorganic anions or anions, which, if desired, can balance the charge (s) For example, halides such as chlorides, bromides, fluorides or iodides; hydroxide; sulfate; Hydrogen peroxide; Alkyl sulfate (wherein the linear or branched alkyl moiety is C ₁ -C ₆ ), such as methyl sulfate or ethyl sulfate ions; Carbonate and bicarbonate; Salts of carboxylic acids such as formate, acetate, citrate, tartrate and oxalate; Alkyl sulfonates wherein the linear or branched alkyl moieties are C ₁ -C ₆ , such as methylsulfonate ions; Arylsulfonates wherein the aryl moiety, preferably phenyl, is optionally substituted with one or more C ₁ -C ₄ alkyl radicals, such as 4-tolylsulfonate; And alkyl sulfonates such as mesylate.

The nonionic or anionic oxidizing polysaccharide comprises at least one aldehyde group and optionally at least one anionic group. The anionic group is preferably a carboxyl group or a carboxylate group.

The nonionic or anionic oxidative polysaccharide used may be represented by the formula (I)

P- (CHO) m (COOX) n (I)

[Wherein,

P represents a polysaccharide chain composed of a monosaccharide having 5 or more carbon atoms, preferably 6 or more carbon atoms and more particularly 6 carbon atoms,

X is a hydrogen atom, an alkali metal or alkaline earth metal such as sodium or potassium, ammonia, organic amines such as monoethanolamine, diethanolamine, triethanolamine and 3-amino-1,2-propanediol and basic amino acids such as lysine, Arginine, sarcosine, ornithine, and citrulline.

m + n is 1 or more,

m is the degree of substitution (DS (CHO)) of the polysaccharide having at least one aldehyde group within the range of from 0.001 to 2, and preferably from 0.005 to 1.5,

and n is the degree of substitution (DS (COOX)) of the polysaccharide having at least one carboxyl group within the range of 0 to 2 and preferably in the range of 0.001 to 1.5.

The term "substitution degree DS (CHO) or DS (COOX) of the polysaccharide according to the present invention" means the number of carbon atoms oxidized as an aldehyde or carboxyl group for all the repeating units and the basic monosaccharide constituting the polysaccharide (opening by preoxidation) Lt; / RTI >

The CHO and COOX groups can be obtained, for example, during the oxidation of certain carbon atoms at the C2, C3 or C6 position of a saccharide unit of 6 carbon atoms. Preferably, oxidation can occur at C2 and C3, more particularly at 0.01% to 75% and preferably at 0.1% to 50% of the number of rings that can be opened.

The polysaccharide chain is preferably selected from the group consisting of inulin, cellulose, starch, pectin, guar gum, xanthan gum, pullulan gum, alginate gum, agar-agar gum, carrageenan gum, gellan gums, , Gum arabic, xylose and tragacanth gum, and derivatives thereof.

The term "derivative" means a compound obtained by chemical modification of the above-mentioned compounds. This may be an ester, an amide or an ether of the compound.

Oxidation can be carried out according to methods known in the art, for example in FR 2 842 200, FR 2 854 161 or in the literature ["Hydrophobic films from maize bran hemicelluloses" by E. Fredon et al., Carbohydrate Polymers 49, 2002, pages 1 - 12]. ≪ / RTI > Another oxidation method is described in the article "Water soluble oxidized starches by peroxide reaction extrusion" Industrial Crops and Products 75 (1997) 45-52 - R. E. Wing, J. L. Willet. The oxidation process is simple, efficient, and does not produce any toxic by-products or by-products that are difficult to remove.

The peroxide may be an alkali or alkaline earth metal and a carbonate or perborate, an alkyl peroxide, peracetic acid or hydrogen peroxide. The amount of peroxide in the reaction medium is generally from 0.05 to 1 molar equivalents per glucose unit of the polysaccharide.

Mixtures of single phthalocyanines or phthalocyanines, for example mixtures of cobalt phthalocyanine and iron phthalocyanine, can be used as catalysts. The amount of catalyst depends on the desired degree of substitution. Generally, small amounts, e. G., Amounts corresponding to 0.003 to 0.016 mole equivalents per 100 glucose units of polysaccharide are suitable for use.

The method may also be carried out by contacting the polysaccharide in powder form with a catalyst and peroxide dissolved in a small amount of water. The process is referred to as a "semi-dry" process.

More preferably, the polysaccharide is selected from the group consisting of inulin, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, starch, starch acetate, hydroxyethyl starch, hydroxypropyl starch, Is obtained by oxidation of carboxymethyl cellulose, guar gum, carboxymethyl guar gum, carboxymethyl hydroxypropyl guar gum, hydroxyethyl guar gum, hydroxypropyl guar gum, xylose, xanthan gum or carrageenan gum, or mixtures thereof.

Most particularly preferred polysaccharides in the present invention correspond to formula (I) wherein P represents a polymer chain derived from inulin and starch; m is the degree of substitution (DS (CHO)) of the polysaccharide having at least one aldehyde group within the range of 0.005 to 2.5; and n is the degree of substitution (DS (COOX)) of the polysaccharide having at least one carboxyl group within the range of 0.001 to 2.

Examples of oxidized oligosaccharides and polysaccharides comprising one or more compounds of formulas (i) and (ii), especially one or more aldehyde or imine functional groups, which are particularly suited for the practice of the present invention include the following compounds, their salts, isomers and their solvates , And these compounds exist singly or as a mixture:

Preferably, the composition comprises at least one compound of formula (i).

Advantageously, the formula (i) is as follows:

* m is 0 or 1;

The radicals R ' ₁ and R' ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl radical;

* X represents an oxygen atom;

A represents:

* Optionally substituted with one or more hydroxyl groups, linear or branched C ₅ - C ₁₀ Alkyl Radical ;

A C ₂ -C ₈ alkenyl radical containing a carbon-carbon double bond;

A hydroxycarbonyl group (-COOH);

* At least optionally substituted C ₆ Aryl group :

a hydroxyl group,

a C ₁ -C ₄ alkyl radical,

-CO-OR ' ₄ or -O-COR' ₄ group (wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical),

o -OR ' ₅ group (wherein R' ₅ represents a C ₁ -C ₆ alkyl radical),

aryl-ethylenyl radical, wherein the aryl group is C ₆ , optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals,

O, N and NR _'12 , wherein R' ₁₂ represents a C ₁ -C ₂ alkyl group optionally fused to a saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered ring, An unsaturated cationic or non-cationic 5- or 6-membered heterocycle comprising a heteroatom, wherein one of said heteroatoms may be contained within two rings, said heterocycle or fused ring containing one or more C ₁ -C ₂ Which may be substituted by an alkoxy radical,

- the aryl group O, N and NR _'13 (wherein, R' ₁₃ is C ₁ -C ₄ represents an alkyl radical), 1 or 2 cyclic 5-or 6-membered heterocycloalkyl containing heteroatoms selected from the groups Optionally fused;

* Preferably from O, N and NR _'14 (wherein, R' ₁₄ represents a hydrogen atom, (R _{'15) 2} NCO- or (R' ₁₅₎ CO-NH- group (wherein, R _'15 is C ₁ - represents a C ₂ alkyl radical) in an optionally substituted C ₆ aryl radical or a C ₁ -C ₆ alkyl refers to the radical) containing 1 or 2 identical or different heteroatoms selected from cationic or non-cationic, saturated Or an unsaturated , aromatic or non-aromatic 5- or 6-membered heterocyclic group ;

Said heterocyclic group is optionally fused to a 6-membered aryl group itself optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₄ alkoxy groups;

Said heterocyclic group is optionally substituted at least one of:

a hydroxyl group,

a C ₁ -C ₂ alkyl radical optionally substituted with a hydroxyl radical,

о amino radical -N (R _{'16) 2} (wherein, R' ₁₆ is the same as or may be different and represents a C ₁ -C ₄ alkyl radical optionally substituted by a hydroxyl group, the radicals R _'16 is this together with the nitrogen atom-containing, and optionally O, N and NR _'17 (wherein, R' ₁₇ is C ₁ -C ₂ alkyl refers to the radical) or other heteroatoms, saturated or unsaturated 5-or 6-containing selected from Lt; RTI ID = 0.0 > heterocyclic < / RTI &

If appropriate, the compound of formula (i) comprises a cosmetically acceptable anion or mixture of anions An, which ensures electrical neutrality of the formulation;

The compound (s) of formula (i) may be in the form of an acetal or hemiacetal as described above.

