Composition for brightening keratin fibres and method for brightening keratin fibres using said composition
By using a composition containing hydrogen peroxide, carbonate, silicate and organic amine, the problems of unnatural chromaticity and fiber deterioration when bleaching dark hair in the prior art are solved, and the effects of effective brightening and color accumulation are achieved.
Patent Information
- Application Number
- CN202380048410.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-06-22
- Filing Date
- 2023-06-21
- Publication Date
- 2025-05-23
AI Technical Summary
The prior art is difficult to effectively brighten dark hair when bleaching hair, and often leads to unnatural yellow-orange color and fiber quality deterioration.
Compositions containing hydrogen peroxide, carbonates, silicates, organic amines and specific compounds are used for brightening keratin fibers. The composition can also be compatible with direct dyes and oxidized dyes, allowing for a wider color range.
Effective brightening of dark hair is achieved, reducing yellow ingredients, achieving more natural results while protecting fiber quality and compatible with existing dyes.
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Figure CN120035427A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a composition for lightening keratin fibers, comprising at least one chemical oxidizing agent, at least one (bi)carbonate, at least one silicate, at least one organic amine and at least one compound chosen from alcohols, amphoteric or zwitterionic compounds, esters and / or amides and / or imines, organic acids, alkanes and / or alkenes and / or ethers and mixtures thereof, and also to a method for lightening keratin fibers using said composition. Background Art
[0002] When a person wishes to change the colour of the hair, especially when he or she wishes to obtain a lighter colour than its original colour, it is often necessary to perform a preliminary lightening or bleaching of the hair. To do this, lightening or bleaching products are used.
[0003] The lightening of hair is evaluated by the "depth of tone" which characterizes the degree or level of lightening. The concept of "tone" is based on a classification of natural shades, a tone separating each shade from the shade immediately behind or before it. This definition and classification of natural shades is well known to hair styling professionals and is disclosed in the book Sciences destraitements capillaires [The Science of Hair Care] by Charles Zviak, 1988, published by Masson, pages 215 and 278.
[0004] The hue scale ranges from 1 (black) to 10 (very light gold), with one integer corresponding to one hue; the higher the number, the lighter the hue.
[0005] It is known practice to lighten or bleach the hair, in the vast majority of cases, under alkaline pH conditions, with a lightening or bleaching composition containing at least one chemical oxidizing agent. The action of this oxidizing agent is to degrade the melanin of the hair, which, depending on the nature of the oxidizing agent present and the pH conditions, results in a more or less pronounced lightening of the fibers. Thus, for relatively mild lightening, the oxidizing agent is generally hydrogen peroxide. When a greater lightening is desired, especially when the hair to be treated is dark, persulfates are generally used in the presence of hydrogen peroxide. However, the lightening obtained by the action of this combination is not always satisfactory, since it produces hair with an unattractive yellow-orange hue that is far from the natural hue, which complicates subsequent coloring by limiting it to the production of warm tones. Moreover, lightening compositions based on persulfates may lead to a deterioration of the fiber quality. Moreover, persulfate-based compositions are generally chemically incompatible with the oxidation dyes and / or direct dyes present, so as to be able to bleach and dye the hair fibers in a single step. Therefore, when it is desired to bleach and dye keratin fibers simultaneously, a two-step process is used, wherein the first step is to bleach the keratin fibers and then the second step is to dye the keratin fibers using a dye composition comprising one or more direct dyes and / or one or more oxidative dyes.
[0006] Therefore, there is a real need to develop a composition that allows an effective lightening of keratin fibers, especially dark keratin fibers, with less yellow and more natural results. Such a composition should also be more respectful of the quality of the fibers, especially by minimizing their degradation. Finally, such a composition should also be compatible with the direct and / or oxidative dyes present, so as to obtain a good color build-up, intense and vivid colors, and also allow a wider range of colors to be obtained.
[0007] The Applicant has surprisingly found that all or some of these objects can be achieved by the composition according to the invention. Summary of the invention
[0008] According to a first aspect, the subject of the present invention is a composition comprising:
[0009] i) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating systems other than peroxide salts, and mixtures thereof;
[0010] ii) one or more compounds selected from bicarbonate, bicarbonate generating system and mixtures thereof, preferably selected from bicarbonate;
[0011] iii) one or more silicates;
[0012] iv) one or more organic amines;
[0013] iv') one or more compounds different from compound iv) selected from:
[0014] a) alcohol;
[0015] b) amphoteric or zwitterionic compounds selected from the group consisting of phospholipids such as lecithin, amino acids, amphoteric or zwitterionic surfactants and mixtures thereof;
[0016] c) esters, amides, imines and mixtures thereof;
[0017] d) organic acids;
[0018] e) compounds consisting of a saturated or unsaturated, linear or branched hydrocarbon-based chain containing 1 to 30 carbon atoms, which is optionally substituted by one or more cyclic groups and / or optionally interrupted by one or more non-adjacent oxygen atoms; saturated or unsaturated, optionally aromatic, monocyclic or polycyclic, fused or non-fused carbocyclic compounds containing 3 to 22 carbon atoms, which are optionally substituted by one or more identical or different groups selected from: (C 1 -C 6 ) alkyl or (C 1 -C 6 ) alkenyl or (C 1 -C 6 ) alkoxy and / or optionally interrupted by one or more carbonyl (CO) groups; monocyclic or polycyclic, fused or non-fused, saturated or unsaturated, especially aromatic heterocyclic compounds, which contain 5 to 22 members and 1 to 3 oxygen atoms, optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl or (C 1 -C 6 ) alkoxy and / or optionally interrupted by one or more carbonyl (CO) groups and mixtures thereof;
[0019] f) and mixtures thereof.
[0020] According to a second aspect, a subject of the invention is a method for lightening keratin fibres, which method comprises applying to the keratin fibres a composition comprising ingredients i) to iv) and iv′) as previously defined.
[0021] According to a third aspect, the subject of the invention is a process for the simultaneous bleaching and dyeing of keratin fibers, which comprises applying to the keratin fibers a composition comprising ingredients i) to iv) and iv') as previously defined and v) one or more colorants preferably chosen from direct dyes, oxidative dyes and mixtures thereof.
[0022] According to a fourth aspect, a subject of the present invention is the use of a composition comprising ingredients i) to iv) and iv′) as previously defined for lightening keratin fibres, preferably for lightening keratin fibres while simultaneously deyellowing them.
[0023] According to a fifth aspect, a subject of the invention is the use of a composition comprising ingredients i) to iv) and iv') as previously defined and v) one or more colorants preferably chosen from direct dyes, oxidation dyes and mixtures thereof for the simultaneous bleaching and dyeing of keratin fibres.
[0024] According to a sixth aspect, the subject of the invention is a device comprising a plurality of separate compartments (kit), comprising:
[0025] ■ A first compartment containing a composition (A) comprising:
[0026] - one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating systems other than peroxide salts and mixtures thereof, preferably hydrogen peroxide; and
[0027] - optionally one or more organic amines iv) and / or one or more compounds iv') as defined previously; and
[0028] ■ A second compartment containing a composition (B) comprising:
[0029] - one or more compounds selected from bicarbonate, bicarbonate generating system and mixtures thereof, preferably selected from bicarbonate; and
[0030] - one or more silicates; and
[0031] - optionally one or more colorants, preferably chosen from direct dyes and oxidation dyes and mixtures thereof; and
[0032] - optionally one or more organic amines iv) and / or one or more compounds iv') as defined previously; and
[0033] ■ A third compartment optionally containing a composition (C) comprising:
[0034] - one or more colorants, preferably chosen from direct dyes and oxidation dyes and mixtures thereof; and
[0035] - optionally one or more organic amines iv) and / or one or more compounds iv') as defined previously;
[0036] It should be understood that:
[0037] - at least one of compositions (A) or (B) or at least one of compositions (A) or (B) or (C) if composition (C) is present comprises one or more organic aminesiv); and
[0038] - at least one of the compositions (A) or (B) or at least one of the compositions (A) or (B) or (C) if composition (C) is present comprises one or more compounds iv') as defined previously. BRIEF DESCRIPTION OF THE DRAWINGS
[0039] Figure 1 is a graph representing the variation of the intensity L* of a composition according to the invention (Example 2) and a comparative composition based on persulfate (Example 1) as a function of the parameter b*, the values of L* and b* being measured in the CIE L*a*b* system. DETAILED DESCRIPTION
[0040] For the purposes of the present invention and unless otherwise indicated:
[0041] ■ The term "keratin fibers" means fibers of human or animal origin, such as hair, body hair, eyelashes, eyebrows, wool, angora wool, cashmere or fur. According to the present invention, the keratin fibers are preferably human keratin fibers, more preferably hair;
[0042] ■The term "alcohol" means an organic compound in which one of the carbon atoms is attached to a -OH hydroxyl group or a phenolic group.
[0043] ■ The term "ester" means a compound comprising at least one ester functional group.
[0044] ■ The term "amide" means a compound comprising at least one amide functional group.
[0045] ■ The term "imine" means a compound comprising at least one imine functional group.
[0046] ■ The term "organic acid" means an organic compound comprising at least one -X(O)OH functional group, wherein X represents a carbon atom or S=O or P-OH, preferably a carbon atom.
[0047] ■ The term "organic amine" means an organic compound containing at least one primary, secondary or tertiary amine functional group.
[0048] ■ The term "salt" means an addition salt with an organic or inorganic acid or base. The addition salt with an acid is especially chosen from the addition salt with an acid, such as hydrochloric acid, hydrobromic acid, sulfuric acid, citric acid, succinic acid, tartaric acid, lactic acid, toluenesulfonic acid, benzenesulfonic acid, phosphoric acid or acetic acid. The addition salt with a base is especially chosen from the addition salt with a base, such as an alkalizing agent as defined below, especially an alkali metal hydroxide, alkaline earth metal hydroxide, ammonia, an amine or an alkanolamine.
[0049] ■The term "alkyl" means a straight-chain or branched saturated hydrocarbon-based group containing 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 26 carbon atoms, and even more preferably 1 to 22 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, butyl, n-pentyl, n-hexyl, n-decyl, n-dodecyl, tetradecyl, hexadecyl or eicosyl.
[0050] ■Term "(C x -C y )alkyl" means an alkyl group containing from x to y carbon atoms.
[0051] ■The term "alkenyl" means a straight or branched hydrocarbon-based group containing one or more olefinic unsaturations and 1 to 30 carbon atoms, preferably 1 to 26 carbon atoms, more preferably 1 to 22 carbon atoms, such as ethenyl, n-propenyl, isopropenyl, butenyl, n-pentenyl, n-hexenyl, n-decenyl, n-dodecenyl, tetradecenyl, hexadecenyl or eicosenyl.
[0052] ■Term "(C x -C y The term "alkenyl" refers to an alkenyl group containing from x to y carbon atoms.
[0053] ■The term "alkoxy" means an alkyl group bonded to an oxygen atom.
[0054] ■Term "(C x -C y )alkoxy" means an alkoxy group containing x to y carbon atoms.
[0055] ■ The term "(poly)(hydroxy)alkyl" means alkyl or hydroxyalkyl or polyhydroxyalkyl.
[0056] ■The term "hydroxyalkyl" means an alkyl group substituted with a hydroxy group (-OH);
[0057] ■ The term "polyhydroxyalkyl" means an alkyl group substituted with at least two hydroxyl (-OH) groups.
[0058] ■The term "(poly)hydroxyalkyl" means a hydroxyalkyl group or a polyhydroxyalkyl group.
[0059] ■The term "alkylamino" refers to the group R'-NR a -, wherein R' represents an alkyl group, and R a represents a hydrogen atom or (C 1 -C 4 )alkyl, wherein X represents a carbon atom or S=O or P-OH, preferably wherein X represents a carbon atom; R' and R acan form, with their nitrogen atoms, a saturated or unsaturated cyclic group having 4 to 8 chain members, preferably 5 or 6 chain members, which cyclic group is optionally especially substituted by one or more identical or different groups selected from (C 1 -C 4 )(poly)hydroxyalkyl or (C 1 -C 4 ) alkoxy.
[0060] ■ The term "alkylamido" means the group R"-NR a -CO-, where R" represents an alkyl group and R a represents a hydrogen atom or an optionally (C 1 -C 4 ) alkyl group substituted by one or more groups -X(O)OH, where X represents a carbon atom or S=O or P-OH, preferably where X represents a carbon atom; R" and R a can form, with their nitrogen atoms, a saturated or unsaturated cyclic group having 4 to 8 chain members, preferably 5 or 6 chain members, which cyclic group is optionally especially substituted by one or more identical or different groups selected from (C 1 -C 4 )(poly)hydroxyalkyl or (C 1 -C 4 ) alkoxy.
[0061] ■ The term "(hetero)cyclic group" means a cyclic or heterocyclic group.
[0062] ■ The term "cyclic group" means a fused or unfused, saturated or unsaturated, especially aromatic, monocyclic or polycyclic carbocyclic ring containing 6 to 22 carbon atoms, which cyclic group may be substituted by one or more identical or different groups especially selected from the following: (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy, (C 1 -C 6 )(poly)hydroxyalkyl, hydroxy (-OH) or carboxy (-COOH).
[0063] ■ The term "heterocyclic group" means a fused or unfused, saturated or unsaturated, especially aromatic, monocyclic or polycyclic group containing 5 to 22 members and having 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur atoms, which heterocyclic group may be substituted by one or more identical or different groups especially selected from the following: (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy, (C 1 -C6 () (poly)hydroxyalkyl, hydroxy (-OH) or carboxyl (-COOH).
[0064] ■ The term "silicate" means a salt of silicic acid.
[0065] ■ The term "colorant" means oxidation dye, direct dye or pigment.
[0066] ■ The term "oxidation dye" means an oxidation dye precursor selected from oxidation bases and couplers. Oxidation bases and couplers are colorless or slightly colored compounds which form colored species via condensation reactions in the presence of oxidizing agents;
[0067] ■ The term "direct dyes" means natural and / or synthetic dyes other than oxidation dyes, including in the form of one or more extracts. These are colored compounds that will spread on the surface on the fibers. They can be ionic or nonionic, that is, anionic, cationic, neutral or nonionic.
[0068] ■ The term "chemical oxidant" means an oxidant other than atmospheric oxygen.
[0069] Unless otherwise indicated, when a compound is mentioned in the present patent application, this also includes its optical isomers, its geometric isomers, its tautomers, its salts or solvates thereof (such as hydrates), and mixtures thereof.
[0070] The terms "at least one" and "one or more" are synonymous and can be used interchangeably.
[0071] The terms "lightening" and "bleaching" are synonymous and can be used interchangeably.
[0072] Composition
[0073] According to a first aspect, a subject of the present invention is a composition comprising ingredients i) to iv) and iv′) as previously defined.
[0074] The Applicant has surprisingly found that the composition according to the invention allows an effective lightening of keratin fibers, with a less yellow and more natural result. When the color of keratin fibers treated with a composition according to the invention is compared with the color of keratin fibers treated with a lightening composition known in the art, it is observed that at equal intensity levels L*, the b* values measured in the CIE L*a*b* system are lower for the composition according to the invention than for the lightening compositions known in the art.
[0075] Furthermore, the composition according to the invention is more respectful of the qualities of the fibres and in particular minimizes their degradation.
[0076] According to a preferred embodiment, the composition according to the present invention comprises:
[0077] i) hydrogen peroxide;
[0078] ii) one or more compounds selected from bicarbonates;
[0079] iii) one or more silicates;
[0080] iv) one or more organic amines;
[0081] iv') one or more compounds different from compound iv) selected from:
[0082] a) alcohol;
[0083] b) amphoteric or zwitterionic compounds selected from the group consisting of phospholipids such as lecithin, amino acids, amphoteric or zwitterionic surfactants and mixtures thereof;
[0084] c) esters, amides, imines and mixtures thereof;
[0085] d) organic acids;
[0086] e) compounds consisting of a saturated or unsaturated, linear or branched hydrocarbon-based chain containing 1 to 30 carbon atoms, which is optionally substituted by one or more cyclic groups and / or optionally interrupted by one or more non-adjacent oxygen atoms; saturated or unsaturated, optionally aromatic, monocyclic or polycyclic, fused or non-fused carbocyclic compounds containing 3 to 22 carbon atoms, which are optionally substituted by one or more identical or different groups selected from: (C 1 -C 6 ) alkyl or (C 1 -C 6 ) alkenyl or (C 1 -C 6 ) alkoxy and / or optionally interrupted by one or more carbonyl (CO) groups; monocyclic or polycyclic, fused or non-fused, saturated or unsaturated, especially aromatic heterocyclic compounds, which contain 5 to 22 members and 1 to 3 oxygen atoms, optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl or (C 1 -C 6 ) alkoxy and / or optionally interrupted by one or more carbonyl (CO) groups and mixtures thereof;
[0087] f) and mixtures thereof.
[0088] Chemical oxidants
[0089] The composition according to the invention comprises i) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide generating systems other than peroxygenated salts, and mixtures thereof.
[0090] The hydrogen peroxide generating system other than peroxide salts may be selected from urea peroxide, polymer complexes capable of releasing hydrogen peroxide, oxidases and mixtures thereof.
[0091] As examples of polymer complexes which can release hydrogen peroxide, mention may be made of polyvinylpyrrolidone / H2O2, in particular in powder form. 2 O 2 and other polymer complexes described in US Pat. No. 5,008,093, US Pat. No. 3,376,110 and US Pat. No. 5,183,901.
[0092] Oxidase enzymes can generate hydrogen peroxide in the presence of a suitable substrate, such as glucose in the case of glucose oxidase or uric acid in the case of uricase.
[0093] According to a particular embodiment, hydrogen peroxide and / or a hydrogen peroxide generating system other than peroxygenated salts may be incorporated into the composition according to the invention just before applying the composition according to the invention to the keratin fibers. The intermediate composition comprising hydrogen peroxide and / or a hydrogen peroxide generating system other than peroxygenated salts may be called an oxidizing composition and may also comprise various additional compounds or various auxiliaries conventionally used in compositions for lightening keratin fibers.
[0094] According to a preferred embodiment, the composition according to the invention comprises hydrogen peroxide as chemical oxidizing agent.
[0095] The chemical oxidizing agent is preferably present in the composition in a total content ranging from 1% to 12% by weight, more preferably ranging from 3% to 9% by weight and even more preferably ranging from 3.5% to 8.5% by weight relative to the total weight of the composition.
[0096] According to a preferred embodiment, hydrogen peroxide is present in the composition in a total content ranging from 1% to 12% by weight, preferably ranging from 3% to 9% by weight, more preferably ranging from 3.5% to 8.5% by weight relative to the total weight of the composition.
[0097] Bicarbonate and / or bicarbonate generating system
[0098] The composition according to the invention further comprises ii) one or more compounds selected from bicarbonate, bicarbonate generating system and mixtures thereof.
[0099] The term "bicarbonate generating system" means a system that generates bicarbonate in situ, such as carbon dioxide in water or by buffering carbonate with an inorganic or organic acid.
[0100] Preferably, the bicarbonate salt is selected from:
[0101] - alkali metal bicarbonates;
[0102] - alkaline earth metal bicarbonates;
[0103] -Formula N + R 1 R 2 R 3 R 4 HCO 3 - A compound wherein R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom or (C 1 -C 4 )alkyl;
[0104] -aminoguanidine bicarbonate;
[0105] - mixtures thereof.
[0106] More preferably, the bicarbonate salt is selected from the group consisting of sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate, choline bicarbonate, triethylammonium bicarbonate, aminoguanidine bicarbonate, and mixtures thereof.
[0107] Even more preferably, the bicarbonate salt is selected from sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate and mixtures thereof.
[0108] Most preferably, the bicarbonate salt is selected from sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and mixtures thereof.
[0109] According to a particularly preferred embodiment, the bicarbonate salt contained in the composition is ammonium bicarbonate.
[0110] The bicarbonate may originate from natural water, for example spring water from the Vichy basin or from La Roche Posay or Badoit water.
[0111] The bicarbonate and / or bicarbonate generating system is preferably present in the composition in a total content ranging from 0.01% to 20% by weight, more preferably ranging from 1% to 15% by weight, even more preferably ranging from 2% to 15% by weight, most preferably ranging from 4% to 15% by weight relative to the total weight of the composition.
[0112] According to a preferred embodiment, the bicarbonate is present in a total content ranging from 0.01% to 20% by weight, preferably ranging from 1% to 15% by weight, more preferably ranging from 2% to 15% by weight, even more preferably ranging from 4% to 15% by weight relative to the total weight of the composition.
[0113] According to a preferred embodiment, compound ii) is selected from bicarbonates.
[0114] Carbonates and / or carbonate generating systems
[0115] The composition according to the invention may also comprise one or more compounds selected from carbonates, carbonate generating systems and mixtures thereof, preferably selected from carbonates.
[0116] The term "carbonate generating system" means a system that generates carbonates in situ, such as carbon dioxide in water or percarbonate in water.
[0117] Preferably, the carbonate is selected from:
[0118] - alkali metal carbonates;
[0119] - Alkaline earth metal carbonates;
[0120] - lanthanide carbonates;
[0121] - Transition metal carbonates;
[0122] - bismuth carbonate;
[0123] - cadmium carbonate;
[0124] - thallium carbonate;
[0125] - zinc carbonate;
[0126] -Formula (N + R 1 R 2 R 3 R 4 ) 2 CO 3 2- A compound wherein R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom or (C 1 -C 4 )alkyl;
[0127] -guanidine carbonate;
[0128] - mixtures thereof.
[0129] More preferably, the carbonate is selected from the group consisting of sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, strontium carbonate, cerium carbonate, lanthanum carbonate, yttrium carbonate, copper (II) carbonate, manganese carbonate, nickel carbonate, silver carbonate, zirconium carbonate, bismuth carbonate, cadmium carbonate, thallium carbonate, zinc carbonate, ammonium carbonate, guanidine carbonate, tetraethylammonium carbonate, and mixtures thereof.
[0130] Even more preferably, the carbonate is selected from the group consisting of sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, cerium carbonate, manganese carbonate, zinc carbonate, ammonium carbonate, guanidine carbonate and mixtures thereof.
[0131] Most preferably, the carbonate is selected from sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, ammonium carbonate and mixtures thereof.
[0132] According to a particularly preferred embodiment, the carbonate contained in the composition is ammonium carbonate.
[0133] The carbonates and / or carbonate generating systems are preferably present in the composition in a total content ranging from 0.01% to 20% by weight, more preferably ranging from 1% to 20% by weight, and even more preferably ranging from 1% to 10% by weight relative to the total weight of the composition.
[0134] According to a preferred embodiment, the carbonate is present in the composition in a total content ranging from 0.01% to 20% by weight, preferably ranging from 1% to 20% by weight, more preferably ranging from 1% to 10% by weight relative to the total weight of the composition.
