Keratin fibre treatment process comprising applications of a dye composition based on a particular polymer, followed by a composition based on a fatty substance and a surfactant
A two-step hair dyeing process using a polymer-based dye composition and a surfactant-fatty substance composition addresses the challenges of achieving uniform, long-lasting hair color that is resistant to shampoo washing and external factors, while being easily removable.
Patent Information
- Application Number
- PCT/EP2024/086212
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-12-20
- Filing Date
- 2024-12-13
- Publication Date
- 2025-06-26
AI Technical Summary
Existing hair dyeing methods struggle to provide uniform, long-lasting color that is resistant to shampoo washing and external factors, while also being easily removable when desired.
A two-step process involving the application of a dye composition containing a polymer with acetoacetate units, followed by a composition with a non-silicone fatty substance and a nonionic surfactant, to achieve uniform coloration and easy removal.
The process results in uniform, long-lasting hair color that is resistant to shampoo washing and external factors, while allowing for easy removal of the color when desired.
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Abstract
Description
[0001] Keratin fibre treatment process comprising applications of a dye composition based on a particular polymer, followed by a composition based on a fatty substance and a surfactant
[0002] The present invention relates to the field of the cosmetic treatment of keratin fibres, preferably the hair. The invention is thus directed towards proposing novel treatment processes comprising, in a first stage, dyeing of said keratin fibres by applying a dye composition based on a particular polymer bearing acetoacetate units, which has excellent technical performance qualities, notably in terms of the persistence of the colourings that it affords, then in a second stage removing the colouring from said keratin fibres (or “keratin fibre makeup removal”) by applying a second composition based on a non-silicone fatty substance and a nonionic surfactant to the dyed keratin fibres.
[0003] More precisely, a subject of the present invention is a process for treating keratin fibres such as the hair, comprising the application to the keratin fibres of at least one dye composition B comprising at least one colouring agent and at least one polymer P comprising repeating units obtained from at least one monomer of formula (III), followed by the application to the keratin fibres thus dyed of at least one composition D, different from composition B, comprising at least one nonionic surfactant and at least one non-silicone fatty substance.
[0004] In the field of dyeing hair keratin fibres, it is known practice to dye fibres via various techniques using direct dyes or pigments in order to obtain non-permanent dyeing, or dye precursors in order to obtain permanent dyeing.
[0005] There are essentially three types of process for dyeing the hair: a) “permanent” dyeing, the function of which is to afford a substantial modification to the natural colour and which uses oxidation dyes which penetrate into the hair fibre and form the dye via an oxidative condensation process; b) non-permanent, semi-permanent or direct dyeing, which does not use the oxidative condensation process and withstands four or five shampoo washes; it consists in dyeing keratin fibres with dye compositions containing direct dyes; c) temporary dyeing, which gives rise to a modification of the natural colour of the head of hair which lasts from one shampoo wash to the next, and which serves to enhance or correct a shade that has already been obtained. It may also be likened to a hair “makeup” process. Another dyeing method consists in using pigments. Specifically, the use of pigments on the surface of keratin fibres generally makes it possible to obtain colourings that are visible on dark hair, since the surface pigment masks the natural colour of the fibre. However, the colourings obtained via this dyeing method have the drawback of having poor resistance to shampoo washing and also to external agents such as sebum, perspiration, brushing and / or rubbing.
[0006] Thus, “hair makeup” products have recently been developed, proposing temporary hair dyeing that lasts after one to three shampoos washes. They are a particularly attractive alternative for consumers to permanent hair dyeing, provided that the colouring effect is effectively guaranteed to last after contact with water and a few shampoo washes. This requirement may notably be satisfied by the use of effective film-forming agents.
[0007] Thus, FR 2 741 530 proposes for this purpose, for the temporary dyeing of keratin fibres, the use of a dispersion of film-forming polymer particles including at least one acidic function and at least one pigment dispersed in the continuous phase of said dispersion. The colourings obtained via this dyeing method nevertheless have the drawback of being removed too quickly on shampoo washing.
[0008] It is moreover proposed in FR 2 907 678 to perform coloured coating of the hair using a composition comprising a polysiloxane / polyurea block copolymer and a pigment. However, with such a composition, the coating results obtained are not always very uniform and the individualization of the hair strands is not always satisfactory.
[0009] In addition, users of temporary hair dyes may wish to restore their natural colour at some point. However, there are no satisfactory compositions for totally eliminating (“makeup-removing”) this type of temporary colouring from keratin fibres, when it is persistent with respect to shampoo washing.
[0010] There is thus still a real need for treatment processes that allow keratin fibres, notably the hair, to be dyed, with the advantage that the fibres are uniformly coloured, while forming a coating that is resistant to shampoo washing, sebum and the various attacking factors to which the hair may be subjected, such as brushing, perspiration and / or friction, but which is easy to remove using a specific composition.
[0011] The present invention enables these needs to be met.
[0012] One subject of the present invention is a process, preferably a cosmetic process, for treating keratin fibres such as the hair, comprising at least the following steps: i) a step of applying to the keratin fibres at least one dye composition B comprising at least one colouring agent and at least one polymer P comprising repeating units obtained from at least one monomer of formula (III): in which:
[0013] - Rarepresents a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
[0014] - Rband Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
[0015] - Rdrepresents a linear or branched (Ci-C4)alkyl group, and
[0016] - L represents a linear or branched (Ci-Ce)alkylene, or cycloalkylene, group; and then ii) a step of applying to the dyed keratin fibres at least one composition D, different from composition B, comprising:
[0017] - at least one nonionic surfactant, and
[0018] - at least one non-silicone fatty substance.
[0019] According to the invention, step i) of applying the dye composition B is thus performed before step ii) of applying composition D, which does not preclude one or more intermediate steps between steps i) and ii).
[0020] Application of the dye composition B according to the invention allows smooth, uniform coloured coatings to be obtained. It affords visible colouring on all types of fibre, the colouring being resistant to sebum and water, and notably to shampoo washing. Such a coating may be resistant to the various external attacking factors to which keratin fibres may be subjected, for instance blow-drying, brushing, friction and perspiration.
[0021] In addition, the temporary dyeing of keratin fibres treated with dye composition B may readily be eliminated with composition D, either immediately after application of dye composition B (i.e. within a few minutes to a few hours), or after a certain time (i.e. from a few days to a few weeks), after application of dye composition B. Users then regain the original colour of their keratin fibres (i.e. prior to performing the treatment process according to the invention).
[0022] Another subject of the present invention is a multi -compartment device comprising a first compartment containing a composition B comprising at least one colouring agent and at least one polymer P as described hereinbelow, and a second compartment containing a composition D different from composition B, comprising at least one nonionic surfactant and at least one non-silicone fatty substance as described hereinbelow.
[0023] Other subjects, features, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.
[0024] In the present description, and unless otherwise indicated:
[0025] - the term “at least one” is equivalent to the term “one or more” and can be replaced therewith;
[0026] - the term “between... and...” is equivalent to the term “ranging from... to...” and can be replaced therewith, and implies that the limits are included;
[0027] - for the purposes of the present invention, the term “greater than” and, respectively, the term “less than” refer to an open range which is strictly greater, or, respectively, strictly less, and thus that the limits are not included.
[0028] - according to the present patent application, the term “keratin fibres” particularly means human keratin fibres such as head hair, eyelashes, eyebrows, and bodily hair, preferentially head hair, eyebrows and eyelashes, even more preferentially head hair;
[0029] - for the purposes of the present invention, the term “hair” means head hair. This term does not correspond to bodily hairs, the eyebrows or the eyelashes.
[0030] - an “alkyl” radical denotes a linear or branched saturated radical containing, for example, from 1 to 30 carbon atoms;
[0031] - an “ammoalkyF radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;
[0032] - a “hydroxyalkyF radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;
[0033] - an “alkylene” radical denotes a linear or branched divalent saturated C1-C10 hydrocarbon-based group such as methylene, ethylene or propylene; - a “cycloalkyF or “alicycloalkyF radical denotes a cyclic saturated monocyclic or polycyclic, preferably monocyclic, hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 40 carbon atoms, in particular comprising from 3 to 24 carbon atoms, more particularly from 3 to 20 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl or isobornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is then an isobomyl group;
[0034] - an “aryl” radical is a monocyclic, bicyclic or tricyclic, fused or non-fused, unsaturated and aromatic hydrocarbon-based cyclic radical, comprising from 6 to 30 carbon atoms, preferably between 6 and 14 carbon atoms, more preferentially between 6 and 12 carbon atoms; preferably, the aryl group comprises 1 ring of 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl; preferably, the aryl group represents phenyl;
[0035] - an “aryloxy” radical denotes an aryl-oxy radical with “aryF as defined previously;
[0036] - an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously.
[0037] Unless otherwise indicated, when compounds are mentioned in the present patent application, this also includes the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof or the salts thereof, alone or as a mixture.
[0038] The invention is not limited to the illustrated examples. The characteristics of the various examples may notably be combined within variants which are not illustrated.
[0039] Composition B:
[0040] The process according to the invention comprises at least one step i) of applying to the keratin fibres at least one dye composition B comprising at least one colouring agent and at least one polymer P comprising repeating units obtained from at least one monomer of formula (III) described below. The colouring agents:
[0041] According to the invention, the dye composition B comprises at least one colouring agent.
[0042] Preferably, composition B comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.
[0043] More preferentially, composition B comprises at least one pigment.
[0044] The term “pigment” refers to any pigment that gives colour to keratin materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01% by weight (i.e. gram of pigment per litre of water).
[0045] The pigments that may be used are notably chosen from the organic and / or mineral pigments known in the art, notably those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and in Ullmann ’s Encyclopedia of Industrial Chemistry.
[0046] They may be natural, of natural origin, or non-natural.
[0047] These pigments may be in pigment powder or paste form. They may be coated or uncoated.
[0048] The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, special-effect pigments such as nacres or glitter flakes, and mixtures thereof.
[0049] The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’ s encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, titanium oxide and stannic oxide (tin oxide).
[0050] The pigment may be an organic pigment. The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’ s encyclopedia in the chapter on organic pigments.
[0051] The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds. In particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.
[0052] Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:
[0053] - Cosmenyl Yellow 10G: Yellow 3 pigment (CI 11710);
[0054] - Cosmenyl Yellow G: Yellow 1 pigment (CI 11680);
[0055] - Cosmenyl Orange GR: Orange 43 pigment (CI 71105);
[0056] - Cosmenyl Red R: Red 4 pigment (CI 12085);
[0057] - Cosmenyl Carmine FB: Red 5 pigment (CI 12490);
[0058] - Cosmenyl Violet RL: Violet 23 pigment (CI 51319);
[0059] - Cosmenyl Blue A2R: Blue 15.1 pigment (CI 74160);
[0060] - Cosmenyl Green GG: Green 7 pigment (CI 74260);
[0061] - Cosmenyl Black R: Black 7 pigment (CI 77266).
[0062] The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including an inorganic core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.
[0063] The organic pigment may also be a lake. The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
[0064] The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium. 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 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green 5 (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).
[0065] An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850: 1).
[0066] The pigment may also be a special-effect pigment. The term “special-effect pigments” means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.
[0067] Several types of special -effect pigments exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.
[0068] Examples of special-effect pigments that may be mentioned include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the nacres Cellini sold by BASF (mica-TiCh-lake), Prestige sold by Eckart (mica-TiCE), Prestige Bronze sold by Eckart (mica-Fe2O3) Syncrystal sold by Eckart (Mica-TiCE-SnCh) and Colorona sold by Merck (mica-TiO2-Fe2O3).