As preferred examples of the compound (i), the following compounds, isomers thereof, salts thereof or solvates thereof may be mentioned, and these compounds may be present singly or as a mixture:

More particularly, the content of the oxidized oligosaccharide or polysaccharide comprising compound (s) of formula (i) or (ii), or one or more aldehyde or imine functional groups, is from 0.001% to 30% by weight,

As examples of preferred oxidized oligosaccharides or polysaccharides, the following compounds may be mentioned:

- oxidized starch (Rn 9047-50-1), starch known under the trade name Caldas 10; Caldas 5; Caldas 5H; Caldas 5S; Caldas C 5; Caldas C 5GP; Caldas C 5GT; Caldas No. 5; DAS 100; Dialdehyde starch; Dialdehydostarch; Formamyl; Periodate starch; Polyaldehyde starch; Starch dialdehyde; Sumstar; Sumstar 150; Sumstar 190;

Cellulose oxide (Rn 9032-52-4), known under the name: 2,3-Dialdehyde cellulose; 2,3-Dialdehydocellulose; Aldehydocellulose; Cellulose 2,3-dialdehyde; Cellulose dialdehyde; Dialdehyde cellulose;

- oxidized inulin (Rn 82446-43-3);

- dextranaldehyde (Rn 37317-99-0).

Amine

According to one embodiment of the present invention, the composition may comprise one or more primary or secondary amines or addition salts thereof, ammonia or hydroxylamine, or mixtures thereof.

In general, such addition salts of amine compounds which can be used in the context of the present invention are those which are obtained by addition of an acid addition salt such as a hydrochloride, hydrobromide, sulphate, citrate, succinate, tartrate, lactate, Benzenesulfonate, dodecylbenzenesulfonate, phosphates and acetates, and preferably hydrochloride, citrate, succinate, tartrate, phosphate and lactate.

In particular, the primary or secondary amine (s) that can be used in the context of the present invention are selected from amines, amino polymers, purine bases, and also addition salts thereof of formula (III) as described in detail below and combinations thereof.

In particular, the formula (III) is as follows:

R ' _7R ' ₈ NH (III)

Wherein, in formula (III), R ' ₇ and R' ₈ independently of one another denote:

- a hydrogen atom;

- one or more groups which may contain from 1 to 5 carbon-carbon double bonds and / or which may optionally be substituted and which optionally contain one or more heteroatoms and / or one or more heteroatoms or groups comprising one or more heteroatoms Branched and / or cyclic, saturated and / or unsaturated, aromatic (preferably selected from oxygen, nitrogen, sulfur, C = O, C = S, SO and SO ₂ or combinations thereof) Or non-aromatic C ₁ -C ₂₀ hydrocarbon radicals; Wherein said hydrocarbon radicals R ' ₇ and R' ₈ together with the nitrogen atom to which they are attached are optionally substituted and optionally aromatic and optionally substituted by a 6-membered aromatic or heteroaromatic ring containing another nitrogen or non- Form a saturated or unsaturated 5- or 7-membered heterocycle fused to a heteroaromatic nucleus; The hydrocarbon radical does not include any nitro, nitroso, peroxo or diazo functional groups.

The compound of formula (III) is advantageously not an oxidizing base or an oxidizing linkage group used for dyeing keratin fibers.

Among the groups present as substituents of the heterocyclic hydrocarbon group, the following groups may be mentioned:

The carboxyl, sulfone, phosphone,

Hydroxyl, C ₁ -C ₄ alkoxy, (C ₁ -C ₈ ) alkoxycarbonyl,

(C ₁ -C ₄ ) alkylsulfonate, (C ₁ -C ₈ ) alkylphosphonate,

Tree (C ₁ -C ₄₎ alkylsilyl, tri (C ₁ -C ₄₎ alkoxy carbonyl silanol,

Amino, (di) (C ₁ -C ₄ ) alkylamino, tri (C ₁ -C ₄ ) alkylammonium,

Thiol, (C ₁ -C ₄₎ alkylthio,

Aminosulfonyl, (di) (C ₁ -C ₄ ) alkylaminosulfonyl,

Aminocarbonyl, (di) (C ₁ -C ₄ ) alkylaminocarbonyl,

(C ₁ -C ₄ ) alkylcarbonylamino,

Guanidine,

Ureido _{(N (R) 2 -CO-} NR'-) ( where the radicals R and R 'are, independently of each other, hydrogen atom or C ₁ -C ₄ alkyl or (C ₁ -C ₄₎ alkylsulfonylamino Radicals);

Phenyl, indolyl, pyrrolyl, imidazolyl optionally substituted with one or more C ₁ -C ₂ alkyl or hydroxyl.

Preferably, the groups present as substituents are selected from the following groups: carboxyl in the acidic or chlorinated form; Hydroxyl; C ₁ -C ₄ alkoxy; (C ₁ -C ₈₎ alkoxycarbonyl; Thiol; (C ₁ -C ₄₎ alkylthio; Amino; Mono- and di (C ₁ -C ₄₎ alkylamino; Aminocarbonyl; Mono- and di (C ₁ -C ₂₎ alkyl-aminocarbonyl; (C ₁ -C ₄₎ alkylcarbonylamino; Phenyl, indolyl, pyrrolinyl, imidazolyl optionally substituted with one or more C ₁ -C ₂ alkyl or hydroxyl.

In particular, the amine (s) of formula (III) may be the same or different and comprise from 1 to 5 primary and / or secondary amine functionalities; The amine (s) do not contain any N-N bonds. In addition, the amine (s) of formula (III) do not include two or more heteroatoms bonded together.

Preferably, the amine (s) is a compound of formula (III), more particularly a compound of formula (IIIa) to (IIIi), and further addition salts thereof.

Amino acids and / or derivatives of formula ( IIIa ):

In the formula (IIIa):

- R ₉ is a linear or branched C ₁ -C ₆ substituted by a hydrogen atom, preferably with one or more hydroxyl, hydroxycarbonyl, thiol, (C ₁ -C ₄ ) alkylthio, amido, amino or guanidine group An alkyl radical, a phenyl radical optionally substituted by one or more hydroxyl, an indolyl radical optionally substituted by one or more hydroxyl, an imidazolyl radical, a pyrrolinyl radical optionally substituted by a C ₁ -C ₂ alkyl group; Or an unsubstituted phenyl radical;

- R _"9 is hydrogen, C ₁ -C ₄ alkyl radical or unsubstituted represents the unsubstituted phenyl radical;

R ₁₀ represents hydrogen or a C ₁ -C ₄ alkyl radical;

-R " ₉ and R ₉ , together with the nitrogen atom to which they are attached, may form a saturated 5- or 6-membered heterocycle.

Examples of compounds of formula (IIIa) that may be mentioned most particularly include asparagine, cysteine, glutamine, histidine, lysine, methionine, phenylalanine, proline, pyrrolizine, serine, threonine, tryptophan and tyrosine, .

According to another variant, the compound of formula (IIIa) is advantageously 2-amino-2-methylpropanoic acid; alpha -methyl-D, L-phenylalanine; D, L-? - (hydroxymethyl) alanine; D, L- alpha -methyl-meta-tyrosine; alpha -methyl-D, L-tryptophan; D, L-? - methylhistidine dihydrochloride; L-2-methylserine; (S) -2-methylcysteine dihydrochloride; (S) -2-methyl-2-pyrrolidinecarboxylic acid.

o from the amino acid of formula ( IIIb ) Derived esters and / or derivatives:

In formula (IIIb):

- R ₉ is a hydrogen atom, preferably one or more hydroxyl, hydroxycarbonyl, (C ₁ -C ₄ ) alkoxycarbonyl, thiol, (C ₁ -C ₄ ) alkylthio, amido, amino or guanidine group A substituted or unsubstituted linear or branched C ₁ -C ₆ alkyl radical, a phenyl radical optionally substituted with one or more hydroxyl, an indolyl radical optionally substituted with one or more hydroxyl, an imidazolyl radical, a C ₁ -C ₂ alkyl group, Substituted pyrrolinyl radicals; Or an unsubstituted phenyl radical;

- R _"9 is hydrogen, C ₁ -C ₄ alkyl radical or unsubstituted represents the unsubstituted phenyl radical;

R ₁₀ represents hydrogen or a C ₁ -C ₄ alkyl radical;

- R _"9 and R ₉ may, together with the nitrogen atom to which they are attached, may form a saturated 5- or 6-membered heterocycle.

- R ₁₁ represents:

Optionally containing 1 to 5 conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as indicated above, optionally substituted with one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, C = Linear or branched, saturated or unsaturated C ₁ -C ₁₈ hydrocarbon radical in which one or more groups comprising at least one heteroatom selected from S, SO and SO ₂ or a combination thereof is interrupted, wherein said alkyl radical is any nitro, nitro, Nor contain peroxo or diazo functional groups;

- unsubstituted benzyl radical.

According to one particular variation, R ₉ and R ₁₁ may optionally form a saturated 5-membered carbon-based ring.

Preferably, R ₁₁ is a linear or branched, optionally substituted C ₁ -C ₁₀ alkyl radical; Benzyl radical; And even more preferably a linear or branched C ₁ -C ₄ alkyl radical optionally substituted with one or more hydroxyl groups, preferably one to two hydroxyl groups; Benzyl radical.

