Process for treating keratin fibers using a composition comprising at least one alkoxysilane of formula (I), at least one non-amino silicone of formula (II) having a weight-average molecular weight less than or equal to 1500 g / mol, and at least one colorant

Abstract

The subject of the present invention is a method for treating keratin fibers such as hair, which method comprises applying to these keratin fibers a composition comprising at least one alkoxysilane chosen from compounds of formula (I), at least one non-amino silicone of formula (II) having a weight-average molecular weight less than or equal to 1500 g / mol, and at least one colorant chosen from pigments, direct dyes and mixtures thereof, followed by a phase of applying heat to the keratin fibers covered with the composition, using a heating tool, at a temperature greater than or equal to 45° C., for a period of time greater than or equal to 15 minutes.

Description

[0001] The subject of the present invention is a method for treating keratin fibers such as hair, which method comprises applying to these keratin fibers a composition comprising at least one alkoxysilane chosen from compounds of formula (I), at least one non-amino silicone of formula (II) having a weight-average molecular weight less than or equal to 1500 g / mol, and at least one colorant chosen from pigments, direct dyes and mixtures thereof, followed by a phase of applying heat to the keratin fibers covered with the composition, using a heating tool, at a temperature greater than or equal to 45° C., for a period of time greater than or equal to 15 minutes.

[0002] Another subject of the invention is a method for treating keratin fibres such as the hair using a mixture of two compositions (A) and (B). Technical Field

[0003] In the field of dyeing keratin fibres, in particular human keratin fibres, it is a known practice to dye the keratin fibres by various techniques starting from direct dyes or pigments for non-permanent dyeing, or dye precursors for permanent dyeing.

[0004] There are basically three types of methods for dyeing hair:

[0005] a) "permanent" coloring, the function of which is to provide a substantial change in the natural color and which uses oxidative dyes which penetrate into the hair fiber and form the coloration by a process of oxidative condensation;

[0006] b) non-permanent, semi-permanent or direct dyeing which does not use an oxidative condensation process and which withstands four or five shampooing operations; it consists in dyeing keratin fibres with a dyeing composition containing direct dyes;

[0007] c) Temporary coloring, which causes a change in the natural color of the entire head of hair that is preserved from one shampooing operation to the next and serves to enhance or correct an already acquired hue. It can also be likened to a "make-up" process.

[0008] For this last type of dyeing, it is known practice to use colored polymers formed by grafting onto the polymer chain one or more dyes of an azo, triphenylmethane, azine, indoleamine or anthraquinone nature. These colored polymers are not entirely satisfactory, in particular as regards the homogeneity of the coloration obtained and its resistance, not to mention the problems associated with their manufacture and, in particular, with their reproducibility.

[0009] Another dyeing method involves the use of pigments. In particular, the use of pigments at the surface of keratin fibers generally makes it possible to obtain visible coloring on dark hair, since the surface pigments mask the natural color of the fibers. However, the coloring obtained by this dyeing method exhibits the disadvantage of having a poor resistance to shampooing operations and also to external agents such as sebum, sweat, brushing and / or rubbing actions.

[0010] There is therefore still a need to obtain a method for treating keratin fibres, in particular the hair, which has the advantage of obtaining a uniform and smooth coloured shell on the hair, while forming a coating that is durable to the shampooing operation and to the various aggressors to which the hair may be subjected, such as brushing and / or rubbing actions, without deteriorating the hair.

[0011] The object of the present invention is therefore to develop a method for treating keratin fibers, in particular the hair, which has the advantage of obtaining a uniform and smooth colored shell on the hair while forming a coating that is durable to shampooing operations and to the various aggressors to which the hair may be subjected, such as brushing and / or rubbing actions, without deteriorating the hair. Summary of the invention

[0012] The present invention relates to a method for treating keratin fibers such as hair, which method comprises applying to these keratin fibers a composition comprising:

[0013] a) at least one alkoxysilane selected from the compounds of formula (I), oligomers thereof and / or mixtures thereof as described below;

[0014] b) at least one non-amino silicone of formula (II) as described below, the non-amino silicone of formula (II) having a weight average molecular weight less than or equal to 1500 g / mol; and

[0015] c) at least one coloring agent chosen from pigments, direct dyes and mixtures thereof, followed by a phase of applying heat to the keratin fibers covered with the composition using heating means at a temperature greater than or equal to 45° C. for a period greater than or equal to 15 minutes.

[0016] The invention also relates to a method for treating keratin fibers such as hair, which method comprises mixing two compositions (A) and (B) extemporaneously at the time of use and applying the mixture to the fibers, wherein:

[0017] - the composition (A) comprises at least one alkoxysilane selected from the compounds of formula (I) as described below, their oligomers and / or mixtures thereof;

[0018] - the composition (B) comprises at least one non-amino silicone of formula (II) as described below;

[0019] It is understood that composition (A) and / or composition (B) comprises at least one colorant selected from pigments, direct dyes and mixtures thereof,

[0020] This is followed by a phase of applying heat to the keratin fibers covered with the composition using heating means at a temperature greater than or equal to 45° C. for a period greater than or equal to 15 minutes.

[0021] By using this method for treating keratin fibers, a colored shell is obtained on the hair in a manner that is durable to shampooing operations, which makes it possible to obtain a coloring that is visible on all types of hair, while preserving the physical characteristics of the keratin fibers. This colored shell is resistant to external aggressions to which the hair may be subjected, such as blow-drying and sweat. The colored shell in particular makes it possible to obtain a smooth and uniform deposit.

[0022] Within the meaning of the present invention, "alkoxysilane" is understood to mean an alkoxysilane of the formula (I) or an alkoxysilane oligomer.

[0023] Within the meaning of the present invention, “coloration that is durable for a shampooing cycle” is understood to mean that the coloration obtained persists after one shampooing cycle, preferably after three shampooing cycles, more preferably after five shampooing cycles.

[0024] The expression "at least one" means one or more than one.

[0025] The invention is not limited to the examples shown. Features of the different examples may in particular be combined in alternative forms not shown.

[0026] Within the meaning of the present invention and unless otherwise indicated,

[0027] - an "alkyl" group indicates a saturated and straight-chain or branched group containing, for example, 1 to 20 carbon atoms;

[0028] - An "aminoalkyl" group indicates an alkyl group as defined above comprising NH 2 Group;

[0029] - A "cycloalkyl" group indicates a saturated cyclic hydrocarbon group containing 1 to 3 rings, preferably 2 rings, and containing 3 to 20 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, which cycloalkyl group may be replaced by one or more (C 1 -C 4 ) alkyl such as methyl substituted,

[0030] - an "aryl" group is an aromatic unsaturated cyclic group containing from 6 to 12 carbon atoms, which is monocyclic or bicyclic and fused or non-fused; preferably, the aryl group contains 1 ring with 6 carbon atoms, such as phenyl;

[0031] - An "alkoxy" group indicates an alkyl-oxy group wherein "alkyl" is as defined above.

[0032] The process for treating keratin fibres according to the invention is preferably a process for dyeing keratin fibres such as the hair.

[0033] “Keratin fibers” are understood in particular as meaning human keratin fibers such as hair, eyelashes, eyebrows, and body hair, preferably hair, eyebrows and eyelashes, even more preferably hair.

[0034] Alkoxysilane of formula (I):

[0035] The method according to the invention comprises a composition comprising at least one alkoxysilane selected from the group consisting of compounds of the following formula (I), oligomers thereof and / or mixtures thereof:

[0036]

[0037] in:

[0038] - Ra and Rb are identical or different and represent a hydrogen atom; an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms and in particular 1 to 4 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms, preferably 5 or 6 carbon atoms; an aryl group having 6 to 12 carbon atoms; an aminoalkyl group having 1 to 20 carbon atoms;

[0039] -Rc represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms and especially 1 to 2 carbon atoms, such as a methyl group; an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms and especially 1 to 2 carbon atoms, such as an ethoxy group;

[0040] - Rd and Re are identical or different and represent an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms, such as an ethyl group;

[0041] -k indicates an integer of 0-5, in particular 1-3.