[0135] Silicate
[0136] The composition according to the invention also comprises iii) one or more silicates.
[0137] The silicate is preferably water soluble.
[0138] The term "water-soluble silicate" means a silicate having a solubility in water of greater than 0.5% by weight, preferably greater than 1% by weight, at ordinary room temperature (25°C) and atmospheric pressure (760 mmHg).
[0139] Preferably, the silicate is selected from alkali metal silicates, alkaline earth metal silicates, aluminum silicates, trimethylammonium silicate and mixtures thereof.
[0140] More preferably, the silicate is selected from the group consisting of sodium silicate, potassium silicate, calcium silicate, aluminum silicate, trimethylammonium silicate, and mixtures thereof.
[0141] Even more preferably, the silicate is selected from sodium silicate.
[0142] Preferably, the silicate is chosen from compounds having the INCI name sodium silicate (CAS: [1344-09-8]) and / or sodium metasilicate (CAS: [6834-92-0]).
[0143] Silicate is preferably present in the composition in a total content ranging from 1% to 40% by weight, more preferably ranging from 2% to 35% by weight, even more preferably ranging from 3% to 35% by weight, most preferably ranging from 4% to 20% by weight relative to the total weight of the composition.
[0144] The weight ratio of the total amount of carbonates and / or carbonate generating systems / the total amount of silicates is preferably from 0.00025 to 20, more preferably from 0.028 to 10 and even more preferably from 0.028 to 3.4.
[0145] According to a preferred embodiment, the weight ratio of the total amount of carbonates / the total amount of silicates is 0.00025 to 20, preferably 0.028 to 10, more preferably 0.028 to 3.4.
[0146] The weight ratio of total amount of carbonates and / or carbonate generating system / total amount of chemical oxidant is preferably from 0.0008 to 20, more preferably from 0.1 to 6.6 and even more preferably from 0.1 to 2.9.
[0147] According to a preferred embodiment, the weight ratio of the total amount of carbonates / the total amount of chemical oxidants is 0.0008 to 20, preferably 0.1 to 6.6 and more preferably 0.1 to 2.9.
[0148] According to a preferred embodiment, the weight ratio of the total amount of carbonates / the total amount of hydrogen peroxide is 0.0008 to 20, preferably 0.1 to 6.6 and more preferably 0.1 to 2.9.
[0149] The weight ratio of the total amount of bicarbonate and / or bicarbonate generating system / the total amount of silicate is preferably 0.00025 to 20, more preferably 0.02 to 7.5, and even more preferably 0.05 to 5.
[0150] According to a preferred embodiment, the weight ratio of the total amount of bicarbonate / the total amount of silicate is 0.00025 to 20, preferably 0.02 to 7.5, more preferably 0.05 to 5.
[0151] The weight ratio of total amount of bicarbonate and / or bicarbonate generating system / total amount of chemical oxidant is preferably from 0.0008 to 20, more preferably from 0.11 to 5 and even more preferably from 0.2 to 4.2.
[0152] According to a preferred embodiment, the weight ratio of the total amount of bicarbonate salts / the total amount of chemical oxidizing agent is 0.0008 to 20, preferably 0.11 to 5 and more preferably 0.2 to 4.2.
[0153] According to a more preferred embodiment, the weight ratio of the total amount of bicarbonate / the total amount of hydrogen peroxide is 0.0008 to 20, preferably 0.11 to 5 and more preferably 0.2 to 4.2.
[0154] The weight ratio of total amount of carbonates and / or carbonate producing system / total amount of bicarbonates and / or bicarbonate producing system is preferably 0.0005-2000, more preferably 0.06-20 and even more preferably 0.06-5.
[0155] According to a preferred embodiment, the weight ratio of the total amount of carbonates / the total amount of bicarbonates is 0.0005-2000, preferably 0.06-20 and more preferably 0.06-5.
[0156] Organic amine
[0157] The composition according to the invention also comprises iv) one or more organic amines.
[0158] The organic amines of the present invention may or may not be polymeric.
[0159] According to a preferred embodiment of the invention, the polymeric organic amine is polyaminated and hydrocarbon-based and therefore does not contain any Si atoms.
[0160] The organic amine may be chosen especially from amino polymers having a range of 500 g.mol -1 Up to 1000 000 g.mol -1 , preferably in the range of 500 g.mol -1 Up to 500 000 g.mol -1 , and preferably in the range of 500 g.mol -1 to 100000 g.mol -1 The weight average molecular weight.
[0161] According to a particular embodiment of the invention, the organic amine is a diamine and is in particular selected from the group consisting of, in particular, 2 N-ALK-O-[ALK'-O] m -ALK"-NH 2 The polyether diamine, wherein ALK, ALK' and ALK", which may be the same or different, represent a linear or branched (C 1 -C 6)alkylene, and m represents an integer greater than or equal to 0, such as 4,7,10-trioxa-1,13-tridecanediamine or the compounds known under the reference Jeffamine from Huntsman, and more particularly α,ω-diaminopolyethylene glycol and / or polypropylene glycol (having an amine function at the end of the chain), such as the products sold under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-9000 and ED-2003.
[0162] According to a particular embodiment of the invention, the organic amines are triaminated, ie they contain three primary and / or secondary amine groups, preferably primary amine groups (NH 2 ). More particularly, they are chosen especially from the formula ALK"'[(O-ALK') m -NH 2 ] 3 The polyether triamine, wherein ALK' is as previously defined and ALK"' represents a linear or branched trivalent (C 1 -C 6 ) alkylene, and m represents an integer greater than or equal to 0.
[0163] As triaminoorganic amines, mention may be made in particular of polyethertriamines and especially of α,ω-diaminopolyethylene glycols and / or polypropylene glycols (having an amine function at the end of the chain), such as the product sold under the name Jeffamine T-403.
[0164] According to another particular embodiment of the present invention, the organic amine comprises more than three primary and / or secondary amine groups, preferably primary amine groups (NH 2 ).
[0165] In this variant, the organic amine is selected from poly(meth)acrylates or poly(meth)acrylamides carrying primary or secondary amine side functional groups, such as poly(3-aminopropyl)methacrylamide and poly(2-aminoethyl)methacrylate.
[0166] According to another embodiment, the organic amine is chosen from chitosan, in particular poly(D-glucosamine) and polydimethylsiloxane comprising primary amine groups at the end of the chain and / or on the side chains.
[0167] According to another embodiment, the organic amine is particularly selected from poly(alkylene(C 2 -C 5)imines), and preferably polyethyleneimines and polypropyleneimines, especially poly(ethyleneimine), especially the product sold under the reference number 408700 by Aldrich Chemical or under the trade name Lupasol by BASF, especially with a molecular weight of 1200 to 25 000; poly(allylamine), especially the product sold under the reference number 479136 by Aldrich Chemical; polyvinylamine and copolymers thereof, especially copolymers with vinylamides, especially vinylamine / vinylformamide copolymers, such as those sold under the name BASF; Those sold in 9030; containing NH 2 amino acids based on acrylamide groups, such as polylysine, especially the products sold by JNC Corporation (formerly known as Chisso); aminodextran, especially the products sold by CarboMer Inc; aminopolyvinyl alcohol, especially the products sold by Carbomer Inc; 1 -C 6 ) alkylamine copolymers, in particular copolymers based on acrylamidopropylamine; and poly(D-glucosamine), for example marketed by the company Kytozyme under the reference number Kinutrime For sale.
[0168] As organic amines, mention may also be made of α,ω-diaminopolytetrahydrofuran (or polybutylene glycol) and α,ω-diaminopolybutadiene.
[0169] According to a particular embodiment of the invention, the organic amine is selected from hyperbranched polymers comprising at least one amino group and dendrimers carrying at least one amino group, such as PAMAM polyamidoamine dendrimers having an ethylenediamine core and terminal amine functional groups.
[0170] Preferably, the organic amine is selected from the following compounds 1d to 37d, chitosan, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof:
[0171]
[0172]
[0173]
[0174]
[0175]
[0176] More preferably, the organic amine is selected from compounds 1d, 2d, 3d, 22d, 30d, chitosan, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0177] Even more preferably, the organic amine is selected from the group consisting of compounds 2d, 30d, chitosan, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof.
[0178] Most preferably, the organic amine is selected from the group consisting of compounds 2d, 30d, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof.
[0179] The organic amine is preferably selected from the compounds of the following formula (D), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof:
[0180] R aa N(R bb )(R cc )(D)
[0181] in:
[0182] R aa , R bb and R cc Independently means:
[0183] - Hydrogen atoms;
[0184] -C 1 -C 40 Alkyl or C 2 -C 40 Alkenyl, preferably C 1 -C 40 Alkyl, the alkyl or alkenyl group is optionally substituted by at least one group selected from the group consisting of amino (-NH 2 ), acylamino (-CONH 2 ), imines such as -N=N-NH 2 (NH 2 ), hydroxyl (-OH), ester-O-CO-Ak or -CO-O-Ak, amide-NR-CO-Ak or -CO-NR-Ak1, or substituted by a (hetero)cyclic group, which is optionally substituted by one or more groups selected from the following: (poly)(hydroxy)alkyl, amino (-NH 2 ), amine-NR dd (R ee ), hydroxyl (-OH) or imine such as -N=N-NH 2 (NH 2), the alkyl or alkenyl group may also be inserted with an oxygen atom, NR, -OCO-, -CO-O-, -CO-NR-, -NR-CO- or CO group, preferably with an oxygen atom or -OCO- or -CO-O-ester;
[0185] -heterocyclic group, which is optionally substituted by one or more groups selected from the group consisting of (poly)(hydroxy)alkyl, amino (-NH 2 ), amine-NR dd (R ee ), hydroxyl (-OH) or imine such as -N=N-NH 2 (NH 2 );
[0186] R aa and R bb Together with the nitrogen atom carrying them, they can form an aromatic or non-aromatic heterocyclic group, preferably with 5 or 6 chain members, which is optionally substituted by one or more groups selected from the group consisting of (poly)(hydroxy)alkyl, amino (-NH 2 ), amine-NR dd (R ee ), hydroxyl (-OH);
[0187] It should be understood that R aa , R bb and R cc It cannot indicate hydrogen atoms at the same time;
[0188] Ak represents an alkyl or alkenyl group, preferably an alkyl group, which group is optionally substituted by at least one hydroxyl group (-OH), and which group may also be interrupted by an oxygen atom, NR or CO group;
[0189] Ak1 represents a hydrogen atom or an alkyl or alkenyl group, preferably an alkyl group, which is optionally substituted by at least one hydroxyl group (-OH) and which may also be interrupted by an oxygen atom, a group NR or CO;
[0190] R dd and R ee independently represent an alkyl or alkenyl group optionally substituted by at least one group selected from hydroxyl (-OH), said alkyl or alkenyl group possibly also interrupted by an oxygen atom, a group NR or CO;
[0191] R dd and R ee Together with the nitrogen atom carrying them, they can form an aromatic or non-aromatic heterocyclic group, preferably with 5 or 6 chain members, which is optionally substituted by one or more groups selected from the group consisting of (poly)(hydroxy)alkyl, amino (-NH 2 ) and hydroxyl (-OH);
[0192] R represents a hydrogen atom or preferably C 1 -C 4 Alkyl groups such as methyl.
[0193] According to the first embodiment, the organic amine is preferably selected from the compounds of formula (D), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof, wherein R bb and R cc Represents a hydrogen atom.
[0194] Preferably, according to this embodiment, R aa instruct:
[0195] -C 1 -C 40 Alkyl or C 2 -C 40 Alkenyl, preferably C 1 -C 40 Alkyl, wherein the alkyl or alkenyl group is optionally substituted by at least one group selected from the group consisting of hydroxyl (-OH), amino (-NH 2 ), acylamino (-CONH 2 ), imines such as -N=N-NH 2 (NH 2 ), ester-O-CO-Ak or -CO-O-Ak, or substituted by a (hetero)cyclic group, which is optionally substituted by one or more groups selected from the following: (poly)(hydroxy)alkyl, amino (-NH 2 ), amine-NR dd (R ee ), hydroxyl (-OH) or imine such as -N=N-NH 2 (NH 2 ), the alkyl or alkenyl group may also be inserted with an oxygen atom, NR, -OCO-, -CO-O-, -CO-NR-, -NR-CO- or CO group, preferably with an oxygen atom or -OCO- or -CO-O-ester;
[0196] -heterocyclic group, which is optionally substituted by one or more groups selected from the group consisting of (poly)(hydroxy)alkyl, amino (-NH 2 ), amine-NR dd (R ee ), hydroxyl (-OH) or imine such as -N=N-NH 2 (NH 2 ), preferably hydroxy or (poly)(hydroxy)alkyl.
[0197] As examples of the compound according to this embodiment, compounds 2d, 3d, 5d to 18d, 22d to 27d, 29d, 32d to 34d, 36d and 37d may be mentioned.
[0198] According to a particular variant of this embodiment, the organic amine is preferably selected from the group consisting of compounds of formula (D), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof, wherein R bb and R cc represents a hydrogen atom, and R aa represents a heterocyclic group selected from sugars as described previously, preferably a monosaccharide or polysaccharide containing 2 to 5 sugar units, preferably 2 to 3 sugar units; preferably, sugar denotes a compound (monosaccharide or disaccharide) containing 1 or 2 sugar units, in particular glucosamine or galactosamine.
[0199] According to another specific variant of this embodiment, the organic amine is preferably selected from the compounds of formula (D), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in which R bb and R cc represents a hydrogen atom, and R aa represents an alkyl or alkenyl group, preferably an amino group -NH 2 Substituted C 1 -C 40 The alkyl group, the alkyl group or the alkenyl group may be optionally substituted by at least one hydroxyl group (-OH) and / or interrupted by an oxygen atom.
[0200] According to a particular variant of this embodiment, the organic amine is preferably selected from the group consisting of compounds of formula (D), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof, wherein R bb and R cc represents a hydrogen atom, and R aa represents an alkyl or alkenyl group, preferably optionally substituted with an amino group -NH 2 Substituted C 1 -C 40 Alkyl, said alkyl or alkenyl being interrupted by at least one NR group, wherein R is as defined above, preferably represents a hydrogen atom.
[0201] According to yet another specific variant of this embodiment, the organic amine is preferably selected from the compounds of formula (D), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in which R bb and R cc indicates a hydrogen atom, and R aa represents an alkyl or alkenyl group, preferably C 1 -C 10 Alkyl, more preferably C 2 -C 10Alkyl groups optionally substituted by one or more groups selected from hydroxyl groups as described for (D) or (hetero)cyclic groups such as phenyl groups optionally substituted by OH, said alkyl or alkenyl groups further interrupted by oxygen atoms, esters -OCO- or -CO-O-.
[0202] According to another embodiment, the organic amine is preferably selected from the compounds of formula (D), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof, wherein R aa represents a hydrogen atom, and R as defined previously bb and R cc is not a hydrogen atom; preferably, R bb and R cc Independently represents C 1 -C 10 Alkyl or C 2 -C 10 Alkenyl, preferably C 1 -C 10 Alkyl, more preferably C 1 -C 6 alkyl, the alkyl or alkenyl group is optionally substituted with one or more hydroxyl (-OH) groups, or R aa and R bb Together with the nitrogen atom carrying them, they form an aromatic or non-aromatic, preferably non-aromatic, 5- or 6-membered heterocyclic group, which may be optionally substituted by one or more selected from C 1 -C 4 (poly)(hydroxy)alkyl and hydroxy (-OH) groups.
[0203] According to another embodiment, the organic amine is preferably selected from the compounds of formula (D), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof, wherein R as previously defined aa , R bb and R cc is not a hydrogen atom; preferably, R aa , R bb and R cc Independently represents C 1 -C 10 Alkyl or C 2 -C 10 Alkenyl, preferably C 1 -C 10 Alkyl, more preferably C 1 -C 6 Alkyl, the alkyl or alkenyl group is optionally substituted by one or more groups selected from hydroxyl (-OH), aromatic or non-aromatic, preferably aromatic 5-membered or 6-membered (hetero)cyclic groups, the (hetero)cyclic groups are optionally substituted by one or more groups selected from C 1 -C4 (Poly)(hydroxy)alkyl, hydroxyl (-OH) and C 1 -C 4 Preferably, R aa and R bb Independently represents C 1 -C 10 Alkyl, more preferably C 1 -C 6 alkyl, which is optionally substituted with one or more hydroxyl (-OH) groups, and R cc represents an aromatic or non-aromatic, preferably aromatic, 5- or 6-membered (hetero)cyclic group, the (hetero)cyclic group being optionally substituted by one or more selected from C 1 -C 4 (Poly)hydroxyalkyl, hydroxyl (-OH) and C 1 -C 4 Alkoxy groups are substituted.
[0204] The organic amine iv) is preferably present in the composition in a total content ranging from 0.01% to 50% by weight, more preferably ranging from 1% to 30% by weight, even more preferably ranging from 1% to 15% by weight relative to the total weight of the composition.
[0205] Compound iv')
[0206] The composition according to the invention further comprises iv') one or more compounds selected from:
[0207] a) alcohol;
[0208] b) amphoteric or zwitterionic compounds selected from the group consisting of phospholipids such as lecithin, amino acids, amphoteric or zwitterionic surfactants and mixtures thereof;
[0209] c) esters, amides, imines and mixtures thereof;
[0210] d) organic acids;
[0211] e) compounds consisting of a saturated or unsaturated, linear or branched hydrocarbon-based chain containing 1 to 30 carbon atoms, which is optionally substituted by one or more cyclic groups and / or optionally interrupted by one or more non-adjacent oxygen atoms; saturated or unsaturated, optionally aromatic, monocyclic or polycyclic, fused or non-fused carbocyclic compounds containing 3 to 22 carbon atoms, which are optionally substituted by one or more identical or different groups selected from: (C 1 -C 6 ) alkyl or (C 1 -C 6 ) alkenyl or (C 1 -C 6)an alkoxy group and / or optionally interrupted by one or more carbonyl groups (CO); a monocyclic or polycyclic, fused or non-fused, saturated or unsaturated, especially aromatic heterocyclic compound, containing 5 to 22 members and having 1 to 3 oxygen atoms, optionally substituted by one or more identical or different groups selected from: (C 1 -C 6 )alkyl or (C 1 -C 6 )alkoxy group and / or optionally interrupted by one or more carbonyl groups (CO) and mixtures thereof;
[0212] f) and mixtures thereof.
[0213] Alcohol a)
[0214] Preferably, the alcohol is selected from compounds of formula (Ia), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof:
[0215]
[0216] In formula (Ia):
[0217] ■R 1 and R 2 independently represent:
[0218] -a hydrogen atom; or
[0219] -a straight-chain or branched-chain, saturated or unsaturated hydrocarbon-based group containing 1 to 30 carbon atoms, optionally interrupted by one or more non-adjacent oxygen atoms and / or optionally substituted by one or more identical or different groups selected from: hydroxy (-OH) or (poly)(hydroxy)alkyl; or
[0220] -(hetero)cyclic group, optionally substituted by one or more identical or different groups selected from: -OR” or hydroxy (-OH);
[0221] R 1 and R 2 may together with the carbon atoms bearing them form a (hetero)cyclic group, which (hetero)cyclic group is optionally substituted by one or more identical or different groups selected from:
[0222] -hydroxy (-OH);
[0223] -(poly)(hydroxy)alkyl;
[0224] -the group -OR”;
[0225] -alkyl, which is optionally interrupted by one or more carbonyl (CO) groups and / or is optionally substituted by a (hetero)cyclyl group, which itself is optionally substituted by one or more identical or different groups selected from the group consisting of hydroxy (-OH) or (poly)(hydroxy)alkyl;
[0226] - optionally substituted by a (hetero)cyclic group, which itself is optionally substituted by one or more identical or different groups selected from the group consisting of hydroxy (-OH) or (poly)(hydroxy)alkyl;
[0227] ■R 3 express:
[0228] - a linear or branched, saturated or unsaturated or aromatic hydrocarbon-based radical comprising 1 to 30 carbon atoms, which is optionally interrupted by one or more non-adjacent oxygen atoms or one or more carbonyl groups (CO) and / or is optionally substituted by one or more identical or different radicals selected from the group consisting of hydroxyl (-OH) or (poly)(hydroxy)alkyl or -CHO or a (hetero)cyclyl radical, which itself is optionally substituted by one or more identical or different radicals selected from the group consisting of hydroxyl (-OH) or (poly)(hydroxy)alkyl or -OR" or -CHO; or
[0229] -(hetero)cyclyl, which may be optionally substituted by one or more identical or different groups selected from: -OR" or (poly)(hydroxy)alkyl or -CHO;
[0230] ■p = 0 or 1;
[0231] ■R” stands for:
[0232] - a linear or branched, saturated or unsaturated hydrocarbon-based group containing 1 to 30 carbon atoms, which is optionally substituted by one or more hydroxyl groups (-OH); or
[0233] -(hetero)cyclyl, which is optionally substituted by one or more identical or different groups selected from hydroxy (-OH) or (poly)(hydroxy)alkyl.
[0234] Preferably, the alcohol does not contain any amino groups (primary amine NH 2 , secondary amine or tertiary amine).
[0235] More preferably, the alcohol is selected from the following compounds 1a to 50a, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof:
[0236]
[0237]
[0238]
[0239]
[0240]
[0241]
[0242] Even more preferably, the alcohol is selected from Compounds 1a to 29a, 45a, 49a and 50a, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0243] More preferably, the alcohol is selected from compounds 1a, 2a, 3a, 12a, 15a, 16a, 18a, 21a, 22a, 26a, 29a, 45a and 49a, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0244] Even more preferably, the alcohol is selected from the group consisting of Compound 1a, a salt thereof, an optical isomer thereof, a geometric isomer thereof, a tautomer thereof, a solvate thereof, and a mixture thereof.
[0245] According to one form of the invention, the alcohol is chosen from compounds of formula (Ia) wherein p=1, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof.
[0246] According to another form of the invention, the alcohol is chosen from compounds of formula (Ia) wherein p=0, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof.
[0247] According to a particular variant of the invention, the alcohol is selected from the group consisting of compounds of formula (Ia), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in which p=1, R 1 and R 2 represents a hydrogen atom and R 3 express:
[0248] - a linear or branched, saturated or unsaturated or aromatic hydrocarbon-based radical comprising 1 to 30 carbon atoms, preferably linear or branched and saturated or unsaturated, which is optionally interrupted by one or more non-adjacent oxygen atoms or one or more carbonyl groups (CO), preferably not interrupted, and / or is optionally substituted by one or more identical or different radicals selected from hydroxyl (OH), -CHO or (hetero)cyclyl, such as phenyl, which itself is optionally substituted by one or more identical or different radicals selected from OH, -OR" or -CHO; or
[0249] -(hetero)cyclyl, optionally substituted by one or more identical or different groups selected from OH, -OR" or (poly)(hydroxy)alkyl or -CHO; R" is as previously defined.