As examples of the formula (IIIb), methoxytrosine, 2-ethylpiperidine carboxylate; D, L-phenylalanine methyl ester; L-cysteine dimethyl ester dihydrochloride; L-leucine methyl ester; Methyl 2-amino-3-methylbutyrate; L-phenylalanine ethyl ester hydrochloride; L-glutamic acid diethyl ester hydrochloride; Ethyl (S) -2-amino-3-methylbutanoate hydrochloride; D, L-serine methyl ester hydrochloride; Tyrosine methyl ester hydrochloride; L-cysteine ethyl ester hydrochloride; L-histidine methyl ester hydrochloride; Methyl (S) -pyrrolidine-2-carboxylate hydrochloride; Methyl 2-aminoacetate hydrobromide; Ethyl glycine; H-D, L-alanine ethyl ester hydrochloride; D, L-tyrosine ethyl ester hydrochloride; Methyl 2- (phenylamino) acetate; Ethyl glutamate; Bis (?,? - tert-butyl) D, L-aspartate hydrochloride; Ethyl L- alpha -aminoisocaproate hydrochloride; Benzyl glycinate para-toluenesulfonate; D, L-alanine ethyl ester hydrochloride; 5-hydroxy-D, L-tryptophan methyl ester hydrochloride; D, L-threonine methyl ester hydrochloride; D, L-proline tert-butyl ester; D, L-phenylalanine methyl ester hydrochloride can be mentioned.

amides and thioesters and / or derivatives derived from the amino acids of formula ( IIIc ) :

In formula (IIIc):

- R ₉ is a hydrogen atom, preferably one or more hydroxyl, (C ₁ -C ₄ ) alkoxycarbonyl, hydroxycarbonyl, thiol, (C ₁ -C ₄ ) alkylthio, amido, amino or guanidine group A substituted or unsubstituted linear or branched C ₁ -C ₆ alkyl radical, a phenyl radical optionally substituted with one or more hydroxyl, an indolyl radical optionally substituted with one or more hydroxyl, an imidazolyl radical, a C ₁ -C ₂ alkyl group, A substituted pyrrolinyl radical;

R " ₉ represents a C ₁ -C ₄ alkyl radical optionally substituted with hydrogen or a hydroxysulfonyl radical;

R ₁₀ represents hydrogen or a C ₁ -C ₄ alkyl radical;

- R _"9 and R ₉ may, together with the nitrogen atom to which they are attached, may form a saturated 5-membered heterocycle;

- R ₁₂ represents -

A hydrogen atom;

Preferably a C ₁ -C ₆ alkyl radical substituted with one or more hydroxyl, thiol, (C ₁ -C ₄ ) alkylthio, amido or amino, a phenyl radical optionally substituted with one or more hydroxyl, Indolyl radicals optionally substituted with hydroxyl, imidazolyl radicals, pyrrolinyl radicals optionally substituted with C ₁ -C ₂ alkyl groups;

- X represents a sulfur or nitrogen atom.

According to one particular variation, R ₉ and R ₁₂ may optionally form a saturated 5-, 6- or 7-membered carbon-based ring.

Wherein X is a nitrogen atom and R ₁₂ is an alkyl radical as defined above and most particularly an alkyl radical as defined above and most especially an alkyl radical as defined above and an aryl radical as defined above, The compound of formula (IIIc) represents a dipeptide or an oligopeptide when the amino acid residue is an amino acid residue selected from the group consisting of glucose, serine, threonine, tryptophan, tyrosine, valine, leucine or isoleucine and / or its corresponding methyl or ethyl ester.

As examples of the compound of the formula (IIIc), 3-amino dihydrothiophen-2-one hydrochloride; D, L-homocysteine thiolactone; D, L-leucyl-D, L-alanine, aspartame; (S) -pyrrolidine-2-carboxamide; [N - (- acetamido)] - 2-aminoethanesulfonic acid; D, L-alanyl-D, L-phenylalanine; 2- (2-aminoacetamido) -3- (4-hydroxyphenyl) propanoic acid; 2- (2-aminoacetylamino) acetic acid; (R) -3-aminoazepan-2-one; Glycine amide hydrochloride; L-leucine amide hydrochloride; 2-aminopropanediamide; 2- (2-amino-3-methylbutanamido) propanoic acid; L-tyrosyl-L-alanine; L-valyl-L-phenylalanine; Sarcosyl-L-phenylalanine; L-tyrosyl- beta -alanine; Glycyl-L-proline; Glycyl-D, L-valine; 2-aminomalonamide; L-methionamide hydrochloride; 2-amino-3-methylbutanamide; D-alaninamide hydrochloride; L-tyrosinamide hydrobromide; Aspartic acid amide; L-tyrosine amide hydrochloride; L-argininamide dihydrochloride; Lysine amide dihydrochloride; Threonamide hydrochloride; Isoleucine amide hydrochloride; Histidine amide dihydrochloride; D, L-alaninamide hydrochloride; 2-Amino-3- (4-hydroxyphenyl) propionamide; D, L-tryptophanamide hydrochloride; N-hydroxy-L-arginine acetate (H-ARG-NH2 2 AcOH); Asparagine amide hydrochloride; L-glutamic acid?,? - diamide hydrochloride; D-phenylalanine amide; D-leucine amide hydrochloride; L-glutamic acid? -Amide; L-methionine amide; L-cysteine bisamide hydrochloride; Glycine amide acetate; D-lysine amide dihydrochloride; Glycine amide; L-isoglutamine gamma-methyl ester hydrochloride; D-argininamide dihydrochloride; (S) -pyrrolidine-2-carboxamide; Porphyryl histamine hydrochloride can be mentioned.

- Amino compound of formula ( IIId ) :

In formula (IIId):

- R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ independently of one another represent:

A hydrogen atom;

Optionally containing 1 to 5 optionally aromatic carbon-carbon double bonds, optionally substituted as indicated above, optionally substituted with one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, C = S, SO and SO _2, or it is inserted into at least one group containing one or more heteroatoms selected from combinations thereof, optionally containing a one or more hydroxyl or C ₁ -C ₂ alkoxy, linear, branched and / or cyclic, saturated And / or an unsaturated C ₁ -C ₂₀ hydrocarbon radical, wherein said radicals R ₁₃ and R ₁₄ or R ₁₄ and R ₁₅ or R ₁₅ and R ₁₆ , together with the carbon atom to which they are attached are optionally substituted as indicated above , Optionally saturated or unsaturated 5- or 7-membered heterocycle containing another nitrogen or non-nitrogen heteroatom, said alkyl radical being optionally aromatic, Nor include nitro, nitro, peroxo or diazo functional groups; More particularly an optionally substituted C ₁ -C ₁₀ alkyl radical; And preferably a linear or branched C ₁ -C ₈ alkyl radical optionally substituted with one or more hydroxyl groups, preferably one or two hydroxyl groups, a hydroxycarbonyl radical, a ureido radical, (C ₁ - C ₄ ) alkoxycarbonyl radical; Unsubstituted phenyl radical;

X represents a nitrogen, oxygen or sulfur atom;

- R < ₁₇ > represents -

A hydrogen atom;

Optionally containing 1 to 5 conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as indicated above, optionally substituted with one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, A linear or branched, saturated or unsaturated C ₁ -C ₁₈ hydrocarbon radical in which one or more groups comprising at least one heteroatom selected from SO and SO ₂ or a combination thereof is interrupted, wherein said alkyl radical is any nitro, nitroso, More particularly, R ₁₇ represents hydrogen, an optionally substituted linear or branched C ₁ -C ₁₀ alkyl radical; And preferably a hydrogen atom, a linear or branched C ₁ -C ₄ alkyl radical optionally substituted with one or more hydroxyl groups, preferably one to two hydroxyl groups;

- R < ₁₈ > represents -

A hydrogen atom;

One optionally substituted as indicated above and optionally containing one or more heteroatoms and / or one or more heteroatoms selected from oxygen, nitrogen, sulfur, CO, C = S, SO and SO ₂ or combinations thereof A linear or branched C ₁ -C ₈ alkyl radical wherein said radical is interrupted and optionally containing one or more hydroxyl or C ₁ -C ₂ alkoxy groups wherein said alkyl radical has any of the nitro, nitroso, peroxo or diazo functional groups Not included);

- o is an integer from 0 to 5;

According to a further variant of the invention the radicals R ₁₆ and R ₁₇ are optionally substituted, as indicated above, optionally together with the carbon atom attached to R ₁₆ and the X atom attached to the radical R ₁₇ , , Optionally form another saturated or unsaturated 5- or 6-membered heterocycle containing another nitrogen or non-nitrogen heteroatom.