[0042] "Oligomer" is understood to mean a compound comprising at least two silicon atoms which is obtained by oligomerization or polymerization of a compound of formula (I).

[0043] Preferably, the alkoxysilane of formula (I) is such that:

[0044] - Ra and Rb are identical and represent a hydrogen atom; or Ra indicates a hydrogen atom and Rb indicates a cycloalkyl group having 3 to 20 carbon atoms, in particular 5 or 6 carbon atoms;

[0045] - Rc represents an alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms and especially 1 to 2 carbon atoms, preferably a methyl group, or an alkoxy group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, preferably an ethoxy group;

[0046] - Rd and Re are the same or different and represent an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, such as an ethyl group;

[0047] -k indicates an integer of 1 to 3 and more specifically 1 or 3.

[0048] More preferably, the alkoxysilane of formula (I) is such that:

[0049] -Ra and Rb are the same, representing a hydrogen atom;

[0050] -Rc represents an alkoxy group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, preferably an ethoxy group;

[0051] - Rd and Re are the same or different and represent an alkyl group having 1 to 4 carbon atoms, preferably an ethyl group;

[0052] -k indicates an integer equal to 1 or 3, preferably equal to 3.

[0053] Still more preferably, the alkoxysilane of formula (I) is such that: Ra and Rb represent hydrogen atoms, Rc represents an ethoxy group, Rd and Re are identical and represent an ethyl group and k is equal to 3.

[0054] Among the alkoxysilanes of formula (I), their oligomers and / or their mixtures, mention may in particular be made of 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldiethoxysilane (APMDES) or N-cyclohexylaminomethyltriethoxysilane.

[0055] For example, APTES is available commercially from Dow Corning as Xiameter OFS-6011 silane, from Momentive Performance Materials as Silsoft A-1100, or from Shin-Etsu as KBE-903.

[0056] The compound of formula (I) may also be designated as Dynasylan SIVO 210 or Dynasylan 1505 sold by Evonik.

[0057] N-Cyclohexylaminomethyltriethoxysilane is commercially available, for example, under the name Geniosil XL 926 from Wacker.

[0058] Preferably, the alkoxysilane of formula (I) is selected from 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldiethoxysilane (APMDES), N-cyclohexylaminomethyltriethoxysilane and mixtures thereof, more preferably 3-aminopropyltriethoxysilane (APTES).

[0059] The alkoxysilane of formula (I), its oligomers and / or mixtures thereof are present in a total amount of 0.1% to 30% by weight, preferably 0.5% to 25% by weight, more preferably 1% to 20% by weight and better still 5% to 20% by weight relative to the total weight of the composition.

[0060] Non-amino silicone of formula (II):

[0061] The method according to the invention comprises a composition comprising at least one non-amino silicone of the following formula (II):

[0062]

[0063] in:

[0064] -R 1 represents an alkyl group having 1 to 10 carbon atoms; or an alkoxy group having 1 to 2 carbon atoms or -O X -(X) p -Si(OR 3 ) 3 A group wherein X represents a saturated divalent hydrocarbon group having 1 carbon atom, R3 represents an alkyl group having 1 to 4 carbon atoms, x represents an integer equal to 0 or 1, and p represents an integer from 0 to 4;

[0065] -R 2 are the same or different and independently represent a hydroxyl group or an alkoxy group having 1 to 2 carbon atoms;

[0066] -i indicates an integer from 0 to 18, and n indicates an integer from 0 to 18, wherein n+i varies from 4 to 18.

[0067] Preferably, the non-amino silicone of formula (II) is such that:

[0068] -R 1 independently represents an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably methyl;

[0069] - R2 independently represents a hydroxyl group or an alkoxy group having 1 to 2 carbon atoms;

[0070] -i indicates an integer from 0 to 18, and n indicates an integer from 0 to 18, wherein n+i varies from 4 to 18.

[0071] More preferably, the non-amino silicone of formula (II) is such that:

[0072] -R 1 independently represents an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group;

[0073] -R 2 independently represents a hydroxyl group;

[0074] -i indicates an integer from 0 to 18, and n indicates an integer from 0 to 18, wherein n+i varies from 4 to 18.

[0075] "Non-amino silicone" is understood to mean any silicone which does not contain primary, secondary or tertiary amine groups or quaternary ammonium groups.

[0076] The non-amino silicone of formula (II) has a weight average molecular weight of less than or equal to 1500 g / mol.

[0077] Preferably, the non-amino silicone of formula (II) has a weight average molecular weight less than or equal to 1300 g / mol.

[0078] Preferably, the non-amino silicone of formula (II) has a weight average molecular weight of 460 to 1500 g / mol, more preferably 500 to 1300 g / mol.

[0079] Preferably, the non-amino silicone of formula (II) that can be used in the context of the present invention is represented by the following formula (III):

[0080]

[0081] Here, n indicates an integer from 4 to 18.

[0082] Among the non-amino silicones of formula (II), mention may be made of polydimethylsiloxanes (PDMS) with alkoxy terminal functional groups, such as those sold by the company Gelest under the reference number DMS-XM11, or polydimethylsiloxanes (PDMS) with hydroxyl terminal functional groups, such as those sold by the company Sigma Aldrich under the reference number 481939 (Mn of about 550).

[0083] The non-amino silicone of formula) II) is present in a total amount of 0.1% to 30% by weight, preferably 0.5% to 25% by weight, more preferably 1% to 20% by weight, still more preferably 5% to 15% by weight relative to the total weight of the composition.

[0084] Weight Ratio:

[0085] The method according to the invention comprises a composition comprising a weight ratio of alkoxysilane of formula (I) / non-amino silicone of formula (II) varying from 95:5 to 5:95.

[0086] Preferably, the weight ratio of alkoxysilane of formula (I) / non-amino silicone of formula (II) varies from 90:10 to 10:90, preferably from 80:20 to 20:80 and more preferably from 70:30 to 30:70.

[0087] According to a specific embodiment, the mass ratio of APTES / non-amino silicone of formula (II) varies from 90:10 to 10:90, preferably from 80:20 to 20:80 and more preferably from 70:30 to 30:70.

[0088] According to a specific embodiment, the mass ratio of APTES / non-amino silicone of formula (III) varies from 90:10 to 10:90, more preferably from 70:30 to 30:70.

[0089] Colorants:

[0090] The process according to the invention comprises a composition comprising at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0091] Preferably, the composition according to the invention comprises one or more pigments.

[0092] Preferably, the colorant is selected from pigments.

[0093] "Pigment" is understood to mean any pigment which imparts color to keratin materials. Their solubility in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight and preferably less than 0.01% by weight.

[0094] The pigments that can be used are chosen in particular from the organic and / or mineral pigments known in the art, in particular those described in the Kirk-Othmer Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

[0095] They may be natural, of natural origin, or non-natural.

[0096] These pigments can be provided in the form of pigment powders or pastes. They can be coated or uncoated.

[0097] The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as pearlescent agents or glitter, and mixtures thereof.

[0098] The pigment may be a mineral pigment. A mineral pigment is understood to mean any pigment corresponding to the definition in Ullmann's Encyclopedia in the chapter Inorganic Pigments. Among the mineral pigments used in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine, chromium hydrate, iron blue and titanium oxide.

[0099] The pigment may be an organic pigment. "Organic pigment" is understood to mean any pigment corresponding to the definition of Ullmann's Encyclopedia in the chapter on Organic Pigments.

[0100] The organic pigments may in particular be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, peronone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine and quinophthalone compounds.