[0069] Mention may also be made of the gold-coloured nacres sold notably by the company BASF under the name Brilliant Gold 212G(Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); the bronze nacres sold notably by the company Merck under the name Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super Bronze (Cloisonne); the orange nacres sold notably by the company BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion Orange (Colorona) and Matte Orange (17449) (Microna); the brown nacres sold notably by the company BASF under the name Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold notably by the company BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna Fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by the company BASF under the name Sunstone GO 12 (Gemtone); the pink nacres sold notably by the company BASF under the name Tan Opale G005 (Gemtone); the black nacres with a gold tint sold notably by the company BASF under the name Nu-antique Bronze 240 AB (Timica), the blue nacres sold notably by the company Merck under the name Matte Blue (17433) (Microna), the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold notably by the company Merck under the name Indian Summer (Xirona), and mixtures thereof.
[0070] Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.
[0071] Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.
[0072] Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
[0073] The special-effect pigments may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. brighter points that contrast with their environment, making them appear to sparkle.
[0074] The reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or coppery colour or tint.
[0075] These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.
[0076] The reflective particles, whatever their form, may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.
[0077] When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.
[0078] When the reflective particles have a multilayer structure, they may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material. The substrate may be made of one or more organic and / or mineral materials.
[0079] More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.
[0080] The reflective material may include a layer of metal or of a metallic material.
[0081] Reflective particles are notably described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.
[0082] Again as an example of reflective particles including a mineral substrate coated with a layer of metal, mention may also be made of particles including a silver- coated borosilicate substrate.
[0083] Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal. Particles with a glass substrate coated with a nickel / chromium / molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.
[0084] Use may also be made of particles comprising a metal substrate, such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof. Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiCh, sold under the name Visionaire by the company Eckart.
[0085] Mention may also be made of interference pigments which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f / x from Spectratek). Special-effect pigments also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
[0086] The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.
[0087] The size of the pigment used in the composition according to the present invention is generally between 5 nm and 200 pm, preferably between 7 nm and 80 pm and more preferentially between 10 nm and 50 pm.
[0088] The pigments may be dispersed in the composition by means of a dispersant.
[0089] The dispersant serves to protect the dispersed particles against their agglomeration or flocculation. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with 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 pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxy stearic acid in particular and of Cs to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly( 12-hydroxy stearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.
[0090] As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane / oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.
[0091] The pigments used in the composition may be surface-treated with an organic agent.
[0092] Thus, the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been totally or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.
[0093] The surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and / or may have undergone several surface treatments.
[0094] The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.
[0095] Preferably, the surface-treated pigments are coated with an organic layer.
[0096] The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.
[0097] The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266. An organic agent covalently bonded to the pigments will preferably be used.
[0098] The agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.
[0099] Preferably, the surface treatments of the pigments are chosen from the following treatments:
[0100] - a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW;
[0101] - a methicone treatment, for instance the SI surface treatment sold by LCW;
[0102] - a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW;
[0103] - a dimethicone / trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW;
[0104] - a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;
[0105] - an aluminium dimyristate treatment, for instance the MI surface treatment sold by Miyoshi;
[0106] - a perfluoropolymethyl isopropyl ether treatment, for instance the FHC surface treatment sold by LCW;
[0107] - an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;
[0108] - a perfluoroalkyl phosphate treatment, for instance the PF surface treatment sold by Daito;
[0109] - an acrylate / dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the FSA surface treatment sold by Daito;
[0110] - a polymethylhydrogenosiloxane / perfluoroalkyl phosphate treatment, for instance the FS01 surface treatment sold by Daito;
[0111] - an acrylate / dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito;
[0112] - an isopropyl titanium triisostearate treatment, for instance the ITT surface treatment sold by Daito;
[0113] - an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito; - a perfluoroalkyl phosphate / isopropyl titanium triisostearate treatment, for instance the PF + ITT surface treatment sold by Daito.
[0114] According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form in the dye composition.
[0115] The term “submicron-sized” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.
[0116] According to one embodiment, the dispersant and the pigment(s) are present in an amount (dispersantpigment) of between 1 :4 and 4: 1, particularly between 1.5:3.5 and 3.5: 1 or better still between 1.75:3 and 3: 1.
[0117] The dispersant(s) may thus have a silicone backbone, such as silicone polyether and dispersants of amino silicone type other than the amino alkoxysilanes described in the patent application. Among the suitable dispersants that may be mentioned are:
[0118] - amino silicones, i.e. silicones comprising one or more amine groups such as those sold under the names and references: BYK LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, sold by Genesee Polymers,
[0119] - silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 and Tego® RC 1043, sold by Evonik,
[0120] - polydimethyl siloxane (PDMS) silicones bearing carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 by Evonik.
[0121] According to a particular embodiment, the dispersant(s) are of amino silicone type other than the amino alkoxysilanes described in the patent application and are cationic.
[0122] Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments or special-effect pigments.
[0123] In one variant of the invention, the pigment(s) according to the invention are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds.
[0124] In another variant of the invention, the pigment(s) according to the invention are mineral pigments. In another variant of the invention, the pigments according to the invention are special-effect pigments, preferably nacreous pigments, more preferentially coloured nacreous pigments.
[0125] Composition B may comprise one or more direct dyes.
[0126] The term “direct dye’’’ means natural and / or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fibre. They may be ionic, for example cationic or anionic, or nonionic.
[0127] 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, alone or in the form of mixtures.
[0128] The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. The term “anionic direct dye” means any direct dye including in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen 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.
[0129] As acid dyes that are useful for the invention, mention may be made of the dyes of formulae (XIX), (XIX’), (XX), (XX’), (XXI), (XXI’), (XXII), (XXII’), (XXIII), (XXIV), (XXV) and (XXVI) below: a) the diaryl anionic azo dyes of formula (XIX) or (XIX1):
[0130] (XIX'), in which formulae (XIX) and (XIX’):
[0131] - R7, Rs, R9, Rio, R’7, R’s, R’9 and R’10, which may be identical or different, represent a hydrogen atom or a group chosen from:
[0132] - alkyl;
[0133] - alkoxy, alkylthio;
[0134] - hydroxyl, mercapto;
[0135] - nitro, nitroso;
[0136] - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
[0137] - (O)2S(O')-, M+with M+representing a hydrogen atom or a cationic counterion;
[0138] - (O)CO -, M+with M+as defined previously;
[0139] - R”-S(O)2-, with R” representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;
[0140] - R’”-S(O)2-X’- with R’” representing an optionally substituted alkyl or aryl group, X’ as defined previously;
[0141] - (di)(alkyl)amino;
[0142] - aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M+and iv) alkoxy with M+as defined previously;
[0143] - optionally substituted heteroaryl; preferentially a benzothiazolyl group;
[0144] - cycloalkyl, notably cyclohexyl;
[0145] - Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (O)2S(O )-, M+or phenylamino groups;
[0146] - or alternatively two contiguous groups R7 with Rs or Rs with R9 or R9 with Rio together form a fused benzo group A’; and R’7 with R’s orR’s with R’9 or R’9 with R’10 together form a fused benzo group B’; with A’ and B’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’- C(X)-X”-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X’, X” and Ar as defined previously; - W represents a sigma bond o, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and Rb form, together with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that formulae (XIX) and (XIX’) comprise at least one sulfonate radical (O)2S(O )-, M+or one carboxylate radical (O)CO -, M+on one of the rings A, A’, B, B’ or C; preferentially sodium sulfonate.
[0147] As examples of dyes of formula (XIX), 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, Acid 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; and, as examples of dyes of formula (XIX’), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38; b) the pyrazolone anionic azo dyes of formulae (XX) and (XX1):
[0148] (xx'): in which formulae (XX) and (XX’):
[0149] - Rn, R12 and R13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O ), M+with M+as defined previously;
[0150] - R14 represents a hydrogen atom, an alkyl group or a group -C(O)O', M+with M+as defined previously;
[0151] - R15 represents a hydrogen atom;
[0152] - Rie represents an oxo group, in which case R’i6 is absent, or alternatively R15 with Rie together form a double bond;
[0153] - R17 and Ris, which may be identical or different, represent a hydrogen atom, or a group chosen from:
[0154] - (O)2S(O')-, M+with M+as defined previously;
[0155] - Ar-O-S(O)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups;
[0156] - R19 and R20 together form either a double bond, or a benzo group D’, which is optionally substituted;
[0157] - R’ 16, R’ 19 and R’20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group;
[0158] - R21 represents a hydrogen atom or an alkyl or alkoxy group;
[0159] - Ra and Rb, which may be identical or different, are as defined previously; preferentially, Ra represents a hydrogen atom and Rb represents an aryl group;
[0160] - Y represents either a hydroxyl group or an oxo group;
[0161] <■* «■> W
[0162] > —represents asingle bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that formulae (XX) and (XX’) comprise at least one sulfonate radical (O)2S(O )-, M+or one carboxylate radical -C(O)O', M+on one of the rings D or E; preferentially sodium sulfonate.
[0163] As examples of dyes of formula (XX), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (XX’), mention may be made of: Acid Yellow 17; c) the anthraquinone dyes of formulae (XXI) and (XXI’):
[0164] (xxr), in which formulae (XXI) and (XXI’):
[0165] - R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
[0166] - alkyl;
[0167] - hydroxyl, mercapto;
[0168] - alkoxy, alkylthio;
[0169] - optionally substituted aryloxy or arylthio, preferentially substituted with one or more groups chosen from alkyl and (O)2S(O )-, M+with M+as defined previously;
[0170] - aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (O)2S(O )-, M+with M+as defined previously;
[0171] - (di)(alkyl)amino;
[0172] - (di)(hydroxyalkyl)amino;
[0173] - (O)2S(O')-, M+with M+as defined previously;
[0174] - Z’ represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:
[0175] - alkyl;
[0176] - polyhydroxy alkyl such as hydroxy ethyl;
[0177] - aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O )-, M+with M+as defined previously; iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R°, X, X’ and X” as defined previously, preferentially R° represents an alkyl group;
[0178] - cycloalkyl, notably cyclohexyl;
[0179] - Z represents a group chosen from hydroxyl and NR’28R’29 with R’28 and R’29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulae (XXI) and (XXI’) comprise at least one sulfonate radical (O)2S(O )-, M+or one carboxylate radical -C(O)O', M+; preferentially sodium sulfonate.
[0180] As examples of dyes of formula (XXI), 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; and, as an example of a dye of formula (XXI’), mention may be made of: Acid Black 48; d) the nitro dyes of formulae (XXII) and (XXII’):
[0181] (xxir), in which formulae (XXII) and (XXII’):
[0182] - R30, R31 and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
[0183] - alkyl;
[0184] - alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;
[0185] - hydroxyl, mercapto;
[0186] - nitro, nitroso;
[0187] - polyhaloalkyl; - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R°, X, X’ and X” as defined previously;
[0188] - (O)2S(O')-, M+with M+as defined previously;
[0189] - (O)CO -, M+with M+as defined previously;
[0190] - (di)(alkyl)amino;
[0191] - (di)(hydroxyalkyl)amino;
[0192] - heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R30, R31 and R32 represent a hydrogen atom;
[0193] - Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;
[0194] - W is as defined previously; W particularly represents an -NH- group;
[0195] - ALK represents a linear or branched divalent Ci-Ce alkylene group; in particular, ALK represents a -CH2-CH2- group;
[0196] - n is 1 or 2;
[0197] - p represents an integer inclusively between 1 and 5;
[0198] - q represents an integer inclusively between 1 and 4;
[0199] - u is 0 or 1;
[0200] - when n is 1, J represents a nitro or nitroso group; particularly nitro;
[0201] - when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0)m- with m representing an integer 1 or 2; preferentially, J represents an -SO2- radical;
[0202] - M’ represents a hydrogen atom or a cationic counterion; , which may be present or absent, represents a benzo group optionally substituted with one or more groups R30 as defined previously; it being understood that formulae (XXII) and (XXII’) comprise at least one sulfonate radical (O)2S(O )-, M+or one carboxylate radical -C(O)O', M+; preferentially sodium sulfonate.