According to a further variant of the invention, the radicals R ₁₈ and R ₁₅ , together with the nitrogen atom attached to R ₁₈ and the carbon atom attached to the radical R ₁₅ , respectively, are optionally substituted as indicated above and are optionally aromatic , Optionally form another saturated or unsaturated 5- or 6-membered heterocycle containing another nitrogen or non-nitrogen heteroatom.

As examples of the compound of formula (IIId), L-2-aminohexanoic acid amide hydrochloride; L-phenylalanine amide; (S) - (+) - aminosuccinic acid; (R) -2- (methylamino) succinic acid; Ethylnipecotate; 3-piperidinecarboxylic acid; 3-phenyl-beta-alanine; Ethyl 3-aminobutyrate; 2-carbonylamine; D, L- [beta] -amino adipic acid; β-alanine ethyl ester hydrochloride; Ethyl 3-amino-3-ureido-N-butyrate; Dimethyl (S) -aminosuccinate hydrochloride; β-L-alanine methyl ester hydrochloride; 4-carboxyethoxypiperidine; 4-aminobutyric acid; D, L- [beta] -amino adipic acid; 4- (methylamino) butyric acid hydrochloride; Ethyl? -Aminobutyrate hydrochloride; Hexahydro nicotinamide; Piperidine-4-carboxamide; 3-Carbamoyl-2,2,5,5-tetramethylpyrrolidine can be mentioned.

- Amino compound of formula ( IIIe ):

In the formula (IIIe):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as above;

- R < ₁₉ > represents -

A hydrogen atom;

One optionally substituted as indicated above and optionally containing one or more heteroatoms and / or one or more heteroatoms selected from oxygen, nitrogen, sulfur, CO, C = S, SO and SO ₂ or combinations thereof A linear or branched C ₁ -C ₈ alkyl radical wherein said radical is interrupted and optionally containing one or more hydroxyl or C ₁ -C ₂ alkoxy groups wherein said alkyl radical has any of the nitro, nitroso, peroxo or diazo functional groups Not included);

p is an integer from 0 to 7;

u is an integer of 1 or 2, and when u is 2, the radical R < ₁₈ > represents hydrogen.

According to a further variant of the invention, the radicals R ₁₃ and R ₁₄ , optionally together with the carbon atoms of the substituents R ₁₃ and R ₁₄ , may form a saturated 5- or 6-membered heterocycle.

As examples of the compound (IIIe), the following acids, their enantiomers, if any, and their salts and their hydrates can be mentioned: (1-aminoethyl) phosphonic acid, (aminomethyl) (1-aminopropyl) phosphonic acid, (1-aminobutyl) phosphonic acid, iminovis (methylphosphonic acid), (1-amino- (1-amino-3-methylbutyl) phosphonic acid, 1-aminobenzylphosphonic acid, 1-amino (Aminomethylen) bisphosphonic acid (especially its salt), (1-amino-2,2-dimethylpropyl) phosphonic acid, N, N'-dicyclohexylphosphonic acid, (1-amino-2-methylbutyl) phosphonic acid, (1-aminooctyl) phosphonic acid, (1-amino-1-methylpropyl) phosphonic acid, , (1-amino-1, 3-dimethylbutyl) phosphonic acid, (1-amino- (1-amino-1-methylethyl) phosphonic acid, 1-amino-2-methylbutylphosphonic acid, 1-phosphono-2- Aminopropylphosphonic acid, 2-amino-2-methyl-4-phosphonobutanoic acid and its ethyl ester, (diethyl (3-aminopropyl) phosphonic acid Amino-2-methyl-4-phosphonobutyric acid, diethyl (3-aminopropyl) phosphonate, 2-amino- (2 - ((2-aminoethyl) phosphonic acid, 2-aminoethylphosphonic acid, 2-aminoethylphosphoric acid, - < / RTI > pyrrolidinylcarbonyl) amino) ethyl) phosphine Di (2-amino-2-phenyl) ethylphosphonate, and / or mixtures thereof.

- Amino compound of general formula ( IIIf ):

In the formula (IIIf):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as above and the radicals R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ independently of one another are a hydroxyalkyl radical, (C ₁ -C ₄ ) alkoxycarbonyl radical, a carboxaldehyde radical, (C ₁ -C ₃ ) alkoxy;

q is an integer from 1 to 18;

X represents an oxygen atom, a SH or OH group, or a methylene group optionally substituted by a hydroxyl radical;

When X is an oxygen atom, R ₁₈ forms a 5- or 6-membered ring optionally substituted with one or more hydroxy (methyl), preferably 1 to 4 hydroxy (methyl) groups.

According to a further variant of the invention, the radicals R ₁₆ and R ₁₈ or R ₁₃ and R ₁₈ optionally together with the carbon atom attached to R ₁₆ (or to R ₁₃ ) and the nitrogen atom attached to the radical R ₁₈ , , Optionally substituted as indicated above, optionally aromatic, and optionally a further nitrogen or non-nitrogen heteroatom, may form a 5- or 6-membered heterocycle.

According to another variant of the invention, the amine of the formula (IIIf) can be a? -Aminoalcohol derived from the reduction of one of the 20 esterified or non-esterified amino acids of the acid or ester functional group with an alcohol have.

As examples of the compound (IIIf), the following compounds, enantiomers thereof, if any, and salts thereof and hydrates thereof can be mentioned: isopropanolamine, isopropylamine, methylethanolamine, methylglucamine, stearamine, Amino-1-phenylpropane-1, 3-diol, 1,3-dihydroxypropane, 1,3-dimethylpentylamine, octadrine, spermidine, theanine, octamethylamine, 2-methylpropane, 2-amino-2- (hydroxymethyl) propane-1,3-diol tris, 2-amino-1,3-dihydroxy- 2-methylpropan-1-ol, phenylglycinol, 2-aminopropanol, 2-hydroxyethylamine, 2-aminohexan-1-ol, 1 Amino-1-cyclopentanemethanol, histidinol, 2-amino-3- (3-indolyl) propanol, 3- (4-hydroxyphenyl) , 2-amino-1-propanol, 2-amino-1 Amino-3-methyl-1-butanol,? -Aminobenzenepropanol, 2-aminopropane-1-ol, 2-amino- Amino-4-methylpentan-1-ol, 3-aminopropane thiol, ethyl 2-amino-4-mercaptobutanoate, 6-hydroxyhexylamine, Amino-1-deoxy-D-fructose, D-glucosamine, 2-pyrrolidine Propanol amine, 3 - [(2-hydroxyethyl) amino] propan-1-ol, di- beta -hydroethylamine, bis N-propanolamine, 4-amino-N-butanol, methyl 3-amino-3-deoxy- alpha -D-mannopyranoside, N-butyl Heptanediol, 1-hexylamine, 1-octylamine, 1-nonylamine, 1-decylamine, 1-ethylhexylamine, For example, Amino-2-hydroxy-4-phenylbutanoic acid, 4-amino-3-hydroxybutyric acid, ethyl 4- Hydroxy-2-pyrrolidinecarboxylate, and mixtures thereof.

- Amino compound of formula ( IIIg ):

[In the formula (IIIg):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as above;

- R < ₂₀ > represents -

Linear C ₁ -C ₄ alkyl radicals,

A linear C ₁ -C ₄ alkoxy radical,

o is an integer from 0 to 5,

- v is an integer of 1 or 2, and when v is 2, R < ₁₈ > represents hydrogen.

Examples of the compound (IIIg) include aminopropyltriethoxysilane, (aminomethyl) trimethylsilane, 2- (trimethylsilyl) ethanamine, 3- (trimethylsilyl) propan- (Trimethylsilyl) propylamine, 3- (trimethoxysilyl) propylamine, 3-triethoxysilyl-1-propanamine and (3- Aminopropyl) trimethoxysilane, and mixtures thereof.

o Amino compounds of formula ( IIIh ):

[In the formula (IIIh):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meanings as defined above and the radicals R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ independently of one another are hydroxyl radicals, (C ₁ -C ₄ ) alkoxycarbonyl radical, a carboxaldehyde radical, (C ₁ -C ₃ ) alkoxy;

- R < ₂₁ & R < ₂₂ > independently of one another represent:

A hydrogen atom;

Optionally substituted with one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, C = S, SO and SO, optionally substituted as indicated above, _2, or it is inserted into at least one group containing one or more heteroatoms selected from combinations thereof, optionally containing a one or more hydroxyl or C ₁ -C ₂ alkoxy, linear, branched and / or cyclic, saturated and / or Unsaturated C ₁ -C ₂₀ hydrocarbon radicals, more particularly optionally substituted C ₁ -C ₁₀ alkyl radicals; And preferably a linear or branched C ₁ -C ₄ alkyl radical optionally substituted with one or more hydroxyl groups, preferably one to two hydroxyl groups;

R ₂₁ and R ₂₂ together with the nitrogen atom to which they are attached form a saturated or unsaturated 5- to 7-membered ring optionally substituted as indicated above and optionally further aromatic or optionally further nitrogen or non-nitrogen heteroatom Lt; / RTI > may form a heterocycle; The alkyl radical does not include any nitro, nitroso, peroxo or diazo functional groups,

w is an integer from 1 to 10;

According to a further variant of the invention, the alkyl radicals R ₁₆ and R ₂₁ are optionally substituted, as indicated above, optionally together with a carbon atom attached to R ₁₆ and a nitrogen atom attached to radical R ₂₁ , And may optionally form a saturated or unsaturated 5- or 6-membered heterocycle containing another nitrogen or non-nitrogen heteroatom.