[0101] In particular, the white or colored organic pigment can be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments numbered in the Color Index with the index numbers CI42090, 69800, 69825, 74100, 74160, yellow pigments numbered in the Color Index with the index numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments numbered in the Color Index with the index numbers CI 61565, 61570, 74260, Orange pigments numbered 11725, 45370, 71105, red pigments numbered in the color index with index numbers CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, as obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

[0102] Mention may also be made, by way of example, of pigment pastes of organic pigments, such as the products sold under the following names by Hoechst:

[0103] - Cosmenyl Yellow 1OG: Pigment Yellow 3 (CI 11710);

[0104] - Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680);

[0105] - Cosmenyl Orange GR: Pigment Orange 43 (CI 71105);

[0106] -Cosmenyl Red R: Pigment Red 4 (CI 12085);

[0107] -Cosmenyl Carmine FB: Pigment Red 5 (CI 12490);

[0108] -Cosmenyl Violet RL: Pigment Violet 23 (CI 51319);

[0109] - Cosmenyl Blue A2R: Pigment Blue 15.1 (Cl 74160);

[0110] - Cosmenyl Green GG: Pigment Green 7 (CI 74260);

[0111] - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0112] The pigments according to the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may in particular consist of particles comprising an inorganic core, at least one binder providing fixation of the organic pigment to the core, and at least one organic pigment at least partially covering the core.

[0113] The organic pigments may also be lakes. Lakes are understood to mean dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use.

[0114] The inorganic substrate on which the dye is adsorbed is, for example, alumina, silica, sodium calcium borosilicate, or calcium aluminum borosilicate and aluminum.

[0115] Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (CI 45380), D&C Orange 5 (CI 45370), D&C Red 27 (CI 45410), D&C Orange 10 (CI 45425), D&C Red 3 (CI 45430), D&C Red 4 (CI 15510), D&C Red 33 (CI 17200), D&C Yellow 5 (CI 19140), D&C Yellow 6 (CI 15985), D&C Green (CI 61570), D&C Yellow 10 (CI 77002), D&C Green 3 (CI 42053), D&C Blue 1 (CI 42090).

[0116] As example of a lake, mention may be made of the product known under the name: D&C Red 7 (CI 15850:1).

[0117] Pigments may also be special effect pigments. Special effect pigments are understood to mean pigments which, in a general manner, produce a colored appearance (characterized by a certain hue, a certain vividness and a certain brightness) which is non-uniform and changes with changes in viewing conditions (light, temperature, viewing angle, etc.). They are thus in contrast to colored pigments which provide conventional, uniform opaque, translucent or transparent hues.

[0118] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as pearlescent agents, interference pigments or glitter.

[0119] As examples of special effect pigments, mention may be made of pearlescent pigments, such as micas coated with titanium or bismuth oxychloride; colored pearlescent pigments, such as micas covered with titanium and iron oxides, micas covered with iron oxides, micas covered with titanium and, in particular, iron blue or chromium oxides, micas covered with titanium and an organic pigment as defined above, and also pearlescent pigments based on bismuth oxychloride. Mention may be made, as pearlescent pigments, of the pearlescent agent Cellini (mica-TiO 2 - lakes), Prestige (mica-TiO 2 ), Prestige Bronze (Mica-Fe 2 O 3 ) or Colorona (mica-TiO 2 -Fe 2 O 3 ).

[0120] Mention may also be made of the gold pearlescent agents sold, in particular, by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); bronze pearlescent agents sold, in particular, by Merck under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super Bronze (Cloisonne); orange pearlescent agents sold, in particular, by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); and Nu-Antique Copper 340XB (Cloisonne) and Brown by BASF. a pearlescent agent with a coppery shimmer, sold in particular by BASF under the name Copper 340A (Timica); a pearlescent agent with a red shimmer, sold in particular by Merck under the name Sienna Fine (17386) (Colorona); a pearlescent agent with a yellow shimmer, sold in particular by BASF under the name Yellow (4502) (Chromalite); a red pearlescent agent with a gold shimmer, sold in particular by BASF under the name Sunstone G012 (Gemtone); a pink pearlescent agent, sold in particular by BASF under the name Tan Opale G005 (Gemtone); a black pearlescent agent with a gold shimmer, sold in particular by BASF under the name Nu-Antique Bronze 240 AB (Timica); a blue pearlescent agent, sold in particular by Merck under the name Matte Blue (17433) (Microna); a blue pearlescent agent, sold in particular by Merck under the name Xirona Silver; and a golden green pinkish orange pearlescent sold, inter alia, by Merck under the name Indian Summer (Xirona); and mixtures thereof.

[0121] Still as an example of a pearlescent agent, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

[0122] Particles having a glass substrate coated with titanium oxide are sold in particular by Toyal under the name Metashine MC1080RY.

[0123] Finally, as examples of pearlescent agents, mention may also be made of polyethylene terephthalate glitters, in particular that sold under the name Silver 1P 0.004X0.004 (silver glitter) by Meadowbrook Inventions. Multilayer pigments based on synthetic substrates such as alumina, silica, sodium calcium borosilicate, calcium aluminum borosilicate and aluminum are also conceivable.

[0124] The special effect pigments may also be chosen from reflective particles, that is to say in particular particles having a size, a structure, in particular the thickness of the layer or layers consisting of them, and their physical and chemical properties and surface conditions that allow them to reflect incident light. If appropriate, this reflection may be of sufficient intensity to produce, at the surface of the composition or mixture, highlights visible to the naked eye, that is to say brighter points that contrast with their environment by shining, when the latter is applied to the support to be made up.

[0125] The reflective particles may be selected so as not to adversely affect to a significant extent the coloring effect produced by the colorant with which they are combined and more particularly so as to optimize this effect in terms of color reproduction. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or shimmer.

[0126] These particles may exhibit different forms and may in particular be in the form of flakes or spheres, especially in the form of spheres.

[0127] Whatever their form, the reflective particles may or may not exhibit a multilayer structure and, in the case of a multilayer structure, may exhibit, for example, at least one layer of uniform thickness, in particular of a reflective material.

[0128] When the reflective particles do not exhibit a multilayer structure, they may consist, for example, of metal oxides, in particular synthetically obtained titanium or iron oxides.

[0129] When the reflective particles exhibit a multilayer structure, they can include, for example, a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one reflective material, in particular at least one metal or a layer of a metallic material. The substrate can be made of one or more organic and / or inorganic materials.

[0130] More particularly, it may be chosen from glass, ceramics, graphite, metal oxides, alumina, silica, silicates (especially aluminosilicates and borosilicates), synthetic mica, and mixtures thereof, this list not being limiting.

[0131] The reflective material may include a metal layer or a layer of metallic material.

[0132] Reflective particles are described in particular in the documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0133] Still as an example of reflective particles comprising an inorganic substrate coated with a metal layer, mention may also be made of particles comprising a borosilicate substrate coated with silver.

[0134] Particles comprising a glass substrate coated with silver are sold in the form of flakes under the name Microglass Metashine REFSX 2025 PS by Toyal. Particles comprising a glass substrate coated with a nickel / chromium / molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by the same company.

[0135] It is also possible to use particles comprising a metal substrate, such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, which is coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0136] As an example, mention may be made of a 2 Aluminum, bronze or copper powder sold under the name Visionaire by the company Eckart.

[0137] Mention may also be made of pigments with interference effects which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitters (Geometric Pigments or Spectra f / x from Spectratek). Pigments with special effects also include fluorescent pigments (whether these are substances that fluoresce in daylight or produce UV fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, such as sold by Quantum Dots Corporation.

[0138] The various pigments which can be used in the present invention make it possible to obtain a rich variety of colors, and also specific optical effects, such as metallic effects or interference effects.

[0139] The size of the pigments used in the composition according to the invention is generally from 10 nm to 200 μm, preferably from 20 nm to 80 μm and more preferably from 30 nm to 50 μm.

[0140] The pigment may be dispersed in the composition by a dispersant.