[0203] As examples of dyes of formula (XXII), mention may be made of Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXII’), mention may be made of Acid Yellow 1, the sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4’-N,N-(2”-hydroxyethyl)amino-2’- nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7; e) the triarylmethane dyes of formula (XXIII): in which formula (XXIII):
[0204] - R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted with a group (O) m S(O )-, M+with M+and m as defined previously;
[0205] - R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group chosen from:
[0206] - alkyl;
[0207] - alkoxy, alkylthio;
[0208] - (di)(alkyl)amino;
[0209] - hydroxyl, mercapto;
[0210] - nitro, nitroso;
[0211] - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
[0212] - (O)2S(O')-, M+with M+representing a hydrogen atom or a cationic counterion;
[0213] - (O)CO -, M+with M+as defined previously;
[0214] - or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: I’; with I’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’- C(X)-X”-; with M+, R°, X, X’ and X” as defined previously; in particular, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be identical or different, represent a hydroxyl group or (O)2S(O )-, M+; and when R43 with R44 together form a benzo group, it is preferentially substituted with an (O)2S(O )- group; it being understood that at least one of the rings G, H, I or I’ comprises at least one sulfonate radical (O)2S(O )- or one carboxylate radical -C(O)O'; preferentially sulfonate.
[0215] As examples of dyes of formula (XXIII), 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. f) the xanthene-based dyes of formula (XXIV):
[0216] (XXIV), in which formula (XXIV):
[0217] - R45, R46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;
[0218] - R49, R50, R51 and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
[0219] - alkyl;
[0220] - alkoxy, alkylthio;
[0221] - hydroxyl, mercapto;
[0222] - nitro, nitroso;
[0223] - (O)2S(O')-, M+with M+representing a hydrogen atom or a cationic counterion;
[0224] - (O)CO -, M+with M+as defined previously; particularly, R49, R50, R51 and R52 represent a hydrogen or halogen atom;
[0225] - G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; in particular, G represents an oxygen atom;
[0226] - L represents an alkoxide O', M+; a thioalkoxide S', M+or a group NRf, with Rf representing a hydrogen atom or an alkyl group, and M+as defined previously; M+is particularly sodium or potassium; - L’ represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom or an optionally substituted alkyl or aryl group; L’ particularly represents an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O)mS(O‘)-, M+groups with m and M+as defined previously;
[0227] - Q and Q’, which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q’ represent an oxygen atom;
[0228] - M+is as defined previously.
[0229] As examples of dyes of formula (XXIV), 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; g) the indole-based dyes of formula (XXV):
[0230] (XXV), in which formula (XXV):
[0231] - R53, R54, R55, R56, R57, R58, R59 and Reo, which may be identical or different, represent a hydrogen atom or a group chosen from:
[0232] - alkyl;
[0233] - alkoxy, alkylthio;
[0234] - hydroxyl, mercapto;
[0235] - nitro, nitroso;
[0236] - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
[0237] - (O)2S(O')-, M+with M+representing a hydrogen atom or a cationic counterion;
[0238] - (O)CO -, M+with M+as defined previously;
[0239] - G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; in particular, G represents an oxygen atom; - Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (XXIII) comprises at least one sulfonate radical (O)2S(O )-, M+or one carboxylate radical -C(O)O', M+; preferentially sodium sulfonate.
[0240] As examples of dyes of formula (XXV), mention may be made of: Acid Blue 74; h) the quinoline-based dyes of formula (XXVI): in which formula (XXVI):
[0241] - Rei represents a hydrogen or halogen atom or an alkyl group;
[0242] - R62, Res and R64, which may be identical or different, represent a hydrogen atom or a group (O)2S(O )-, M+with M+representing a hydrogen atom or a cationic counterion; or alternatively Rei with Re2, or Rei with Re4, together form a benzo group optionally substituted with one or more groups (O)2S(O )-, M+with M+representing a hydrogen atom or a cationic counterion; it being understood that formula (XXVI) comprises at least one sulfonate radical (O)2S(O )-, M+, preferentially sodium sulfonate.
[0243] As examples of dyes of formula (XXVI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
[0244] Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and notably henna-based poultices or extracts.
[0245] Preferably, the direct dyes are chosen from anionic direct dyes.
[0246] Preferably, the total content of colouring agent(s) in composition B ranges from 0.001% to 20% by weight, more preferentially from 0.01% to 15% by weight, even more preferentially from 0.1% to 10% by weight, better still from 0.5% to 10% by weight, even better still from 1% to 10% by weight, relative to the total weight of composition B.
[0247] More preferentially, the total content of pigment(s) in the composition according to the invention ranges from 0.001% to 20% by weight, more preferentially from 0.01% to 15% by weight, even more preferentially from 0.1% to 10% by weight, better still from 0.5% to 10% by weight, even better still from 1% to 10% by weight, relative to the total weight of the composition.
[0248] Polymers P:
[0249] According to the invention, the dye composition B comprises at least one polymer P comprising repeating units obtained from at least one monomer of formula (III) below: in which:
[0250] - Rarepresents a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
[0251] - Rband Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
[0252] - Rdrepresents a linear or branched (Ci-C4)alkyl group, and
[0253] - L represents a linear or branched (Ci-Ce)alkylene, or cycloalkylene, group.
[0254] In this formula (III):
[0255] • Rapreferably represents a hydrogen atom or a methyl group, more preferentially a methyl group,
[0256] • Rband Rcpreferably represent a hydrogen atom,
[0257] • Rdpreferably represents a methyl group, and
[0258] • L preferably represents a (Ci-C4)alkylene group, and more preferentially L represents ethylene. According to a preferred embodiment, the monomer of formula (III) is chosen from acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof.
[0259] The polymer(s) P may be chosen from homopolymers, i.e. polymers formed entirely from repeating units of a single monomer of formula (III), and copolymers obtained by copolymerization of at least two monomers, at least one of which is of formula (III).
[0260] According to a preferred embodiment, the polymer(s) P are chosen from “CP” copolymers, obtained by polymerization of:
[0261] - 0% to 99% by weight, in particular from 50% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (1) chosen from 2- ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobomyl methacrylate, and mixtures thereof;
[0262] - 1% to 20% by weight, relative to the total weight of the monomers, at least one monomer (2) of formula (III) as defined above; and
[0263] - 0% to 99% by weight, in particular 0% to 45% by weight, relative to the total weight of the monomers, of at least one monomer (3) chosen from C1-C4 alkyl acrylates, C1-C4 alkyl methacrylates, silicone macromonomers and mixtures thereof, it being understood that said copolymers CP are obtained by polymerization of at least one monomer (2) with at least one monomer (1) and / or at least one monomer (3).
[0264] Said copolymer CP may be a statistical, alternating (block) or gradient copolymer.
[0265] Preferably, the copolymer CP is a statistical copolymer.
[0266] For the purposes of the present invention, the term “statistical copolymer” means a copolymer formed of macromolecules in which the sequential distribution of the monomer units (2), (1) if present, and (3) if present, obeys known statistical laws. In other words, in a statistical copolymer, the various monomers follow each other in any order. Statistical copolymers are also known as random copolymers. For example, the sequence of a statistical copolymer, formed from monomers A and B, may be as follows A-A-B-A-B-B-B-B-A-A-B-A.
[0267] The copolymer CP according to the present invention is in particular free of monomer units different from monomers (2), (1) and (3) defined above. Monomer (1)
[0268] As mentioned above, the copolymer CP according to the invention may comprise at least one monomer (1) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobomyl methacrylate, and mixtures thereof.
[0269] According to a first variant of the invention, the copolymer CP according to the invention does not comprise any monomer (1). In other words, the copolymer CP according to the invention then consists of monomer(s) (2) and monomer(s) (3) as defined above.
[0270] According to a second variant of the invention, the copolymer CP comprises from 50% to 99% by weight, and preferably from 55% to 95% by weight, of at least one monomer (1) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobomyl acrylate, isobomyl methacrylate, and mixtures thereof, relative to the total weight of the monomers.
[0271] 2-Ethylhexyl acrylate, also known as 2-ethylhexyl prop-2-enoate, is a compound of empirical formula C11H20O2, and of structural formula:
[0272] As 2-ethylhexyl acrylate, mention may notably be made of the product sold under the name 2-Ethylhexyl acrylate by the company Sigma- Aldrich.
[0273] 2-Ethylhexyl methacrylate, also known as 2-ethylhexyl 2-methylprop-2- enoate, is a compound of empirical formula C12H22O2 and of structural formula:
[0274] As 2-ethylhexyl methacrylate, mention may notably be made of the product sold under the name 2-Ethylhexyl methacrylate by the company Sigma- Aldrich.
[0275] Isobornyl acrylate is a compound of empirical formula C13H20O2, and of structural formula: As isobornyl acrylate, mention may notably be made of the product sold under the name Isobornyl acrylate by the company Sigma-Aldrich.
[0276] Isobornyl methacrylate is a compound of empirical formula C14H22O2, and of structural formula:
[0277] As isobornyl methacrylate, mention may notably be made of the product sold under the name Isobomyl methacrylate by the company Sigma- Aldrich.
[0278] Preferably, monomer (1) is at least 2-ethylhexyl acrylate and / or isobomyl acrylate.
[0279] According to a third variant of the invention, the copolymer CP comprises at least one monomer (1) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobomyl acrylate, isobornyl methacrylate, and mixtures thereof, in an amount of less than 50% relative to the total weight of the monomers, preferably between 0.01% and 49.9% relative to the total weight of the monomers.
[0280] Monomer (2)
[0281] According to the invention, the copolymer CP comprises from 1% to 20% by weight, and preferably from 5% to 15% by weight, relative to the total weight of the monomers, of at least one monomer (2) of formula (III): in which:
[0282] • Rarepresents a hydrogen atom or a linear or branched (Ci-C4)alkyl group; preferably, Rarepresents a methyl group,
[0283] • Rband Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group; preferably, Rband Rcrepresent a hydrogen atom,
[0284] • Rdrepresents a linear or branched (Ci-C4)alkyl group; preferably, Rdrepresents a methyl group, and • L represents a linear or branched (Ci-Ce)alkylene or cycloalkylene group; preferably, L represents a (Ci-C4)alkylene group, in particular ethylene.
[0285] In particular, the monomer (2) is chosen from acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof, and preferably, monomer (2) is acetoacetoxyethyl methacrylate.
[0286] Acetoacetoxy ethyl acrylate is a compound of empirical formula C9H12O5, and of structural formula:
[0287] As acetoacetoxyethyl acrylate, mention may notably be made of the product sold under the name Butanoic acid, 3-oxo-2-[(l-oxo-2-propen-l-yl)oxy]ethyl ester by the company Alfa Chemistry.
[0288] Acetoacetoxyethyl methacrylate is a compound of empirical formula C10H14O5, and of structural formula:
[0289] As acetoacetoxyethyl methacrylate, mention may notably be made of the product sold under the name Eastman™ AAEM by the company Eastman.
[0290] Monomer (3)
[0291] According to the invention, the copolymer comprises from 0% to 99% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates, C1-C4 alkyl methacrylates, silicone macromonomers and mixtures thereof, relative to the total weight of the monomers.
[0292] Thus, according to a variant of the invention, the copolymer CP according to the invention does not comprise any monomer (3). In other words, the copolymer CP according to the invention then consists of monomer(s) (2) and monomer(s) (1) as defined above.
[0293] Among the C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates that may be used as monomers (3), mention may be made in particular of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertbutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate and mixtures thereof.
[0294] Preferably, the monomer (3) is a C1-C4 alkyl acrylate, in particular chosen from butyl acrylate, isobutyl acrylate and tert-butyl acrylate.