According to a further variant of the invention, the alkyl radicals R ₁₈ and R ₂₁ are optionally substituted, as indicated above, optionally together with the first nitrogen atom attached to R ₁₈ and the last nitrogen atom attached to radical R ₂₁ , respectively , Optionally saturated or unsaturated 5- to 14-membered heterocycle optionally further nitrogen or non-nitrogen heteroatom.

Among the compounds of formula (IIIh), mention may be made in particular of the following amines, their enantiomers, if any, and their salts and their hydrates: gerontine, N- [3-aminopropyl] Butanediamine, 4- (ethylamino) -N-butylamine, 2- [3- (2-hydroxy- 1,3-diol, 1,4,8,11-tetraazacyclotetradecane, 1,4-diazacycloheptane, 1,3-diamino-2-hydroxypropane, N , N'-bis (2-aminoethyl) propane-1,3-diamine, 3-methylaminopropylamine, 1,3-diaminopropane, N, N'-dimethyltrimethylenediamine, 2,2- Methylene diamine, 2,2-dimethyl-1,3-diaminopropane, N- (2-hydroxyethyl) -1,3-diaminopropane, N- (2-hydroxyethyl) Aminopropane, cystamine, 1,5-diaminopentane, 1,6-diaminohexane, lauraminopropylamine, 2-methyl (2-hydroxyethyl) ethylenediamine, 3-aminoalanine, piperazine-2-carboxylic acid,? -N- Methylaminoarnine, methylpiperazine-2-carboxylate, ethyl 3-aminoprolinate, 2,4-diamino-N-butyric acid, N- [3- (trimethoxysilyl) propyl] ethylenediamine, or Mixture thereof.

о General formula ( IIIi ) And / or ( IIIi ' ) ≪ / RTI >

[In the formula (IIIi) and / or (IIIi '):

- R < ₂₃ & R < ₂₄ > independently of one another represent:

Optionally substituted C ₁ -C 8 alkyl, optionally interrupted by one or more heteroatoms and / or one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, SO and SO ₂ or combinations thereof ₆ alkyl radical wherein said alkyl radical does not contain any nitro, nitroso, peroxo or diazo functional groups;

* Alkylcarbonyl radical (R-CO-) (wherein, R represents a -C ₄ alkyl radical, C _1);

* An alkylsulfonyl radical (RSO ₂ -), wherein R represents a C ₁ -C ₄ alkyl radical;

* (Di) (alkyl) aminosulfonyl radicals ((R) ₂ N-SO ₂ -), wherein the radicals R independently represent hydrogen or a C ₁ -C ₄ alkyl radical;

* (Di) (alkyl) aminocarbonyl radicals ((R) ₂ N-CO-), wherein the radicals R independently represent hydrogen or a C ₁ -C ₄ alkyl radical;

A halogen atom, preferably selected from bromine, chlorine and fluorine;

A C ₁ -C ₄ alkoxy group;

A C ₂ -C ₄ (poly) hydroxyalkoxy group;

A hydroxycarbonyl group (HO-CO-);

* An alkoxycarbonyl group (RO-CO-), wherein R represents a C ₁ -C ₄ alkyl radical;

An alkylcarbonylamino group (RCO-NR'-), wherein the radical R represents a C ₁ -C ₄ alkyl radical and the radical R 'represents a hydrogen atom or a C ₁ -C ₄ alkyl radical;

An alkylsulfonyl radical (RSO ₂ -), wherein the radical R represents a C ₁ -C ₄ alkyl radical;

Y represents a carbon or nitrogen atom;

- z, z 'and z "independently of each other represent a carbon atom, a nitrogen atom or a nitrogen atom substituted by hydrogen;

x is an integer from 0 to 2; When x is less than 2, the unsubstituted carbon atom (s) contain a hydrogen atom;

- x 'is an integer of 0 or 1; When x 'is less than 1, the unsubstituted carbon atom (s) contains a hydrogen atom.

Of the compounds of formula (IIIi) and / or (IIIi '), in particular the following listed compounds, if any, their enantiomers, and also their salts and their hydrates can be mentioned: α-pyridylamine, Amino-3-methylpyridine, 3-amino-4-pyridylamine, 2,5-dihydroxypyridine, Aminosalicylic acid, methyl para-aminobenzoate, benzocaine, aminobenzoic acid, 4-amino-m-anisic acid, 4-amino 3-hydroxybenzoic acid, methyl 3,4-diaminobenzoate, methyl-4-amino-3-methoxybenzenecarboxylic acid, 2- Hydroxybenzoic acid, ethyl 3-aminobenzoate, 1-amino-3-carboxybenzene, methyl 2-aminobenzoate, ethyl anthranilate, Aminophenol, 1-methyl-2-imidazoline, 1-methylbenzimidazole-2-amine, and mixtures thereof .

The following amines, which may or may not be in the form of a salt, can also be used: lauroylethylenediamine, octopamine, oleamine, palmitamine, 2- (2-aminoethoxy) ethanol, Methyl [2- (3-trimethoxysilylpropylamino) ethylamine], bis (trimethylsilyl) aminomethylamine, (Triethoxysilylpropyl) amine, N1- (3- (trimethoxysilyl) propyl) hexane-1,6-diamine, diethylenetriaminopropyltrimethoxysilane, N- ) Ethylenediamine, N- (3-trimethoxysilylethyl) ethylenediamine.

According to another variant of the invention, the amines are selected from amino polymers, and also addition salts thereof. The term "amino polymer" means a macromolecule of higher molecular weight that contains one or more primary or secondary amine functionalities. The term "polymer" refers to a compound comprising five or more repeating units in turn linked through a covalent bond.

The amino polymer may be synthesized as follows:

- through a radical reaction (polyacrylate, polymethacrylate, polyvinyl, etc.),

- through condensation (polyester, polyether, polyamide, polyurethane, polydimethylsiloxane, polypeptide, etc.)

- through a ring opening reaction (such as a polyester).

Which may be optionally chemically modified natural sources such as polysaccharides (cellulose, dextran, chitosan, guar) and amino or thiol derivatives thereof.

The polymer may be of any type of topology: linear, branched, star shaped or hyperbranched chains (e. G., Dendrimers), blocks, random or alternating chains.

The chemical group may be naturally occurring on the polymer chain, at the chain end grafted along the main chain or side chain, or on a branch of the star or hyperbranched polymer.

The following are most particularly preferred:

1 / polyamino acids containing free OH or NH ₂ or SH or COOH groups, such as polylysine,

2 / NH ₂ or SH functional groups, natural or modified polysaccharides,

3 / aminosilicone,

4 / NH ₂ or SH functional groups, especially polyvinylvinyl substituted with amine functional groups, and polymers made from the following commercial monomers:

,

,

And in particular polylysine; Chitosan; Polyethoxylated amines such as carboxy PEG-8 amine, carboxy PEG-12 amine or carboxy PEG-24 amine; Or a combination thereof.

According to a further variant of the invention, the amine (s) are selected from the group consisting of purine bases, especially adenine, adenosine, guanine, guanosine G, thymine, thymidine T, uracil, uridine U, cytosine, cytidine C, , And combinations thereof.

It is not possible to configure it to depart from the context of the present invention in order to combine some of these variations.

Preferably, when the composition containing at least one amine, which is ammonia, the general formula (IIIa), (IIIb), (IIIc), (IIIe) and (IIIg) compounds, in particular R ₂₀ is linear C ₁ -C of ₄ alkoxy group, and (IIIi '), or a mixture thereof.