[0250] As examples of alcohols of formula (Ia) according to this variant, mention may be made of compounds 1a, 2a, 3a, 6a, 7a, 8a, 9a, 11a, 12a, 13a, 14a, 15a, 16a, 18a, 19a, 20a, 21a, 22a, 23a, 24a, 25a, 26a, 28a, 29a, 31a, 32a, 33a, 34a, 37a, 43a, 45a, 46a, 49a, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof.
[0251] According to a preferred variant, the alcohol is selected from the group consisting of compounds of formula (Ia), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in which p=1, R 1 and R 2 represents a hydrogen atom and R 3 denotes a linear or branched, saturated or unsaturated hydrocarbon-based radical comprising 1 to 30 carbon atoms, which is optionally interrupted by one or more non-adjacent oxygen atoms or one or more carbonyl groups (CO), preferably not interrupted, and / or is optionally substituted by one or more hydroxyl groups (OH).
[0252] According to a specific embodiment, the alcohol is selected from the group consisting of compounds of formula (Ia), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof, wherein p=1, R 1 and R 2 represents a hydrogen atom and R 3 denotes a (hetero)cyclic radical, preferably having 5 or 6 chain members, more preferably a pyranose ring or a furanose ring, which is optionally substituted by one or more identical or different radicals selected from: OH, -OR" or (poly)(hydroxy)alkyl or -CHO; R" is as defined previously.
[0253] According to another particular embodiment, the alcohol is indicative of a sugar or a sugar derivative.
[0254] For the purposes of the present invention, the term "sugar" means a monosaccharide or polysaccharide comprising 2 to 5 saccharide units, preferably 2 to 3 saccharide units, more preferably sugar indicates a compound (monosaccharide or disaccharide) comprising 1 or 2 saccharide units.
[0255] It should be understood that for sugar, when sugar represents a monosaccharide, it can be in pyranose form (the sugar heterocycles constituting it have 6 chain members) or furanose form (the sugar heterocycles constituting it have 5 chain members); and when sugar represents a polysaccharide group, it comprises a sequence of 2 to 5 sugar units, which can be identical or different from each other and can be in furanose or pyranose form. Preferably, the polysaccharide is a disaccharide, which is produced by the connection of a sugar unit in the form of furanose to a unit in the form of pyranose, or a sugar unit in the form of pyranose to a unit in the form of furanose. Whether it is a monosaccharide or a polysaccharide, each sugar unit can be in L left-handed or D right-handed form, as well as in α or β anomeric form.
[0256] Preferably, the monosaccharide is selected from the group consisting of glucose, galactose, mannose, xylose, lyxose, fucose, arabinose, rhamnose, isorhamnose, fructose, sorbose, talose and mixtures thereof. Preferably, the disaccharide is selected from the group consisting of lactose, maltulose, palatinose, lactulose, amygdalin, turanose, cellobiose, isomaltose, rutinose, maltose and mixtures thereof.
[0257] For the purposes of the present invention, the term "sugar derivative" means a compound in which one or more hydroxyl groups (OH) carried by a furanose or pyranose ring are replaced by one or more alkoxy groups (OR) (wherein R" is as defined previously). As an example of a sugar derivative, mention may be made of compound 13a.
[0258] According to another particular embodiment, the alcohol is selected from the compounds of formula (Ia) (such that p=0), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof, and R 1 and R 2 Together with the carbon atoms carrying them, they form an aromatic or non-aromatic, preferably 6-membered (hetero)cyclic radical, which may be optionally substituted by one or more identical or different radicals selected from:
[0259] -Hydroxy (-OH);
[0260] -(poly)(hydroxy)alkyl;
[0261] - a group -OR", wherein R" is as previously defined;
[0262] -alkyl or alkenyl, which is optionally interrupted by one or more carbonyl (CO) groups, preferably not interrupted, and / or is optionally substituted by a (hetero)cyclic group, which itself is optionally substituted by one or more identical or different groups selected from the following: hydroxy (-OH) or (poly)(hydroxy)alkyl; more preferably, alcohol indicates a saturated or aromatic 5- or 6-membered ring with at least one hydroxy (-OH), preferably hydroxy (-OH), group, and optionally substituted by one or more groups -OR" (wherein R" is as previously defined).
[0263] As examples of alcohols of formula (Ia) according to this variant, mention may be made of compounds 17a, 38a, 39a and 41a.
[0264] When present in the composition, the alcohol is preferably present in the composition in a content ranging from 0.01% to 50% by weight, more preferably ranging from 0.1% to 30% by weight, even more preferably ranging from 0.2% to 15% by weight relative to the total weight of the composition.
[0265] Amphoteric or zwitterionic compounds b)
[0266] The amphoteric or zwitterionic compound is selected from the group consisting of phospholipids such as lecithin, amino acids, amphoteric or zwitterionic surfactants, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof.
[0267] Phospholipids
[0268] The phospholipids may be of vegetable or animal origin and may be present in pure form or as a mixture.
[0269] Preferably, the phospholipids are of vegetable origin.
[0270] The phospholipids are preferably selected from lecithin.
[0271] The lecithin that can be used according to the invention can be hydrogenated or non-hydrogenated.
[0272] Unhydrogenated lecithin is usually obtained from vegetable or animal fatty substances by lipid extraction using non-polar solvents. This lipid fraction usually contains mainly glycerophospholipids, including phosphatidylcholine.
[0273] Animal or vegetable sources from which unhydrogenated lecithins can be extracted are, for example, soy beans, sunflowers or eggs. The glycerophospholipids included in these lecithins in high proportions are mainly phosphatidylcholine and phosphatidylethanolamine.
[0274] Preferably, the lecithin is of vegetable origin.
[0275] Unhydrogenated lecithin suitable for use herein may be lecithin derived from soy, sunflower or egg and / or mixtures thereof.
[0276] Lecithin is usually supplied dissolved in fatty acids, triglycerides or other solvents, or in powder or block form.
[0277] They are generally mixtures of lecithins, wherein the glycerophospholipid content in the commercially available products generally ranges from about at least 15% to about at least 95%.
[0278] Among the unhydrogenated lecithins that may be suitable for use in the cosmetic compositions according to the invention, mention may be made of the lecithins sold under the trade name Nattermann Phospholipon and Phosale Lecithins sold as lecithin, Epikuron 145V, Topcithin 300, Emulmetik 930, Ovothin 200 and organic lecithin sold by Lucas Meyer, Lipoid S20 sold by Lipoid Kosmetik, and Alcolec F 100 sold by American Lecithin Company.
[0279] The phospholipids may be selected from hydrogenated lecithin.
[0280] These hydrogenated lecithins are obtained by controlled hydrogenation of non-hydrogenated lecithins as described above.
[0281] As hydrogenated lecithin that can be used in the composition according to the invention, mention may be made of the product sold by Nikko under the reference Nikkol Lecinol S10.
[0282] Amino Acids
[0283] The amino acid may be selected from acidic amino acids, basic amino acids, polar neutral amino acids and non-polar neutral amino groups and mixtures thereof. The amino acid may be in D or L form or in a mixture.
[0284] The term "acidic amino acid" means an amino acid containing more acidic functional groups than basic functional groups, in particular a protein-forming amino acid whose side chain contains an acidic functional group. As examples of acidic amino acids, mention may be made of aspartic acid, glutamic acid and mixtures thereof.
[0285] The term "basic amino acid" means an amino acid containing more basic functional groups than acidic functional groups, in particular a protein-forming amino acid whose side chain contains a basic functional group. As examples of basic amino acids, arginine, histidine, lysine and mixtures thereof may be mentioned.
[0286] The term "polar neutral amino acid" means an amino acid that is uncharged at pH = 7 and contains a polar chemical functional group (such as a thiol, alcohol or phenol, or a basic amide CONH 2 As examples of polar neutral amino acids, there may be mentioned serine, threonine, cysteine, asparagine, glutamine, tyrosine and mixtures thereof.
[0287] The term "non-polar neutral amino acid" means an amino acid that is uncharged and non-polar at pH = 7. As examples of non-polar neutral amino acids, there may be mentioned amino acids selected from glycine, alanine, valine, leucine, isoleucine, methionine, phenylalanine, tryptophan, proline and mixtures thereof.
[0288] Amphoteric or zwitterionic surfactants
[0289] Amphoteric or zwitterionic surfactants may be optionally quaternized aliphatic secondary or tertiary amine derivatives, wherein the aliphatic radical is a straight or branched chain containing 8 to 22 carbon atoms and the amine derivative contains at least one anionic group, for example a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.
[0290] Special mention can be made of (C 8 -C 20 ) alkyl betaine, (C 8 -C 20 ) alkyl sulfobetaine, (C 8 -C 20 ) alkylamide (C 3 -C 8 ) alkyl betaine, (C 8 -C 20 ) alkylamide (C 6 -C 8 ) alkyl sulfobetaine and (C 8 -C 20 ) alkylamide (C 3 -C 8 )Alkyl hydroxysulfonate.
[0291] Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that can be used as defined above, mention may also be made of the compounds of the corresponding formulae (3) and (4) below:
[0292] R a -CONHCH 2 CH 2 -N + (R b )(R c )-CH 2 COO - ,M + ,X - (3)
[0293] in:
[0294] -R a denotes an acid R derived from preferably present in hydrolyzed coconut kernel oil a C of COOH10 To C 30 alkyl or alkenyl, or heptyl, nonyl or undecyl;
[0295] -R b represents β-hydroxyethyl; and
[0296] -R c represents carboxymethyl;
[0297] -M + represents a cationic counter ion derived from an alkali metal or alkaline earth metal such as sodium, an ammonium ion, or an ion derived from an organic amine, and
[0298] -X - represents an organic or inorganic anion counterion, such as selected from halide, acetate, phosphate, nitrate, (C 1 -C 4 ) alkyl sulfate, (C 1 -C 4 ) alkyl sulfonate or (C 1 -C 4 ) anionic counterions of alkylarylsulfonates, in particular methylsulfate and ethylsulfate; or alternatively, M + and X - does not exist;
[0299] R a' -CONHCH 2 CH 2 -N(B)(B')(4)
[0300] in:
[0301] -B represents the group -CH 2 CH 2 OX';
[0302] -B' represents a group -(CH 2 ) z Y', where z = 1 or 2;
[0303] -X' represents the group -CH 2 COOH, -CH 2 -COOZ'、-CH 2 CH 2 COOH or CH 2 CH 2 -COOZ', or a hydrogen atom;
[0304] -Y' represents a group -COOH, -COOZ' or -CH 2 CH(OH)SO 3 H or group CH 2 CH(OH)SO3 -Z';
[0305] -Z' represents a cationic counter ion derived from an alkali metal or alkaline earth metal such as sodium, an ammonium ion, or an ion derived from an organic amine;
[0306] -R a’ represents the acid R preferably present in hydrolyzed linseed oil or coconut oil a’ -COOH C 10 To C 30 Alkyl or alkenyl, alkyl, especially C 17 Alkyl and its isomeric forms, or unsaturated C 17 Group.
[0307] These compounds are classified in the CTFA Dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caproamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caproamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.
[0308] By way of example, mention may be made of the product sold by Rhodia under the trade name Cocoamphodiacetate sold by C2M Concentrate.
[0309] Compounds of formula (5) may also be used:
[0310] R a” -NHCH(Y”)-(CH 2 ) n CONH(CH 2 ) n’ -N(R d )(R e ) (5)
[0311] in:
[0312] -Y" represents a group -COOH, -COOZ" or -CH 2 CH(OH)SO 3 H or group CH 2 CH(OH)SO 3 -Z";
[0313] -R d and R e Independently represent C 1 To C 4 Alkyl or hydroxyalkyl;
[0314] -Z" represents a cationic counter ion derived from an alkali metal or alkaline earth metal such as sodium, an ammonium ion, or an ion derived from an organic amine;
[0315] -R a” represents the acid R preferably present in hydrolyzed linseed oil or coconut oil a” -COOH C 10 To C 30 Alkyl or alkenyl;
[0316] -n and n' indicate an integer ranging from 1 to 3 independently of each other.
[0317] Among the compounds of formula (5), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoyl aspartamide and sold under the name Chimexane HB by the company Chimex.
[0318] These compounds may be used alone or as a mixture.
[0319] Preferably, the amphoteric or zwitterionic surfactants are selected, alone or as a mixture, from (C 8 -C 20 ) alkyl betaine, (C 8 -C 20 ) alkyl sulfobetaine, (C 8 -C 20 ) alkylamide (C 3 -C 8 ) alkyl betaine, (C 8 -C 20 ) alkylamide (C 6 -C 8 ) alkyl sulfobetaine and (C 8 -C 20 ) alkylamide (C 3 -C 8 ) alkylhydroxysultaines, and also compounds of formula (3), (4) and (5) as defined above.
[0320] More preferably, the amphoteric or zwitterionic surfactants are selected, alone or as a mixture, from (C 8 -C 20 ) alkyl betaine (such as cocoyl betaine), (C 8 -C 20 ) alkylamide (C 3 -C 8 ) alkyl betaines (such as cocamidopropyl betaine) and (C 8 -C 20 ) alkylamide (C 3 -C 8) alkyl hydroxysultaines (such as cocamidopropyl hydroxysultaine).
[0321] Even more preferably, the amphoteric or zwitterionic surfactant is selected from (C 8 -C 20 ) alkylamide (C 3 -C 8 ) alkyl betaines (such as cocamidopropyl betaine) and (C 8 -C 20 ) alkylamide (C 3 -C 8 ) alkyl hydroxysultaines (such as cocamidopropyl hydroxysultaine).
[0322] Preferably, the amphoteric or zwitterionic compound is selected from the following compounds 1b to 28b, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof:
[0323]
[0324]
[0325]
[0326]
[0327]
[0328] More preferably, the amphoteric or zwitterionic compound is selected from compounds 2b, 10b, 12b, 15b, 17b, 18b, 24b, 27b and 28b, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0329] Even more preferably, the amphoteric or zwitterionic compound is selected from compound 28b, a salt thereof, a solvate thereof, and a mixture thereof.
[0330] According to an embodiment, the amphoteric or zwitterionic compound has the formula R b -CO-XZ(B1), where R b Indicates (C 1 -C 30 ) alkyl, preferably (C 1 -C 20 ) alkyl, more preferably (C 8 -C 16 ) alkyl, X represents an oxygen atom or NH, preferably NH, and Z represents a straight or branched hydrocarbon-based group containing 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, the group Z being substituted by a carboxyl group (COOH) and an amino group.
[0331] As an example of a compound of formula (B1), mention may be made of compound 3b.
[0332] According to another embodiment, the amphoteric or zwitterionic compound has the formula R 1 -N(R 2 )-[Y] t -Z(B2), where R 1 and R 2 independently represent a hydrogen atom or an alkyl group; preferably, R 1 represents a hydrogen atom and R 2 represents an alkyl group, Y represents CO or CONH, t is 0 or 1, and Z represents a linear or branched hydrocarbon-based group having 1 to 30 carbon atoms, the group Z being substituted with a carboxyl group (COOH) and an amino group.
[0333] As examples of compounds of formula (B2), mention may be made of compounds 5b, 20b and 26b.
[0334] According to a preferred embodiment, the amphoteric or zwitterionic compound has the formula R 1 -N + (R 2 )(R 3 )-Z'-COO - (B3), where R 1 , R 2 and R 3 independently represent an alkyl group, preferably C 1 -C 20 Alkyl groups such as methyl groups, which may be optionally substituted with amide groups -NH-CO-R 4 Substitution, where R 4 Represents C 1 -C 30 (Hydroxy)alkyl, Z' represents a divalent straight or branched hydrocarbon-based group containing 1 to 30 carbon atoms, the group Z' being optionally substituted with one or more hydroxyl (OH) groups.
[0335] As examples of compounds of formula (B3), mention may be made of compounds 15b, 19b and 27b.
[0336] According to another embodiment, the amphoteric or zwitterionic compound has the formula NH 2 -Z'-COOH(B4), wherein Z' represents a linear or branched divalent hydrocarbon-based group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, which group Z' is optionally substituted by one or more hydroxyl (OH) groups, preferably unsubstituted.
[0337] As examples of compounds of formula (B4), mention may be made of compounds 21b, 22b and 28b.
[0338] When amphoteric or zwitterionic compounds are present in the composition, they are preferably present in the composition in a content ranging from 0.01% to 50% by weight, more preferably ranging from 0.1% to 30% by weight, even more preferably ranging from 0.2% to 15% by weight relative to the total weight of the composition.
[0339] Esters, amides and imines c)
[0340] Preferably, compound c) is selected from the group consisting of compounds of the following formula (Ic), salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof:
[0341]
[0342] In formula (Ic):
[0343] ■ A represents a linear or branched, saturated or unsaturated hydrocarbon-based radical comprising 1 to 30 carbon atoms, which is optionally interrupted by one or more non-adjacent oxygen atoms and / or one or more identical or different radicals selected from: -CO-, -OCO-, -COO-, and / or is optionally substituted by one or more identical or different radicals selected from: hydroxyl (-OH), a radical -COOAk1, a (hetero)cyclic radical optionally substituted by one or more hydroxyl (-OH);
[0344] ■X 1 independently represents an oxygen atom or a group -NR-, preferably an oxygen atom;
[0345] ■X 2 represents an oxygen atom or a group -NR-, preferably an oxygen atom;
[0346] ■p = 0 or 1;
[0347] ■ B represents a saturated or unsaturated, linear or branched or cyclic hydrocarbon-based group containing 1 to 40 carbon atoms, which is optionally substituted by one or more identical or different groups selected from:
[0348] - (hetero)cyclyl, which is optionally substituted by one or more identical or different groups selected from the group consisting of hydroxy (-OH), -OR", -COOA', -OCOA', (poly)(hydroxy)alkyl;
[0349] -group -OR';
[0350] -group -COOA';
[0351] -group-OCOA';
[0352] and / or optionally interrupted by one or more non-adjacent oxygen atoms and / or one or more identical or different groups selected from: -OCO-, -COO-;
[0353] ■ A' represents a linear or branched, saturated or unsaturated hydrocarbon-based group containing 1 to 30 carbon atoms, which is optionally interrupted by one or more non-adjacent oxygen atoms and / or one or more identical or different groups selected from the following: -CO-, -OCO-, -COO-, and / or is optionally substituted by one or more identical or different groups selected from the following: hydroxyl (-OH), -COOAk1;
[0354] ■ R represents a hydrogen atom or an alkyl group, especially (C 1 -C 4 )alkyl;
[0355] ■ R' represents a hydrogen atom or an alkyl group which is optionally substituted by one or more identical or different groups selected from the group consisting of: hydroxyl (-OH) or -OCOA';
[0356] ■R” stands for:
[0357] - an alkyl group optionally substituted with one or more hydroxyl groups (-OH); or
[0358] - (hetero)cyclyl, which may be optionally substituted by one or more identical or different groups selected from: hydroxy (-OH), (poly)(hydroxy)alkyl;
[0359] ■Ak1 represents an alkyl group optionally substituted with -COOAk2;
[0360] ■Ak2 represents an alkyl group;
[0361] R and B may form a heterocyclic ring together with the nitrogen atom carrying them;
[0362] A and B may together form a heterocyclic ring which is optionally substituted, in particular, by one or more identical or different groups selected from:
[0363] - (hetero)cyclyl, which is optionally substituted, in particular, by one or more identical or different radicals selected from: hydroxy (-OH), (poly)(hydroxy)alkyl;
[0364] -Hydroxy (-OH);
[0365] -group-OR";
[0366] -(poly)(hydroxy)alkyl;
[0367] It should be understood that if X 1 represents a group -NR-, then A and B may represent hydrogen atoms.
[0368] More preferably, compound c) is selected from the following compounds 1c to 94c, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof:
[0369]
[0370]
[0371]
[0372]
[0373]
[0374]
[0375]
[0376]
[0377]
[0378]
[0379]
[0380]
[0381]
[0382]
[0383]
[0384]
[0385] Even more preferably, compound c) is selected from compounds 1c to 63c and 94c, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof.
[0386] Preferably, compound c) is selected from compounds 1c, 4c, 5c, 6c, 8c, 12c, 15c, 16c, 22c, 24c, 26c, 27c, 31c, 33c, 37c, 41c, 53c, 54c, 55c, 58c, 60c, 62c, 63c and 94c, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof.
[0387] Even more preferably, compound c) is selected from compound 12c, a salt thereof, an optical isomer thereof, a geometric isomer thereof, a tautomer thereof, a solvate thereof, and a mixture thereof.
[0388] According to a preferred variant of the invention, compound c) is selected from compounds of formula (Ic), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in which p=0 and X1 and X2 represent oxygen atoms. According to this variant, compound c) preferably refers to compounds of the following formula (C1), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof:
[0389] A 1 -CO-OB 1 (C1)
[0390] in:
[0391] -A 1 Represents C 1 -C 40 Alkyl or alkenyl, which is optionally substituted by one or more hydroxyl (OH) groups, and / or optionally interrupted by -OCO-, CO-O-, -O- or CO-NR or CO, wherein R is as defined above, preferably (C 1 -C 4 ) alkyl such as methyl;
[0392] -B 1 Represents C 1 -C 40 Alkyl or alkenyl, which may be substituted by one or more identical or different groups selected from the following: hydroxyl (OH), (hetero) cyclyl, which may be substituted by one or more identical or different groups selected from the following: hydroxyl (OH), -OR b 、-O-CO-A 3 The group substituted, wherein A 3 Represents C 1 -C 40 alkyl or alkenyl, and R b Preferably, C 1 -C 6 Alkyl; and / or optionally inserted with -O-CO-, -CO-O-, -CO-NR' a -、-NR' a -CO-, oxygen atom -O- or -CO-, where R' a Represents a hydrogen atom or C 1 -C 10 Alkyl, preferably C 1 -C 4 Alkyl groups, such as methyl.
[0393] As examples of compounds of formula (C1), mention may be made of compounds 1c to 8c, 9c to 30c, 32c to 35c, 36c to 39c, 41c to 48c, 50c to 63c, 65c to 69c, 73c, 74c, 76c, 78c to 82c, 84c, 85c, 91c, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in particular compounds 1c, 4c, 5c, 6c, 8c, 12c, 15c, 16c, 22c, 24c, 26c, 27c, 33c, 37c, 41c, 53c, 54c, 55c, 58c, 60c, 62c and 63c, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in particular compounds 8c and 58c, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof.