[0295] Butyl acrylate is a compound of empirical formula C7H13O2 and of structural formula:
[0296] As a butyl acrylate, mention may notably be made of the product sold under the name Butyl acrylate by the company Sigma-Aldrich.
[0297] According to a preferred embodiment, the monomer (3) is at least one monomer chosen from C1-C4 alkyl acrylates and / or C1-C4 alkyl methacrylates, preferably chosen from C1-C4 alkyl acrylates, and more preferentially the monomer (3) is at least butyl acrylate.
[0298] Isobutyl acrylate is a compound of empirical formula C7H12O2 and of structural formula:
[0299] As isobutyl acrylate, mention may notably be made of the product sold under the name Isobutyl acrylate by the company Sigma-Aldrich. tert-Butyl acrylate is a compound of empirical formula C7H12O2 and of structural formula:
[0300] As tert-butyl acrylate, mention may notably be made of the product sold under the name tert-Butyl acrylate by the company Sigma-Aldrich.
[0301] According to another preferred embodiment, monomer (3) is at least one silicone macromonomer.
[0302] The term “silicone macromonomer” means a silicone macromolecule bearing an end group that enables it to act as a monomer. The silicone macromonomers will provide a single monomer unit to a chain of the finished macromolecule. As regards the silicone macromonomers, they may in particular be polydimethylsiloxanes bearing a monoacryloyloxy or monomethacryloyloxy end group, and notably those of formula (II):
[0303] (II) in which:
[0304] - Rs denotes a hydrogen atom or a methyl group, preferably methyl;
[0305] - R9 denotes a linear or branched, preferably linear, divalent hydrocarbonbased group containing from 1 to 10 carbon atoms and optionally containing one or two -O- ether bonds; preferably ethylene, propylene or butylene;
[0306] - Rio denotes a linear or branched alkyl group containing from 1 to 10 carbon atoms, notably from 2 to 8 carbon atoms; preferably methyl, ethyl, propyl, butyl or pentyl;
[0307] - n denotes an integer ranging from 1 to 300, preferentially ranging from 3 to 200.
[0308] These may notably be polydimethylsiloxane methacrylates and in particular the products sold under the name MCR-M17 by Gelest Inc. or x-22-2475 and x-22- 2426 by Shin-Etsu.
[0309] The silicone macromonomers that are most particularly suitable for use in the invention have a weight-average molecular mass (Mw) ranging from 200 g.mol'1to 100 000 g.mol'1, and more preferentially from 400 g.mol'1to 20 000 g.mol'1.
[0310] In particular, monomer (3) is at least one silicone macromonomer, more particularly chosen from silicone macromonomers with a glass transition temperature Tgof less than or equal to 25°C, more particularly between -100°C and 25°C, and preferably between -90°C and 0°C.
[0311] According to a preferred embodiment, the monomer (3) is at least one polydimethylsiloxane bearing a mono(meth)acryloyloxy end group.
[0312] According to a preferred embodiment of the invention, the copolymer CP comprises from 0% to 45% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates, C1-C4 alkyl methacrylates, silicone macromonomers, and mixtures thereof, relative to the total weight of the monomers, preferably from 0% to 45% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates, C1-C4 alkyl methacrylates, silicone macromonomers, and mixtures thereof, relative to the total weight of the monomers, and at least one monomer (1) as defined previously, more preferentially 50% to 99% of at least one monomer (1) as defined previously.
[0313] According to another preferred embodiment of the invention, the copolymer CP comprises from 80% to 99% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates, and preferably the copolymer CP comprises from 80% to 99% by weight of at least one monomer (3) chosen from Ci- C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers, and no monomer (1) as defined previously.
[0314] According to another preferred embodiment of the invention, the copolymer CP comprises from 80% to 99% by weight of at least one monomer (3) chosen from silicone macromonomers, and mixtures thereof with C1-C4 alkyl acrylates or with Ci- C4 alkyl methacrylates, relative to the total weight of the monomers, preferably 80% to 99% by weight of a mixture of at least one monomer (3) chosen from silicone macromonomers and at least one monomer (3) chosen from Ci-C4-alkyl acrylates and / or Ci-C4-alkyl methacrylates, relative to the total weight of the monomers; more preferentially, the copolymer CP comprises 80% to 99% by weight of a mixture of at least one monomer (3) chosen from silicone macromonomers and at least one monomer (3) chosen from C1-C4 alkyl acrylates and / or C1-C4 alkyl methacrylates, and no monomer (1) relative to the total weight of the monomers.
[0315] According to another particular embodiment of the invention, the copolymer CP comprises more than 30% by weight of at least one monomer (3) chosen from Ci- C4 alkyl acrylates and C1-C4 alkyl methacrylates, and preferably CP comprises from 30.01% to 99% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers and at least one monomer (1) as defined previously in a non-zero amount and less than 50% relative to the total weight of the monomers. According to this embodiment, the monomers (3) preferably denote C4 alkyl acrylates, C4 alkyl methacrylates or mixtures of C1-C3 alkyl acrylates and / or C1-C3 alkyl methacrylates with C4 alkyl acrylates or C4 alkyl methacrylates.
[0316] According to another particular embodiment of the invention, the copolymer CP comprises more than 30% by weight of at least one monomer (3) chosen from silicone macromonomers and mixtures thereof with C1-C4 alkyl acrylates or with Ci- C4 alkyl methacrylates, relative to the total weight of the monomers, and preferably CP comprises from 30.01% to 99% by weight of at least one monomer (3) chosen from silicone macromonomers and mixtures thereof with C1-C4 alkyl acrylates or with Ci- C4 alkyl methacrylates, relative to the total weight of the monomers, and at least one monomer (1) as defined previously in a non-zero amount and less than 50% relative to the total weight of the monomers.
[0317] According to another particular embodiment of the invention, the copolymer CP comprises more than 45% and less than 49% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates, C1-C4 alkyl methacrylates, silicone macromonomers, and mixtures thereof and preferably CP comprises from 45.01% to 48.99% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers, and at least one monomer (1) as previously defined in an amount of from 50% to 99% relative to the total weight of the monomers. According to this embodiment, the monomers (3) preferably denote C4 alkyl acrylates, C4 alkyl methacrylates or mixtures of C1-C3 alkyl acrylates and / or C1-C3 alkyl methacrylates with C4 alkyl acrylates or C4 alkyl methacrylates.
[0318] Most particularly, the copolymer CP according to the present invention is preferably obtained by copolymerization of isobutyl acrylate, tert-butyl acrylate and acetoacetoxyethyl methacrylate, more preferentially in an isobutyl acrylate / tert-butyl acrylate / acetoacetoxy ethyl methacrylate mass ratio of 25 / 65 / 10.
[0319] Preferably, composition B comprises the polymer(s) P in a total content ranging from 1% to 30% by weight, more preferentially from 2% to 20% by weight, and even more preferentially ranging from 5% to 15% by weight, relative to the total weight of composition B.
[0320] According to a preferred embodiment, composition B comprises the polymer(s) CP in a total content ranging from 1% to 30% by weight, more preferentially from 2% to 20% by weight, and even more preferentially ranging from 5% to 15% by weight, relative to the total weight of composition B.
[0321] According to a preferred embodiment, when composition B according to the invention comprises the polymer(s) CP chosen from isobutyl acrylate, tert-butyl acrylate and acetoacetoxyethyl methacrylate copolymer, the total content of copolymer(s) CP is in the range from 1% to 30% by weight, more preferentially from 2% to 20% by weight, and even more preferentially from 5% to 15% by weight, relative to the total weight of composition B.
[0322] Non-amino silicones:
[0323] Preferably, composition B also comprises at least one non-amino silicone, i.e. at least one silicone other than amino silicones.
[0324] In a manner known per se, the term “ silicone" denotes any organosilicon polymer or oligomer of linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond -Si-O-Si-), optionally substituted hydrocarbon-based radicals being directly linked via a carbon atom to said silicon atoms.
[0325] The term “amino silicone” denotes any silicone including at least one primary, secondary or tertiary amine group and / or at least one quaternary ammonium group.
[0326] The non-amino silicones according to the invention are different from the polymers P described previously and from the alkoxysilanes and oligomers thereof described hereinbelow.
[0327] The non-amino silicones that may be used may be volatile or non-volatile.
[0328] The non-amino silicones that may be used may be soluble or insoluble in composition B according to the invention; they may be in oil, wax, resin or gum form; silicone oils and silicone resins are preferred.
[0329] Silicones are notably described in detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.
[0330] The volatile silicones may be chosen from those with a boiling point of between 60°C and 260°C (at atmospheric pressure) and more particularly from: i) cyclic polydialkylsiloxanes including from 3 to 7 and preferably 4 to 5 silicon atoms, such as
[0331] - octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
[0332] Mention may be made of the products sold under the name Volatile Silicone 7207 by Union Carbide or Silbione 70045 V 2 by Rhodia, Volatile Silicone 7158 by Union Carbide or Silbione 70045 V 5 by Rhodia;
[0333] - cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type having the chemical structure:
[0334] Mention may be made of Volatile Silicone FZ 3109 sold by the company Union Carbide;
[0335] - mixtures of cyclic silicones with silicon-based organic compounds, such as the mixture of octamethylcyclotetrasiloxane and of tetratrimethylsilylpentaerythritol (50 / 50) and the mixture of octamethylcyclotetrasiloxane and of oxy-1,1’- bis(2,2,2’,2’,3,3’-hexatrimethylsilyloxy)neopentane; ii) linear polydialkylsiloxanes containing 2 to 9 silicon atoms, which generally have a viscosity of less than or equal to 5><10'6m2 / s at 25°C, such as decamethyltetrasiloxane.
[0336] Other silicones belonging to this category are described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pages 27-32 - Todd & Byers Volatile silicone fluids for cosmetics,' mention may be made of the product sold under the name SH 200 by the company Toray Silicone.
[0337] Among the non-volatile silicones, mention may be made, alone or as a mixture, of polydialkylsiloxanes and notably polydimethylsiloxanes (PDMS), polydiarylsiloxanes, poly alkylaryl siloxanes, silicone gums and resins, and also organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more organofunctional groups, generally attached via a hydrocarbon-based group, and preferably chosen from aryl groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups.
[0338] The organomodified silicones may be polydiarylsiloxanes, notably polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously. The polyalkylarylsiloxanes are particularly chosen from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes.
[0339] Among the organomodified silicones, mention may be made of organopolysiloxanes including: - polyoxyethylene and / or polyoxypropylene groups optionally including C6- C24 alkyl groups, such as dimethicone copolyols, and notably those sold by the company Dow Coming under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711 from the company Union Carbide; or alternatively (C12)alkylmethicone copolyols, and notably those sold by the company Dow Corning under the name Q2- 5200;
[0340] - thiol groups, such as the products sold under the names GP 72 A and GP 71 from Genesee;
[0341] - alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt;
[0342] - hydroxylated groups, for instance polyorganosiloxanes bearing a hydroxyalkyl function;
[0343] - acyloxyalkyl groups, such as the polyorganosiloxanes described in patent US-A-4 957 732;
[0344] - anionic groups of the carboxylic acid type, as described, for example, in EP 186 507, or of the alkylcarboxylic type, such as the product X-22-3701E from the company Shin-Etsu; or alternatively of the 2-hydroxy alkyl sulfonate or 2- hydroxyalkylthiosulfate type, such as the products sold by the company Goldschmidt under the names Abil® S201 and Abil® S255.