[0141] Dispersants are used to protect the dispersed particles from agglomeration or flocculation thereof. Such dispersants may be surfactants, oligomers, polymers or mixtures of several of them carrying one or more functional groups having a strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigment. Furthermore, these dispersants exhibit at least one functional group that is compatible with or soluble in the continuous medium. In particular, 12-hydroxystearic acid and in particular C 8 To C 20 Esters of fatty acids with polyols, for example glycerol or diglycerol, such as poly(12-hydroxystearic acid) stearate having a molecular weight of about 750 g / mol (such as sold under the name Solsperse 21 000 by Avecia), polyglyceryl-2 dipolyhydroxystearate (CTFA name) (sold under the reference Dehymyls PGPH by Henkel), or polyhydroxystearic acid (such as sold under the reference Arlacel P100 by Uniqema), and mixtures thereof.

[0142] As other dispersants that can be used in the composition according to the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17 000 sold by Avicia, and polydimethylsiloxane / propylene oxide mixtures, such as those sold by Dow Corning under the references DC2-5185 and DC2-5225C.

[0143] The pigments used in the composition may be surface treated with an organic agent.

[0144] Thus, the pigments used in the context of the present invention which have been previously surface treated are pigments which have been subjected in whole or in part to a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, and which are then dispersed in the composition according to the invention. These organic agents may be chosen, for example, from waxes, such as carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and its derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, such as aluminum stearate or aluminum laurate; metal alkoxides; polyethylene; (meth)acrylic acid polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, such as silicones, in particular polydimethylsiloxanes; organic fluorine compounds, such as perfluoroalkyl ethers; or fluorosilicone compounds.

[0145] The surface-treated pigments used in the composition may also have been treated with mixtures of these compounds and / or may have undergone several surface treatments.

[0146] The surface-treated pigments used in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art, or can be found commercially as such.

[0147] Preferably, the surface treated pigment is covered with an organic layer.

[0148] The organic agent for treating the pigment may be attached to the pigment by evaporation of the solvent, chemical reaction between molecules of the surfactant, or formation of a covalent bond between the surfactant and the pigment.

[0149] The surface treatment can thus be carried out, for example, by chemical reaction of the surface agent with the pigment surface and formation of covalent bonds between the surface agent and the pigment or filler. This method is described in particular in patent US Pat. No. 4,578,266.

[0150] Preferably, an organic agent will be used which is covalently bonded to the pigment.

[0151] The agent for surface treatment may account for 0.1 to 50% by weight, preferably 0.5 to 30% by weight and still more preferably 1 to 20% by weight of the total weight of the surface-treated pigment.

[0152] Preferably, the surface treatment of the pigment is selected from the following treatment agents:

[0153] - PEG-silicone treatments, such as AQ surface treatment sold by LCW;

[0154] - polymethylsiloxane treatment agents, such as SI surface treatment agents sold by LCW;

[0155] - polydimethylsiloxane treatment agents, such as Covasil 3.05 surface treatment agent sold by LCW;

[0156] - polydimethylsiloxane / trimethylsiloxysilicate treatment agents, such as Covasil 4.05 surface treatment agent sold by LCW;

[0157] - magnesium myristate treatments, such as MM surface treatment sold by LCW;

[0158] - Aluminum dimyristate treatment agents, such as MI surface treatment agent sold by Miyoshi;

[0159] - perfluoropolymethylisopropyl ether treatment agents, such as the FHC surface treatment agent sold by LCW;

[0160] - Isostearyl sebacate treatment agents, such as HS surface treatment agent sold by Miyoshi Chemicals;

[0161] -Perfluoroalkyl phosphate treatment agents, such as those manufactured by Daito Corporation (Dait o ) PF surface treatment agent sold;

[0162] - Acrylate / polydimethylsiloxane copolymers and perfluoroalkyl phosphate treatments, such as FSA surface treatments sold by Dadong Corporation;

[0163] - Polymethylhydrogensiloxane / perfluoroalkyl phosphate treatment agent, such as FS01 surface treatment agent sold by Dadong Company;

[0164] - Acrylate / polydimethylsiloxane copolymer treatments, such as ASC surface treatments sold by Dadong Corporation;

[0165] - isopropyl triisostearate titanate treatment agents, such as ITT surface treatment agents sold by Dadong Company;

[0166] - Acrylate copolymer treatment agents, such as APD surface treatment agents sold by Dadong Company;

[0167] - Perfluoroalkyl phosphate / isopropyl triisostearate titanate treatment agent, such as PF+ITT surface treatment agent sold by Daito Corporation.

[0168] According to a particular embodiment of the invention, the dispersant is present in the dyeing composition together with the organic or inorganic pigment in the form of particles of submicron size.

[0169] “Submicron” is understood to mean a pigment whose particle size has been micronized by a micronization process and whose average particle size is less than a micron (μm), in particular 0.1 to 0.9 μm and preferably 0.2 to 0.6 μm.

[0170] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) of 1:4 to 4:1, in particular 1.5:3.5 to 3.5:1 or better still 1.75:3 to 3:1.

[0171] Thus, the dispersants may have a silicone backbone, such as silicone polyethers and dispersants of aminosilicone type in addition to the abovementioned alkoxysilanes. Among suitable dispersants, mention may be made of:

[0172] aminosilicones, i.e. silicones comprising one or more amino groups, such as those sold under the following names and reference numbers: Byk LPX 21879 from Byk, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 sold by Genesee Polymers,

[0173] - Silicone acrylates, such as those sold by Evonik RC 902, RC 922, RC 1041 and RC 1043,

[0174] - polydimethylsiloxane (PDMS) silicones with carboxyl groups, such as X-22162 and X-22370 sold by Shin-Etsu, epoxy silicones, such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 sold by Biostime Polymers, or RC 1401, RC 1403 and RC 1412.

[0175] According to a particular embodiment, the dispersant is of the aminosilicone type other than the abovementioned alkoxysilanes and is cationic.

[0176] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments or organic pigments.

[0177] In an alternative form of the invention, the pigment according to the invention is an organic pigment, preferably an organic pigment surface-treated with an organic agent selected from silicone compounds. In another alternative form of the invention, the pigment according to the invention is a mineral pigment.

[0178] The composition according to the invention may comprise one or more direct dyes.

[0179] "Direct dyes" are understood to mean natural and / or synthetic dyes, with the exception of oxidation dyes. These are dyes that will diffuse on the fiber superficially.

[0180] They may be ionic or nonionic, preferably anionic, cationic or nonionic.

[0181] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes, such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, either alone or in mixtures.

[0182] The direct dye is preferably a cationic direct dye. Mention may be made of the following hydrazine cationic dyes of formula (IV) and (V) and azo cationic dyes (VI) and (VII):

[0183] Het + -C(Ra)=NN(Rb)-Ar Q- (IV)

[0184] Het + -N(Ra)-N=C(Rb)-Ar Q- (V)

[0185] Het + -N=N-Ar Q- (VI)

[0186] Ar + -N=N-Ar"Q- (VII)

[0187] In formulae (IV) to (VII):

[0188] -Het + represents a cationic heteroaryl group preferably having an intra-ring 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;

[0189] -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;

[0190] -Ar represents an aryl group, in particular a phenyl group, which is optionally, preferably substituted 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 in addition Ar represents a julolidine group;

[0191] -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;

[0192] -Ra and Rb are the same or different and represent a hydrogen atom or (C 1 -C 8 )alkyl;

[0193] Alternatively, the substituents Ra and Het + The substituents and / or Rb together with the Ar substituents together with the atoms carrying them form a (hetero)cycloalkyl group; in particular, Ra and Rb represent a hydrogen atom or (C 1 -C 4 )alkyl;

[0194] -Q - represents an organic or inorganic anionic counterion, such as a halide or an alkyl sulfate.

[0195] In particular, mention may be made of the azo and hydrazono direct dyes with an intra-ring cationic charge of formulae (IV) to (VII) as defined above, more particularly of the cationic direct dyes with an intra-ring cationic charge described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954, preferably the following direct dyes:

[0196]

[0197] In formulae (VIII) and (IX):

[0198] -R 1 Indicates (C 1 -C 4 ) alkyl, such as methyl;

[0199] -R 2 and R 3 The same or different, representing a hydrogen atom or (C 1 -C 4 ) alkyl, such as methyl; and

[0200] -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, R4 is a hydrogen atom;

[0201] -Z represents a CH group or a nitrogen atom, preferably CH,

[0202] -Q - is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or methanesulfonate.