[0394] According to another variant of the invention, compound c) is selected from compounds of formula (Ic), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, wherein p=0 and X1 and X2 indicate oxygen atoms, and compounds of the following formula (C2), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof:
[0395] A 2 -CO-OB 2 (C2)
[0396] in:
[0397] -A 2 and B 2 Together with the atoms carrying them, they form an aromatic or nonaromatic heterocyclic group which is optionally substituted, in particular, by one or more identical or different groups selected from:
[0398] - (hetero)cyclyl, which is optionally substituted, in particular, by one or more identical or different radicals selected from: hydroxy (-OH), (poly)(hydroxy)alkyl;
[0399] -Hydroxy (-OH);
[0400] -group -OR", wherein R" is as previously defined; in particular, R" indicates C 1 -C 6 Alkyl groups, such as ethyl;
[0401] -(Poly)(hydroxy)alkyl.
[0402] As examples of the compound of formula (C2), there can be mentioned compounds 40c, 75c, 90c, 92c, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0403] According to another variant of the invention, compound c) is chosen from compounds of formula (Ic), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in which formula (Ic), p=1 and X1 and X2 indicate oxygen atoms.
[0404] According to this variant, compound c) preferably refers to a compound of the following formula (C3), its salts, its optical isomers, its geometric isomers, its tautomers, its solvates and mixtures thereof:
[0405] A 4 -O-CO-OB 4 (C3)
[0406] in:
[0407] ■A 4 and B 4 Independently represents C 1 -C 40 , preferably C 1 -C 20 , more preferably C 1 -C 10 alkyl or alkenyl, which may be optionally substituted by one or more hydroxyl groups (OH), -OR", wherein R" is as defined above, in particular R" represents C 1 -C 6 Alkyl, such as methyl or (poly)(hydroxy)alkyl, which is preferably unsubstituted and / or optionally interrupted by -OCO-, CO-O-, -O-, CO-NR a , where R a Indicates hydrogen atoms or preferably C 1 -C 4 an alkyl or CO group, which is preferably interrupted by -O-, more preferably not interrupted; or
[0408] A 4 and B 4 Together with the atoms carrying them, they form an aromatic or nonaromatic heterocyclic group which is optionally substituted, in particular, by one or more identical or different groups selected from:
[0409] - (hetero)cyclyl, which is optionally substituted, in particular, by one or more identical or different radicals selected from: hydroxy (-OH), (poly)(hydroxy)alkyl;
[0410] -Hydroxy (-OH);
[0411] - a group -OR", wherein R" is as previously defined; in particular, R" represents C 1 -C 6 Alkyl groups, such as methyl;
[0412] -(poly)(hydroxy)alkyl, such as C 1 -C 6 Alkyl, C 1 -C 6 Hydroxyalkyl or C 1 -C 6 Polyhydroxyalkyl.
[0413] Preferably, the compound of formula (C3) is such that A 4 and B 4 are the same.
[0414] Preferably, A 4 and B 4 Independently indicate the preference for linear C 1 -C 10 Alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, heptyl or octyl.
[0415] Preferably, when A 4 and B 4 When together with the atoms carrying them form an aromatic or non-aromatic heterocyclic group, the heterocyclic group may be optionally substituted by one or more identical or different groups selected from:
[0416] - a group -OR", wherein R" is as previously defined; in particular, R" represents C 1 -C 6 Alkyl groups, such as methyl or ethyl;
[0417] -(poly)(hydroxy)alkyl, such as C 1 -C 6 Alkyl, C 1 -C 6 Hydroxyalkyl or C 1 -C 6 Polyhydroxyalkyl.
[0418] As examples of the compound of formula (C3), there can be mentioned compounds 31c, 70c, 71c, 72c, 77c, 93c, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0419] According to another variant of the invention, compound c) is chosen from compounds of formula (Ic), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in which formula (Ic), p=0 and X1 and X2 indicate oxygen atoms.
[0420] According to this variant, compound c) preferably refers to a compound of the following formula (C4), its salts, its optical isomers, its geometric isomers, its tautomers, its solvates and mixtures thereof:
[0421] A 5 -CO-NR b -B 5 (C4)
[0422] in:
[0423] ■A 5 and B 5 Independently represents C 1 -C 40 , preferably C 1 -C 20 alkyl or alkenyl, which may be optionally substituted with one or more hydroxyl groups (OH), -OR", wherein R" is as previously defined; in particular, R" represents C 1 -C 6 Alkyl, such as methyl or (poly)(hydroxy)alkyl, which is preferably unsubstituted and / or optionally interrupted by -OCO-, CO-O-, -O-, CO-NR a , where R a represents a hydrogen atom or preferably C 1 -C 4 Alkyl or CO, preferably interrupted by -O-, more preferably not interrupted; or
[0424] A 5 and B 5 Together with the atoms carrying them, they form an aromatic or nonaromatic heterocyclic group which is optionally substituted, in particular, by one or more identical or different groups selected from:
[0425] - heterocyclic groups, which are optionally substituted, in particular, by one or more identical or different groups selected from the group consisting of hydroxy (-OH) and (poly)(hydroxy)alkyl, said heterocyclic groups possibly also containing one or more CO;
[0426] -Hydroxy (-OH);
[0427] - a group -OR", wherein R" is as previously defined; in particular, R" represents C 1 -C 6 Alkyl groups, such as methyl or ethyl;
[0428] -(poly)(hydroxy)alkyl, such as C 1 -C 6 Alkyl, C 1 -C 6 Hydroxyalkyl or C 1 -C 6polyhydroxyalkyl; and
[0429] ■R b Indicates hydrogen atoms or C 1 -C 20 Alkyl, preferably C 1 -C 10 Alkyl, more preferably C 1 -C 4 Alkyl groups, such as methyl or ethyl.
[0430] As examples of the compound of formula (C4), there can be mentioned compounds 88c, 71c, 72c, 77c, 93c, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0431] According to another variant of the invention, compound c) is selected from compounds of formula (Ic), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, in which p=1, and X1 represents a group -NR-, and X2 represents a group -NR- or an oxygen atom, wherein R represents a hydrogen atom or an alkyl group, in particular (C 1 -C 4 )alkyl;
[0432] According to this variant, compound c) preferably refers to a compound of the following formula (C5), its salts, its optical isomers, its geometric isomers, its tautomers, its solvates and mixtures thereof:
[0433] A 6 -NR-C=X1-NR-B 6 (C5)
[0434] in:
[0435] ■A 6 and B 6 independently represent hydrogen atoms, C 1 -C 20 , preferably C 1 -C 10 Alkyl or alkenyl, which is optionally substituted, preferably unsubstituted, by one or more hydroxyl (OH), -OR" or (poly)(hydroxy)alkyl, and / or optionally interrupted, preferably not interrupted, by -OCO-, CO-O-, -O- or CO; or
[0436] A 6 and B 6 Together with the atoms carrying them, they form an aromatic or nonaromatic heterocyclic group which is optionally substituted, in particular, by one or more identical or different groups selected from:
[0437] -Hydroxy (-OH);
[0438] -group -OR", wherein R" is as previously defined; in particular, R" indicates C 1 -C 6 Alkyl groups, such as methyl;
[0439] -(poly)(hydroxy)alkyl, such as C 1 -C 6 Alkyl, C 1 -C 6 Hydroxyalkyl or C 1 -C 6 Polyhydroxyalkyl, preferably C 1 -C 4 Alkyl groups, such as methyl;
[0440] ■ R represents a hydrogen atom or an alkyl group, especially (C 1 -C 4 ) alkyl, such as methyl or ethyl.
[0441] Preferably, when A 6 and B 6 When together with the atoms carrying them form an aromatic or non-aromatic heterocyclic group, the heterocyclic group may be optionally substituted by one or more identical or different groups selected from the following: 1 -C 6 Alkyl, preferably C 1 -C 4 Alkyl groups, such as methyl;
[0442] As examples of the compound of formula (C5), there can be mentioned compounds 49c, 64c, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0443] When compounds c) are present in the composition, they are preferably present in a content ranging from 0.01% to 50% by weight, more preferably ranging from 0.1% to 30% by weight and even more preferably ranging from 0.2% to 15% by weight relative to the total weight of the composition.
[0444] Organic acid d)
[0445] Preferably, the organic acid is selected from the compounds of the following formula (I) and / or (II), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof:
[0446]
[0447] In formula (I):
[0448] ■X represents a carbon atom or S=O or P-OH, preferably a carbon atom;
[0449] ■A represents the group -OR 4 or group-CR 1 (R 2 )p(R 3 ), it is understood that if X represents P-OH, then A represents a group -OR 4 ;
[0450] ■p = 0 or 1;
[0451] ■R 1 represents a hydrogen atom or a hydroxyl group (-OH) or a group -NR a -R c or group -NR a -CO-R c ;
[0452] ■R 2 represents a hydrogen atom or a hydroxyl group (-OH) or a group -X(O)OH, wherein X is as defined previously, in particular wherein X represents a carbon atom;
[0453] ■R 3 represents a hydrogen atom or a hydroxyl group (-OH) or a (hetero)cyclic group which is optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl, especially (C 1 -C 4 ) alkyl such as methyl, alkylcarbonyl-(CO)-R c , alkylcarbonyloxy-O-CO-R c , alkoxycarbonyl-CO-OR c , -OH, (C 1 -C 6 ) alkoxy, especially (C 1 -C 4 )alkoxy such as methoxy, -X(O)OH, wherein X is as previously defined, in particular wherein X represents a carbon atom, or -OX(O)OH, wherein X is as previously defined, or R 3 represents an alkyl or alkenyl group or an alkylamino group or an alkylamide group, wherein the alkyl or alkenyl group or an alkylamino group or an alkylamide group is:
[0454] - optionally substituted by one or more identical or different groups selected from the group -X(O)OH, wherein X is as defined previously, in particular wherein X represents a carbon atom; a hydroxyl (-OH) group or a (hetero)cyclyl group; and / or
[0455] - optionally interrupted by one or more heteroatoms or groups selected from: -O-, -NR a -, -S-, -CO- or a combination thereof, such as -O-CO-, -(CO)-O-, -NRa -(CO)- or -(CO)-NR a -;
[0456] R 1 and R 3 Together with the carbon atoms carrying them, they may form a (hetero)cyclic group, which may be optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl, especially (C 1 -C 4 ) alkyl such as methyl, alkylcarbonyl-(CO)-R c , alkylcarbonyloxy-O-CO-R c , alkoxycarbonyl-CO-OR c 、-OH、(C 1 -C 6 ) alkoxy, especially (C 1 -C 4 )alkoxy such as methoxy, -X(O)OH, wherein X is as previously defined, in particular wherein X represents a carbon atom or -OX(O)OH, wherein X is as previously defined, in particular wherein X═P-OH;
[0457] R 1 and R 3 can form carbonyl -CO- together with the carbon atom that bears them;
[0458] ■R 4 represents a hydrogen atom or an alkyl or alkenyl or (hetero)cyclyl group, which may be optionally substituted by one or more identical or different groups selected from: a group -X(O)OH, wherein X is as defined previously, in particular wherein X represents a carbon atom or P-OH; a hydroxyl (-OH) or (hetero)cyclyl group;
[0459] ■R a represents a hydrogen atom or (C 1 -C 4 )alkyl, wherein X is as previously defined, in particular wherein X represents a carbon atom;
[0460] ■R c represents an alkyl or alkenyl group or an alkylamino group or an alkylamide group, wherein the alkyl or alkenyl group or an alkylamino group or an alkylamide group is:
[0461] - optionally substituted by one or more identical or different groups selected from: a group -X(O)OH, wherein X is as defined previously, in particular wherein X represents a carbon atom; a hydroxyl (-OH) group or a (hetero)cyclyl group; and / or
[0462] - optionally interrupted by one or more heteroatoms or groups selected from: -O-, -S-, -CO-, -O-CO-, -O-CO-, -NR a -(CO)- or -(CO)-NR a -;
[0463] P-(CHO) m (COOY) n (II)
[0464] In formula (II):
[0465] ■ P represents a polysaccharide chain composed of monosaccharides containing 5 carbon atoms or more than 5 carbon atoms, preferably 6 carbon atoms or more than 6 carbon atoms and more particularly 6 carbon atoms;
[0466] ■ Y is selected from a hydrogen atom, ions derived from alkali metals or alkaline earth metals 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;
[0467] ■m+n is greater than or equal to 1;
[0468] ■ m is the degree of substitution of the polysaccharide by one or more aldehyde groups (DS(CHO)), which is in the range of 0.001 to 2 and preferably 0.005 to 1.5;
[0469] ■ n is the degree of substitution of the polysaccharide by one or more carboxyl groups (DS(COOX)), which ranges from 0 to 2 and preferably from 0.001 to 1.5.
[0470] The expression "degree of substitution DS(CHO) or DS(COOX) of the polysaccharide according to the invention" means the ratio between the number of carbons oxidized to give aldehyde or carboxyl groups and the number of basic monosaccharides constituting the polysaccharide (even ring-opened by pre-oxidation) for all repeating units.
[0471] The groups CHO and COOX may be obtained during the oxidation of certain carbon atoms of a sugar unit containing 6 carbon atoms, for example at position C2, C3 or C6. Preferably, the oxidation may be carried out at C2 and C3, more particularly at 0.01% to 75% and preferably at 0.1% to 50%, based on the number of rings that may have been opened.
[0472] The polysaccharide chain represented by P is preferably selected from inulin, cellulose, starch, guar gum, xanthan gum, pullulan, alginate gum, agar-agar gum, carrageenan, gellan gum, gum arabic, xylose and tragacanth, and derivatives thereof, cellobiose, maltodextrin, scleroglucan, chitosan, ulvan, fucoidan, alginate, pectin, heparin, hyaluronic acid or mixtures thereof, more preferably selected from inulin or starch. Even more preferably, the polysaccharide chain is inulin.
[0473] The term "derivatives" means compounds obtained by chemical modification of the compounds mentioned. They may be esters, amides or ethers of said compounds.
[0474] The oxidation can be carried out according to methods known in the art, for example according to FR 2 842 200, document FR 2 854161 or the method described in the article "Hydrophobic films from maize bran hemicelluloses", E. Fredon et al., Carbohydrate Polymers 49, 2002, pages 1 to 12. Another oxidation method is described in the article "Water soluble oxidized starches by peroxide reaction extrusion", Industrial Crops and Products 75 (1997) 45-52-REWing, JL Willet. These oxidation methods are easy to carry out, effective and do not produce any toxic by-products or by-products that are difficult to remove.
[0475] The peroxides which can be used in these oxidation processes can be alkali metal or alkaline earth metal percarbonates or perborates, alkyl peroxides, peracetic acid or hydrogen peroxide. Hydrogen peroxide is particularly preferred because it is readily available and does not produce interfering by-products.
[0476] The amount of peroxide in the reaction medium is from 0.05 to 1 molar equivalent, preferably from 0.1 to 0.8 molar equivalent per glucose unit of the polysaccharide.The peroxide is preferably added in portions continuously, stirring the reaction medium between two additions.
[0477] In the oxidation process, a single phthalocyanine or a mixture of phthalocyanines, such as a mixture of cobalt phthalocyanine and iron phthalocyanine, can be used as a catalyst. The amount of the catalyst depends on the desired degree of substitution. Usually, a small amount, such as 0.003 to 0.016 molar equivalents per 100 glucose units of the polysaccharide is suitable.
[0478] The process can also be carried out by contacting the polysaccharide in comminuted form with a catalyst dissolved in a small amount of water and with a peroxide. This process is known as a "semi-dry" process.
[0479] The process can be carried out by reactive extrusion in the presence of peroxide.
[0480] More preferably, the polysaccharide is obtained by oxidation of inulin, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, starch, acetic starch, hydroxyethyl starch, hydroxypropyl starch, guar gum, carboxymethyl guar gum, carboxymethyl hydroxypropyl guar gum, hydroxyethyl guar gum, hydroxypropyl guar gum, xylose or xanthan gum, carrageenan, cellobiose, maltodextrin, scleroglucan, chitosan, ulvan, fucoidan, alginate, pectin, heparin and hyaluronic acid, or a mixture thereof.
[0481] Preferably, the polysaccharide is obtained by oxidation of inulin or starch, more preferably by oxidation of inulin.
[0482] According to one embodiment, the polysaccharide is obtained by oxidizing inulin by a reactive extrusion process in the presence of hydrogen peroxide.
[0483] The polysaccharide chains before and after oxidation preferably have a weight-average molecular weight ranging from 400 to 15 000 000, better still from 500 to 10 000 000 and more particularly from 500 to 50 000 g / mol.
[0484] The most particularly preferred polysaccharides in the present invention are those corresponding to formula (II), in which: P represents a polymer chain derived from inulin or starch; m is the degree of substitution of the polysaccharide by one or more aldehyde groups (DS(CHO)), which is in the range of 0.005 to 2.5; n is the degree of substitution of the polysaccharide by one or more carboxyl groups (DS(COOX)), which is in the range of 0.001 to 2.
[0485] Even more preferably, the group P of formula (II) as defined previously represents a polymer chain derived from inulin; m is the degree of substitution of the polysaccharide by one or more aldehyde groups (DS(CHO)) in the range of 0.01 to 1; n is the degree of substitution of the polysaccharide by one or more carboxyl groups (DS(COOX)) in the range of 0.01 to 2.
[0486] More preferably, the organic acid is selected from the compounds of formula (I) as defined previously, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof.
[0487] Even more preferably, the organic acid is selected from the following compounds 1 to 40, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof:
[0488]
[0489]
[0490]
[0491]
[0492]
[0493]
[0494] More preferably, the organic acid is selected from Compounds 1, 2, 6, 7, 8, 9, 10, 15, 18, 20, 22, 23, 26, 28 and 31, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0495] Even more preferably, the organic acid is selected from Compounds 1, 2, 20, 26, 28 and 31, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0496] Still more preferably, the organic acid is selected from the group consisting of Compound 26, a salt thereof, an optical isomer thereof, a geometric isomer thereof, a tautomer thereof, a solvate thereof, and a mixture thereof.
[0497] According to a preferred embodiment of the present invention, the organic acid is selected from the compound of formula (I), its salt, its optical isomer, its geometric isomer, its tautomer, its solvate and its mixture, wherein X represents a carbon atom, A represents a group -CR 1 (R 2 )p(R 3 ), where p = 1, R 1 Represents a hydrogen atom or group -NR a -CO-R c , where R a and R c As defined previously, preferably R a indicates a hydrogen atom and R c Indicates alkyl group, R 2 represents a hydrogen atom or a hydroxyl group (-OH), R 3 represents a (hetero)cyclic group which is optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl, especially (C 1 -C4 ) alkyl such as methyl, alkylcarbonyl-(CO)-R c , alkylcarbonyloxy-O-CO-R c , alkoxycarbonyl-CO-OR c , -OH, (C 1 -C 6 ) alkoxy, especially (C 1 -C 4 ) alkoxy such as methoxy or -C(O)OH, or R 3 represents an alkyl or alkenyl group, wherein:
[0498] - optionally substituted by one or more identical or different groups selected from: -C(O)OH group; hydroxyl group (-OH); and / or
[0499] -optionally inserted with -CO-, -O-CO-, -(CO)-O-, -NR a -(CO)-, -(CO)-NR a -, where R a As defined previously, preferably there is optionally intervening -CO-, -O-CO-, -(CO)-O-.
[0500] According to a specific embodiment, the organic acid is selected from the compounds of formula (I), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, wherein X represents a carbon atom, A represents a group -CR 1 (R 2 )(R 3 ), where R 1 represents a hydrogen atom, R 2 represents a hydrogen atom or a hydroxyl group (-OH), R 3 represents a (hetero)cyclic group, preferably a group based on aromatic hydrocarbons such as phenyl, which is optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl, especially (C 1 -C 4 ) alkyl such as methyl, (C 1 -C 6 ) alkoxy, especially (C 1 -C 4 ) alkoxy such as methoxy or -C(O)OH, or R 3 represents an alkyl or alkenyl group, which is optionally interrupted by -NR a -(CO)- or -(CO)-NR a -, where R aAs defined previously, preferably not inserted, and / or optionally substituted by hydroxyl. According to this embodiment, the organic acid is preferably selected from compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 32, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, more preferably selected from compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, even more particularly selected from compounds 1, 2, 6, 7, 8, 9, 10, 15, their salts, their optical isomers, their solvates and mixtures thereof.
[0501] According to another preferred embodiment of the present invention, the organic acid is selected from the compound of formula (I), its salt, its optical isomer, its geometric isomer, its tautomer, its solvate and its mixture, wherein X represents a carbon atom, A represents a group -CR 1 (R 2 )(R 3 ), where R 1 Represents a hydrogen atom or group -NR a -CO-R c , where R a and R c As defined previously, preferably R a represents a hydrogen atom and R c represents an alkyl group, R 2 represents a hydrogen atom or a hydroxyl group (-OH), R 3 represents an alkyl or alkenyl group which is substituted by one or more -C(O)OH groups, in particular by one or two -C(O)OH groups, and:
[0502] - optionally substituted with one or more hydroxyl (-OH) groups; and / or
[0503] -optionally interspersed with -CO-, -O-CO-, -(CO)-O-, -(CO)-NR a -, where R a As defined previously.
[0504] According to this embodiment, the organic acid is preferably selected from compounds 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, more preferably selected from compounds 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof, even more preferably selected from compounds 18, 20, 22, 23, 26, 28, 31, most preferably selected from compounds 20, 26, 31, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof.
[0505] According to another embodiment of the present invention, the organic acid is selected from the compound of formula (I), its salt, its optical isomer, its geometric isomer, its tautomer, its solvate and its mixture, wherein X represents a carbon atom, A represents a group -CR 1 (R 3 ), where R 1 and R 3 Together with the carbon atoms carrying them, they form a (hetero)cyclic group, preferably an aromatic group, which may be optionally substituted by one or more identical or different groups selected from: (C 1 -C 6 ) alkyl, especially (C 1 -C 4 ) alkyl such as methyl, alkylcarbonyl-(CO)-R c , alkylcarbonyloxy-O-CO-R c , alkoxycarbonyl-CO-OR c , -OH, (C 1 -C 6 ) alkoxy, especially (C 1 -C 4 ) alkoxy such as methoxy, -C(O)OH, where R c As defined previously. According to this embodiment, the organic acid is preferably selected from compounds 34, 36, 37, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof.
[0506] When organic acids d) are present in the composition, they are preferably present in a content ranging from 0.01% to 50% by weight, more preferably ranging from 0.1% to 30% by weight, even more preferably ranging from 0.2% to 15% by weight relative to the total weight of the composition.
[0507] Compound e)
[0508] Preferably, compound e) is selected from the following compounds 1e to 18e, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof:
[0509]
[0510]
[0511]
[0512] More preferably, compound e) is selected from compounds 1e, 2e, 4e and 18e, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof.