[0345] The silicones may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes bearing trimethyl silyl end groups. Among these polydialkylsiloxanes, mention may be made of the following commercial products:
[0346] - the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500 000;
[0347] - the oils of the Mirasil® series sold by the company Rhodia;
[0348] - the oils of the 200 series from the company Dow Corning, such as DC200, with a viscosity of 60 000 mm2 / s;
[0349] - the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
[0350] Mention may also be made of polydimethylsiloxanes bearing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia. In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are poly(Cl-C20)dialkylsiloxanes.
[0351] Products that may be used more particularly in accordance with the invention are mixtures such as:
[0352] - mixtures formed from a polydimethylsiloxane with a hydroxy-terminated chain, or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2-1401 sold by the company Dow Corning.
[0353] The polyalkylarylsiloxanes are chosen particularly from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes with a viscosity ranging from 1 * 10'5to 5* 10'2m2 / s at 25°C.
[0354] Among these polyalkylarylsiloxanes, mention may be made of the products sold under the following names:
[0355] - the Silbione® oils of the 70 641 series from Rhodia;
[0356] - the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;
[0357] - the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;
[0358] - the silicones of the PK series from Bayer, such as the product PK20;
[0359] - the silicones of the PN and PH series from Bayer, such as the products PN1000 and PHlOOO;
[0360] - certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.
[0361] The silicones may also be chosen from silicone resins. Generally, the term “resin” means a compound whose structure is three-dimensional. “Silicone resins” are also referred to as “siloxane resins”. Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.
[0362] The silicone resin(s) according to the invention may be chosen from silicone resins with a molecular weight of between 300 and 100 000 g / mol, preferably between 300 and 50 000 g / mol, more preferentially between 300 and 30 000 g / mol. The term “molecular weight” means the average molecular weight (Mw).
[0363] The nomenclature of silicone resins (also known as siloxane resins) is known under the name “MDTQ”, the resin being described as a function of the various siloxane monomer units it comprises, each of the letters “MDTQ” characterizing a type of unit. The leter "M" represents the monofunctional unit of formula RlR2R3SiOi / 2, the silicon atom being bonded to just one oxygen atom in the polymer comprising this unit.
[0364] The leter “D” means a difunctional unit RlR2SiO2 / 2 in which the silicon atom is bonded to two oxygen atoms.
[0365] The letter "T" represents a trifunctional unit of formula R. I SiCh 2.
[0366] Such resins are described, for example, in the Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley & Sons, New York, (1989), pp. 265- 270, and US 2 676 182, US 3 627 851, US 3 772 247, US 5 248 739 or US 5 082 706, US 5 319 040, US 5 302 685 and US 4 935 484.
[0367] In the units M, D and T defined previously, R, namely Rl, R2 and R3, represents a hydrocarbon-based radical (notably alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group.
[0368] Finally, the letter “Q” means a tetrafunctional unit SiO4 / 2 in which the silicon atom is bonded to four hydrogen atoms, which are themselves bonded to the rest of the polymer.
[0369] Various silicone resins with different properties may be obtained from these different units, the properties of these polymers varying as a function of the type of monomer (or unit), the nature and number of the radical R, the length of the polymer chain, the degree of branching and the size of the side chains.
[0370] As silicone resins that may be used in composition B according to the invention, use may be made, for example, of silicone resins of MQ type, of T type or of MQT type.
[0371] MQ resins:
[0372] As examples of silicone resins of MQ type, mention may be made of the alkyl siloxy silicates of formula [(Rl)3SiOi / 2]x(SiO4 / 2)y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group Rl represents a radical as defined previously, and is preferably an alkyl group containing from 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group.
[0373] As examples ofMQ-type solid trimethylsiloxysilicate silicone resins, mention may be made of those sold under the reference SR1000®, E 1 170-002® or SS 4230® by the company General Electric, under the reference TMS 803®, WACKER 803® and 804® by the company Wacker, under the name KF-7312J® by the company Shin-Etsu, DC 749® or DC 593® by the company Dow Corning, or under the name Silsoft 74 by the company Momentive Performance Materials. As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151® sold by the company General Electric). The preparation of such resins is notably described in patent US 5 817 302.
[0374] T resins:
[0375] Examples of silicone resins of type T that may be mentioned include the polysilsesqui oxanes of formula (RSiO3 / 2)x (T units) in which x is greater than 100 and such that the group R is an alkyl group containing from 1 to 10 carbon atoms, said polysilsesquioxanes also possibly comprising Si-OH end groups.
[0376] Polymethylsilsesquioxane resins that may preferably be used are those in which R represents a methyl group, for instance those sold:
[0377] - by the company Wacker under the reference Resin MK®, such as Belsil PMS MK®: polymer comprising CEESiOs / ? repeating units (T units), which may also comprise up to 1% by weight of (CH3)2SiO2 / 2units (D units) and having an average molecular weight of about 10 000 g / mol, or
[0378] - by the company Shin-Etsu under the references KR-220L®, which are composed of T units of formula CEESiCh / ? and contain Si-OH (silanol) end groups, under the reference KR-242A®, which comprise 98% of T units and 2% of dimethyl D units and contain Si-OH end groups, or else under the reference KR251®, comprising 88% of T units and 12% of dimethyl D units and contain Si-OH end groups, or
[0379] - by the company Grant Industries under the name Granresin PMSQ ID containing 80% polymethylsilsesquioxane in isododecane.
[0380] MQT resins:
[0381] Resins comprising MQT units that are notably known are those mentioned in US 5 110 890.
[0382] A preferred form of resins of MQT type are MQT-propyl (also known as MQTPr) resins. Such resins that may be used in the compositions according to the invention are notably the resins described and prepared in patent application WO 2005 / 075 542, the content of which is incorporated herein by reference.
[0383] The MQ-T-propyl resin preferably comprises the units:
[0384] (i) (Rl3SiOl / 2)a
[0385] (ii) (R22SiO2 / 2)b
[0386] (iii) (R3SiO3 / 2)cand
[0387] (iv) (SiO4 / 2)d Rl, R2 and R3 independently representing a hydrocarbon-based radical (notably alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical containing from 1 to 8 carbon atoms or a phenyl group, a, b, c and d being mole fractions, a being between 0.05 and 0.5, b being between 0 and 0.3, c being greater than zero, d being between 0.05 and 0.6, a + b + c + d = l, provided that more than 40 mol% of the groups R3 of the siloxane resin are propyl groups.
[0388] Preferably, the siloxane resin comprises the units:
[0389] (i) (Rl3SiOl / 2)a
[0390] (iii) (R3SiO3 / 2)c and
[0391] (iv) (SiO4 / 2)d with Rl and R3 independently representing an alkyl group containing from 1 to 8 carbon atoms, Rl preferably being a methyl group and R3 preferably being a propyl group, a being between 0.05 and 0.5 and preferably between 0.15 and 0.4, c being greater than zero, preferably between 0.15 and 0.4, d being between 0.05 and 0.6, preferably between 0.2 and 0.6 or alternatively between 0.2 and 0.55, a + b + c + d = 1, and a, b, c and d being mole fractions, provided that more than 40 mol% of the groups R3 of the siloxane resin are propyl groups.
[0392] The siloxane resins that may be used according to the invention may be obtained via a process comprising the reaction of:
[0393] A) an MQ resin comprising at least 80 mol% of units (R13SiOi / 2)aand (SiO4 / 2)d,
[0394] Rl representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, a and d being greater than zero, the ratio a / d being between 0.5 and 1.5; and
[0395] B) a T-propyl resin comprising at least 80 mol% of units (R3SiO3 / 2)c, R3 representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, c being greater than zero, provided that at least 40 mol% of the groups R3 are propyl groups, in which the mass ratio A / B is between 95 / 5 and 15 / 85 and preferably the mass ratio A / B is 30 / 70.
[0396] Advantageously, the mass ratio A / B is between 95 / 5 and 15 / 85. Preferably, the ratio A / B is less than or equal to 70 / 30. These preferred ratios have proven to afford comfortable deposits.
[0397] Preferably, composition B according to the invention comprises at least one non-amino silicone chosen from polydialkylsiloxanes, notably cyclic polydialkylsiloxanes containing from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, and dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols); silicone resins, notably MQ-type resins and T-type resins, in particular polymethylsilsesquioxane resins; and mixtures thereof.
[0398] Preferably, composition B according to the invention comprises the non- amino silicone(s) in a total content ranging from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight, and even more preferentially ranging from 2% to 15% by weight, relative to the total weight of composition B.
[0399] Preferably, the total content of non-amino silicone(s) chosen from polydialkylsiloxanes and silicone resins, notably MQ type resins and T type resins, in composition B ranges from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight, and even more preferentially ranging from 2% to 15% by weight, relative to the total weight of composition B.
[0400] Preferably, the total content of non-amino silicone(s) chosen from cyclic polydialkylsiloxanes including from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols), polymethylsilsesquioxane resins, and mixtures thereof, in composition B ranges from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight and even more preferentially ranges from 2% to 15% by weight, relative to the total weight of composition B. Hydrocarbon-based oils:
[0401] Preferably, composition B also comprises at least one hydrocarbon-based oil.
[0402] The term “oi means a water-immiscible non-aqueous compound that is liquid at room temperature (20°C) and at atmospheric pressure (i.e. 1.013xl05Pa).
[0403] The term “hydrocarbon-based oil” means an oil formed essentially from, or even consisting of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.
[0404] In particular, composition B may comprise at least one hydrocarbon-based oil chosen from:
[0405] - Cs-Cie hydrocarbon-based oils, and notably: branched Cs-Ci6 alkanes, such as Cs-Ci6 and preferably Cs-Cu isoalkanes (also known as isoparaffins), such as isododecane (also known as 2, 2, 4,4,6- pentamethylheptane), isodecane and, for example, the oils sold under the Isopar or Permethyl trade names, linear Cs-Ci6 alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (C11) and of n-tridecane (C13) obtained in examples 1 and 2 of patent application WO 2008 / 155059 from the company Cognis, and mixtures thereof,
[0406] - short-chain C3-C8 esters (containing from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate and butyl acetate;
[0407] - hydrocarbon -based oils of plant origin such as triglycerides constituted of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; shea butter; or else caprylic / capric acid triglycerides, for instance those sold by the company Stearinerie Dubois,
[0408] - synthetic ethers containing from 10 to 40 carbon atoms, - linear or branched hydrocarbons of mineral or synthetic origin comprising more than 16 carbon atoms, in particular petroleum jelly, poly decenes, hydrogenated polyisobutene, in particular Parleam®, squalane and liquid paraffins, and mixtures thereof,
[0409] - synthetic esters such as oils of formula R1COOR2 in which Ri represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a, notably branched, hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that the sum of the number of carbon atoms in Ri and R2 is greater than or equal to 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, alcohol or polyalcohol heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters,
[0410] - fatty alcohols that are liquid at room temperature, with a branched and / or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2 -undecylpentadecanol .
[0411] Preferably, the hydrocarbon-based oil present in composition B according to the present invention is apolar, consisting only of carbon and hydrogen atoms.
[0412] Preferably, the hydrocarbon-based oil is chosen from:
[0413] - Cs-Cie hydrocarbon-based oils, and more preferentially among branched Cs- C14 alkanes such as isododecane or isodecane;
[0414] - C3-C8 short-chain esters such as ethyl acetate, methyl acetate, propyl acetate or butyl acetate;
[0415] - and mixtures thereof.
[0416] Preferably, the composition B according to the invention comprises a) at least one C3-C8 short-chain ester such as ethyl acetate, methyl acetate, propyl acetate or butyl acetate, in particular butyl acetate, and optionally b) at least one C2-C6 polyol. More preferentially the composition B according to the invention comprises a) at least one C3-C8 short-chain ester and b) at least one C2-C6 polyol. C2-C6 polyols are described thereafter.