[0203] In particular, the dyes of formula (VIII) and (IX) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof, wherein Q - is an anionic counterion as defined above, in particular a halide such as chloride, or an alkyl sulfate such as methyl sulfate or methanesulfonate.

[0204] The direct dyes may be selected from anionic direct dyes. Anionic direct dyes of the present invention are dyes which are usually referred to as "acid" direct dyes due to their affinity for alkaline substances. "Anionic direct dyes" are understood to mean dyes which contain at least one CO in their structure. 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 acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

[0205] As acid dyes according to the invention, mention may be made of the dyes of the following formulae (X), (X′), (XI), (XI′), (XII), (XII′), (XIII), (XIII′), (XIV), (XV), (XVI) and (XVII):

[0206] a) Diaryl anionic azo dyes of formula (X) or (X′):

[0207]

[0208]

[0209] In formula (X) and (X'):

[0210] -R 7 , R 8 , R 9 , R 10 , R′ 7 , R′ 8 , R′ 9 and R′ 10 The same or different, represents a hydrogen atom or a group selected from the following:

[0211] -alkyl;

[0212] - alkoxy, alkylthio;

[0213] -Hydroxy, thiol;

[0214] -Nitro, nitroso;

[0215] -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 group or an aryl group; X, X′ and X″ are the same or different and represent an oxygen or sulfur atom, or NR, wherein R represents a hydrogen atom or an alkyl group;

[0216] -M + (O) 2 S(O - )-, where M + represents a hydrogen atom or a cationic counterion;

[0217] -M + (O)CO - , where M + As defined above;

[0218] -R″-S(O) 2 -, wherein R" represents a hydrogen atom or an alkyl group, an aryl group, a (di)(alkyl)amino group or an aryl(alkyl)amino group; preferably, a phenylamino group or a phenyl group;

[0219] -R″′-S(O) 2 -X', wherein R'" represents an optionally substituted alkyl or aryl group, and X' is as defined above;

[0220] -(di)(alkyl)amino;

[0221] - aryl (alkyl) amino, optionally substituted by one or more groups selected from the group consisting of: i) nitro; ii) nitroso; iii) M + (O) 2 S(O - )- and iv) alkoxy, wherein M + As defined above;

[0222] - optionally substituted heteroaryl; preferably benzothiazolyl;

[0223] - cycloalkyl; in particular cyclohexyl,

[0224] -Ar-N=N-, wherein Ar represents an optionally substituted aryl group; preferably, optionally substituted with one or more alkyl groups, M + (O) 2 S(O - )- or phenyl substituted with phenylamino;

[0225] - 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 and R′ 8 or R′ 8 and R′ 9 or R′ 9 and 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 following: i) nitro; ii) nitroso; iii) M + (O) 2 S(O - )-; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) Ro -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(alkyl)amino; wherein M + , R o , X, X′, X″ and Ar are as defined above;

[0226] -W represents a sigma bond, an oxygen or sulfur atom, or a divalent radical i) -NR-, in which R is as defined above, or ii) a methylene group -C(Ra)(Rb)-, in which Ra and Rb are identical or different, represent a hydrogen atom or an aryl group, or else Ra and Rb together with the carbon atom carrying them form a spirocycloalkyl group; preferably, W represents a sulfur atom or Ra and Rb together form a cyclohexyl group;

[0227] It is understood that formula (X) and (X') contain at least one sulfonate group M on one of the rings A, A', B, B' or C. + (O) 2 S(O - )- or carboxylate group M + (O)CO - -; Preferably, sodium sulfonate;

[0228] As examples of dyes of formula (X), 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 184 , 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;

[0229] And as examples of dyes of formula (X′), mention may be made of: Acid Red 111, Acid Red 134 or Acid Yellow 38;

[0230] b) Anionic pyrazolone azo dyes of formula (XI) and (XI′):

[0231]

[0232] In formula (XI) and (XI'):

[0233] -R 11 , R 12 and R 13 are the same or different, representing a hydrogen atom, a halogen atom, an alkyl group or M + (O) 2 S(O - )-group, where M + As defined above;

[0234] -R 14 represents a hydrogen atom, an alkyl group or M + C(O)O - - group, where M + As defined above;

[0235] -R 15 represents a hydrogen atom;

[0236] -R 16 represents an oxo group, in which case R' 16 Does not exist, or another R 15 With R 16 together to form a double bond;

[0237] -R 17 and R 18 The same or different, represents a hydrogen atom or a group selected from the following:

[0238] -M + (O) 2 S(O - )-, wherein M+ is as defined above;

[0239] -Ar-OS(O) 2 -, wherein Ar represents an optionally substituted aryl group; preferably a phenyl group optionally substituted by one or more alkyl groups;

[0240] -R 19 and R2 0 together forming a double bond or an optionally substituted benzo group D';

[0241] -R′ 16 , R′ 19 and R′ 20 The same or different, represents a hydrogen atom, an alkyl group or a hydroxyl group;

[0242] -R 21 represents a hydrogen atom, an alkyl group or an alkoxy group;

[0243] -R a and R b The same or different, are as defined above; preferably, R a represents a hydrogen atom and R brepresents an aromatic group;

[0244] -Y represents a hydroxyl group or an oxo group;

[0245] - When Y is an oxo group it represents a single bond, and when Y represents a hydroxyl group it represents a double bond;

[0246] It is understood that formula (XI) and (XI') contain at least one sulfonate group M on one of the rings D or E. + (O) 2 S(O - )- or a carboxylate group M + C(O)O - -; Preferably, sodium sulfonate;

[0247] As examples of dyes of formula (XI), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, or Acid Yellow 76, and as examples of dyes of formula (XI′), mention may be made of: Acid Yellow 17;

[0248] c) Anthraquinone dyes of formula (XII) and (XII'):

[0249]

[0250] In formulae (XII) and (XII'):

[0251] -R 22 , R 23 , R 24 , R 25 , R 26 and R 27 The same or different, represents a hydrogen atom, a halogen atom or a group selected from the following:

[0252] -alkyl;

[0253] -Hydroxy, thiol;

[0254] - alkoxy, alkylthio;

[0255] - optionally substituted aryloxy or arylthio, preferably substituted with one or more selected from alkyl and M + (O) 2 S(O - )-, wherein M + As defined above;

[0256] -aryl(alkyl)amino, optionally substituted by one or more selected from alkyl and M + (O) 2 S(O - )-, wherein M + As defined above;

[0257] -(di)(alkyl)amino;

[0258] -(di)(hydroxyalkyl)amino;

[0259] -M + (O) 2 S(O - )-, where M + As defined above;

[0260] Z' represents a hydrogen atom or NR 28 R 29 Group, where R 28 and R 29 The same or different, represents a hydrogen atom or a group selected from the following:

[0261] -alkyl;

[0262] - (poly)hydroxyalkyl, such as hydroxyethyl;

[0263] - aryl, optionally substituted by one or more groups, in particular: i) alkyl, such as methyl, n-dodecyl or n-butyl; ii) M + (O) 2 S(O - )-, where M + As defined above; iii) R o -C(X)-X′、R o -X′-C(X)-or R o -X′-C(X)-X″-, where R o , X, X' and X" are as defined above; preferably, R o represents an alkyl group;

[0264] - cycloalkyl; in particular cyclohexyl;

[0265] Z represents a group selected from hydroxyl and NR' 28 R′ 29 A group, wherein R′ 28 and R′ 29 Same or different, means R as defined above 28 and R 29 The same atoms or groups;

[0266] It is understood that formula (XII) and (XII') contain at least one sulfonate group M + (O) 2 S(O - )- or a carboxylate group M + C(O)O - ; Preferably, sodium sulfonate;

[0267] As examples of dyes of formula (XII), 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 or Ext. Violet No. 2; and, as examples of dyes of formula (XII′), mention may be made of: Acid Black 48:

[0268] d) Nitro dyes of formula (XIII) and (XIII′):

[0269]

[0270] In formulae (XIII) and (XIII'):

[0271] -R 30 , R 31 and R 32 The same or different, represents a hydrogen atom, a halogen atom or a group selected from the following:

[0272] -alkyl;

[0273] - alkoxy optionally substituted by one or more hydroxyl groups, or alkylthio optionally substituted by one or more hydroxyl groups;

[0274] -Hydroxy, thiol;

[0275] -Nitro, nitroso;

[0276] -polyhaloalkyl;

[0277] -R o -C(X)-X′、R o -X′-C(X)-or R o -X′-C(X)-X″-, where R o , X, X′ and X″ are as defined above;

[0278] -M + (O) 2 S(O - )-, where M + As defined above;

[0279] -M + (O)CO - , where M + As defined above;

[0280] -(di)alkyl)amino;

[0281] -(di)(hydroxyalkyl)amino;

[0282] -heterocycloalkyl, such as piperidino, piperazino or morpholino; in particular, R 30 , R 31 and R 32 represents a hydrogen atom;

[0283] -R c and R d The same or different, represents a hydrogen atom or an alkyl group;

[0284] -W is as defined above; W in particular represents a -NH- group;

[0285] -ALK represents a linear or branched divalent C 1 -C 6 Alkylene; in particular, ALK represents -CH 2 -CH 2 - groups;

[0286] The value of -n is 1 or 2;

[0287] -p represents an integer from 1 to 5, inclusive;

[0288] -q represents an integer from 1 to 4, inclusive;

[0289] The value of -u is 0 or 1;

[0290] - when the value of n is 1, J represents a nitro or nitroso group; in particular a nitro group;

[0291] -When the value of n is 2, J represents an oxygen or sulfur atom, or a divalent -S(O) m - group, wherein m represents an integer of 1 or 2; preferably, J represents -SO 2 - groups;

[0292] -M' represents a hydrogen atom or a cationic counterion;

[0293] - The presence or absence of R 30 a benzo group substituted with a radical;

[0294] It is understood that formula (XIII) and (XIII') contain at least one sulfonate group M + (O) 2 S(O - )- or a carboxylate group M + C(O)O - -; Preferably, sodium sulfonate.

[0295] As examples of dyes of formula (XIII), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XIII′), mention may be made of: Acid Yellow 1, the sodium salts of the following acids: 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidinyl-5-nitrobenzenesulfonic acid, 2-(4′-N,N-(2″-hydroxyethyl)amino-2′-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; Ext. D&C Yellow 7;

[0296] e) Triarylmethane dyes of formula (XIV):

[0297]

[0298] In formula (XIV):

[0299] -R 33 , R 34 , R 35 and R 36 are the same or different and represent a hydrogen atom or a group selected from the group consisting of an alkyl group, an optionally substituted aryl group and an optionally substituted aralkyl group; in particular, an alkyl group or an optionally substituted aryl group + (O) m S(O - )-substituted benzyl, wherein M + and m are as defined above; R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 The same or different, represents a hydrogen atom or a group selected from the following:

[0300] -alkyl;

[0301] - alkoxy, alkylthio;

[0302] -(di)(alkyl)amino;

[0303] -Hydroxy, thiol;

[0304] -Nitro, nitroso;

[0305] -R o -C(X)-X′、R o -X′-C(X)-or R o -X′-C(X)-X″-, where R o represents a hydrogen atom, an alkyl group or an aryl group, and X, X′ and X″ are the same or different and represent an oxygen or sulfur atom or NR, wherein R represents a hydrogen atom or an alkyl group;

[0306] -M + (O) 2 S(O - )-, where M + represents a hydrogen atom or a cationic counterion;

[0307] -M + (O)CO - , where M + As defined above;

[0308] - 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: I'; wherein I' is optionally substituted with one or more groups selected from the group consisting of: i) nitro; ii) nitroso; iii) M + (O) 2 S(O - )-; 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″-; where M + , R o , X, X′, X″ are as defined above;

[0309] In particular, R 37 To R 40 represents a hydrogen atom, and R 41 To R 44 Same or different, indicating hydroxyl or M + (O) 2 S(O - )-group; and when R 43 With R 44 When together forming a benzo group, it is preferably (O) 2 S(O - )-group substitution;

[0310] It is understood that at least one of the rings G, H, I or I' contains at least one sulfonate group (O) 2 S(O - )- or a carboxylate group C(O)O - -; preferably sulfonate;

[0311] As examples of dyes of formula (XIV), 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;

[0312] e) Xanthene-based dyes of formula (XV):

[0313]

[0314] In formula (XV):

[0315] -R 45 , R 46 , R 47 and R 48 The same or different, represents a hydrogen atom or a halogen atom;

[0316] -R 49 , R 50 , R 51 and R 52 The same or different, represents a hydrogen atom, a halogen atom or a group selected from the following:

[0317] -alkyl;

[0318] - alkoxy, alkylthio;

[0319] -Hydroxy, thiol;

[0320] -Nitro, nitroso;

[0321] -M + (O) 2 S(O - )-, where M + represents a hydrogen atom or a cationic counterion;

[0322] -M + (O)CO - , where M + As defined above;

[0323] In particular, R 53 , R 54 , R 55 and R 48 represents a hydrogen atom or a halogen atom;

[0324] -G represents oxygen or sulfur atom or NR e Group, where R e As defined above; in particular, G represents an oxygen atom;

[0325] -L represents alkoxide M + O - ; Thiol salt M + S - or NRf Group, where R f represents a hydrogen atom or an alkyl group, and M + As defined above; M + especially sodium or potassium;

[0326] -L' represents an oxygen or sulfur atom or an ammonium group: N + R f R g , where R f and R g are the same or different and represent a hydrogen atom, an alkyl group or an optionally substituted aryl group; L' represents in particular an oxygen atom or an optionally substituted aryl group with one or more alkyl groups or M + (O) m S(O - )-substituted phenylamino, wherein m and M + As defined above;

[0327] - Q and Q' are the same or different and represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom;

[0328] -M + As defined above;

[0329] As examples of dyes of formula (XV), mention may be made of: Acid Yellow 73, Acid Red 51, Acid Red 52, Acid Red 87, Acid Red 92, Acid Red 95 and Acid Violet 9;

[0330] f) Indole-based dyes of formula (XVI):

[0331]

[0332] R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 The same or different, represents a hydrogen atom or a group selected from the following:

[0333] -alkyl;

[0334] - alkoxy, alkylthio;

[0335] -Hydroxy, thiol;

[0336] -Nitro, nitroso;

[0337] -R o -C(X)-X′、R o -X′-C(X)-or R o-X′-C(X)-X″-, where R o represents a hydrogen atom or an alkyl group or an aryl group, and X, X′ and X″ are the same or different and represent an oxygen or sulfur atom or NR, wherein R represents a hydrogen atom or an alkyl group;

[0338] -M + (O) 2 S(O - )-, where M + represents a hydrogen atom or a cationic counterion;

[0339] -M + (O)CO - , where M + As defined above;

[0340] -G represents oxygen or sulfur atom or NR e Group, where R e As defined above; in particular, G represents an oxygen atom;

[0341] -R i and R h The same or different, represents a hydrogen atom or an alkyl group;

[0342] It is understood that formula (XVI) contains at least one sulfonate group M + (O) 2 S(O - )- or a carboxylate group M + C(O)O - -; preferably sodium sulfonate;

[0343] As example of dye of formula (XVI) mention may be made of: Acid Blue 74.

[0344] g) Quinoline-derived dyes of formula (XVII):

[0345]

[0346] -R 61 represents a hydrogen or halogen atom or an alkyl group;

[0347] -R 62 , R 63 and R 64 Same or different, represents hydrogen atom or M + (O) 2 S(O - )-group, where M + represents a hydrogen atom or a cationic counterion;

[0348] Or another R 61 With R 62 or R 61 With R64 together to form a benzo group, which is optionally substituted by one or more M + (O) 2 S(O - )-group substituted, where M + represents a hydrogen atom or a cationic counterion;

[0349] It is understood that formula (XVII) contains at least one sulfonate group M + (O) 2 S(O - )-, preferably sodium sulfonate;

[0350] As examples of dyes of formula (XVII) there may be mentioned: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0351] 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 and orcein. It is also possible to use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

[0352] Preferably, the direct dyes are selected from anionic direct dyes.