When the composition comprises one or more primary or secondary amines, ammonia or hydroxylamine, its content is in the range of 0.001% to 65% by weight and preferably in the range of 0.001% to 30% by weight, By weight.

enzyme

The compositions according to the present invention may optionally be formulated with, for example, β-glucosidase (EC 3.2.1.21), alcohol oxidase (EC 1.1.3.13), alcohol dehydrogenase Dehydrogenase EC 1.1.1.1, alcohol dehydrogenase EC 1.1.1.2, alcohol dehydrogenase EC 1.1.1.71, aromatic alcohol dehydrogenase EC 1.1.1.90 (also known as aryl alcohol dehydrogenase , Aromatic alcohol dehydrogenase EC 1.1.1.97, 3-hydroxybenzyl alcohol dehydrogenase EC 1.1.1.97, coniferyl alcohol dehydrogenase EC 1.1.1.194, cinnamyl alcohol dehydrogenase EC 1.1 .1.195, methanol dehydrogenase EC 1.1.1.244, aromatic alcohol oxidase EC 1.1.3.7 (also known as aryl alcohol oxidase), alcohol oxidase EC 1.1.3.13, 4-hydroxymandelerate oxidase EC 1.1 , The long-hydrocarbon-chain alcohol oxidase EC 1.1.3.20, the methanol oxidase EC 1.1.3.31, the alcohol dehydrogenase EC 1.1.99.20, the methyl glutamate dehydrogenase EC 1.5.99.5, the 2-oxo acid decarboxylase At least one enzyme selected from azeotriazole EC 4.1.1.1, benzoylformate decarboxylase EC 4.1.1.7, phenylpyruvate decarboxylase EC 4.1.1.43 and threonine aldolase EC 4.1.2.5.

When present, the concentration of the enzyme used in the dye composition is from 0.005% to 40% by weight, and preferably from 0.05% to 10% by weight, relative to the weight of the composition, in proportion to the total weight of the composition.

salt

Compositions comprising compound (s) of formula (I) and / or (II) may optionally comprise one or more salts.

When present, the salts are generally selected from organic solvents and / or inorganic salts, and combinations thereof.

In particular, the anion constituting the salt may be an inorganic salt such as an inorganic salt (chloride, carbonate, bicarbonate, sulfate, hydrogen sulfate, hydroxide, silicate, phosphate, hydrogen phosphate or the like) or organic (aspartate, formate, acetate, lactate, Gluconate, succinate, malate, fumarate, orotite, and the like).

The cation constituting the salt together with the anion may be an alkali metal (preferably lithium, sodium or potassium), an alkaline earth metal (preferably magnesium or calcium) or a transition metal (scandium, titanium, vanadium, manganese, molybdenum, Iron, cobalt, nickel, copper, zinc, silver or gold). Other cations, such as ammonium, can also form salts. Preferably the cation is selected from alkali metals (lithium, sodium or potassium), alkaline earth metals (magnesium or calcium), ammonium and also the following transition metals (manganese, molybdenum, iron, copper, zinc, silver and gold) .

When present, the content is from 0.001% to 40% by weight, and even more preferably from 0.001% to 20% by weight, relative to the weight of the composition, in proportion to the weight of the composition.

Other ingredients

Cosmetically acceptable vehicles generally comprise at least water or a mixture of water and one or more organic solvents. Examples of organic solvents that may be mentioned include C ₁ -C ₄ lower alkanols such as ethanol and isopropanol; Polyols such as 1,3-propanediol or 1,6-hexanediol and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and Also included are aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

If present, the solvent is preferably present in a proportion of from 1% to 99% by weight, and more preferably from 5% to 95% by weight, relative to the weight of the composition, proportionally to the weight of the composition.

The composition used in the process according to the invention may also contain various auxiliaries conventionally used in hair dye compositions such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic , Nonionic, amphoteric or biphilic polymers or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric mixed thickeners, antioxidants, penetrants, sequestrants, flavoring agents, , Modifying agents such as volatile or nonvolatile, modified or unmodified silicon such as amino silicone, film formers, ceramides, preservatives, opacifiers and conductive polymers.

The adjuvants are generally present in amounts of from 0.01% to 20% by weight, respectively, in proportion to the weight of the composition.

Needless to say, those skilled in the art will appreciate that the optional additions of the above-mentioned compounds (i), (ii), (iii), (iii), (S).

The pH of the composition is generally about 3 to 14, preferably about 4 to 11, and more preferably 6 to 11. Can be adjusted to the desired value using acidic or basic agents commonly used in dyeing keratin fibers, or alternatively using standard buffer systems.

Among the acidifying agents which may be mentioned are, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acid.

Among the basic agents, examples which may be mentioned include aqueous ammonia, alkali metal carbonates and the above-mentioned amines.

The composition may be in various forms, such as liquid, cream or gel, powders, solutions, or keratin fibers that are mixed before use to obtain a poultice, and in any other form suitable for dyeing hair in particular.

The components of the above-mentioned compositions are advantageously stored separately. In particular, the oxidized oligosaccharides or polysaccharides containing the compounds of formula (I) or (II) or plant extracts containing them and the aldehyde or imine compound (s) or aldehyde or imine functional groups are individually stored.

In addition, it should be noted that where more than one amine compound is present, such compounds are also separately stored with the compound (s) (I) and (II) or plant extracts comprising the same.

In addition, it may be advantageous to store the compound (s) of the formula (I) / (II) or the plant extract containing them in at least a closed container.

The composition used in the process according to the invention may also comprise one or more oxidizing agents. In this case, it is referred to as a ready-to-use composition.

Oxidant

In particular, when an oxidizing agent is present, the instantaneous composition is advantageously obtained by instantly mixing the composition as described above with one or more compositions comprising one or more oxidizing agents, prior to application.

The oxidizing agent is preferably selected from the group consisting of hydrogen peroxide, urea peroxide, alkali metal bromate or ferricyanide, peroxides, such as persulfates, perborates and percarbonates of alkali metals or alkaline earth metals such as sodium, potassium and magnesium .

Suitable oxidizing agents for use also include, in the presence of an oxidizing agent of the enzyme type, e. G., Where appropriate, each of the donors or cofactors, a 4-electron oxidoreductase (such as laccase), a 2-electron oxidoreductase Uricase), and peroxidase.

It is particularly preferred to use hydrogen peroxide.

The oxidizing agent is advantageously formed by hydrogen peroxide in an aqueous solution (an aqueous hydrogen peroxide solution), the inverse thereof being more particularly in the range from 1 to 40 parts by volume, and even more preferably from 5 to 40 parts by volume.

Thus, it should be noted that the composition used in the present invention can be obtained by instant mixing several compositions.

Thus, the composition just described above is applied to human keratinous fibers, especially hair.

Dyeing method

According to a first embodiment, the composition applied does not contain any oxidizing agent.

This embodiment is particularly suitable when the composition does not comprise an oxidation dye (base or linking group).

According to a second embodiment, the instantaneous composition obtained by the above-described detailed, pre-application, instantaneous mixing of the above described composition without oxidizer with the oxidizing composition is applied to the fibers.

This embodiment is particularly suitable when the composition comprises one or more oxidation dyes (bases or linking groups) or when it is desired to obtain a lightening effect.

According to a second variant of this embodiment, the oxidizer-free composition and the oxidizer composition are applied continuously without intermediate cleaning.

The oxidizing composition used comprises at least one oxidizing agent as defined above.

With regard to the organic solvent which may be present in the oxidizing composition, reference can be made to the list given above in the context of the description of the composition according to the invention.

Typically, the pH of the oxidizing composition is less than 7.

The oxidizing composition may take the form of a solution, emulsion or gel.

Which may optionally comprise one or more additives commonly used in the art of dyeing human keratinous fibers, depending on the function of the desired herbal form. Once again, a list of the above-mentioned additives can be referred to.

Regardless of the embodiment selected (with or without oxidizing agent, instantaneous mixing or continuous application of the composition and the oxidizing agent), the mixture applied to the fibers will generally be in the range of from about 1 minute to 5 hours and preferably from 10 minutes to 3 hours .

With respect to the temperature at which the composition (s) is applied, is generally from 20 to 200 캜 and advantageously from 20 캜 to 55 캜.

Thus, the work can be performed using, for example, a heating hood, an infrared lamp, or straightening iron or curling iron.

The method according to the invention can advantageously be carried out in the presence of a light stimulus.

More specifically, UVA radiation as described above (in particular a continuous-spectrum lamp or Sun-delivered by the spectrum lamp, from 0.01 to 0.40 mW / cm ² and preferably irradiance of 0.1 to 0.2 mW / cm ²⁾ and / or UVB Is applied to treated keratinous fibers, in particular irradiated with 0.01 to 0.20 mW / cm ² and preferably 0.01 to 0.1 mW / cm ² , delivered by continuous-spectrum lamps or pre-spectral lamps.

Preferably, such compounds are alkali metals, alkaline earth metals or ammonium, carbonate, bicarbonate, chloride, sulfate, silicate, monobasic phosphate or acetate salts.

According to a preferred variant of the invention, the stimulating agent is selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate or ammonium carbonate in a cosmetically acceptable medium; Sodium hydrogencarbonate or potassium hydrogencarbonate; Calcium chloride, lithium chloride or sodium chloride; Ammonium sulphate, magnesium sulphate or magnesium sulphate; Sodium silicate; Monobasic sodium phosphate or potassium phosphate; Lt; / RTI > and sodium acetate.