[0417] Preferably, the total content of hydrocarbon-based oil(s) in composition B ranges from 5% to 80% by weight, more preferentially from 10% to 75% by weight, even more preferentially from 20% to 70% by weight and better still from 35% to 65% by weight relative to the total weight of composition B.
[0418] Preferably, the total content of hydrocarbon-based oil(s) chosen from branched Cs-Cu alkanes, short-chain Cs-Cs esters and mixtures thereof, in composition B, ranges from 5% to 80% by weight, more preferentially from 10% to 75% by weight, even more preferentially from 20% to 70% by weight, and better still from 35% to 65% by weight relative to the total weight of composition B.
[0419] Preferably, the total content of short-chain Cs-Cs esters in composition B, ranges from 5% to 80% by weight, more preferentially from 10% to 75% by weight, even more preferentially from 20% to 70% by weight, and better still from 35% to 65% by weight relative to the total weight of composition B.
[0420] Alkoxysilanes'.
[0421] Composition B may also optionally comprise at least one alkoxysilane.
[0422] Preferably, the composition comprises at least one alkoxysilane chosen from the compounds of formula (I), (I’) or (II) hereinbelow, oligomers thereof and / or mixtures thereof.
[0423] The compounds of formula (I) or (I’) have the following formulae: in which:
[0424] - Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms;
[0425] - Rb and Rc, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms, notably an ethyl group, it being understood that if Ra does not represent an alkoxy group, then Rb and Rc cannot simultaneously represent a hydrogen atom;
[0426] - Rd and Re, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms; a cycloalkyl group containing from 3 to 20 carbon atoms; an aryl group containing from 6 to 12 carbon atoms; an aminoalkyl group containing from 1 to 20 carbon atoms;
[0427] - A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;
[0428] - Q represents a carbonyl group (CO);
[0429] - r denotes an integer ranging from 0 to 1.
[0430] Among the alkoxysilanes of formula (I), oligomers thereof and / or mixtures thereof, mention may notably be made of 3 -aminopropyltri ethoxy silane (APTES), 3- aminopropylmethyldiethoxysilane (APMDES), 3-ureidopropyltrimethoxysilane and N-cy cl ohexy 1 aminomethy Itri ethoxy sil ane .
[0431] APTES may be purchased, for example, from the company Dow Coming under the name Xiameter OFS-6011 Silane or from the company Momentive Performance Materials under the name Silsoft A-l 100 or from the company Shin-Etsu under the name KBE-903.
[0432] The compounds of formula (I) may also denote Dynasylan SIVO 210 or Dynasylan 1505 sold by the company Evonik.
[0433] 3 -Ureidopropyltrimethoxy silane may be purchased, for example, from the company Gelest under the reference SIU9058.0.
[0434] N-Cycloheylaminomethyltriethoxysilane may be purchased, for example, from the company Wacker under the name Geniosil XL 926. Among the alkoxysilanes of formula (I’), oligomers thereof and / or mixtures thereof, mention may notably be made of N,N-bis[3- (trimethoxysilyl)propyl]ethylenediamine (CAS RN: 74956-86-8), Nl,Nl-bis[3- (triethoxysilyl)propyl]-l,2-ethanediamine (CAS RN: 457065-96-2), 1,2- ethanediamine, Nl-[3-(triethoxysilyl)propyl]-Nl-[3-(trimethoxysilyl)propyl]- (CAS RN: 1638528-78-5), and mixtures thereof.
[0435] Preferably, the alkoxysilane(s) of formula (I) are chosen from the compounds of formula (I) for which:
[0436] - Ra represents an alkyl group containing from 1 to 10 carbon atoms, notably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, preferably a methyl, or an alkoxy group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, preferably an ethoxy;
[0437] - Rb and Re, which may be identical or different, represent an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, such as an ethyl;
[0438] - Rd and Re, which are identical, represent a hydrogen atom or Rd denotes a hydrogen atom and Re denotes a Cs-G, cycloalkyl radical such as cyclohexyl;
[0439] - A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;
[0440] - r denotes an integer equal to 0.
[0441] More preferentially, the alkoxysilane(s) of formula (I) are chosen from the compounds of formula (I) in which Ra represents an ethoxy group, Rb and Re are identical and represent ethyl, Rd and Rerepresent a hydrogen atom, A represents propylene and r denotes an integer equal to 0.
[0442] According to a preferred embodiment, the alkoxysilane of formula (I) is 3- aminopropyltriethoxysilane (APTES).
[0443] The compounds of formula (II) have the following formula: in which:
[0444] - Rarepresents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms;
[0445] - Rb represents a hydrogen atom or an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms, notably an ethyl group;
[0446] - Rcrepresents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms; it being understood that if Ra and Rcdo not represent an alkoxy group, then Rb cannot represent a hydrogen atom;
[0447] - k denotes an integer ranging from 0 to 5, preferably ranging from 0 to 3;
[0448] - Rf represents a hydrogen atom; an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms; or a group of formula (Ila) below: in which Rn represents a hydroxyl group (OH); an alkyl group containing from 1 to 10 carbon atoms, preferably a methyl.
[0449] Among the alkoxysilanes of formula (II), oligomers thereof and / or mixtures thereof, mention may notably be made of tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltri ethoxy sil ane, i sobuty Itri ethoxy sil ane, pheny Itri ethoxy sil ane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltriethoxysilane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxymethyltriethoxysilane, octytri ethoxy sil ane (OTES) and mixtures thereof.
[0450] TEOS may be purchased, for example, from the company Evonik under the name Dynasylan® A or Dynasylan® A SQ. MTES may be purchased, for example, from the company Evonik under the name Dynasylan® MTES.
[0451] DMDES may be purchased, for example, from the company Gelest under the reference SID3404.0.
[0452] Preferably, the alkoxysilane(s) of formula (II), oligomers thereof and / or mixtures thereof are such that:
[0453] - Rarepresents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methoxy or an ethoxy; or an alkyl group containing from 1 to 10 carbon atoms optionally substituted with an aryl group, preferably 1 to 2 carbon atoms optionally substituted with an aryl group;
[0454] - Rb represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
[0455] - Rcrepresents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as a methoxy or an ethoxy;
[0456] - k denotes an integer ranging from 0 to 3, preferably equal to 0;
[0457] - Rf represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms such as a methyl or an ethyl.
[0458] Preferably, the alkoxysilane(s) of formula (II), oligomers thereof and / or mixtures thereof are such that:
[0459] - Rarepresents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
[0460] - Rb represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
[0461] - Rcrepresents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as a methoxy or an ethoxy;
[0462] - k denotes an integer equal to 0;
[0463] - Rf represents an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms such as a methyl or an ethyl. According to a preferred embodiment, the alkoxysilane(s) of formula (II) are chosen from octyltriethoxysilane (OTES), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES) and mixtures thereof.
[0464] According to a more preferred embodiment, the alkoxysilane(s) of formula (II) are methyltrimethoxysilane (MTMS) and / or methyltriethoxysilane (MTES).
[0465] For the purposes of the present invention, the term “oligomer” means compound(s) including at least two silicon atoms, obtained by oligomerization or polymerization of compounds of formula (I), (f) or (II).
[0466] Preferably, the alkoxysilane(s) are chosen from amino alkoxysilanes.
[0467] More preferentially, the alkoxysilane(s) are chosen from the compounds of formula (I), the compounds of formula (I’), oligomers thereof and / or mixtures thereof.
[0468] Even more preferentially, the alkoxysilane(s) are chosen from those of formula (I), such as 3 -aminopropyltri ethoxy silane (APTES), 3- aminopropylmethyldiethoxysilane (APMDES), and mixtures thereof.
[0469] According to a particular embodiment of the invention, the alkoxysilane(s) are chosen from those of formula (II), oligomers thereof and / or mixtures thereof, such as octyltriethoxysilane (OTES), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES) and mixtures thereof.
[0470] Preferably, the total content of alkoxysilane(s) in composition B according to the invention ranges from 0.01% to 20% by weight, more preferentially from 0.05% to 15% by weight, even more preferentially from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.2% to 2% by weight, relative to the total weight of composition B.
[0471] Preferably, the total content of alkoxysilane(s) chosen from those of formula (I), (I’) or (II), oligomers and / or mixtures thereof, in composition B according to the invention is in the range from 0.01% to 20% by weight, more preferentially from 0.05% to 15% by weight, even more preferentially from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.2% to 2% by weight, relative to the total weight of composition B.
[0472] Preferably, the total content of alkoxysilane(s) chosen from those of formula (I) or (I’), oligomers thereof and / or mixtures thereof, in composition B according to the invention is in the range from 0.01% to 20% by weight, more preferentially from 0.05% to 15% by weight, even more preferentially from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.2% to 2% by weight, relative to the total weight of composition B.
[0473] Preferably, the total content of alkoxysilane(s) chosen from those of formula (I), oligomers thereof and / or mixtures thereof, in composition B according to the invention is in the range from 0.01% to 20% by weight, more preferentially from 0.05% to 15% by weight, even more preferentially from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.2% to 2% by weight, relative to the total weight of composition B.
[0474] Preferably, the total content of 3 -aminopropyltri ethoxy silane in composition B according to the invention is in the range from 0.01% to 20% by weight, more preferentially from 0.05% to 15% by weight, even more preferentially from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.2% to 2% by weight, relative to the total weight of composition B.
[0475] Composition B is preferably anhydrous.
[0476] The term “anhydrous composition” means a composition comprising an amount of water of less than 5% by weight, preferably less than 3% by weight relative to the weight of the composition. Preferably, this water content is less than 1% by weight, better still less than 0.5% or even less than 0.3% by weight, relative to the weight of the composition. More particularly, the composition does not comprise any water (0%).
[0477] In particular, said anhydrous composition does not comprise any water added during its preparation, the residual water that may be present possibly originating from the starting materials used during the preparation.
[0478] Composition D:
[0479] The process according to the invention comprises at least one step ii) of applying to dyed keratin fibres at least one composition D, different from composition B, comprising:
[0480] - at least one nonionic surfactant,
[0481] - at least one non-silicone fatty substance.
[0482] According to the invention, composition D is different from composition B described previously. Preferably, composition D does not comprise any anionic surfactant.
[0483] Nonionic surfactants:
[0484] According to the invention, composition D comprises at least one nonionic surfactant.
[0485] Examples of nonionic surfactants that may be used in the compositions of the present invention are described, for example, in the Handbook of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991, pages 116-178. They are notably chosen from alcohols, a-diols, (Ci-C2o)alkylphenols or fatty acids, these compounds being polyethoxylated, polypropoxylated or polyglycerolated and bearing at least one fatty chain including, for example, from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly ranging notably from 1 to 100, and the number of glycerol groups possibly ranging notably from 1 to 30.
[0486] Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably containing from 1 to 30 ethylene oxide units, polyglycerolated fatty amides including on average 1 to 5, and in particular 1.5 to 4 glycerol groups, ethoxylated fatty acid esters of sorbitan containing from 2 to 30 ethylene oxide units, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, (Ce to C24 alkyl)polyglycosides, N-(Ce to C24 alkyl)glucamine derivatives, amine oxides such as (C10 to C14 alkyl)amine oxides or N-(Cio to C14 acyl)aminopropylmorpholine oxides.
[0487] The nonionic surfactant(s) that may be used according to the present invention may be chosen more particularly from polyoxyalkylenated fatty alcohols such as polyethoxylated and / or polypropoxylated and / or polyglycerolated fatty alcohols, the number of ethylene oxide and / or propylene oxide groups possibly ranging from 1 to 100, and the number of glycerol groups possibly ranging from 2 to 30.
[0488] Preferably, the polyoxyethylenated fatty alcohols are chosen from the nonionic surfactants of formula (I):
[0489] R-O-(CH2-CH2-O)n-H (I) in which:
[0490] R is a linear or branched Cs to C40 alkenyl radical; and n is an integer ranging from 6 to 20.