[0353] The coloring agents may be present in a total amount ranging from 0.001% to 15% by weight, preferably from 0.005% to 10% by weight relative to the total weight of the composition.

[0354] The pigments may be present in a total amount ranging from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight relative to the total weight of the composition.

[0355] The direct dyes may be present in a total amount ranging from 0.001% to 10% by weight relative to the total weight of the composition, preferably from 0.005% to 5% by weight relative to the total weight of the composition.

[0356] Preferably, the composition according to the invention comprises water. Preferably, the water is present in a content ranging from 0.1% to 50% by weight, more preferably from 0.5% to 40% by weight relative to the total weight of the composition.

[0357] The composition may comprise less than 2% by weight of water relative to the total weight of the composition.

[0358] Organic solvents:

[0359] The process according to the invention comprises a composition according to the invention, which may comprise one or more organic solvents.

[0360] As the organic solvent, there can be mentioned, for example, lower C 1 -C 4 Alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0361] Preferably, the composition comprises one or more selected from low C 1 -C 4 An organic solvent is preferably an alkanol, more preferably ethanol.

[0362] The organic solvents may be present in a total amount ranging from 0.5% to 80% by weight and inclusive, relative to the total weight of the composition, preferably from 1% to 70% by weight, more preferably from 5% to 60% and inclusive, better still from 10% to 50% by weight relative to the total weight of the composition.

[0363] additive:

[0364] The method according to the invention comprises the composition according to the invention, which may contain any adjuvants or additives usually used.

[0365] Among the additives that can be included in the composition, mention may be made of reducing agents, thickeners, softeners, defoamers, humectants, UV-screening agents, peptizers, solubilizers, perfumes, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers, preservatives, waxes and mixtures thereof.

[0366] The composition according to the invention can in particular be provided in the form of a suspension, dispersion, gel, emulsion (in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion, or a multiple (W / O / W or polyol / O / W or O / W / O) emulsion), in the form of a cream, foam, stick, vesicular dispersion (in particular a vesicular dispersion of ionic or non-ionic lipids), or a two-phase or multi-phase lotion.

[0367] In a preferred embodiment, the composition according to the invention is water and / or a water-alcohol system.

[0368] A person skilled in the art can select a suitable formulation form, and also a method for its preparation, based on his / her general knowledge, taking into account firstly the properties of the ingredients used, in particular their solubility in the carrier, and secondly the application envisaged for the composition.

[0369] According to a preferred embodiment, the composition according to the invention comprises 3-aminopropyltriethoxysilane (APTES), at least one non-amino silicone of formula II) as described above and at least one pigment.

[0370] According to a more preferred embodiment, the composition according to the invention comprises 3-aminopropyltriethoxysilane (APTES), at least one non-amino silicone of formula (III) as described above and at least one pigment.

[0371] Method for treating keratin fibers

[0372] The present invention relates to a method for treating keratin fibers such as hair, which method comprises applying to these keratin fibers a composition as described above, followed by a phase of applying heat to the keratin fibers covered with the composition using heating means at a temperature greater than or equal to 45° C. for a period greater than or equal to 15 minutes.

[0373] Preferably, the composition according to the invention is a composition for dyeing keratin fibres such as the hair.

[0374] The compositions according to the invention can be used on wet or dry keratin fibers, and also on all types of fibers, light or dark, natural or dyed, permanently waving, bleached or relaxed.

[0375] According to a particular embodiment of the method according to the invention, the fibers are washed before applying the above-mentioned composition.

[0376] The application of the dye composition to the keratin fibres can be carried out by any customary means, in particular with the aid of a comb, a fine brush, a coarse brush or with the fingers.

[0377] The dyeing process, ie the application of the dye composition to the keratin fibres, is generally carried out at ambient temperature (15° C. to 25° C.).

[0378] Preferably, after application of the composition according to the invention and before a phase of applying heat to the keratin fibers, for example using a hair dryer, the keratin fibers are subjected to a drying phase for a period ranging from 1 minute to 5 minutes.

[0379] Preferably, after applying the composition according to the invention to the keratin fibres, there is a waiting time of at least 30 seconds, preferably at least 1 minute and more preferably at least 5 minutes before the stage of drying the keratin fibres.

[0380] After a phase of applying a composition according to the invention and optionally drying the keratin fibres, the method according to the invention comprises a phase of applying heat to the keratin fibres using heating means at a temperature greater than or equal to 45° C. for a period greater than or equal to 15 minutes.

[0381] Preferably, the following stage is carried out: heat is applied to the keratin fibers using heating means at a temperature greater than or equal to 45°C for a period greater than or equal to 30 minutes, more preferably at a temperature greater than or equal to 45°C for a period greater than or equal to 1 hour.

[0382] Still more preferably, the following phase is carried out: heat is applied to the keratin fibers using a heating tool at a temperature greater than or equal to 60°C for a period greater than or equal to 15 minutes, better still at a temperature greater than or equal to 60°C for a period greater than or equal to 30 minutes.

[0383] The heat application phase of the method of the present invention may be performed using a hood, a hair dryer, a straightening iron, a curling iron, a Climazon, or the like.

[0384] Preferably, the heat application phase of the method of the invention is carried out using a hair dryer.

[0385] Preferably, the heating means is a hair dryer.

[0386] During the stage of applying heat to the keratin fibres, a mechanical action may be applied to the locks, such as combing, brushing or running the fingers through.

[0387] In a particular alternative form, the method of the invention employs a stage (b1) of applying heat using a hood, a hair dryer or a Climazon, preferably a hair dryer, and a stage (b2) of applying heat using a straightener or a curling iron, preferably a straightener.

[0388] Stage (b1) may be performed before stage (b2).

[0389] During stage (b1 ), also called drying stage, the fiber is dried for a period greater than or equal to 15 minutes at a temperature greater than or equal to 45°C. According to a particular embodiment, this temperature is greater than or equal to 45°C and less than 110°C.

[0390] Preferably, if the fibers are dried, they are dried with a stream of air in addition to the supply of heat. This stream of air during the drying process enables improved personalization of the outer shell.

[0391] During drying, the locks may be subjected to mechanical action such as combing, brushing or running the fingers through.

[0392] During stage (b2), the passage of a straightener or curling iron, preferably a straightener, can be carried out at a temperature ranging from 110°C to 220°C, preferably from 140°C to 200°C.

[0393] Preferably, after applying the composition according to the invention to the keratin fibers and after the stage of applying heat to the keratin fibers using heating means, there is a waiting time of at least 30 minutes before the first shampooing operation, preferably a waiting time of at least 1 hour before the first shampooing operation, more preferably a waiting time of at least 10 hours before the first shampooing operation, and even better a waiting time of at least 24 hours before the first shampooing operation.

[0394] The invention also relates to a method for treating keratin fibers such as hair, which method comprises mixing two compositions (A) and (B) extemporaneously at the time of use and applying the mixture to the fibers, wherein:

[0395] - the composition (A) comprises at least one alkoxysilane selected from compounds of formula (I) as described above, their oligomers and / or mixtures thereof;

[0396] - the composition (B) comprises at least one non-amino silicone of formula (II) as described above;

[0397] It is understood that the composition (A) and / or the composition (B) comprises at least one colorant chosen from pigments, direct dyes and mixtures thereof;

[0398] This is followed by a phase of applying heat to the keratin fibers covered with the composition using heating means at a temperature greater than or equal to 45° C. for a period greater than or equal to 15 minutes.

[0399] Preferably, composition (A) does not comprise at least one non-amino silicone of formula (II) and composition (B) does not comprise at least one alkoxysilane selected from compounds of formula (I), oligomers thereof and / or mixtures thereof.