[0513] Even more preferably, compound e) is selected from compound 1e, solvates thereof and mixtures thereof.
[0514] Preferably, compound e) does not contain amine, ester, amide, alcohol, imine or acid functions.
[0515] Compound e) is preferably selected from linear or branched C 7 -C 40 Alkanes, such as compounds 1e, 14e, 15e and 18e, ethers of the following formula (E):
[0516] R e1 -OR e2 (E)
[0517] in:
[0518] -R e1 and R e2 independently represents a linear or branched C optionally interrupted by one or more oxygen atoms 1 -C 20 Alkyl, or a 5-membered or 6-membered carbon ring, such as cyclohexyl or cyclopentyl;
[0519] R e1 and R e2 can form with the oxygen atoms carrying them an aromatic or nonaromatic heterocyclic group, preferably with 5 or 6 chain members, said heterocyclic group being optionally substituted in particular with one or more selected from (C 1 -C 4 ) alkyl group substitution.
[0520] When compounds e) are present in the composition, they are preferably present in a content ranging from 0.01% to 50% by weight, more preferably ranging from 0.1% to 30% by weight, even more preferably ranging from 0.02% to 15% by weight relative to the total weight of the composition.
[0521] Compound iv') is preferably present in the composition in a total content ranging from 0.01% to 50% by weight, more preferably ranging from 0.1% to 30% by weight, even more preferably ranging from 0.2% to 15% by weight relative to the total weight of the composition.
[0522] The organic amine iv) and the compound iv') are present in the composition in a total content preferably ranging from 0.01% to 70% by weight, more preferably ranging from 1% to 60% by weight, even more preferably ranging from 10% to 60% by weight, calculated on the weight of iv) and iv') relative to the total weight of the composition.
[0523] The composition preferably comprises a total content of magnesium carbonate of less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, most preferably less than 0.01% by weight and better still less than 0.001% by weight.
[0524] According to a particularly preferred embodiment, the composition contains no magnesium carbonate.
[0525] The composition preferably comprises a total persulfate content of less than 10% by weight, more preferably less than 5% by weight, even more preferably less than 1% by weight, most preferably less than 0.1% by weight, better still less than 0.01% by weight, and even better still less than 0.001% by weight.
[0526] According to a particularly preferred embodiment, the composition is free of persulfates.
[0527] According to a particular embodiment, the composition further comprises v) one or more dyes preferably chosen from direct dyes, oxidation dyes and mixtures thereof.
[0528] When dyes are present, they are preferably present in a total content ranging from 0.001% to 10% by weight, preferably from 0.01% to 4% by weight and more preferably from 0.1% to 1% by weight relative to the total weight of the composition.
[0529] Oxidation dyes
[0530] Oxidation dyes are generally chosen from one or more oxidation bases, optionally in combination with one or more coupling agents (also called couplers).
[0531] Oxidation base
[0532] The composition may optionally comprise one or more oxidation bases, advantageously chosen from those conventionally used in dyeing keratin fibres.
[0533] For example, the oxidation base is selected from p-phenylenediamine, bis(phenyl)alkylenediamine, p-aminophenol, o-aminophenol and heterocyclic bases, and the corresponding addition salts.
[0534] Among the p-phenylenediamines, mention may be made, for example, of p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2-fluoro-p-phenylenediamine, Phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-p-phenylenediamine, N-(β,γ-dihydroxypropyl)-p-phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-β-hydroxyethyloxy-p-phenylenediamine, 2-β-acetylaminoethyloxy-p-phenylenediamine, N-(β-methoxyethyl)-p-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-p-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and corresponding addition salts with acids.
[0535] Among the p-phenylenediamines mentioned above, p-phenylenediamine, p-toluenediamine, 2-isopropyl-p-phenylenediamine, 2-β-hydroxyethyl-p-phenylenediamine, 2-β-hydroxyethyloxy-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, N,N-bis(β-hydroxyethyl)-p-phenylenediamine, 2-chloro-p-phenylenediamine and 2-β-acetylaminoethyloxy-p-phenylenediamine, and the corresponding addition salts with acids are particularly preferred.
[0536] Among the bis(phenyl)alkylenediamines, mention may be made, for example, of N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine, N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(4-methylaminophenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the corresponding addition salts.
[0537] Among the p-aminophenols, there may be mentioned, for example, p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the corresponding addition salts with acids.
[0538] Among the o-aminophenols, mention may be made, for example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the corresponding addition salts.
[0539] Among the heterocyclic bases, mention may be made, for example, of pyridine, pyrimidine and pyrazole derivatives.
[0540] Among the pyridine derivatives, mention may be made of the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the corresponding addition salts.
[0541] Other pyridine oxidation bases useful in the present invention are the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or the corresponding addition salts described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[1,5-a]pyridin-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyridin-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1,5-a]pyridin-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyridin-3-ylamine, (3-aminopyrazolo[1,5-a]pyridin-7-yl)methoxypyrazolo[1,5-a]pyridin-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1,5-a]pyridin-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyridin-3-ylamine, 3-aminopyrazolo[1,5-a]pyridin-7-yl)methoxypyrazolo[1,5-a]pyridin-3-ylamine, 3-aminopyrazolo[1,5-a]pyridin-2-carboxylic acid, 3-aminopyrazolo[1,5-a]pyridin-3-ylamine, 3-aminopyrazolo[1,5-a]pyridin-7-yl)methoxypyrazolo[1,5-a]pyridin-3-ylamine, 3-amino ... alcohol, 2-(3-aminopyrazolo[1,5-a]pyridin-5-yl)ethanol, 2-(3-aminopyrazolo[1,5-a]pyridin-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyridin-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-(morpholine-4- 2-[(3-aminopyrazolo[1,5-a]pyridin-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-3-ylamine, 3-(morpholin-4-yl)pyrazolo[1,5-a]pyridin-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyridin-5-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-7-yl)(2-hydroxyethyl)amino]ethanol, 3-(morpholin-4-yl)pyrazolo[1,5-a]pyridin-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyridin-5-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-3-ylamine ... oxazolo[1,5-a]pyridine-5-ol, 3-aminopyrazolo[1,5-a]pyridine-4-ol, 3-aminopyrazolo[1,5-a]pyridine-6-ol, 3-aminopyrazolo[1,5-a]pyridine-7-ol, 2-β-hydroxyethoxy-3-aminopyrazolo[1,5-a]pyridine and 2-(4-dimethylpiperazinium-1-yl)-3-aminopyrazolo[1,5-a]pyridine; and the corresponding addition salts.
[0542] More particularly, the oxidation bases useful in the present invention are chosen from 3-aminopyrazolo[1,5-a]pyridines preferably substituted at carbon atom 2 by:
[0543] a)(ii)(C 1 -C 6 )(alkyl)amino, the alkyl group may be substituted with at least one hydroxyl, amino or imidazolium group;
[0544] b) a 5- to 7-membered heterocycloalkyl group containing 1 to 3 heteroatoms, which may be optionally substituted by one or more (C 1 -C 6 ) alkyl substituted, such as di(C 1 -C 4 ) an alkylpiperazinium group; or
[0545] c) optionally substituted with one or more hydroxyl groups (C 1 -C 6 )alkoxy, such as β-hydroxyalkoxy, and the corresponding addition salts.
[0546] Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or in patent application WO 96 / 15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and addition salts thereof and also their tautomeric forms in the presence of tautomeric equilibrium.
[0547] Among the pyrazole derivatives, mention may be made of the pyrazoles described in patents DE 3843892 and DE 4133957 and in patent applications WO 94 / 08969, WO 94 / 08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5 -diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and corresponding addition salts. 4,5-diamino-1-(β-methoxyethyl)pyrazole can also be used.
[0548] Preference will be given to using 4,5-diaminopyrazole and even more preferably 4,5-diamino-1-(β-hydroxyethyl)pyrazole and / or the corresponding salts.
[0549] Pyrazole derivatives that may also be mentioned include diamino-N,N-dihydropyrazolopyrazolones and in particular those described in patent application FR-A-2 886 136, such as the following compounds and the corresponding addition salts: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-a]pyrazol-1-one, 2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-bis(2-hydroxyethyl) -1,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazin-1-one -a]pyrazol-1-one, 4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one and 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.
[0550] Preference will be given to using 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and / or the corresponding salts.
[0551] Heterocyclic bases to be used with preference are 4,5-diamino-1-(β-hydroxyethyl)pyrazole and / or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and / or the corresponding salts.
[0552] Color former
[0553] The composition may optionally comprise one or more couplers, advantageously chosen from those conventionally used in dyeing keratin fibres.
[0554] Among these couplers, mention may in particular be made of meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene-based couplers and heterocyclic couplers, and also the corresponding addition salts.
[0555] Mention may be made, for example, of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethoxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxy- pyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol and 3-amino-2-chloro-6-methylphenol, the corresponding addition salts with acids and the corresponding mixtures.
[0556] In general, the addition salts of oxidation bases and couplers which can be used in the context of the present invention are chosen especially from addition salts with acids such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, toluenesulfonates, benzenesulfonates, phosphates and acetates.
[0557] The oxidation bases each advantageously represent from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.
[0558] The couplers, if they are present, each advantageously represent from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.
[0559] Direct dyes
[0560] The composition may also comprise one or more direct dyes.
[0561] The direct dye may be a neutral, cationic or anionic direct dye, preferably a neutral or cationic direct dye.
[0562] The direct dye may be a neutral, cationic or anionic direct dye selected from the group consisting of acridine; acridone; anthraquinone; anthrapyrimidine; anthraquinone; azine; (poly)azo or azo, hydrazone or hydrazone, in particular arylhydrazone; azomethine; benzanthrone; benzimidazole; benzimidazolone; benzindole; benzoxazole; benzopyran; benzothiazole; benzoquinone; bis-isoindoline; carboxanilide; coumarin; cyanines, such as (di)azacarbocyanines, (di)azahemicyanines, hemicyanines or tetraazacarbocyanines; (di)azines; bis-azines; (di)oxazines; (di)thiazines; (di)phenylamines; (di)phenylmethanes; (di)ketopyrrolopyrroles; flavonoids, such as flavanones and Flavonoids; fluridine; formazan; indamide; indanthrone; indigos, thioindigos and pseudoindigos; indophenols; indoanilines; isoindolines; isoindolinones; isovionanthrones; lactones; (poly)methines, such as dimethines of the stilbene or styryl type; naphthalimides; naphthoanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatic compounds; oxadiazoles; oxazines; perillones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes / carotenoids; porphyrins; pyranthrones; pyrazoloanthrones; pyrazolones; pyrimidoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squalanes; tetrazolines; thiazines; thiopyronines; triarylmethanes or xanthenes and natural direct dyes. Preferably, the direct dye is selected from anthraquinones, (poly)azos, azomethines and stilbenes, more preferably from anthraquinones.
[0563] Direct dyes can be selected in particular from neutral, cationic or anionic nitrobenzene direct dyes, neutral, cationic or anionic azo direct dyes, neutral, cationic or anionic tetraazapentamethine cyanine dyes, cationic or anionic quinone dyes and in particular neutral, cationic or anionic anthraquinone dyes, neutral, cationic or anionic azine direct dyes, neutral, cationic or anionic triarylmethane direct dyes, neutral, cationic or anionic azomethine direct dyes and natural direct dyes. Preferably, the direct dye is selected from neutral or anionic anthraquinone dyes and stilbenes.
[0564] As neutral, anionic or cationic direct dyes which can be used in the present invention, the following may be mentioned: acridine; acridone; anthraquinone; anthrapyrimidine; anthraquinone; azine; (poly)azo, hydrazone or hydrazone, in particular arylhydrazone; azomethine; benzanthrone; benzimidazole; benzimidazolone; benzindole; benzoxazole; benzopyran; benzothiazole; benzoquinone; bisazines; bis-isoindoline; carboxanilides; coumarins; cyanines, such as azacarbocyanines, diazacarbocyanines, diazahemianyanines, hemicyanines or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids, such as flavanones and flavonoids; Ketones; fluoropiperidin; formazan; indamide; indanthrone; indigos and pseudoindigos; indophenols; indoanilines; isoindoline; isoindolinone; isoviolanthrone; lactones; (poly)methines, such as dimethines of the stilbene or styryl type; naphthalimides; naphthoanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatic compounds; oxadiazoles; oxazines; perillones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes / carotenoids; porphyrins; pyranthrones; pyrazoloanthrones; pyrazolones; pyrimidoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squalanes; tetrazoles; thiazines; thioindigos; thiopyronines; triarylmethanes or xanthenes.
[0565] Neutral direct dyes
[0566] The direct dye may be a neutral direct dye, preferably selected from the group consisting of hydrazine dyes of the following formulae (IIIa) and (III'a), azo and styryl dyes (IVa), diazo and distyryl dyes (IV'a) and (IV"a), anthraquinone dyes (Va) and azomethine dyes (VIa) and (VI'a), and mixtures thereof:
[0567]
[0568] In formula (IIIa), (III'a), (IVa), (IV'a), (IV"a), (Va), (VIa) and (VI'a):
[0569] ■ Ar represents an aryl group, such as phenyl or naphthyl, which is substituted by at least one electron donating group, such as i) optionally substituted (C 1 -C 8 ) alkyl, ii) optionally substituted (C 1 -C 8 ) alkoxy, iii) (di) (C 1 -C 8 )(alkyl)amino, iv)aryl(C 1 -C 8) alkylamino, v) optionally substituted N-(C 1 -C 8 )alkyl-N-aryl(C 1 -C 8 ) alkylamino, or Ar represents a julolidine group;
[0570] ■Ar' represents an optionally substituted divalent (hetero)arylene group, such as phenylene, especially p-phenylene, or naphthylene, which is optionally preferably substituted by one or more (C 1 -C 8 ) alkyl, hydroxyl or (C 1 -C 8 ) alkoxy substituted;
[0571] ■Ar" represents a (hetero)aryl group, which is optionally preferably substituted by at least: i) an electron withdrawing group such as a nitro group, a nitroso group, -C(X)-X'-R' or ii) (di) (C 1 -C 6 )(alkyl)amino, iii)hydroxy, iv) (C 1 -C 6 )alkoxy; (hetero)aryl is in particular selected from imidazolyl, triazolyl, indolyl or pyridyl or phenyl, said phenyl being optionally substituted by at least one group selected from nitro, nitroso and amino, preferably substituted in the para position of said phenyl;
[0572] ■ X, X' and X", which may be identical or different, represent an oxygen or sulfur atom, or a group NR", preferably an oxygen atom;
[0573] ■R 1 , R 2 , R 3 and R 4 , which may be the same or different, represent a hydrogen or halogen atom, or a group selected from the following: hydroxyl, thiol, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (di)(C 1 -C 4 )(Alkyl)amino, nitro and nitroso;
[0574] ■R' and R" represent (C 1 -C 4 )alkyl;
[0575] ■R a and R b , which may be the same or different, represent a hydrogen atom or (C 1 -C 8 ) alkyl, which is optionally substituted, preferably with hydroxy;
[0576] Or, as a variant, the substituent R a and Ar" and / or R b and the substituents of Ar and / or R a With R b Together with the atoms that carry them, they form a (hetero)cycloalkyl group;
[0577] In particular, R a and R b represents a hydrogen atom or (C 1 -C 4 ) alkyl, which is optionally substituted with hydroxy;
[0578] ■ T and T', which may be the same or different, represent a group C(R a ) or N, preferably N; and
[0579] ■L represents a divalent group -ALK-, -C(X)-ALK-, -ALK-C(X)- or -C(X)-ALK-C(X')-, wherein ALK represents a linear or branched (C 1 -C 6 ) alkylene, such as methylene, and X and X' are as previously defined;
[0580] ■R 22 , R 23 , R 24 , R 25 , R 26 and R 27 , which may be the same or different, represent a hydrogen or halogen atom, or a group selected from:
[0581] -(C 1 -C 6 )alkyl;
[0582] -Hydroxy, thiol;
[0583] -(C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio;
[0584] - an aryloxy group or an arylthio group;
[0585] -Aryl (C 1 -C 6 )(alkyl)amino;
[0586] -(II)(C 1 -C 6 )(alkyl)amino;
[0587] -(Di)(hydroxy(C 1 -C 6 )alkyl)amino;
[0588] ■Z' represents a hydrogen atom or a group NR 28 R 29 , where R 28 and R 29 , which may be the same or different, represent a hydrogen atom or a group selected from:
[0589] -(C 1 -C 6 )alkyl;
[0590] -polyhydroxy(C 1 -C 6 ) alkyl such as hydroxyethyl;
[0591] - aryl, which is optionally substituted by one or more groups, in particular i) (C 1 -C 6 ) alkyl; iii) R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X"-, where R o Indicates (C 1 -C 6 ) alkyl and X, X' and X" are as previously defined; iv) sulfonate;
[0592] - cycloalkyl; especially cyclohexyl;
[0593] ■ Z represents a group selected from hydroxyl and NR' 28 R' 29 A group in which R' 28 and R' 29 , which may be the same or different, represents R as defined previously 28 and R 29 The same atoms or groups.
[0594] The direct dye of formula (IV"a) preferably has the formula (IV"'a)
[0595]
[0596] In formula (IV"'a):
[0597] ■R 1 and R 3 , which may be identical or different, preferably identical, represent a hydrogen atom, (C 1 -C 4 ) an alkyl group such as a methyl group or a sugar such as a glucosyl group, preferably a hydrogen atom;
[0598] ■R 2 and R 4 , which may be identical or different, preferably identical, represent a hydrogen atom, (C 1 -C 4 ) alkyl or (C 1 -C 4 ) alkoxy or -O-sugar group such as -O-glucosyl, preferably (C 1 -C 4 ) alkoxy; such as methoxy;
[0599] ■ X, which may be identical or different, preferably identical, represents an oxygen or sulfur atom or NR, in which R represents a hydrogen atom or group, preferably an oxygen atom;
[0600] ■ALK stands for (C 1 -C 4 ) an alkylene group, such as a methylene group or an ethylene group, preferably a methylene group.
[0601] The direct dyes of formula (IV"a) may be derived from curcumin, demethoxycurcumin and bis-demethoxycurcumin.
[0602] Preferably, the direct dye is selected from direct dyes of formula (IV"a) and formula (IV"'a) as defined previously, and mixtures thereof.
[0603] According to a particularly preferred embodiment, the direct dye is a neutral direct dye selected from the following compounds (A) to (G) and mixtures thereof:
[0604]
[0605] It is preferably selected from compounds (E), (F) and (G) and mixtures thereof, more preferably selected from compounds (E) and (G) and mixtures thereof.
[0606] Cationic direct dyes
[0607] The direct dyes may be chosen from cationic direct dyes or those generally referred to as "basic dyes" because of their affinity for acidic substances, in particular those containing at least one endocyclic or exocyclic cationic or cationizable group in their structure.
[0608] As cationic azo dyes that can be used in the present invention, there can be mentioned in particular cationic dyes described in Kirk-Othmer's Encyclopedia of Chemical Technology, "Dyes, Azo", J. Wiley & Sons, updated on April 19, 2010.
[0609] Mention may also be made of the cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954.
[0610] Mention may also be made of the cationic azo dyes described in the Colour Index International, 3rd edition, especially the following compounds: Basic Red 22; Basic Red 76; Basic Yellow 57; Basic Brown 16; Basic Brown 17.
[0611] Among the cationic quinone dyes, those mentioned in the International Colour Index, 3rd edition are suitable for use, and among these the following dyes may especially be mentioned: Basic Blue 22; Basic Blue 99.
[0612] Among the azine dyes suitable for use, mention may be made of those listed in the International Colour Index, 3rd edition, for example the following dyes: Basic Blue 17, Basic Red 2.
[0613] Among the cationic triarylmethane dyes that can be used according to the invention, mention may be made of the following dyes, in addition to those listed in the International Colour Index, 3rd edition: Basic Green 1, Basic Violet 3, Basic Violet 14, Basic Blue 7, Basic Blue 26.
[0614] Mention may also be made of the direct dyes described in documents US Pat. No. 5,888,252, EP 1,133,975, WO 03 / 029359, EP 860,636, WO 95 / 01772, WO 95 / 15144 and EP 714,954.
[0615] Mention may also be made of those listed in the encyclopedia "The Chemistry of Synthetic Dyes", 1952, Academic Press, Volumes 1 to 7, in the chapter "Dyes and Dye Intermediates" of the "Kirk-Othmer Encyclopaedia of Chemical Technology", 1993, Wiley and Sons, and in different chapters of "Ullmann's Encyclopaedia of Industrial Chemistry", 7th edition, Wiley and Sons.
[0616] Preferably, the cationic direct dyes are selected from those arising from azo and hydrazono type dyes.
[0617] Cationic direct dyes may be cationic azo dyes as described in EP 850 636, FR 2 788 433, EP 920 856, WO 99 / 48465, FR 2 757 385, EP 850 637, EP 918 053, WO 97 / 44004, FR 2 570 946, FR 2 285 851, DE 2 538 363, FR 2 189 006, FR 1 560 664, FR 1 540 423, FR 1 567 219, FR 1 516 943, FR 1 221 122, DE 4 220 388, DE 4 137 005, WO01 / 66646, US 5 708 151, WO 95 / 01772, WO 515 144, GB 1 195 386, US 3 524842, US 5879 413, EP 1 062 940, EP 1 133 976, GB 738 585, DE 2527 638, FR 2 275 462、GB1974-27645、Acta Histochem.[Acta Histochemica Sinica](1978),61(1),48-52; Tsitologiya[Cytology](1968),10(3),403-5; Zh.Obshch.Khim.(1970),40(1),195-202; Ann.Chim.(Rome)[Annual Review of Chemistry(Rome)](1975),65(5-6),305-14; "Journal of the Chinese Chemical Society" (Taiwan, China) [Journal of the Chinese Chemical Society] (1998), 45 (1), 209-211; Rev. Roum. Chim. (1988), 33 (4), 377-83; Text. Res. J. [Journal of Textile Research] (1984), 54 (2), 105-7; Chim. Ind. (Milan) [Chemical Industry (Milan)] (1974), 56 (9), 600-3; Khim. Tekhnol. [Chemical Technology] (1979), 22 (5), 548-53; Ger. Monatsh. Chem. [German Chemical Monthly] (1975), 106 (3), 643-8; MRL Bull. Res. Dev. [MRL Research and Development Bulletin] (1992), 6 (2), 21-7; Lihua Jianyan, Huaxue Fence[Physical and Chemical Testing, Chemical Section](1993),29(4),233-4; Dyes Pigm.[Dyes and Pigments] (1992), 19 (1), 69-79; Dyes Pigm. [Dyes and Pigments] (1989), 11 (3), 163-72. .