[0491] Preferably, R represents a linear or branched C12 to C30, more preferentially Ci6 to C20, alkenyl radical.
[0492] Preferably, n represents an integer ranging from 8 to 12. Advantageously, R represents a linear or branched Ci6 to C20 alkenyl radical; and / or n represents an integer ranging from 8 to 12.
[0493] Preferably, the nonionic surfactant(s) of formula (I) are chosen from oleyl alcohol containing 8 mol of ethylene oxide, oleyl alcohol containing 10 mol of ethylene oxide and oleyl alcohol containing 12 mol of ethylene oxide, and mixtures thereof; and more preferentially, the nonionic surfactant of formula (I) is oleyl alcohol containing 10 mol of ethylene oxide (INCI name: Oleth-lO).
[0494] Other polyoxyethylenated fatty alcohols such as oleth-3, oleth-5, laureth-4, ceteareth-10, ceteareth-20, oleth-30 and mixtures thereof may also be used.
[0495] Advantageously, the nonionic surfactant(s) may be chosen from ethoxylated fatty acid esters of sorbitan containing from 2 to 30 ethylene oxide units.
[0496] Mention may be made in particular of the polyoxyethylenated C8-C30 (preferably Cn-Cis) fatty acid esters (notably monoesters, diesters and triesters) of sorbitan notably containing from 2 to 30 mol of ethylene oxide, which may be chosen more particularly from polyoxyethylenated esters of C12-C18 fatty acids, in particular lauric, myristic, cetylic or stearic acid, of sorbitan notably containing from 2 to 30 mol of ethylene oxide, such as:
[0497] - polyoxyethylenated sorbitan monolaurate (4 OE) (Polysorbate-21),
[0498] - polyoxyethylenated sorbitan monolaurate (20 OE) (Polysorbate-20),
[0499] - polyoxyethylenated sorbitan monopalmitate (20 OE) (Polysorbate-40),
[0500] - polyoxyethylenated sorbitan monostearate (20 OE) (Polysorbate-60),
[0501] - polyoxyethylenated sorbitan monostearate (4 OE) (Polysorbate-61),
[0502] - polyoxyethylenated sorbitan monooleate (20 OE) (Polysorbate-80),
[0503] - polyoxyethylenated sorbitan monooleate (5 OE) (Polysorbate-81),
[0504] - polyoxyethylenated sorbitan tristearate (20 OE) (Polysorbate-65),
[0505] - polyoxyethylenated sorbitan trioleate (20 OE) (Polysorbate-85).
[0506] The nonionic surfactant(s) that may be used according to the present invention may be chosen from nonionic alkyl(poly)glycoside surfactants and mixtures thereof.
[0507] The term “alkyl(poly)glycoside” denotes an alkylpolyglycoside or an alkylmonoglycoside, also referred to in the present patent application as an alkylglycoside, which may be alkoxylated with one or more alkylene oxide groups, preferentially of C2-C4.
[0508] The alkyl(poly)glycoside nonionic surfactant(s) used, alone or as mixtures, in accordance with the present invention may be represented by formula (II) below: RiO-(R2O)t(G)v(II) in which formula (II):
[0509] - Ri represents a linear or branched, saturated or unsaturated alkyl group including from 8 to 24 carbon atoms, or an alkylphenyl group in which the linear or branched alkyl group includes from 8 to 24 carbon atoms,
[0510] - R.2 represents an alkylene group including from about 2 to 4 carbon atoms,
[0511] - G represents a saccharide unit including 5 or 6 carbon atoms,
[0512] - 1 denotes a value ranging from 0 to 10 and preferably 0 to 4, and
[0513] - v denotes a value ranging from 1 to 15.
[0514] Preferably, the alkyl(poly)glycoside nonionic surfactant(s) correspond to formula (II) in which:
[0515] - Ri denotes a linear or branched, saturated or unsaturated alkyl group including from 8 to 18 carbon atoms,
[0516] - G denotes glucose, fructose or galactose, preferably glucose,
[0517] - 1 denotes a value ranging from 0 to 3, and is preferably equal to 0, and
[0518] - R2and v are as defined previously.
[0519] The degree of polymerization of the alkyl(poly)glycoside nonionic surfactant(s) as represented, for example, by the index v in formula (II) ranges on average from 1 to 15 and preferably from 1 to 4. This degree of polymerization more particularly ranges from 1 to 2 and better still from 1.1 to 1.5, on average.
[0520] The glycoside bonds between the saccharide units are 1,6- or 1,4- bonds; preferably 1,4- bonds.
[0521] The alkyl(poly)glycoside nonionic surfactants that may be used in the present invention are preferably alkyl(poly)glycosides notably represented by the products sold by the company Cognis under the names Plantaren® (600 CS / U, 1200 and 2000) or Plantacare® (818, 1200 and 2000). Use may also be made of the products sold by the company SEPPIC under the names Triton CG 110 (or Oramix CG 110) and Triton CG 312 (or Oramix® NS 10), the products sold by the company BASF under the name Lutensol GD 70 or the products sold by the company Chem Y under the name AGIO LK, or the products sold by the company Evonik Goldschmidt under the trade names Tego Care CG 90 or Tego Care CG 90 MB.
[0522] Preferably, composition D comprises at least one nonionic surfactant chosen from polyoxyethylenated fatty alcohols, alkyl(poly)glycosides, ethoxylated fatty acid esters of sorbitan containing from 2 to 30 ethylene oxide units, and mixtures thereof; more preferentially chosen from ethoxylated fatty acid esters of sorbitan containing from 2 to 30 ethylene oxide units; and even more preferentially Cs-Cso fatty acid esters of sorbitan containing from 4 to 30 mol ethylene oxide.
[0523] Preferably, the total content of nonionic surfactant(s) in composition D ranges from 10% to 60% by weight, more preferentially from 15% to 50% by weight and even more preferentially from 20% to 40% by weight, relative to the total weight of the composition.
[0524] Preferably, the total content of ethoxylated fatty acid ester(s) of sorbitan containing from 2 to 30 ethylene oxide units in composition D ranges from 10% to 60% by weight, more preferentially from 15% to 50% by weight, even more preferentially from 20% to 40% by weight, relative to the total weight of the composition.
[0525] Non-silicone fatty substances:
[0526] According to the invention, composition D comprises at least one non-silicone fatty substance.
[0527] The term “fatty substance” refers to an organic compound that is insoluble in water at ordinary temperature (25 °C) and at atmospheric pressure (760 mmHg or 1.013>< 105Pa) (solubility of less than 5%, preferably less than 1% and even more preferentially less than 0.1% by weight). The non-silicone fatty substances (i.e. the fatty substances not comprising any silicon atoms in their structure) have in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms. In addition, the non-silicone fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
[0528] The non-silicone fatty substances of the invention do not contain any salified carboxylic acid groups.
[0529] In addition, the non-silicone fatty substances of the invention are not (poly)oxyalkylenated or (poly)glycerolated.
[0530] Preferably, the non-silicone fatty substance(s) are chosen from liquid non- silicone fatty substances, solid non-silicone fatty substances, and mixtures thereof. The term “liquid fatty substance” or “oil” means a “fatty substance” that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg or 1.013.10x l05Pa).
[0531] The term “solid fatty substance” means a “fatty substance” that is solid at room temperature (25°C) and at atmospheric pressure (760 mmHg or 1.013* 105Pa).
[0532] - Liquid non-silicone fatty substances
[0533] Composition D may comprise one or more non-silicone liquid fatty substances. These agents may be chosen notably from liquid fatty alcohols; mineral, plant or animal oils; liquid fatty esters; liquid hydrocarbons, and mixtures thereof.
[0534] The liquid fatty alcohols may be linear or branched; they preferably comprise 8 to 30 carbon atoms; they may be saturated or unsaturated.
[0535] The saturated liquid fatty alcohols are preferably branched. They may optionally comprise in their structure at least one aromatic or non-aromatic ring. Preferably, they are acyclic. More particularly, the saturated liquid fatty alcohols are chosen from octyldodecanol, isostearyl alcohol, 2-hexyldecanol, and also palmityl, myristyl, stearyl and lauryl alcohols, and mixtures thereof.
[0536] The unsaturated liquid fatty alcohols contain in their structure at least one double or triple bond, and preferably one or more double bonds. When several double bonds are present, there are preferably 2 or 3 of them, and they may be conjugated or unconjugated. They may optionally comprise in their structure at least one aromatic or non-aromatic ring. Preferably, they are acyclic. More particularly, the unsaturated liquid fatty alcohols are chosen from oleyl alcohol, linoleyl alcohol, linolenyl alcohol and undecylenyl alcohol, and mixtures thereof.
[0537] Among the mineral, plant or animal oils that may be used, mention may notably be made, as oils of plant origin, of sweet almond oil, avocado oil, castor oil, olive oil, jojoba oil, sunflower oil, wheatgerm oil, sesame oil, groundnut oil, grapeseed oil, soybean oil, rapeseed oil, safflower oil, coconut oil, com oil, hazelnut oil, shea butter, palm oil, apricot kernel oil, beauty-leaf oil, evening primrose oil or camelina oil; as oil of animal origin, perhydrosqualene; as oils of mineral origin, liquid paraffin and liquid petroleum jelly; and mixtures thereof.
[0538] The liquid fatty esters may be esters of monoalcohols or of polyols with monoacids or polyacids, at least one of the alcohols and / or acids including at least one chain of more than 7 carbon atoms. Preferably, the liquid fatty ester according to the invention is chosen from esters of a fatty acid and of a monoalcohol. Preferably, at least one of the alcohols and / or acids is branched. Mention may be made of isopropyl myristate, isopropyl palmitate, isononyl or isostearyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate and 2-octyldodecyl myristate, purcellin oil (stearyl octanoate), isopropyl lanolate, and mixtures thereof.
[0539] The term “liquid hydrocarbon” means a hydrocarbon composed solely of carbon and hydrogen atoms, which is liquid at 25°C and 1 atm, which is notably of mineral or plant origin, preferably of plant origin.
[0540] As liquid hydrocarbon that may be used in the composition according to the invention, mention may be made of:
[0541] - linear or branched, optionally cyclic, Ce-Ci6 alkanes; mention may be made of hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane;
[0542] - linear or branched hydrocarbons notably of mineral, animal or synthetic origin with more than 16 carbon atoms, such as volatile or non-volatile liquid paraffins, petroleum jelly, liquid petroleum jelly, poly decenes, hydrogenated polyisobutene such as the product sold under the brand name Parleam® by the company NOF Corporation, and squalane.
[0543] Preferably, the non-silicone liquid fatty substances are chosen from liquid fatty esters; more preferentially from liquid fatty esters of C8-C24 monocarboxylic acid and of C2-C10 monoalcohol; even more preferentially from liquid fatty esters of C8-C24 monocarboxylic acid and of C2-C10 monoalcohol, at least one from among the alcohol or the acid of the ester being branched.
[0544] More preferentially, the non-silicone liquid fatty substances are chosen from isopropyl myristate, isononyl isononanoate, and mixtures thereof.
[0545] Preferably, when composition D comprises one or more non-silicone liquid fatty substances, it comprises them in a total amount ranging from 30% to 90% by weight, preferably from 40% to 80% by weight and better still from 50% to 70% by weight, relative to the total weight of composition D.
[0546] - Non-silicone solid fatty substances
[0547] Composition D may comprise one or more non-silicone solid fatty substances. These substances may be chosen notably from solid fatty alcohols; solid fatty esters, ceramides; animal, plant or mineral waxes other than ceramides; and mixtures thereof.