The composition advantageously has a salt content ranging from 0.001% to 40% by weight, and even more preferably from 0.001% to 20% by weight, relative to the weight of the composition, in proportion to the weight of the composition.

But can not be configured to deviate from the context of the present invention in order to perform several successive steps that combine different stimuli.

After a leave-on time, the keratin fibers can be rinsed with water, optionally shampooed, rinsed with water, dried or allowed to dry.

A final subject of the present invention is a pharmaceutical composition comprising a first compartment containing at least one compound of formula (I) and / or (II) or a plant extract comprising the same and at least one compound of formula (i) or (ii) A second compartment containing an oxidized oligosaccharide or polysaccharide comprising an aldehyde or an imine functional group.

Preferably, the compound (s) of the formula (I) / (II) or the plant extract comprising the same is protected from air and is advantageously stored under an inert atmosphere.

The apparatus may optionally comprise at least one amine, or a third compartment comprising at least one salt.

Embodiments illustrating the present invention are presented below, which are not intended to limit the present invention.

Example One

Among the Jenny pins, 9.4% enriched, Genipa by using an ultrasonic crusher (sonicator) The extract (10 g%) and vanillin (1.5 g%) of americana), in aqueous solution, to give the dye composition was dissolved for 30 minutes.

The following method was performed to obtain the extract:

Less ripe Jenipa Americana americana fruit (100 g) were chopped, frozen, lyophilized, ground and then extracted with milliQ water.

The bath ratio was 1/20 (= 1 g of lyophilisate per 20 ml of solvent).

The suspension was stirred at room temperature for 1 hour. The starting material was then centrifuged at 7500 rpm for 15 minutes to separate from the solvent, and the supernatant was filtered through a Whatman GF / C filter.

The filtered extract was then frozen and lyophilized.

HPLC analysis showed that the extract was concentrated in an amount of 9.4% in the geninin.

Next, organic and / or inorganic salts were added to the composition. The composition was sonicated again for 15 minutes.

Each composition was applied to gray hair containing 90% white hair (1 g of head per 5 g solution) and the head was placed at 40 캜 (hot plate) for 2 hours.

Example 2

Among the Jenny pins, 9.4% enriched Jennipa Americana using a sonicator from extracts (5x10 ^-3 mol%) and the component (10 ^-2 mol%) to, benzoic acid, benzyl alcohol, ethanol and mixtures of water americana) to give the dye composition was dissolved for 30 minutes (the The pH of the composition is 9.5 (addition of NaOH; 0.1M).

Each composition was applied to natural and / or permanent-waved gray hair containing 90% white hair (1 g of head per 10 g of solution) and the head was heated at 50 占 폚 (hot plate) to 30 Min. ≪ / RTI >

Example  3:

Among the Jenny pins, 9.4% enriched Jennipa Americana if extract (3g%) and the presence of americana), the vanillin (0.4g%), by using an ultrasonic crusher in water to give the dye composition was dissolved for 20 minutes (the pH of the composition is 8 Im (KHCO ₃ adding)).

Each composition was applied to natural gray hair containing 90% white hair (1 g of head per 5 g of solution) and the head was placed at 30 캜 (hot plate) for 60 minutes.

The results were as follows:

From the above results it was clear that the color was more intense when vanillin was included.

Example  4

Preparation of imine type compounds

Vanillin (0.4 g%) in a mixture of water (5 ml) / ethanol (1 ml) was reacted with 3-aminopropanol (0.2 g%) in the presence of acetic acid for 30 minutes at ambient temperature to prepare an imine.

The resulting imine was then added to an extract of Genipa americana (3g%) concentrated at 9.4% in the geninin . The pH of the composition was then adjusted to 8 by the addition of KHCO ₃ and then placed in an ultrasonic mill for 20 minutes.

The composition was applied to natural gray hair containing 90% white hair (1 g of head per 6 g of solution) and the head was placed at 40 캜 (hot plate) for 60 minutes.

The color of the hair was dark blue.

Example  5

Among the Jenny pins, 9.4% enriched Jennipa Americana using a sonicator from extract (3g%) and the oxidized Inulin (0.3g%), an aqueous solution of pH 8 (KHCO ₃ added) of americana) to give the dye composition was dissolved for 20 minutes.

Each composition was applied to natural gray hair containing 90% white hair (1 g of head per 5 g solution) and the head was placed at 40 캜 (hot plate) for 60 minutes.

The hair was golden yellow.

Claims (12)

Compositions for lightening keratin fibers, in a cosmetically acceptable medium, comprising:
* doing The compounds of formula (I) and / or formula ( II ) Compound , An optical or geometric isomer thereof, an inorganic or organic acid salt thereof, a solvate thereof, or a plant extract comprising the above:

In formulas (I) and (II):
ㆍ R_One Is a hydrogen atom, a methyl radical, a hydroxymethyl radical, an aldehyde group; -CO₂R₄ Group wherein R₄ Is a hydrogen atom or C_One-C₂ Alkyl radical); -CH₂- represents a glucose group;
ㆍ R₂ Represents a hydrogen atom, a hydroxyl radical or a glucose radical;
ㆍ R₃ May be the same or different and are a hydrogen atom, a hydroxyl radical, (C_One-C₄) Alkyloxy radical; The number of the hydroxyl groups is 2 or less;
N is an integer from 1 to 5;
ㆍ R₅ -CO₂R '₆ (Wherein R '₆ Is a hydrogen atom or C_One-C₂ Alkyl radical; An alkali metal cation, or an ammonium group);
ㆍ R₆ Is hydrogen, -CO₂R '₆ (Wherein R '₆ Is a hydrogen atom, C_One-C₂ An alkyl radical, an alkali metal cation, or an ammonium group);
**Are selected from the following formulas (i) and (ii) At least one aldehyde or imine compound , Optical or geometric isomers thereof, organic or inorganic acid salts thereof, solvates thereof, and also oligo- or polysaccharides comprising at least one aldehyde or imine functional group:

[In the formulas (i) and (ii)
M is an integer of 0 or 1,
X is an oxygen atom, NR "_One (Wherein R "_One Is a hydrogen atom or C_One-C₁₀ Alkyl < / RTI >radical);
When X represents an oxygen atom, the compound may be of the form:
Additional primary monoalcohols (R '₃OH), wherein R '₃ C_One-C₅ Alkyl radical or C₂-C₃ Or a bicyclic acetal obtained by the condensation of a benzene ring, a benzene ring, a benzene ring, a benzene ring, an alkyl chain, a symmetrical 1,2- or 1,3-diol)
о A or A_One Represents an alkyl radical, and when n is 0, A or A_One In the form of a hemiacetal obtained by condensation of a hydroxyl group present on the compound;
The radical R '_One And R '₂ Are each independently a hydrogen atom or an unsubstituted linear C_One-C₆ Alkyl radical;
The monovalent radical A and the bivalent radical A_One Represents a group selected from:
* Hydroxycarbonyl group (- CO - OH ):
* At least optionally substitutedC ₆ Aryl group:
- a hydroxyl group,
- C_One-C₄ Alkyl radical,
-Aryl-ethylenyl radicals (said aryl radicals being C₆ , And one or more C_One-C₂ Alkyl or C_One-C₂ Optionally substituted with an alkoxy radical,
- -CO-OR '₄ Or -O-COR '₄ (Wherein R '₄ C_One-C₂ An alkyl radical or a phenyl group);
-COOH groups in acidic or chlorinated form,
- -OR '₅ (Wherein R '₅ Lt; RTI ID = 0.0 > C < / RTI >_One-C₈ Alkyl radical), -N⁺R "₆ Ammonium group (wherein R "₆ May be the same or different and are C_One-C₂ Alkyl radical), -SiR '₇ (Wherein R '₇ May be the same or different and are C_One-C₂ Alkyl radical); Benzyl radical (-CH₂-C₆H₆),
Depending on the particular variant, C₆ The two radicals -OR 'in the ortho position relative to the aryl group₅ Lt; RTI ID = 0.0 > R '₅ Lt; RTI ID = 0.0 > 5-, < / RTI > or 6-membered heterocycle,
-N (R '₈)₂ (Wherein R '₈ (-COOH) in the form of a hydroxyl group, an acidic or chlorinated form, or a sulfone group (-SO < 2 >) in an acidic or chlorinated form,₃H) < / RTI >_One-C₆ Alkyl radical; The radical R '₈ Together with the nitrogen atom containing it, optionally together with O, N and NR '₉ (Wherein R '₉ C_One-C₂ Lt; RTI ID = 0.0 > R < / RTI > represents an alkyl radical; Wherein the heterocycle is optionally substituted with a hydroxyl group,
--COR '₁₀ (Wherein R '₁₀ Is one or more C_One-C₂ A C 6 fused to a 6-membered hydrocarbon ring optionally substituted with an alkyl radical₆ Aryl group),
- -SR '₁₁ (Wherein R '₁₁ C_One-C₂ Alkyl radical),
- a halogen atom, preferably selected from chlorine and bromine,
- -O-SO₂-C₆H₆ group,
- -SO₃H group,
- O, N and NR '₁₂ (Wherein R '₁₂ Quot; optionally < / RTI > fused to a saturated or unsaturated, aromatic or non-aromatic 5- or 6-_One-C₂ An unsubstituted or non-cationic 5- or 6-membered heterocycle containing one or two heteroatoms selected from nitrogen, oxygen and sulfur, The fused ring may contain one or more C_One-C₂ Which may be substituted by an alkoxy radical,
- the aryl group is O, N and NR '₁₃ (Wherein R '₁₃ C_One-C₄ Alkyl radical, and the heterocycle is optionally fused to a C (O) < RTI ID = 0.0 >₆ Optionally fused to an aryl group,
The aryl group is optionally substituted with one or more C_One-C₂ C < RTI ID = 0.0 >₆ Optionally fused to an aryl group;
Preferably O, N and NR '₁₄ (Wherein R '₁₄ Is a hydrogen atom, (R '₁₅)₂NCO- or (R '₁₅) CO-NH- group wherein R '₁₅ May be the same or different, and C_One-C₂ Alkyl < / RTI > radical)₆ Aryl radical or C_One-C₆ Lt; RTI ID = 0.0 > alkyl < / RTI > radical)Cationic or Non-cationic , Saturated or unsaturated, aromatic or Non-aromatic 5- or 6-membered heterocyclic group;
Said heterocyclic group may itself be substituted by one or more C_One-C₂ Alkyl, C_One-C₄ Optionally fused to a six-membered aryl group optionally substituted with an alkoxy or phenoxy group;
Said heterocyclic group is optionally substituted at least one of:
a hydroxyl group,
< RTI ID = 0.0 > C < / RTI >_One-C₂ Alkyl radical;
amino radical -N (R '₁₆)₂ (Wherein R '₁₆ May be the same or different and are selected from the group consisting of C_One-C₄ Alkyl radical, and the radical R '₁₆ Together with the nitrogen atom containing it, optionally together with O, N and NR '₁₇ (Wherein R '₁₇ C_One-C₂ Or a saturated or unsaturated 5- or 6-membered heterocycle comprising another heteroatom selected from nitrogen, oxygen,
o one or more COOH, R '₁₈CONH- group wherein R '₁₈ C_One-C₂ Alkyl < / RTI > radical)₆ An aryl radical (the C₆ The aryl radical is optionally linked to the nitrogen atom of the heterocyclic group; When the aryl radical is not substituted with a radical mentioned above, the carbon atom is replaced by a hydrogen atom;
* Linear or branched C _One - C ₁₀ Alkyl Radical, Or one or more conjugated or non-conjugated carbon-carbon double bondsC ₂ - C ₁₀ Alkenyl Radical Wherein said alkyl or alkenyl radical is optionally substituted with one or more hydroxyl groups;
ㆍ 2-valent radical A₂ Quot; means that two radicals A through a carbon, oxygen or nitrogen atom_One Linear C connecting_One-C₁₀ Alkylene chain;
Where appropriate, the compounds of formulas (i) and (ii) comprise a cosmetically acceptable anion or mixture of anions An, which ensures electrical neutrality of the formulation. The composition according to claim 1, wherein the plant extract is obtained from the following plant: Veronica persica ); Jenny wave Americana (Genipa americana ) ; Oh, Tess D. Fordyce other media (Apodytes Dimidiata ) ; Grandi ah Khan TiO2 Death (Randia canthioides ) ; Get Lena Guatemala noir Other (Tarenna attenuata) and preferably Jenny wave americana (Genipa americana ) . The composition of claim 1 or 2, wherein the amount of compound (s) of formula (I) and / or formula (II) in the composition is from 0.001% to 10% by weight, relative to the weight of the composition. 4. The composition according to any one of claims 1 to 3, wherein X represents an oxygen atom in the compound of formula (i) or (ii). The composition according to any one of claims 1 to 4, which is a compound (s) of formula (i)
* m is 0 or 1;
The radicals R ' ₁ and R' ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl radical;
* X represents an oxygen atom;
A represents:
* Optionally substituted with one or more hydroxyl groups, linear or branched C ₅ - C ₁₀ Alkyl Radical ;
* Carbon - C ₈ - C ₂ containing a carbon-carbon double bond Alkenyl Radical ;
A hydroxycarbonyl group (-COOH);
* At least optionally substituted C ₆ Aryl group :
- a hydroxyl group,
- a C ₁ -C ₄ alkyl radical,
- CO-OR ' ₄ or -O-COR' ₄ group, wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical,
- -OR ' ₅ group (wherein R' ₅ represents a C ₁ -C ₆ alkyl radical),
- aryl-ethylenyl radical, wherein the aryl group is C ₆ , optionally substituted by one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals,
- O, N and NR _'12 , wherein R' ₁₂ represents a C ₁ -C ₂ alkyl group optionally fused to a saturated or unsaturated, aromatic or nonaromatic 5- or 6-membered ring, An unsaturated cationic or non-cationic 5- or 6-membered heterocycle comprising a heteroatom, wherein one of said heteroatoms may be contained within two rings, said heterocycle or fused ring containing one or more C ₁ -C ₂ Which may be substituted by an alkoxy radical,
- the aryl group O, N and NR _'13 (wherein, R' ₁₃ is C ₁ -C ₄ represents an alkyl radical), 1 or 2 cyclic 5-or 6-membered heterocycloalkyl containing heteroatoms selected from the groups Optionally fused;
* Preferably from O, N and NR _'14 (wherein, R' ₁₄ represents a hydrogen atom, (R _{'15) 2} NCO- or (R' ₁₅₎ CO-NH- group (wherein, R _'15 is C ₁ - represents a C ₂ alkyl radical) in an optionally substituted C ₆ aryl radical or a C ₁ -C ₆ alkyl refers to the radical) containing 1 or 2 identical or different heteroatoms selected from cationic or non-cationic, saturated Or an unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic group ;
Said heterocyclic group is optionally fused to a 6-membered aryl group itself optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₄ alkoxy groups;
Said heterocyclic group is optionally substituted at least one of:
a hydroxyl group,
a C ₁ -C ₂ alkyl radical optionally substituted with a hydroxyl radical,
о amino radical -N (R _{'16) 2} (wherein, R' ₁₆ is the same as or may be different and represents a C ₁ -C ₄ alkyl radical optionally substituted by a hydroxyl group, the radicals R _'16 is this together with the nitrogen atom-containing, and optionally O, N and NR _'17 (wherein, R' ₁₇ is C ₁ -C ₂ alkyl refers to the radical) or other heteroatoms, saturated or unsaturated 5-or 6-containing selected from Lt; RTI ID = 0.0 > heterocyclic < / RTI &
If appropriate, the compound of formula (i) comprises a cosmetically acceptable anion or mixture of anions An, which ensures electrical neutrality of the formulation;
The compound (s) of formula (i) may be in the form of an acetal or hemiacetal. 6. The composition of any one of claims 1 to 5 wherein the content of the oxidized oligosaccharide or polysaccharide comprising compound (s) of formula (i) or (ii), or at least one aldehyde or imine functional group is proportional to the weight of the composition By weight to 30% by weight. 7. A composition according to any one of claims 1 to 6 comprising at least one organic or inorganic salt selected from:
A transition metal such as an alkali metal, an alkaline earth metal, scandium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, silver or gold,
The salts of the compounds of formula (I) may be used in the form of a salt, a carbonate, a bicarbonate, a sulfate, a hydrogen sulfate, a silicate, a phosphate, a hydrogen phosphate or a hydroxide or aspartate, formate, acetate, lactate, citrate, gluconate, succinate, Organic anion selected from oleate. 8. A composition according to any one of the preceding claims wherein the content of salt (s) ranges from 0.001% to 40% by weight relative to the weight of the composition, even more preferably 0.001% % ≪ / RTI > to 20% by weight. 9. A method for dyeing human keratin fibers, wherein the composition according to any one of claims 1 to 8 is applied. The method of claim 9, wherein a temperature of from 30 to 200 캜 is applied. Ninth according to any one of claims 10, wherein the UVA radiation is applied to, in particular from 0.01 to 0.40 mW / applied to the irradiance of cm ² and / or the UVB radiation, in particular irradiance of 0.01 to 0.20 mW / cm ^2.  A pharmaceutical composition comprising a first compartment containing at least one compound of formula (I) and / or (II) or a plant extract comprising the same as set forth in claims 1 or 2, and a first compartment containing at least one compound of formula (I) and / A second compartment containing at least one compound of formula (i) or (ii) according to any one of claims 1 to 3, an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or an imine functional group.