[0618] Preferably, the cationic direct dyes contain quaternary ammonium groups; more preferably, the cationic charge is intracyclic. These cationic groups are, for example, the following cationic groups:
[0619] -With (two / three) (C 1 -C 8 ) alkylammonium external charge, or
[0620] - having an intracyclic charge, such as a cationic heteroaryl group selected from the group consisting of acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolinium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridylium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolinium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiaz ...
[0063] The oxazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenoxazolium, pyrazinium, pyrazolium, pyrazolyltriazolium, pyridinium, pyridoimidazolium, pyrrolium, pyrylium, quinolinium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazolylimidazolium, thiopyrylium, triazolium or xanthenium.
[0621] Mention may be made of the following cationic hydrazono direct dyes of formulae (IIb) and (IIIb) and cationic azo direct dyes of formulae (IVb) and (Vb):
[0622] Het + -C(R a )=NN(R b )-Ar Q - (IIb);
[0623] Het + -N(R a )-N=C(R b )-Ar Q - (IIIb);
[0624] Het + -N=N-Ar Q - (IVb);
[0625] Ar + -N=N-Ar”,Q - (Vb);
[0626] In formulae (IIb) to (Vb):
[0627] ■Het + represents a cationic heteroaryl group preferably with an intracyclic cationic charge, such as an imidazolium, indolium or pyridinium group, which is optionally preferably substituted by at least one (C 1 -C 8 ) alkyl such as methyl substituted;
[0628] ■Ar + denotes an exocyclic cationic charge, preferably ammonium, especially tri(C 1 -C 8 ) an aryl group such as phenyl or naphthyl of an alkylammonium such as trimethylammonium;
[0629] ■ Ar represents an aryl group, especially a phenyl group, which is optionally substituted, preferably by one or more electron donating groups, such as i) optionally substituted (C 1 -C 8 ) alkyl, ii) optionally substituted (C 1 -C 8 ) alkoxy, iii) (di) (C 1 -C 8 )(alkyl)amino, iv)aryl(C 1 -C 8 ) alkylamino, v) optionally substituted N-(C 1 -C 8 )alkyl-N-aryl(C 1 -C 8 ) alkylamino, or, alternatively, Ar represents a julolidine group;
[0630] ■Ar" represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which is optionally preferably substituted with one or more (C 1 -C 8 ) alkyl, hydroxy, (di)(C 1 -C 8 )(alkyl)amino, (C 1 -C 8 ) substituted with alkoxy or phenyl;
[0631] ■R a and R b , which may be the same or different, represent a hydrogen atom or (C 1 -C 8 ) alkyl, which is optionally substituted, preferably with hydroxy;
[0632] ■ Alternatively, the substituent R a With Het + The substituents and / or R b and the substituents of Ar and / or R a With R bTogether with the atoms that carry them, they form a (hetero)cycloalkyl group; in particular, R a and R b represents a hydrogen atom or (C 1 -C 4 )alkyl;
[0633] ■Q - represents an anionic counterion such as a halide, alkyl sulfate or alkyl sulfonate.
[0634] In particular, mention may be made of azo and hydrazono direct dyes with an intracyclic cationic charge of formula (IIb) to (Vb) as defined previously. More particularly, mention may be made of cationic direct dyes of formula (IIb) to (Vb) with an intracyclic cationic charge described in patent applications WO 95 / 15144, WO 95 / 01772 and EP714954.
[0635] Preferably, the following direct dyes may be mentioned:
[0636]
[0637] In formula (II-1) and (IV-1):
[0638] ■R 1 Indicates (C 1 -C 4 ) alkyl such as methyl;
[0639] ■R 2 and R 3 , which may be the same or different, represent a hydrogen atom or (C 1 -C 4 ) alkyl, such as methyl;
[0640] ■R 4 represents a hydrogen atom or an electron-donating group, such as optionally substituted (C 1 -C 8 ) alkyl, optionally substituted (C 1 -C 8 ) alkoxy, or (di) (C 1 -C 8 )(alkyl)amino; in particular, R 4 It is a hydrogen atom;
[0641] ■ Z represents a CH group or a nitrogen atom, preferably CH,
[0642] ■Q - is an anionic counterion as defined previously, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.
[0643] In particular, the dyes of formula (II-1) and (IV-1) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
[0644]
[0645] wherein Q' is an anionic counterion as defined previously, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.
[0646] Fluorescent dyes
[0647] The direct dye may be selected from fluorescent direct dyes.
[0648] As examples of fluorescent dyes that can be used in the present invention, mention may be made of neutral, anionic or cationic dyes selected from the group consisting of acridine, acridone, benzanthrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, coumarin, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}borane, Diketopyrrolopyrroles, fluoroidines, (poly)methines (especially cyanines and styryls / hemicyanines), naphthalimides, naphthoanilides, naphthylamines (e.g. dansyl), oxadiazoles, oxazines, perillones, perylenes, polyenes / carotenoids, squalanes, stilbenes, xanthenes.
[0649] Mention may also be made of the fluorescent dyes described in EP 1 133 975, WO 03 / 029 359, EP 860 636, WO 95 / 01772, WO 95 / 15144 and EP 714 954, as well as those listed in K. Venkataraman's encyclopedia "The Chemistry of Synthetic Dyes", 1952, Academic Press, volumes 1 to 7, the chapter "Dyes and Dye Intermediates" in the "Kirk-Othmer Encyclopaedia of Chemical Technology", 1993, Wiley and Sons, and "Ullmann's Encyclopaedia of Industrial Chemistry", 7th edition, Wiley and Sons. Sons, and the manual circulated on the Internet or in previous printed versions - "A Guide to Fluorescent Probes and Labeling Technologies", 10th edition, Molecular Probes / Invitrogen - Oregon 2005.
[0650] According to a preferred variant, the fluorescent dye is of the cationic polymethine type and comprises at least one quaternary ammonium group, such as those of the following formula (Vb): + -[C(R c )=C(R d )] m’ -Ar,Q -
[0651] In formula (Vb):
[0652] ■W + represents a cationic heterocyclic group or a heteroaryl group, which in particular comprises optionally one or more (C 1 -C 8 ) alkyl-substituted quaternary ammonium, the alkyl group being optionally substituted, in particular, by one or more hydroxyl groups;
[0653] ■ Ar represents an aryl group such as phenyl or naphthyl, which is optionally substituted preferably by: i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (C 1 -C 8 ) alkyl and preferably C1 -C 4 alkyl such as methyl; iii) one or more hydroxyl groups; iv) one or more (C 1 -C 8 ) alkoxy such as methoxy; v) one or more hydroxyl groups (C 1 -C 8 ) alkyl such as hydroxyethyl; vi) one or more amino or (di) (C 1 -C 8 ) alkylamino, preferably having C optionally substituted by one or more hydroxyl groups 1 -C 4 Alkyl moieties such as (di)hydroxyethylamino; vii) one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidinyl or 5- or 6-membered heteroaryl groups such as pyrrolidinyl, pyridinyl and imidazolinyl;
[0654] ■ m' represents an integer ranging from 1 to 4; preferably, m' is equal to 1 or 2; more preferably, m'=1;
[0655] ■R c and R d , which may be identical or different, represent a hydrogen atom or an optionally substituted (C 1 -C 8 ) alkyl, preferably optionally substituted (C 1 -C 4 ) alkyl, or alternatively, R c With W + Adjacency and / or R d and Ar are adjacent to the atoms carrying them to form a (hetero)cycloalkyl group; in particular, R c With W + are adjacent and they form a (hetero)cycloalkyl group, such as cyclohexyl;
[0656] ■Q - is an anionic counterion as previously defined.
[0657] Anionic dyes
[0658] The direct dyes may be chosen from anionic direct dyes or dyes generally referred to as "acid" direct dyes due to their affinity for alkaline substances.
[0659] The term "anionic direct dye" means an anionic direct dye comprising at least one CO 2 R or SO 3Any direct dye having an R substituent, wherein R indicates a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. Anionic dyes may be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.
[0660] Preferably, the anionic direct dye is an anthraquinone acid dye.
[0661] The direct dye may be an anionic direct dye, which is preferably selected from the dyes of the following formulae (III), (III'), (IV), (IV'), (V), (V'), (VI), (VI'), (VII), (VIII), (IX) and (X) and mixtures thereof:
[0662] a) Diaryl anionic azo dyes of formula (III) or (III') :
[0663]
[0664] In formula (III) and (III'):
[0665] ■R 7 , R 8 , R 9 , R 10 , R' 7 , R' 8 , R' 9 and R' 10 , which may be the same or different, represent a hydrogen atom or a group selected from:
[0666] -(C 1 -C 6 )alkyl;
[0667] -(C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio;
[0668] -Hydroxy, thiol;
[0669] -Nitro, nitroso;
[0670] -R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X"-, where R o represents a hydrogen atom or (C 1 -C 6) alkyl or aryl such as phenyl; X, X' and X", which may be the same or different, represent an oxygen or sulfur atom, or NR, wherein R represents a hydrogen atom or (C 1 -C 6 )alkyl;
[0671] -(O) 2 S(O - )-,M + , where M + represents a hydrogen atom or a cationic counterion;
[0672] -(O)CO - -,M + , where M + As previously defined;
[0673] -R"-S(O) 2 -, wherein R" represents a hydrogen atom, an alkyl group, or an aryl group, (di)(C 1 -C 6 )(alkyl)amino or aryl(C 1 -C 6 )(alkyl)amino; preferably phenylamino or phenyl;
[0674] -R"'-S(O) 2 -X'-, wherein R'' represents an optionally substituted (C 1 -C 6 ) alkyl or aryl, X' is as previously defined;
[0675] -(II)(C 1 -C 6 )(alkyl)amino;
[0676] -Aryl (C 1 -C 6 ()(alkyl)amino, which may be optionally substituted by one or more groups selected from the group consisting of: i) nitro; ii) nitroso; iii) (O) 2 S(O - )-,M + and iv)(C 1 -C 6 ) alkoxy, wherein M + As previously defined;
[0677] - optionally substituted heteroaryl; preferably benzothiazolyl;
[0678] - cycloalkyl; especially cyclohexyl;
[0679] -Ar-N=N-, wherein Ar represents an optionally substituted aryl group; preferably optionally substituted by one or more alkyl groups, (O) 2 S(O- ),M + or a phenyl group substituted with a phenylamino group;
[0680] - or two other adjacent groups R 7 With R 8 or R 8 With R 9 or R 9 With R 10 together form a fused benzo group A'; and R' 7 With R' 8 or R' 8 With R' 9 or R' 9 With R' 10 together to form a fused benzo group B'; wherein A' and B' are optionally substituted by one or more groups selected from the group consisting of: i) nitro; ii) nitroso; iii) (O) 2 S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R o -C(X)-X'-; viii)R o -X'-C(X)-;ix)R o -X'-C(X)-X"-; x) Ar-N=N- and xi) optionally substituted aryl (C 1 -C 6 )(alkyl)amino; wherein M + , R o , X, X', X" and Ar are as previously defined;
[0681] ■W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent group i) -NR-, wherein R is as defined above, or ii) a methylene group -C(R a )(R b )-, where R a and R b , which may be the same or different, represent a hydrogen atom or an aromatic group, or alternatively R a and R b Together with the carbon atoms carrying them, they form a spirocycloalkyl group; preferably, W represents a sulfur atom, or R a and R b Together they form a cyclohexyl group;
[0682] It is to be understood that formulae (III) and (III') contain on one of rings A, A', B, B' or C:
[0683] - at least one group (O) 2 S(O - )-,M'+ , where M' + represents a cationic counterion; or
[0684] - at least one group (O)CO - -,M' + , where M' + represents the cationic counterion;
[0685] At least one sodium sulfonate group is preferred.
[0686] As examples of dyes of formula (III), mention may be made of Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 18 4, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow;
[0687] And as examples of dyes of formula (III′), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38;
[0688] b) Pyrazolone anionic azo dyes of formula (IV) or (IV') :
[0689]
[0690] In formula (IV) and (IV'):
[0691] ■R 11 , R 12 and R 13 , which may be the same or different, represent hydrogen or halogen atoms, (C 1 -C 6 )alkyl or -(O) 2 S(O - ),M + , where M + As previously defined;
[0692] ■R 14 represents a hydrogen atom, (C 1 -C 6 )alkyl or -C(O)O - ,M + Group, where M+ As previously defined;
[0693] ■R 15 represents a hydrogen atom;
[0694] ■R 16 represents an oxo group, in which case R' 16 does not exist, or alternatively, R 15 With R 16 together to form a double bond;
[0695] ■R 17 and R 18 , which may be the same or different, represent a hydrogen atom or a group selected from:
[0696] -(O) 2 S(O - )-,M + , where M + As previously defined;
[0697] -Ar-OS(O) 2 -, wherein Ar represents an optionally substituted aryl group; preferably a phenyl group optionally substituted by one or more alkyl groups;
[0698] ■R 19 and R 20 together forming a double bond or an optionally substituted benzo group D';
[0699] ■R' 16 , R' 19 and R' 20 , which may be the same or different, represent a hydrogen atom or (C 1 -C 6 ) alkyl or hydroxy;
[0700] ■R 21 represents a hydrogen atom or (C 1 -C 6 ) alkyl or (C 1 -C 6 ) alkoxy;
[0701] ■R a and R b , which may be the same or different, are as previously defined; preferably, R a represents a hydrogen atom and R b represents an aryl group such as phenyl;
[0702] ■Y represents a hydroxyl group or an oxo group;
[0703] ■ represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;
[0704] It will be appreciated that formulae (IV) and (IV') contain on one of rings D or E:
[0705] - at least one group (O) 2 S(O - )-,M' + , where M' + represents a cationic counterion; or
[0706] - at least one group (O)CO - -,M' + , where M' + represents the cationic counterion;
[0707] At least one sodium sulfonate group is preferred.
[0708] As examples of dyes of formula (IV), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (IV′), mention may be made of: Acid Yellow 17;
[0709] c) Anthraquinone dye of formula (V) or (V'):
[0710]
[0711] In formula (V) and (V'):
[0712] ■R 22 , R 23 , R 24 , R 25 , R 26 and R 27 , which may be the same or different, represent a hydrogen or halogen atom, or a group selected from:
[0713] -(C 1 -C 6 )alkyl;
[0714] -Hydroxy, thiol;
[0715] -(C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio;
[0716] - optionally substituted aryloxy or arylthio, preferably substituted with one or more selected from alkyl and (O) 2 S(O - )-,M + The group substituted, where M + As previously defined;
[0717] -Aryl (C 1 -C 6 (O) (alkyl) amino, which may be substituted by one or more selected from alkyl and (O) 2 S(O - )-,M + The group substituted, where M + As previously defined;
[0718] -(II)(C 1 -C 6 )(alkyl)amino;
[0719] -(di)(hydroxy)(C 1 -C 6 )(alkyl)amino;
[0720] -(O) 2 S(O - )-,M + , where M + As previously defined;
[0721] ■Z' represents a hydrogen atom or a group NR 28 R 29 , where R 28 and R 29 , which may be the same or different, represent a hydrogen atom or a group selected from:
[0722] -(C 1 -C 6 )alkyl;
[0723] -polyhydroxy(C 1 -C 6 ) alkyl such as hydroxyethyl;
[0724] - aryl, which is optionally substituted by one or more groups, in particular i) (C 1 -C 6 ) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O) 2 S(O-)-,M + , where M + As previously defined; iii) R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X"-, where R o , X, X' and X" are as previously defined; preferably R o Indicates (C 1 -C 6 )alkyl;
[0725] - cycloalkyl, especially cyclohexyl;
[0726] ■ Z represents a group selected from hydroxyl and NR' 28 R' 29 A group in which R' 28 and R' 29 , which may be the same or different, represents R as defined previously 28 and R 29 The same atoms or groups;
[0727] It is to be understood that formula (V) and (V') encompass:
[0728] - at least one group (O) 2 S(O - )-,M' + , where M' + represents a cationic counterion; or
[0729] - at least one group (O)CO - -,M' + , where M' + represents the cationic counterion;
[0730] At least one sodium sulfonate group is preferred.
[0731] As examples of dyes of formula (V), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2;
[0732] And as examples of dyes of formula (V′), mention may be made of: Acid Black 48;
[0733] d) Nitro dye of formula (VI) or (VI') :
[0734]
[0735] In formula (VI) and (VI'):
[0736] ■R 30 , R 31 and R 32 , which may be the same or different, represent a hydrogen or halogen atom, or a group selected from:
[0737] -(C 1 -C 6 )alkyl;
[0738] - optionally substituted by one or more hydroxyl groups (C 1 -C6 ) alkoxy or (C 1 -C 6 ) alkylthio;
[0739] -Hydroxy, thiol;
[0740] -Nitro, nitroso;
[0741] -Polyhalogen (C 1 -C 6 )alkyl;
[0742] -R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X"-, where R o , X, X′ and X″ are as previously defined;
[0743] -(O) 2 S(O - )-,M + , where M + As previously defined;
[0744] -(O)CO - -,M + , where M + As previously defined;
[0745] -(II)(C 1 -C 6 )(alkyl)amino;
[0746] -(di)(hydroxy)(C 1 -C 6 )(alkyl)amino;
[0747] - heterocycloalkyl, such as piperidino, piperazino or morpholino;
[0748] In particular, R 30 , R 31 and R 32 represents a hydrogen atom;
[0749] ■R c and R d , which may be the same or different, represent a hydrogen atom or (C 1 -C 6 )alkyl;
[0750] ■ W is as defined previously; W in particular represents an N(H)-group;
[0751] ■ALK represents a linear or branched divalent C 1 -C6 Alkylene; in particular, ALK represents -CH 2 -CH 2 - groups;
[0752] ■n is 1 or 2;
[0753] ■p represents an integer ranging from 1 to 5;
[0754] ■q represents an integer ranging from 1 to 4;
[0755] u is 0 or 1;
[0756] ■When n is 1, J represents nitro or nitroso; in particular nitro;
[0757] ■When n is 2, J represents an oxygen or sulfur atom, or a divalent group -S(O) m -, wherein m represents an integer of 1 or 2; preferably, J represents -SO 2 - groups;
[0758] ■M” represents a hydrogen atom or a cationic counterion;
[0759] ■ may be present or absent, indicating that it is optionally replaced by one or more groups R as defined previously 30 Substituted benzo groups;
[0760] It is to be understood that formula (VI) and (VI') encompass:
[0761] - at least one group (O) 2 S(O - )-,M' + , where M' + represents a cationic counterion; or
[0762] - at least one group (O)CO - -,M' + , where M' + represents the cationic counterion;
[0763] At least one sodium sulfonate group is preferred.
[0764] As examples of dyes of formula (VI), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (VI'), mention may be made of: Acid Yellow 1,2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidinyl-5-nitrobenzenesulfonic acid, 2-(4'-N,N-(2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, sodium salt of 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; Ext. D&C Yellow 7;
[0765] e) Triarylmethane dyes of formula (VII) :
[0766]
[0767] In formula (VII):
[0768] ■R 33 , R 34 , R 35 and R 36 , which may be the same or different, represent a hydrogen atom or a group selected from the following: (C 1 -C 6 )alkyl, optionally substituted aryl and optionally substituted aryl (C 1 -C 6 ) alkyl; in particular (C 1 -C 6 )alkyl and optionally substituted by a group (O) m S(O - )-,M + Substituted benzyl, wherein M + and m as defined previously;
[0769] ■R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 , which may be the same or different, represent a hydrogen atom or a group selected from:
[0770] -(C 1 -C 6 )alkyl;
[0771] -(C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio;
[0772] -(II)(C 1 -C 6 )(alkyl)amino;
[0773] -Hydroxy, thiol;
[0774] -Nitro, nitroso;
[0775] -R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X"-, where Ro represents a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be the same or different, represent an oxygen or sulfur atom, or NR, wherein R represents a hydrogen atom or (C 1 -C 6 )alkyl;
[0776] -(O) 2 S(O - )-,M + , where M + represents a hydrogen atom or a cationic counterion;
[0777] -(O)CO - -,M + , where M + As previously defined;
[0778] - or two other adjacent groups R 41 With R 42 or R 42 With R 43 or R 43 With R 44 together to form a fused benzo group, which is optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O) 2 S(O - )-,M + iv) hydroxyl; v) thiol; vi) (di) (C 1 -C 6 (i) (alkyl) amino group; vii) R o -C(X)-X'-; viii)R o -X'-C(X)-;ix)R o -X'-C(X)-X"-; where M + , R o , X, X′ and X″ are as previously defined;
[0779] In particular, R 37 To R 40 represents a hydrogen atom, and R 41 To R 44 Can be the same or different, representing hydroxyl or (O) 2 S(O - )-,M + Group, where M + As defined previously; and when R 43 With R 44 When together forming a benzo group, it is preferably (O) 2 S(O - )-group substitution;
[0780] It is understood that at least one of rings G, H or I comprises:
[0781] - at least one group (O) 2 S(O - )-,M' + , where M' + represents a cationic counterion; or
[0782] - at least one group (O)CO - -,M' + , where M' + represents the cationic counterion;
[0783] At least one sodium sulfonate group is preferred.
[0784] As examples of dyes of formula (VII), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50.
[0785] f) Xanthene-based dyes of formula (VIII) :
[0786]
[0787] In formula (VIII):
[0788] ■R 45 , R 46 , R 47 and R 48 , which may be the same or different, represent hydrogen or halogen atoms;
[0789] ■R 49 , R 50 , R 51 and R 52 , which may be the same or different, represent a hydrogen or halogen atom, or a group selected from the following:
[0790] -(C 1 -C 6 )alkyl;
[0791] -(C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio;
[0792] -Hydroxy, thiol;
[0793] -Nitro, nitroso;
[0794] -(O) 2 S(O - )-,M + , where M+ represents a hydrogen atom or a cationic counterion;
[0795] -(O)CO - -,M + , where M + As previously defined;
[0796] In particular, R 53 , R 54 , R 55 and R 48 represents a hydrogen or halogen atom;
[0797] ■G represents an oxygen or sulfur atom or a group NR e , where R e As defined previously; in particular, G represents an oxygen atom;
[0798] ■L represents alkoxide O - ,M + ; Thiol salt S - ,M + or group NR f , where R f represents a hydrogen atom or (C 1 -C 6 ) alkyl, and M + As previously defined; M + especially sodium or potassium;
[0799] ■L' represents oxygen or sulfur atom or ammonium group: N + R f R g , where R f and R g , which may be the same or different, represent hydrogen atoms, (C 1 -C 6 )alkyl or optionally substituted aryl; L' represents in particular an oxygen atom or optionally substituted by one or more alkyl or (O) m S(O - )-,M + A phenylamino group substituted with a group, wherein m and M + As previously defined;
[0800] ■ Q and Q', which may be the same or different, represent oxygen or sulfur atoms; in particular, Q and Q' represent oxygen atoms;
[0801] ■M + is as defined previously.