[0400] According to a first embodiment, the coloring agent is present in composition (B).Composition (A) and composition (B) are thus mixed instantaneously at the time of use, before application to the keratin fibres.

[0401] According to a second embodiment, the coloring agent is present in composition (A).Composition (A) and composition (B) are thus mixed instantaneously at the time of use, before application to the keratin fibres.

[0402] According to a third embodiment, the colorant is present in composition (D).Compositions (A), (B) and (D) are thus mixed instantaneously at the time of use, before application to the keratin fibres.

[0403] Preferably, composition (B) comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof.

[0404] The present invention will now be described more specifically by way of examples, which do not limit the scope of the present invention in any way. However, these examples enable support for preferred embodiments, alternative forms and specific features of the present invention.

[0405] Examples:

[0406] In the examples, unless otherwise stated, temperatures are given in degrees Celsius and correspond to ambient temperature (20-25° C.), and pressure is atmospheric pressure unless otherwise stated.

[0407] The following compositions were prepared (in g / 100 g, AM: active material):

[0408] The following composition 1 (i.e., a solution of 3-aminopropyltriethoxysilane (APTES)) was prepared according to the following method:

[0409] - APTES (APTES Silsoft A-1100, sold by Momentive High Performance Materials) was mixed with water to form an aqueous solution, the pH was then adjusted to 11 by adding a pH=1 HCl solution, and the mixture was placed on a VWR brand magnetic stirrer (rotation speed 500 rpm) at ambient temperature for 24 hours. The pH of the mixture was equal to 11.

[0410] [Table 1]

[0411] Composition 1 3-Aminopropyltriethoxysilane (APTES) 30 Hydrochloric acid (HCl) 0.02 water For 100 appropriate

[0412] The following composition 2 (i.e., an alcoholic solution of silicone) was prepared according to the following method:

[0413] - The non-amino silicone compound is diluted in an ethanol solution in which a pigment (sold by Sun Chemical under the name SunPuro Red Iron Iron oxide for sale).

[0414] [Table 2]

[0415]

[0416] Composition 1 and composition 2 were mixed at a ratio of 50:50. The following compositions were prepared according to the above scheme:

[0417] [Table 3]

[0418]

[0419] plan:

[0420] Composition A is applied to a tress of dry natural hair having 90% white hair at a rate of 1 g of composition per gram of tress.

[0421] The tresses of hair were left at ambient temperature for 5 min.

[0422] The locks of hair were then combed and dried with a hairdryer for 3 minutes.

[0423] The locks of hair are subsequently subjected to phases of heat application according to different temperature conditions and for a given time.

[0424] The locks of hair were placed in a temperature controlled oven (Memmert oven).

[0425] The conditions evaluated are as follows:

[0426] -45℃ temperature for 15 minutes,

[0427] -45℃ temperature for 30 minutes,

[0428] -45°C for 1 hour and

[0429] The temperature of -60°C was maintained for 30 minutes.

[0430] After passing through the oven, the tresses of hair were left at ambient temperature for 24 h.

[0431] A control tress dyed with composition A according to the invention and not subjected to a stage of heat application was also prepared according to the above protocol. This tress of hair was left at ambient temperature for 24 h.

[0432] The locks of hair thus dyed and subjected or not to a phase of heat application are then subjected to a number of repeated shampooing operations, according to the shampooing operation protocol described below, in order to evaluate the fastness (permanence) of the coloration obtained to the shampooing operations.

[0433] Shampoo washing operation plan:

[0434] The tresses were washed using a standard shampoo (Garnier Ultra Doux).

[0435] The locks of hair are then rinsed, combed and dried with a hairdryer.

[0436] The next shampooing operation is carried out on the locks obtained after applying the hairdryer.

[0437] result:

[0438] The permanence of the color of the streak was evaluated in the CIE L*a*b* system using a Minolta spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, including specular reflection component).

[0439] In the L*a*b* system, L* represents the intensity of the color, a* represents the green / red axis and b* represents the blue / yellow axis.

[0440] The permanence of the coloration is evaluated by the color difference ΔE between the dyed locks before shampooing and then after undergoing five shampooing operations according to the protocol described above. The lower the ΔE value, the more permanent the color is for the shampooing operation.

[0441] Calculate the ΔE value according to the following equation:

[0442]

[0443] In this equation, L*a*b* represents the values ​​measured after the hair is dyed and after a shampooing operation is performed, and L 0 *a 0 *b 0 *Indicates values ​​measured after the hair was dyed but before the shampooing operation.

[0444] [Table 4]

[0445]

[0446] The locks 1, 2, 3 and 4 of hair dyed with composition A according to the invention, subjected to a phase of application of heat and washed with five consecutive shampooing operations, exhibit low ΔE values ​​compared to the locks of control hair dyed with composition A according to the invention, not subjected to a phase of application of heat and washed with five consecutive shampooing operations.

[0447] Thus, the colored coating of keratin fibers obtained with the process according to the invention exhibits good resistance to shampoo washing. Indeed, locks of hair dyed with the process according to the invention and washed with five shampooing operations exhibit good color permanence.

Claims

1. A non-therapeutic method for treating keratinous fibers, the method comprising applying to the keratinous fibers a composition comprising: a) at least one alkoxysilane chosen from 3-aminopropyltriethoxysilane (APTES); and wherein the alkoxysilane is present in a total amount of 0.1% to 30% by weight relative to the total weight of the composition; b) at least one non-amino silicone of the following formula (II): in: - R1 represents an alkyl group having 1 to 4 carbon atoms; -R2 represents a hydroxyl group; -i indicates an integer from 0 to 18, n indicates an integer from 0 to 18, wherein n+i varies from 4 to 18, The non-amino silicone of formula (II) has a weight average molecular weight less than or equal to 1500 g / mol; and wherein the non-amino silicone of formula (II) is present in a total amount of 0.1% to 30% by weight relative to the total weight of the composition; and c) at least one colorant selected from pigments, direct dyes and mixtures thereof, This is followed by a phase of applying heat to said keratin fibers covered with said composition using heating means at a temperature greater than or equal to 45° C. for a period greater than or equal to 15 minutes.

2. The non-therapeutic method according to claim 1, characterized in that The non-amino silicone of formula (II) has a weight average molecular weight of 460 to 1500 g / mol.

3. The non-therapeutic method according to any one of claims 1 and 2, characterized in that The weight ratio of alkoxysilane selected from 3-aminopropyltriethoxysilane (APTES) / non-amino silicone of formula (II) varies from 95:5 to 5:

95.

4. The non-therapeutic method according to any one of claims 1 and 2, characterized in that The composition comprises water.

5. The non-therapeutic method according to any one of claims 1 and 2, characterized in that The coloring agents are present in a total amount ranging from 0.001% to 15% by weight relative to the total weight of the composition.

6. The non-therapeutic method according to any one of claims 1 and 2, characterized in that The following phase is carried out: heat is applied to said keratin fibres using heating means, at a temperature greater than or equal to 45° C., for a period greater than or equal to 30 minutes.

7. The non-therapeutic method according to claim 6, characterized in that The following phase is carried out: heat is applied to said keratin fibres using heating means, at a temperature greater than or equal to 60° C., for a period greater than or equal to 15 minutes.

8. A non-therapeutic method for treating keratin fibers, said method comprising mixing two compositions (A) and (B) extemporaneously at the time of use and applying said mixture to said fibers, wherein: - the composition (A) comprises at least one alkoxysilane selected from 3-aminopropyltriethoxysilane (APTES) as claimed in claim 1; - the composition (B) comprises at least one non-amino silicone of formula (II) as claimed in any one of claims 1 and 2; It is understood that the composition (A) and / or the composition (B) comprises at least one colorant selected from pigments, direct dyes and mixtures thereof; This is followed by a phase of applying heat to said keratin fibers covered with said composition using heating means at a temperature greater than or equal to 45° C. for a period greater than or equal to 15 minutes.

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