[0802] As examples of dyes of formula (VIII), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;
[0803] g) Indole-based dyes of formula (IX) :
[0804]
[0805] In formula (IX):
[0806] ■R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 , which may be the same or different, represent a hydrogen atom or a group selected from:
[0807] -(C 1 -C 6 )alkyl;
[0808] -(C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio;
[0809] -Hydroxy, thiol;
[0810] -Nitro, nitroso;
[0811] -R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X"-, where R o represents a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be the same or different, represent an oxygen or sulfur atom, or NR, wherein R represents a hydrogen atom or (C 1 -C 6 )alkyl;
[0812] -(O) 2 S(O - )-,M + , where M + represents a hydrogen atom or a cationic counterion;
[0813] -(O)CO - -,M + , where M + As previously defined;
[0814] ■G represents an oxygen or sulfur atom or a group NR e , where R e As defined previously; in particular, G represents an oxygen atom;
[0815] ■R i and R h , which may be the same or different, represent a hydrogen atom or (C 1 -C 6 )alkyl;
[0816] It will be appreciated that formula (IX) comprises:
[0817] - at least one group (O) 2 S(O - )-,M' + , where M' + represents a cationic counterion; or
[0818] - at least one group (O)CO - -,M' + , where M' + represents the cationic counterion;
[0819] At least one sodium sulfonate group is preferred.
[0820] As example of dye of formula (IX) mention may be made of: Acid Blue 74.
[0821] h) Quinoline-based dyes of formula (X) :
[0822]
[0823] In formula (X):
[0824] ■R 61 represents a hydrogen or halogen atom or (C 1 -C 6 )alkyl;
[0825] ■R 62 , R 63 and R 64 , which may be the same or different, represent a hydrogen atom or a radical (O) 2 S(O - )-,M + , where M + represents a hydrogen atom or a cationic counterion; or R 61 With R 62 , or R 61 With R 64 together form a benzo group, which may be optionally substituted by one or more groups (O) 2 S(O - )-,M + Replacement, where M + represents a hydrogen atom or a cationic counterion;
[0826] It is understood that formula (X) contains at least one group (O) 2 S(O - )-,M' + (where M' + represents a cationic counterion), preferably at least one sodium sulfonate group.
[0827] As examples of dyes of formula (X), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
[0828] More particularly, the dyes of formula (III) to (VIII) useful in the present invention are selected from: Acid Red 87 (VIII) (CI45380); Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid (VI') (CI10316); Acid Orange 3 (VI) (CI10383); Acid Yellow 9 / Food Yellow 2 (III) (CI13015); Direct Red 45 / Food Red 13 (III) (CI14780); Acid Black 52 (III) (CI13711); Acid Yellow 36 (III) (CI13065); 1-Hydroxy-2-(2',4'-dimethylphenyl)-5-sulfonic acid Sodium salt of (azo) naphthalene-4-sulfonic acid / Food Red 1 (III) (CI14700); Acid Red 14 / Food Red 3 / Mordant Blue 79 (III) (CI14720); Sodium salt of 4-hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-(phenylamino)naphthalene-2-sulfonic acid / Acid Brown 4 (III) (CI14805); Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (III) (CI15510); Food Yellow 3 / Pigment Yellow 104 (III) (CI15985); Acid Red 27 / Food Red 9 (III) (CI16185); Acid Orange 10 / Food Orange 4 (III) (CI16185). II)(CI16230); Acid Red 44(III)(CI16250); Acid Red 33 / Food Red 12(III)(CI17200); Acid Red 184(III)(CI15685); Acid Violet 3(III)(CI19125); 1-Hydroxy-2-(4'-acetamidophenylazo)-8-acetamidonaphthalene-3,6-disulfonic acid sodium salt / Acid Violet 7 / Food Red 11(III)(CI18055); Acid Red 135(III)(CI18130); Acid Yellow 27(IV)(CI19130); Acid Yellow 23 / Food Yellow 4(IV)(CI 19140); 4'-(sulfonato-2",4"-dimethyl)bis(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24(III)(CI20170); 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxynaphthalene-3,6-disulfonic acid sodium salt / Acid Black 1(III)(CI20470); (4-((4-methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red 111(III')(CI23266); Food Black 2(III)(CI27755); 1-(4'-sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6",8"-disulfonato)naphthylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1(III) (CI25440); Acid Blue 9(VII) (CI42090); Acid Violet 43(V) (CI60730); Acid Green 25(V) (CI61570); 1-amino-4-cyclohexylamino-9,10-anthraquinone-2-sulfonic acid, sodium salt / Acid Blue 62(V) (CI62045); Acid Blue 78(V) (CI62105); 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid, sodium salt / Acid Red 4(III) (CI14710); 2- Piperidino 5-nitrobenzenesulfonic acid (VI'); 2-(4'-N,N-(2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid (VI'); 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid (VI'); Acid Violet 49 (VII) (CI42640); Acid Blue 7 (VII) (CI42080); Sodium salt of 1,2-dihydroxy-3-sulfonanthraquinone / Mordant Red 3 (V) (CI58005); Sodium salt of 1-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)-2-anthracenesulfonic acid / Acid Blue 25 (V) (CI62055); Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid / Acid Red 4 (III) (CI14710).
[0829] Most of these dyes are described in particular in the Colour Index published by The Society of Dyers and Colourists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JB, England.
[0830] The most particularly preferred anionic dyes are those named in the Colour Index with the following codes: CI 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), CI 60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl)amino]-5-methylbenzenesulfonic acid), CI 15510 (monosodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonic acid), CI 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid), CI 17200 (5-amino-4-hydroxy-3-(phenylazo)- CI20470 (disodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid), CI42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[(3-sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadiene-1-ylidene]-3-sulfonobenzenemethanium hydroxide, inner salt), CI61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl]benzenesulfonic acid).
[0831] Compounds corresponding to the meso or tautomeric forms of structures (III) to (X) may also be used.
[0832] Natural dyes
[0833] The direct dyes may be selected from natural direct dyes.
[0834] Among the natural direct dyes that can be used according to the invention, mention may be made of hennaquinone, juglone, alizarin, purpurin, carminic acid, carminic acid, erythrogallol, protocatechaldehyde, indigo, isatin, curcumin, arachidin, apigenin, orcein, brazilwood, brazilwood oxide, heme and hematoxylin. Extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna may also be used.
[0835] According to a preferred embodiment, the direct dye is selected from the following formula (IIa 1 ) and (IIa 2 ) of triarylmethane direct dyes and mixtures thereof:
[0836]
[0837] in:
[0838] ■R1 , R 2 , R 3 and R 4 , which may be identical or different, represent a hydrogen atom or a group from: optionally preferably substituted by a hydroxyl group (C 1 -C 6 ) alkyl; aryl such as phenyl, aryl (C 1 -C 4 ) alkyl such as benzyl, heteroaryl or heteroaryl (C 1 -C 4 ) alkyl, or two additional groups R carried by the same nitrogen atom 1 and R 2 and / or R 3 and R 4 Together with the nitrogen atom carrying them, they form an optionally substituted heterocycloalkyl group, such as morpholino, piperazino or piperidino; preferably, R 1 , R 2 , R 3 and R 4 , which may be the same or different, represent a hydrogen atom or (C 1 -C 4 )alkyl;
[0839] ■R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 , which may be identical or different, represent a hydrogen or halogen atom, or a group selected from the group consisting of: i) hydroxyl, ii) thiol, iii) amino, iv) (di)(C 1 -C 4 (i) (alkyl) amino, v) (di) aryl amino such as (di) phenyl amino, vi) nitro, vii) acylamino (-NR-C(O)R'), wherein the radical R is a hydrogen atom, a C(O) group optionally bearing at least one hydroxyl group 1 -C 4 Alkyl and the group R' is C 1 -C 2 Alkyl; viii) Carbamoyl ((R) 2 NC(O)-), wherein the radicals R, which may be identical or different, represent a hydrogen atom or a C optionally carrying at least one hydroxyl group 1 -C 4ix) carboxylic acid or ester (-OC(O)R') or (-C(O)OR'), wherein the group R' is a hydrogen atom or a C optionally carrying at least one hydroxyl group 1 -C 4 Alkyl and the group R' is C 1 -C 2 alkyl; x) alkyl optionally substituted, especially by hydroxy; xi) alkylsulfonylamino (R'SO 2 -NR-), wherein the radical R represents a hydrogen atom or a C optionally carrying at least one hydroxyl group 1 -C 4 Alkyl and the group R' represents C 1 -C 4 alkyl or phenyl; xii) aminosulfonyl ((R) 2 N-SO 2 -), in which the radicals R, which may be identical or different, represent a hydrogen atom or a C optionally carrying at least one hydroxyl group 1 -C 4 Alkyl; xiii)(C 1 -C 4 ) alkoxy; and xiv) (C 1 -C 4 ) alkylthio;
[0840] ■ or two groups R carried by two adjacent carbon atoms 5 and R 6 and / or R 7 and R 8 and / or R 9 and R 10 and / or R 11 and R 12 and / or R 13 and R 14 and / or R 15 and R 16 Together with the carbon atoms carrying them, they form an aryl or heteroaryl, preferably a benzo 6-membered fused ring, which may also be an optionally substituted, preferably unsubstituted benzo ring;
[0841] ■Q - represents an anionic counterion for achieving electrical neutrality, preferably selected from halides such as chloride or bromide and phosphate;
[0842] According to the preferred embodiment, the direct dye is preferably HC Blue 15.
[0843] According to a variant of the invention, the direct dye is chosen from cationic direct dyes, preferably endocyclic cationic direct dyes, more particularly dyes of formula (IV-1) as defined previously, such as Basic Red 51.
[0844] The direct dyes are preferably selected from cationic direct dyes, more preferably selected from the group consisting of cationic direct dyes of formula (IIa 1 ) and (IIa 2 ) such as the direct dyes of formula (II-1) and (IV-1) as defined previously and mixtures thereof, even more preferably selected from HC Blue 15, Basic Red 51, Basic Yellow 87 and mixtures thereof.
[0845] The direct dyes may be present in the composition in a total content ranging from 0.001% to 5% by weight, preferably from 0.01% to 3% by weight, more preferably from 0.1% to 1% by weight, even more preferably from 0.1% to 0.8% by weight relative to the total weight of the composition.
[0846] According to a preferred embodiment, the composition comprises a total content of colorants of less than 0.1% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight, relative to the total weight of the composition.
[0847] According to a more preferred embodiment, the composition is free of colorants.
[0848] Additional alkalizing agents
[0849] The composition may also comprise one or more additional alkalizing agents in addition to the carbonates, bicarbonates and silicates as previously defined.
[0850] The additional alkalizing agents may be inorganic or organic. They may be selected from i) aqueous ammonia, ii) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and their derivatives, iii) oxyethylidene and / or oxypropylidene ethylenediamine, iv) inorganic or organic hydroxides, v) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and vi) compounds of the following formula (II):
[0851]
[0852] in:
[0853] -W is a divalent (C 1 -C 8 ) alkylene, preferably propylene, which is optionally substituted in particular by hydroxyl or C 1 -C 4 Alkyl substitution;
[0854] -R a , R b , R c and R d , which may be the same or different, represent hydrogen atoms or C 1 -C4 Alkyl or C 1 -C 4 (Poly)hydroxyalkyl;
[0855] vii) and mixtures thereof.
[0856] The inorganic or organic hydroxide is preferably selected from i) alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, ii) alkaline earth metal hydroxides, iii) transition metal hydroxides, such as hydroxides of metals from groups III, IV, V and VI, iv) hydroxides of lanthanides or actinides.
[0857] When they are present, the additional alkalizing agents preferably represent from 0.001% to 20% by weight and more particularly from 0.005% to 16% by weight relative to the total weight of the composition.
[0858] According to a preferred embodiment, the composition according to the invention does not comprise any further alkalizing agent selected from ammonia and / or alkanolamines.
[0859] Inorganic acidifier
[0860] The composition may also comprise one or more inorganic acidifying agents, such as hydrochloric acid, (ortho)phosphoric acid, boric acid, nitric acid and sulfuric acid.
[0861] pH of the composition
[0862] The composition according to the invention preferably has a pH of less than or equal to 11, preferably less than or equal to 10.5, preferably less than or equal to 10.
[0863] The pH range of the composition according to the present invention may be 8 to 11, preferably 8 to 10.5, more preferably 8 to 10.
[0864] According to a particularly preferred embodiment, the pH range of the composition according to the invention is from 8.3 to 10.
[0865] Chelating agents
[0866] The composition according to the invention may optionally contain one or more chelating agents. As examples of chelating agents that can be used in the present invention, mention may be made of N,N-dicarboxymethyl-L-glutamic acid and tetrasodium N,N-bis(carboxymethyl)-L-glutamate.
[0867] Other characteristics of the composition
[0868] The composition preferably comprises water in a content ranging from 5% to 99% by weight, more preferably ranging from 5% to 80% by weight, relative to the total weight of the composition.
[0869] The composition may also comprise at least one organic solvent.
[0870] The term "organic solvent" means an organic substance that is capable of dissolving another substance without chemically modifying it.
[0871] Examples of organic solvents that may be mentioned include lower C 2 -C 4 Alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for example 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether and diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols, for example benzyl alcohol or phenoxyethanol, and mixtures thereof.
[0872] The organic solvent is present in a proportion preferably ranging from 0.1% to 40% by weight, more preferably from 1% to 30% by weight, even more preferably from 1% to 25% by weight, relative to the total weight of the composition.
[0873] The composition according to the invention may be in liquid form, in the form of a slurry, in a thickened form (especially a gel, cream, wax or paste), or in the form of a foam.
[0874] The compositions according to the invention may also comprise one or more additional compounds chosen from nonionic, anionic, cationic or amphoteric surfactants, cationic, anionic, nonionic or zwitterionic, associative or non-associative thickening polymers of natural or synthetic origin, silicone or non-silicone vegetable, mineral or synthetic oils in the form of oils, gums or resins, UV-screening agents, pigments, fillers such as mother-of-pearl and metal oxides such as titanium dioxide, clays, fragrances, peptizers, vitamins and preservatives.
[0875] Method for lightening keratin fibers
[0876] According to a second aspect, a subject of the invention is a method for lightening keratin fibres, which method comprises applying to the keratin fibres a composition comprising ingredients i) to iv) and iv′) as previously defined.
[0877] Method for simultaneously bleaching and dyeing keratin fibers
[0878] According to a third aspect, the subject of the invention is a process for the simultaneous bleaching and dyeing of keratin fibers, which comprises applying to the keratin fibers a composition comprising ingredients i) to iv) and iv') as previously defined and v) one or more colorants preferably chosen from direct dyes, oxidative dyes and mixtures thereof.
[0879] Additional features of the method for simultaneously lightening or bleaching and dyeing keratin fibers
[0880] In particular, the composition is applied to the keratin fibres, wet or dry.
[0881] Preferably, the keratin fibers are dark keratin fibers.
[0882] The term "dark keratin fibers" is intended to mean keratin fibers having a shade depth less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut brown).
[0883] The composition may advantageously be applied to the keratin fibres in an amount ranging from 0.1 g to 20 g of composition per gram of keratin fibres.
[0884] The composition is allowed to stand on the fibers for a period of time generally from 1 minute to 1 hour, preferably from 5 minutes to 60 minutes.
[0885] For example, the composition may be allowed to sit on the fibers for a period of 50 minutes.
[0886] The composition may be left to rest on the fibers under a closing system. Non-limiting examples of closing systems that may be mentioned are those of the encapsulated type made of aluminum or plastic films or hair caps with or without holes.
[0887] During the brightening process, the temperature is conventionally ambient temperature (15°C to 25°C) to 80°C, and preferably ambient temperature to 60°C.
[0888] For example, during the brightening process, the temperature is 33°C.
[0889] After treatment, the keratin fibers are optionally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried naturally or air-dried.
[0890] Drying can be done using absorbent paper, a hair dryer or a styling hood or any other drying means.
[0891] The composition used in the method according to the invention is preferably prepared by mixing at least two compositions. Preferably, the mixing of the at least two compositions is carried out extemporaneously before applying the compositions to the keratin fibres.
[0892] According to a preferred embodiment, the composition used in the method according to the invention results from mixing:
[0893] ■ A composition (A) comprising:
[0894] - one or more chemical oxidizing agents as defined previously, chosen from hydrogen peroxide, hydrogen peroxide generating systems other than peroxygenated salts, and mixtures thereof, preferably hydrogen peroxide; and
[0895] - optionally one or more organic amines iv) as defined previously, and / or one or more compounds iv') as defined previously; and
[0896] ■ A composition (B) comprising:
[0897] - one or more compounds selected from bicarbonate salts, bicarbonate generating systems and mixtures thereof as previously defined, preferably selected from bicarbonate salts as previously defined; and
[0898] - one or more silicates as previously defined; and
[0899] - optionally one or more colorants, preferably chosen from direct dyes and oxidation dyes and mixtures thereof; and
[0900] - optionally one or more organic amines iv) as defined previously, and / or one or more compounds iv') as defined previously; and
[0901] ■Optionally a composition (C) comprising:
[0902] - one or more colorants, preferably chosen from direct dyes and oxidation dyes and / or mixtures thereof; and
[0903] - optionally one or more organic amines iv) as defined previously, and / or one or more compounds iv') as defined previously;
[0904] It should be understood that:
[0905] - at least one of compositions (A) or (B) or at least one of compositions (A) or (B) or (C) if composition (C) is present comprises one or more organic amines as defined previously iv); and
[0906] - at least one of the compositions (A) or (B) or at least one of the compositions (A) or (B) or (C) if composition (C) is present comprises one or more compounds iv') as defined previously.
[0907] The organic amine iv) is preferably present in composition (B) or in at least one of compositions (B) or (C) if composition (C) is present.
[0908] When alcohols a) are present, they are preferably present in composition (B) or in at least one of compositions (B) or (C) if composition (C) is present.
[0909] When amphoteric or zwitterionic compounds b) are present, they are preferably present in composition (A) or in at least one of compositions (A) or (C) if composition (C) is present.
[0910] When compounds c) are present, they are preferably present in composition (B) or in at least one of compositions (B) or (C) if composition (C) is present.
[0911] When organic acids d) are present, they are preferably present in composition (A) or in at least one of compositions (A) or (C), preferably in composition (C) if composition (C) is present.
[0912] Preferably, when the composition according to the invention results from mixing compositions (A), (B) and (C) as previously defined, composition (B) does not comprise any colorant chosen from direct dyes, oxidation dyes and mixtures thereof.
[0913] Preferably, at least one of the compositions (A) or (B) or at least one of the three compositions (A) or (B) or (C) is aqueous. More preferably, composition (A) is aqueous.
[0914] According to a particular embodiment, composition (B) is anhydrous.
[0915] According to a particular embodiment, composition (A) is aqueous, composition (B) is anhydrous, and composition (C) (when present) is aqueous.
[0916] The term "aqueous composition" means a composition comprising at least 2% by weight of water, preferably at least 5% by weight of water, more preferably at least 10% by weight of water and even more advantageously more than 20% by weight of water.
[0917] The term "anhydrous composition" refers to a composition containing less than 2% water by weight, preferably less than 0.5% water by weight, and more preferably no water. Where appropriate, such small amounts of water may be introduced, inter alia, via the ingredients of the composition which may contain residual amounts thereof.
[0918] The composition used in the method according to the invention makes it possible to obtain a lightening of keratin fibers, characterized in that the b* value is lower, preferably 10% lower and more preferably 15% lower than the b* value measured at the same intensity level L* on keratin fibers lightened with a composition comprising one or more persulfates, the b* and L* values being measured in the CIE L*a*b* system.
[0919] Preferably, the values of b* and L* are measured according to the color evaluation method described in the Examples.
[0920] use
[0921] According to a fourth aspect, a subject of the present invention is the use of a composition comprising ingredients i) to iv) and iv′) as previously defined for lightening keratin fibres, preferably for lightening keratin fibres while simultaneously deyellowing them.
[0922] According to a fifth aspect, a subject of the invention is the use of a composition comprising ingredients i) to iv) and iv') as previously defined and v) one or more colorants preferably chosen from direct dyes, oxidation dyes and mixtures thereof for the simultaneous bleaching and dyeing of keratin fibres.
[0923] Multi-compartment device (test kit)
[0924] According to a sixth aspect, the subject of the invention is a device comprising a plurality of separate compartments (kit), comprising:
[0925] ■ A first compartment containing a composition (A) comprising:
[0926] - one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating systems other than peroxide salts and mixtures thereof, preferably hydrogen peroxide; and
[0927] - optionally one or more organic acids and / or one or more compounds iv') as previously defined; and
[0928] ■ A second compartment containing a composition (B) comprising:
[0929] - one or more compounds selected from bicarbonate, bicarbonate generating system and mixtures thereof, preferably selected from bicarbonate; and
[0930] - one or more silicates; and
[0931] - optionally one or more colorants, preferably chosen from direct dyes and oxidation dyes and mixtures thereof; and
[0932] - optionally one or more organic amines iv) and / or one or more compounds iv') as defined previously; and
[0933] ■ A third compartment optionally containing a composition (C) comprising:
[0934] - one or more colorants, preferably chosen from direct dyes and oxidation dyes and mixtures thereof; and
[0935] - optionally one or more organic amines iv) and / or one or more compounds iv') as defined previously;
[0936] It should be understood that:
[0937] - at least one of compositions (A) or (B) or at least one of compositions (A) or (B) or (C) if composition (C) is present comprises one or more organic aminesiv); and
[0938] - at least one of the compositions (A) or (B) or at least one of the compositions (A) or (B) or (C) if composition (C) is present comprises one or more compounds iv') as defined previously.
[0939] Examples
[0940] The following examples will allow the invention to be more clearly understood, however, are not limiting in nature.In the following examples, unless otherwise indicated, all amounts are shown as mass percentages relative to the total weight of the composition.
[0941] Methods used to evaluate color
[0942] In the examples, the color of the locks was evaluated in the CIE L*a*b* system using a colorimeter, which was a Minolta CM3610A spectrophotometer (illuminant D65).
[0943] In this L*a*b* system, L* represents the intensity of the color, a* indicates the chromaticity of the color on the green / red axis, and b* indicates the chromaticity of the color on the blue / yellow axis. The higher the value of L*, the lighter the color. The higher the value of a*, the redder the color, and the higher the value of b*, the yellower the color.
[0944] Example 1 (Comparison)
[0945] The following compositions C1 to C12 were prepared and then applied according to the application regimen described below:
[0946] [Table 1]
[0947]
[0948] [Table 2]
[0949]
[0950]
[0951] Administration regimen
[0952] 10 g of each of compositions C1 to C12 are applied to twelve 1-g Caucasian HT4 dark hair tresses on a hot plate maintained at a temperature of 33° C. The whole is covered with a cellophane film for 50 minutes.
[0953] The tresses are then rinsed, washed with a standard shampoo, rinsed again and then dried.
[0954] Colorimetric measurement
[0955] The colorimetric measurement results are summarized in the following table:
[0956] [Table 3]
[0957] Composition L* b* C1 57.37 30.95 C2 56.34 31.74 C3 54.6 30.25 C4 54.05 30.19 C5 50.62 28.88 C6 48.51 29.48 C7 49.91 29.48 C8 47.53 27.87 C9 46.64 26.82 C10 47.01 27.04 C11 45.33 26.08 C12 41.44 23.77
[0958] The results show that the comparative composition comprising persulfate enables a good level of lightening to be obtained, characterized by a relatively high L* value, but the color shade obtained has a pronounced yellow component, characterized by a high b* value.
[0959] Example 2
[0960] The following compositions C13 to C18 were prepared and then applied according to the application schedule described below:
[0961] [Table 4]
[0962]
[0963] [Table 5]
[0964]
[0965]
[0966] Administration regimen
[0967] 10 g of each of the compositions C13 to C18 were applied to five 1-g Caucasian HT4 dark hair tresses on a hot plate maintained at a temperature of 33° C. The whole was covered with a cellophane film for 50 minutes.
[0968] The tresses are then rinsed, washed with a standard shampoo, rinsed again and then dried.
[0969] Colorimetric measurement
[0970] The colorimetric measurement results are summarized in the following table:
[0971] [Table 6]
[0972] Composition L* b* C13 48.11 20.39 C14 50.82 23.16 C15 52.46 23.31 C16 49.52 24.46 C17 50.96 23.02 C18 44.30 22.69
[0973] The results show that the composition according to the invention makes it possible to obtain a good lightening level characterized by relatively high L* values. Furthermore, the color shades obtained are characterized by lower b* values for the composition according to the invention compared to the comparative persulfate-based composition of Example 1 at equal L* intensity levels, as shown in FIG. Figure 1 shown.
Claims
1. A composition comprising: i) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating systems other than peroxide salts, and mixtures thereof; ii) one or more compounds selected from bicarbonate, bicarbonate generating system and mixtures thereof, preferably selected from bicarbonate; iii) one or more silicates; iv) one or more organic amines; iv') one or more compounds different from compound iv) selected from: a) alcohol; b) amphoteric or zwitterionic compounds selected from the group consisting of phospholipids such as lecithin, amino acids, amphoteric or zwitterionic surfactants and mixtures thereof; c) esters, amides, imines and mixtures thereof; d) organic acids; e) compounds consisting of a saturated or unsaturated, linear or branched hydrocarbon-based chain containing 1 to 30 carbon atoms, optionally substituted by one or more cyclic groups and / or optionally interrupted by one or more non-adjacent oxygen atoms; saturated or unsaturated, optionally aromatic, monocyclic or polycyclic, fused or non-fused carbocyclic compounds containing 3 to 22 carbon atoms, optionally substituted by one or more identical or different groups selected from: (C 1 -C 6 ) alkyl or (C 1 -C 6 ) alkenyl or (C 1 -C 6 ) alkoxy and / or optionally interrupted by one or more carbonyl (CO) groups; monocyclic or polycyclic, fused or non-fused, saturated or unsaturated, especially aromatic heterocyclic compounds, which contain 5 to 22 members and 1 to 3 oxygen atoms, optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl or (C 1 -C 6 ) alkoxy and / or optionally interrupted by one or more carbonyl (CO) groups and mixtures thereof; f) and mixtures thereof.
2. The composition according to the preceding claim, in, The chemical oxidizing agent is hydrogen peroxide.
3. A composition according to any one of the preceding claims, in, The chemical oxidizing agent is present in the composition in a total content ranging from 1% to 12% by weight, preferably ranging from 3% to 9% by weight, more preferably ranging from 3.5% to 8.5% by weight relative to the total weight of the composition.
4. A composition according to any one of the preceding claims, in, The compound ii) is present in the composition in a total content ranging from 0.01% to 20% by weight, preferably ranging from 1% to 15% by weight, more preferably ranging from 2% to 15% by weight, even more preferably ranging from 4% to 15% by weight relative to the total weight of the composition.
5. A composition according to any one of the preceding claims, in, The bicarbonate is selected from: - alkali metal bicarbonates; - alkaline earth metal bicarbonates; -Formula N + R 1 R 2 R 3 R 4 HCO 3 - A compound wherein R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom or (C 1 -C 4 )alkyl; -aminoguanidine bicarbonate; - mixtures thereof; Preferably, it is selected from sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate, choline bicarbonate, triethylammonium bicarbonate, aminoguanidine bicarbonate and mixtures thereof; more preferably, it is selected from sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate and mixtures thereof, more preferably, it is selected from sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate and mixtures thereof, even more preferably, it is selected from sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and mixtures thereof; most preferably, the bicarbonate is ammonium bicarbonate.
6. A composition according to any one of the preceding claims, in, The silicate is chosen from alkali metal silicates, alkaline earth metal silicates, aluminum silicates, trimethylammonium silicate and mixtures thereof, preferably from sodium silicate, potassium silicate, calcium silicate, aluminum silicate, trimethylammonium silicate and mixtures thereof, more preferably from sodium silicate, even more preferably from compounds with the INCI names sodium silicate and / or sodium metasilicate.
7. A composition according to any one of the preceding claims, in, The silicate is present in the composition in a total content ranging from 1% to 40% by weight, preferably from 2% to 35% by weight, more preferably from 3% to 35% by weight, even more preferably in the range of 4% to 20% by weight relative to the total weight of the composition.
8. A composition according to any one of the preceding claims, in, The weight ratio of the total amount of bicarbonate and / or bicarbonate generating system / the total amount of silicate is 0.00025 to 20, preferably 0.02 to 7.5, more preferably 0.05 to 5.
9. A composition according to any one of the preceding claims, in, The weight ratio of the total amount of bicarbonate and / or bicarbonate generating system / the total amount of chemical oxidant is from 0.0008 to 20, preferably from 0.11 to 5, more preferably from 0.2 to 4.
2.
10. A composition according to any one of the preceding claims, in, The organic amine iv) is selected from the following compounds 1d to 35d, chitosan, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof: Preferably selected from compounds 1d, 2d, 3d, 22d, 30d, chitosan, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof; More preferably selected from compounds 2d, 30d, chitosan, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof; Even more preferably, it is selected from the group consisting of compounds 2d and 30d, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof.
11. A composition according to any one of the preceding claims, in: □ The alcohol a) is selected from the compounds of the following formula (Ia), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof: In formula (Ia): ■R 1 and R 2 Independently means: - a hydrogen atom; or - a linear or branched, saturated or unsaturated hydrocarbon-based group comprising 1 to 30 carbon atoms, which is optionally interrupted by one or more non-adjacent oxygen atoms and / or is optionally substituted by one or more identical or different groups selected from: hydroxy (-OH) or (poly)(hydroxy)alkyl; or -(hetero)cyclyl, which is optionally substituted by one or more identical or different groups selected from: -OR" or hydroxyl (-OH); R 1 and R 2 Together with the carbon atoms carrying them, they may form a (hetero)cyclic group, which may be optionally substituted by one or more identical or different groups selected from the following: -Hydroxy (-OH); -(poly)(hydroxy)alkyl; -group-OR"; -alkyl, which is optionally interrupted by one or more carbonyl (CO) groups and / or is optionally substituted by a (hetero)cyclyl group, which itself is optionally substituted by one or more identical or different groups selected from the group consisting of hydroxy (-OH) or (poly)(hydroxy)alkyl; - optionally substituted by a (hetero)cyclic group, which itself is optionally substituted by one or more identical or different groups selected from the group consisting of hydroxy (-OH) or (poly)(hydroxy)alkyl; ■R 3 express: - a linear or branched, saturated or unsaturated or aromatic hydrocarbon-based radical comprising 1 to 30 carbon atoms, which is optionally interrupted by one or more non-adjacent oxygen atoms or one or more carbonyl groups (CO) and / or is optionally substituted by one or more identical or different radicals selected from the group consisting of hydroxyl (-OH) or (poly)(hydroxy)alkyl or -CHO or a (hetero)cyclyl radical, which itself is optionally substituted by one or more identical or different radicals selected from the group consisting of hydroxyl (-OH) or (poly)(hydroxy)alkyl or -OR" or -CHO; or -(hetero)cyclyl, which may be optionally substituted by one or more identical or different groups selected from: -OR" or (poly)(hydroxy)alkyl or -CHO; ■p = 0 or 1; ■R” stands for: - a linear or branched, saturated or unsaturated hydrocarbon-based group containing 1 to 30 carbon atoms, which is optionally substituted by one or more hydroxyl groups (-OH); or - (hetero)cyclyl, which is optionally substituted by one or more identical or different groups selected from: hydroxy (-OH) or (poly)(hydroxy)alkyl; Preferably selected from the following compounds 1a to 50a, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof: More preferably selected from compounds 1a to 29a, 45a, 49a and 50a, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof; Even more preferably selected from compounds 1a, 2a, 3a, 12a, 15a, 16a, 18a, 21a, 22a, 26a, 29a, 45a and 49a, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof; Most preferably selected from compound 1a, its salt, its optical isomer, its geometric isomer, its tautomer, its solvate and mixture thereof; and / or □ The amphoteric or zwitterionic compound b) is selected from the following compounds 1b to 28b, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof: Preferably selected from compounds 2b, 10b, 12b, 15b, 17b, 18b, 24b, 27b and 28b, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof; Most preferably selected from compound 28b, its salt, its solvate and mixture thereof; and / or □ The compound c) is selected from the compound of the following formula (Ic), its salt, its optical isomer, its geometric isomer, its tautomer, its solvate and its mixture: In formula (Ic): ■ A represents a linear or branched, saturated or unsaturated hydrocarbon-based radical comprising 1 to 30 carbon atoms, which is optionally interrupted by one or more non-adjacent oxygen atoms and / or one or more identical or different radicals selected from: -CO-, -OCO-, -COO-, and / or is optionally substituted by one or more identical or different radicals selected from: hydroxyl (-OH), a radical -COOAk1, a (hetero)cyclic radical optionally substituted by one or more hydroxyl (-OH); ■X 1 independently represents an oxygen atom or a group -NR-, preferably an oxygen atom; ■X 2 represents an oxygen atom or a group -NR-, preferably an oxygen atom; ■p = 0 or 1; ■ B represents a saturated or unsaturated, linear or branched or cyclic hydrocarbon-based group containing 1 to 30 carbon atoms, which is optionally substituted by one or more identical or different groups selected from: - (hetero)cyclyl, which is optionally substituted by one or more identical or different groups selected from the group consisting of hydroxy (-OH), -OR", -COOA', -OCOA', (poly)(hydroxy)alkyl; -group -OR'; -group -COOA'; -group-OCOA'; and / or optionally interrupted by one or more non-adjacent oxygen atoms and / or one or more identical or different groups selected from: -OCO-, -COO-; ■ A' represents a linear or branched, saturated or unsaturated hydrocarbon-based group containing 1 to 30 carbon atoms, which is optionally interrupted by one or more non-adjacent oxygen atoms and / or one or more identical or different groups selected from the following: -CO-, -OCO-, -COO-, and / or is optionally substituted by one or more identical or different groups selected from the following: hydroxyl (-OH), -COOAk1; ■ R represents a hydrogen atom or an alkyl group, especially (C 1 -C 4 )alkyl; ■ R' represents a hydrogen atom or an alkyl group which is optionally substituted by one or more identical or different groups selected from the group consisting of: hydroxyl (-OH) or -OCOA'; ■R” stands for: - an alkyl group optionally substituted with one or more hydroxyl groups (-OH); or - (hetero)cyclyl, which may be optionally substituted by one or more identical or different groups selected from: hydroxy (-OH), (poly)(hydroxy)alkyl; ■Ak1 represents an alkyl group optionally substituted with -COOAk2; ■Ak2 represents an alkyl group; R and B may form a heterocyclic ring together with the nitrogen atom carrying them; A and B may together form a heterocyclic ring which is optionally substituted, in particular, by one or more identical or different groups selected from: - (hetero)cyclyl, which is optionally substituted, in particular, by one or more identical or different radicals selected from: hydroxy (-OH), (poly)(hydroxy)alkyl; -Hydroxy (-OH); -group-OR"; -(poly)(hydroxy)alkyl; It should be understood that if X 1 represents a group -NR-, then A and B may represent hydrogen atoms; Preferably, it is selected from the following compounds 1c to 94c, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof: More preferably selected from compounds 1c to 63c and 94c, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof, and mixtures thereof; Even more preferably selected from compounds 1c, 4c, 5c, 6c, 8c, 12c, 15c, 16c, 22c, 24c, 26c, 27c, 31c, 33c, 37c, 41c, 53c, 54c, 55c, 58c, 60c, 62c, 63c and 94c, salts thereof, optical isomers thereof, geometric isomers thereof, tautomers thereof, solvates thereof and mixtures thereof; Most preferably selected from compound 12c, a salt thereof, an optical isomer thereof, a geometric isomer thereof, a tautomer thereof, a solvate thereof, and a mixture thereof; and / or □ The organic acid d) is selected from the compounds of the following formula (I) and / or (II), their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof: In formula (I): ■X represents a carbon atom or S=O or P-OH, preferably a carbon atom; ■A represents the group -OR 4 or group-CR 1 (R 2 )p(R 3 ), it is understood that if X represents P-OH, then A represents a group -OR 4 ; ■p = 0 or 1; ■R 1 represents a hydrogen atom or a hydroxyl group (-OH) or a group -NR a -R c or group -NR a -CO-R c ; ■R 2 represents a hydrogen atom or a hydroxyl group (-OH) or a group -X(O)OH, wherein X is as defined previously, in particular wherein X represents a carbon atom; ■R 3 represents a hydrogen atom or a hydroxyl group (-OH) or a (hetero)cyclic group which is optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl, especially (C 1 -C 4 ) alkyl such as methyl, alkylcarbonyl-(CO)-R c , alkylcarbonyloxy-O-CO-R c , alkoxycarbonyl-CO-OR c , -OH, (C 1 -C 6 ) alkoxy, especially (C 1 -C 4 )alkoxy such as methoxy, -X(O)OH, wherein X is as previously defined, in particular wherein X represents a carbon atom, or -OX(O)OH, wherein X is as previously defined, or R 3 represents an alkyl or alkenyl group or an alkylamino group or an alkylamide group, wherein the alkyl or alkenyl group or an alkylamino group or an alkylamide group is: - optionally substituted by one or more identical or different groups selected from the group -X(O)OH, wherein X is as defined previously, in particular wherein X represents a carbon atom; a hydroxyl (-OH) group or a (hetero)cyclyl group; and / or - optionally interrupted by one or more heteroatoms or groups selected from: -O-, -NR a -, -S-, -CO- or a combination thereof, such as -O-CO-, -(CO)-O-, -NR a -(CO)- or -(CO)-NR a -; R 1 and R 3 Together with the carbon atoms carrying them, they may form a (hetero)cyclic group, which may be optionally substituted by one or more identical or different groups selected from the following: (C 1 -C 6 ) alkyl, especially (C 1 -C 4 ) alkyl such as methyl, alkylcarbonyl-(CO)-R c , alkylcarbonyloxy-O-CO-R c , alkoxycarbonyl-CO-OR c 、-OH、(C 1 -C 6 ) alkoxy, especially (C 1 -C 4 )alkoxy such as methoxy, -X(O)OH, wherein X is as previously defined, in particular wherein X represents a carbon atom or -OX(O)OH, wherein X is as previously defined, in particular wherein X═P-OH; R 1 and R 3 can form carbonyl -CO- together with the carbon atom that bears them; ■R 4 represents a hydrogen atom or an alkyl or alkenyl or (hetero)cyclyl group, which may be optionally substituted by one or more identical or different groups selected from: a group -X(O)OH, wherein X is as defined previously, in particular wherein X represents a carbon atom or P-OH; a hydroxyl (-OH) or (hetero)cyclyl group; ■R a represents a hydrogen atom or (C 1 -C 4 )alkyl, wherein X is as previously defined, in particular wherein X represents a carbon atom; ■R c represents an alkyl or alkenyl group or an alkylamino group or an alkylamide group, wherein the alkyl or alkenyl group or an alkylamino group or an alkylamide group is: - optionally substituted by one or more identical or different groups selected from: a group -X(O)OH, wherein X is as defined previously, in particular wherein X represents a carbon atom; a hydroxyl (-OH) group or a (hetero)cyclyl group; and / or - optionally interrupted by one or more heteroatoms or groups selected from: -O-, -S-, -CO-, -O-CO-, -O-CO-, -NR a -(CO)- or -(CO)-NR a -; P-(CHO) m (COOY) n (II) In formula (II): ■ P represents a polysaccharide chain composed of monosaccharides containing 5 carbon atoms or more than 5 carbon atoms, preferably 6 or more than 6 carbon atoms and more particularly 6 carbon atoms; ■ Y is selected from a hydrogen atom, ions derived from alkali metals or alkaline earth metals 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 greater than or equal to 1; ■ m is the degree of substitution of the polysaccharide by one or more aldehyde groups (DS(CHO)), which is in the range of 0.001 to 2 and preferably 0.005 to 1.5; ■ n is the degree of substitution of the polysaccharide by one or more carboxyl groups (DS(COOX)), which is in the range of 0 to 2 and preferably 0.001 to 1.5; Preferably selected from the compounds of formula (I) as defined previously, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof; More preferably, it is selected from the following compounds 1 to 40, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof: Even more preferably selected from compounds 1, 2, 6, 7, 8, 9, 10, 15, 18, 20, 22, 23, 26, 28 and 31, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof; Most preferably selected from compounds 1, 2, 20, 26, 28 and 31, their salts, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof; and is also more preferably selected from compound 26, its salt, its optical isomer, its geometric isomer, its tautomer, its solvate and a mixture thereof; and / or □ The compound e) is selected from the following compounds 1e to 18e, their optical isomers, their geometric isomers, their tautomers, their solvates and mixtures thereof: Preferably, it is selected from compounds 1e, 2e, 4e and 18e, optical isomers, geometric isomers, tautomers, solvates and mixtures thereof; more preferably, it is selected from compound 1e, solvates thereof and mixtures thereof.
12. A composition according to any one of the preceding claims, in: - said organic amine iv) is present in said composition in a total content ranging from 0.01% to 50% by weight, preferably ranging from 1% to 30% by weight, more preferably ranging from 1% to 15% by weight, relative to the total weight of said composition; and / or - said compounds iv') are present in the composition in a total content ranging from 0.01% to 50% by weight, preferably ranging from 0.1% to 30% by weight, more preferably ranging from 0.2% to 15% by weight relative to the total weight of the composition.
13. A composition according to any one of the preceding claims, in, The composition comprises a total content of magnesium carbonate of less than 5% by weight, preferably less than 1% by weight, more preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, most preferably less than 0.001% by weight, and better still the composition is free of magnesium carbonate.
14. A composition according to any one of the preceding claims, in, The composition comprises a total content of persulfate of less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, most preferably less than 0.01% by weight and better still less than 0.001% by weight, and even better still the composition is free of persulfate.
15. A composition according to any one of the preceding claims, in, The pH range of the composition is 8 to 11, preferably 8 to 10.5, more preferably 8 to 10, even more preferably 8.3 to 10.
16. A composition according to any one of the preceding claims, in, The composition comprises v) one or more colorants preferably selected from direct dyes, oxidation dyes and mixtures thereof.
17. A composition according to any one of claims 1 to 15, in, The composition comprises a total content of colorants of less than 0.1% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight relative to the total weight of the composition; even more preferably, the composition is free of colorants.
18. A method for lightening keratin fibres, the method comprising applying to the keratin fibres a composition according to any one of claims 1 to 15 or 17.
19. The method according to the preceding claim, in, The composition makes it possible to obtain a lightening of keratin fibers, characterized in that the b* value is lower, preferably 10% lower and more preferably 15% lower than the b* value measured at the same intensity level L* on keratin fibers lightened with a composition comprising one or more persulfates, the b* and L* values being measured in the CIE L*a*b* system.
20. A method for simultaneously bleaching and dyeing keratin fibers, said method comprising applying a composition according to claim 16 to said keratin fibers.
21. The method according to any one of claims 18 to 20, in, The composition according to any one of claims 1 to 17 is produced by mixing: ■ A composition (A) comprising: - one or more chemical oxidizing agents as defined in claim 1 or 2, selected from hydrogen peroxide, hydrogen peroxide generating systems other than peroxide salts, and mixtures thereof; and - optionally one or more organic amines iv) as defined in claim 1 or 10 and / or one or more compounds iv') as defined in claim 1 or 11; and ■ A composition (B) comprising: - one or more compounds as defined in claim 1 or 5, selected from bicarbonate, bicarbonate generating system and mixtures thereof; and - one or more silicates as defined in claim 1 or 6; and - optionally one or more colorants, preferably chosen from direct dyes and oxidation dyes and mixtures thereof; and - optionally one or more organic amines iv) as defined in claim 1 or 10 and / or one or more compounds iv') as defined in claim 1 or 11; and ■Optionally a composition (C) comprising: - one or more colorants, preferably chosen from direct dyes and oxidation dyes and / or mixtures thereof; and - optionally one or more organic amines iv) as defined in claim 1 or 10 and / or one or more compounds iv') as defined in claim 1 or 11; It should be understood that: - at least one of the compositions (A) or (B) or at least one of the compositions (A) or (B) or (C) - if composition (C) is present - comprises one or more organic amines iv) as defined in claim 1 or 10; and - at least one of the compositions (A) or (B) or at least one of the compositions (A) or (B) or (C) - if composition (C) is present - comprises one or more compounds iv') as defined in claim 1 or 11.
22. Use of a composition according to any one of claims 1 to 15 or 17 for lightening keratin fibres, preferably for lightening keratin fibres while simultaneously deyellowing them.
23. Use of a composition according to claim 16 for the simultaneous bleaching and dyeing of keratin fibers.
24. A multi-compartment device, the multi-compartment device include: ■ a first compartment containing a composition (A) as defined in claim 21; and ■ a second compartment containing a composition (B) as defined in claim 21; as well as ■optionally, a third compartment containing a composition (C) as defined in claim 21; It should be understood that: - at least one of the compositions (A) or (B) or at least one of the compositions (A) or (B) or (C) - if composition (C) is present - comprises one or more organic amines iv) as defined in claim 1 or 10; and - at least one of the compositions (A) or (B) or at least one of the compositions (A) or (B) or (C) - if composition (C) is present - comprises one or more compounds iv') as defined in claim 1 or 11.
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