[0548] The solid fatty alcohols that may be used are preferably chosen from saturated or unsaturated, linear or branched, preferably linear and saturated, (mono)alcohols including from 8 to 30 carbon atoms, notably from 10 to 24 carbon atoms. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol).
[0549] The solid fatty esters that may be used are preferably chosen from esters derived from C9-C26 monocarboxylic acids and from C9-C26 alcohols. Mention may be made of octyldodecyl behenate, isocetyl behenate, cetyl lactate, stearyl octanoate, octyl octanoate, cetyl octanoate, decyl oleate, myristyl stearate, octyl palmitate, octyl pelargonate, octyl stearate, alkyl myristates such as cetyl myristate, myristyl myristate or stearyl myristate, and hexyl stearate.
[0550] In particular, it is preferred to use C9-C26 alkyl palmitates, notably myristyl, cetyl or stearyl palmitates, and C9-C26 alkyl myristates such as cetyl myristate, stearyl myristate and myristyl myristate or mixtures of myristyl palmitate and myristyl stearate.
[0551] The ceramides or ceramide analogues such as glycoceramides, which may be used in the composition according to the invention, are known per se mention may be made in particular of ceramides of classes I, II, III and V according to the Dawning classification; these are molecules that may correspond to the following formula:
[0552] FLCHOH — CH — CH90R9
[0553] NH
[0554] C=O
[0555] R1 in which:
[0556] - Ri denotes a linear or branched, saturated or unsaturated alkyl group, derived from C14-C30 fatty acids, it being possible for this group to be substituted with a hydroxyl group in the alpha position, or a hydroxyl group in the omega position esterified with a saturated or unsaturated C16-C30 fatty acid;
[0557] - R2 denotes a hydrogen atom, a (glycosyl)ngroup, a (galactosyl)m group or a sulfogalactosyl group, in which n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 8;
[0558] - R3 denotes a C15-C26 hydrocarbon-based group, which is saturated or unsaturated in the alpha position, it being possible for this group to be substituted with one or more C1-C14 alkyl groups; it being understood that, in the case of natural ceramides or glycoceramides, R3 may also denote a C15-C26 alpha-hydroxyalkyl group, the hydroxyl group optionally being esterified with a C16-C30 alpha-hydroxy acid.
[0559] The ceramides more particularly preferred are the compounds for which Ri denotes a saturated or unsaturated alkyl derived from C16-C22 fatty acids; R2 denotes a hydrogen atom and R3 denotes a saturated linear C15 group.
[0560] Preferentially, use is made of ceramides for which Ri denotes a saturated or unsaturated alkyl group derived from C14-C30 fatty acids; R2 denotes a galactosyl or sulfogalactosyl group; and R3 denotes a -CH=CH-(CH2)i2-CH3 group.
[0561] Use may also be made of the compounds for which Ri denotes a saturated or unsaturated alkyl radical derived from C12-C22 fatty acids; R2 denotes a galactosyl or sulfogalactosyl radical and R3 denotes a saturated or unsaturated C12-C22 hydrocarbonbased radical and preferably a -CH=CH-(CH2)i2-CH3 group.
[0562] As compounds that are particularly preferred, mention may also be made of 2-N-linoleoylaminooctadecane- 1 ,3 -diol; 2-N-oleoylaminooctadecane- 1 ,3 -diol; 2-N- palmitoylaminooctadecane- 1 ,3 -diol; 2-N-stearoylaminooctadecane- 1 ,3 -diol; 2-N- behenoylaminooctadecane-l,3-diol; 2-N-[2-hydroxypalmitoyl]aminooctadecane-l,3- diol; 2-N-stearoylaminooctadecane- 1, 3, 4-triol and in particular N- stearoylphytosphingosine, 2-N-palmitoylaminohexadecane- 1 ,3 -diol, N- linoleoyldihydrosphingosine, N-oleoyldihydrosphingosine, N- palmitoyldihydrosphingosine, N-stearoyldihydrosphingosine, and N- behenoyldihydrosphingosine, N-docosanoyl-N-methyl-D-glucamine, cetylic acid N- (2-hydroxyethyl)-N-(3 -cetyloxy-2-hydroxypropyl)amide and bis(N-hydroxyethyl-N- cetyl)malonamide; and mixtures thereof.
[0563] For the purposes of the present invention, a wax is a lipophilic compound, which is solid at room temperature (25°C), with a reversible solid / liquid change of state, having a melting point greater than about 40°C, which may be up to 200°C, and having in the solid state anisotropic crystal organization. In general, the size of the wax crystals is such that the crystals diffract and / or scatter light, giving the composition that comprises them a more or less opaque cloudy appearance. By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but on returning the temperature of the mixture to room temperature, recrystallization of the wax, which is microscopically and macroscopically detectable (opalescence), is obtained in the oils of the mixture. As waxes, other than the ceramides above, that can be used in the present invention, mention may be made of waxes of animal origin, such as beeswaxes or modified beeswaxes (cera bellina), spermaceti, lanolin wax and lanolin derivatives, plant waxes such as carnauba wax, candelilla wax, esparto wax, ouricury wax, Japan wax, cocoa butter, cork-fibre wax, sugarcane wax, olive-tree wax, rice wax, hydrogenated jojoba wax, absolute waxes of flowers; mineral waxes, for example paraffin wax, petroleum jelly wax, lignite wax, microcrystalline waxes, ozokerites, and mixtures thereof.
[0564] Preferably, the non-silicone solid fatty substances are chosen from solid fatty esters; more preferentially from esters of C9-C26 monocarboxylic acids and of C9-C26 alcohols.
[0565] Preferably, when composition D comprises one or more non-silicone solid fatty substances, it comprises them in a total amount ranging from 30% to 90% by weight, preferably from 40% to 80% by weight and better still from 50% to 70% by weight, relative to the total weight of composition D.
[0566] More preferentially, composition D comprises at least one non-silicone fatty substance chosen from liquid fatty esters, solid fatty esters, and mixtures thereof, better still from liquid fatty esters.
[0567] Even more preferentially, composition D comprises at least one non-silicone fatty substance chosen from liquid fatty esters; better still from liquid fatty esters of C8-C24 monocarboxylic acid and of C2-C10 monoalcohol; even better still from liquid fatty esters of C8-C24 monocarboxylic acid and of C2-C10 monoalcohol, at least one from among the alcohol or the acid of the ester being branched.
[0568] Preferably, the total content of non-silicone fatty substance(s) in composition D ranges from 30% to 90% by weight, preferably from 40% to 80% by weight and better still from 50% to 70% by weight relative to the total weight of composition D.
[0569] Preferably, the total content of non-silicone fatty ester(s) in composition D ranges from 30% to 90% by weight, preferably from 40% to 80% by weight and better still from 50% to 70% by weight relative to the total weight of composition D.
[0570] Preferably, the sum of the total contents of nonionic surfactant(s) and non- silicone fatty substance(s) in composition D ranges from 50% to 99% by weight, preferably from 60% to 98% by weight, more preferentially ranging from 70% to 97% by weight, even more preferentially from 80% to 95% by weight, and better still from 85% to 92% by weight, relative to the total weight of composition D.
[0571] Composition D may or may not comprise water.
[0572] Preferably, the water content of composition D is less than or equal to 15% by weight, more preferentially ranges from 0% to 13% by weight, even more preferentially less than or equal to 12% by weight, better still ranges from 0% to 11% by weight, even better still from 2% to 10% by weight, relative to the total weight of composition D.
[0573] Preferably, composition B and / or composition D also comprise at least one alcohol chosen from monoalcohols and polyols; more preferentially from Ci-Ce monoalcohols and C2-C6 polyols.
[0574] These alcohols are different from the fatty alcohols described previously, and from the nonionic surfactants and non-silicone fatty substances described hereinbelow.
[0575] As monoalcohols, use may be made of C1-C4 alkanols, such as ethanol and isopropanol.
[0576] As polyols, use may be made of glycerol, propylene glycol, ethylene glycol, pentaerythritol, trimethylolpropane, 1,3-propanediol, pentane- 1,2-diol, caprylyl glycol (octane- 1,2-diol), butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, glycerol, polyglycerols, such as glycerol oligomers like diglycerol, polyethylene glycols, and mixtures thereof.
[0577] Preferably, the alcohol(s) are chosen from ethanol, hexylene glycol, and mixtures thereof.
[0578] More preferentially, composition B also comprises at least one alcohol chosen from monoalcohols and polyols; even more preferentially Ci-Ce monoalcohols and C2- Ce polyols; and better still from ethanol, hexylene glycol, and mixtures thereof.
[0579] Advantageously, composition D also comprises at least one alcohol chosen from monoalcohols and polyols; even more preferentially Ci-Ce monoalcohols and C2- Ce polyols; and better still from ethanol, caprylyl glycol, and mixtures thereof.
[0580] Preferably, the total content of alcohol(s) in composition B ranges from 2% to 60% by weight, preferably from 5% to 50% by weight, more preferentially from 10% to 40% by weight, better still from 15% to 40% by weight, relative to the total weight of composition B. Preferably, the total content of C2-C6 polyol(s) in composition B ranges from 0,5% to 30% by weight, preferably from 1% to 25% by weight, more preferentially from 2% to 20% by weight, better still from 5% to 15% by weight, relative to the total weight of composition B.
[0581] Preferably, the total content of alcohol(s) in composition D ranges from 0.1% to 15% by weight, preferably from 0.5% to 12% by weight, more preferentially from 1% to 10% by weight, relative to the total weight of composition D.
[0582] Compositions A and C:
[0583] Advantageously, the keratin fibre treatment process may also optionally comprise:
[0584] - at least one step o) of applying to said keratin fibres a pretreatment composition A comprising at least one alkoxysilane, preferably chosen from the compounds of formula (I), (I’) or (II) as described previously, oligomers thereof and / or mixtures thereof; and / or
[0585] - at least one step i’) of applying to said keratin fibres a post-treatment composition C comprising at least one alkoxysilane, preferably chosen from the compounds of formula (I), (I’) or (II) as described previously, oligomers thereof and / or mixtures thereof.
[0586] According to the invention, compositions A and C are different from compositions B and D.
[0587] According to the invention, the pretreatment composition A is identical to or different from the post-treatment composition C.
[0588] The alkoxysilanes present in composition A and / or composition C according to the invention are as described previously for composition B.
[0589] The preferences and embodiments described for composition B also apply to composition A and composition C.
[0590] Composition A and composition C preferably comprise at least one alkoxy silane chosen from the compounds of formula (I), (T) or (II) as described above, oligomers thereof and / or mixtures thereof; and more preferentially also at least one alkoxy silane chosen from the compounds of formula (I), (T) or (II) as described above. Preferably, the alkoxysilane(s) are present in composition A in a total amount ranging from 0.1% to 60% by weight, more preferentially 0.1% to 40% by weight, even more preferentially from 0.5% to 30% by weight, better still from 0.75% to 25% by weight, better still from 1% to 20% by weight and even better still from 5% to 15% by weight, relative to the total weight of composition A.
[0591] Preferably, the alkoxysilane(s) are present in composition C in a total amount ranging from 0.1% to 60% by weight, more preferentially from 0.1% to 40% by weight, even more preferentially from 0.5% to 30% by weight, better still from 0.75% to 25% by weight, better still from 1% to 20% by weight and even better still from 5% to 15% by weight, relative to the total weight of composition C.
[0592] Preferably, the alkoxy silane(s) chosen from the compounds of formula (I), (I’) or (II) as described above, oligomers thereof and / or mixtures thereof, are present in composition A and / or composition C in a total amount ranging from 0.1% to 60% by weight, more preferentially from 0.1% to 40% by weight, even more preferentially from 0.5% to 30% by weight, better still from 0.75% to 25% by weight, better still from 1% to 20% by weight and even better still from 5% to 15% by weight, relative to the total weight of composition A and / or composition C.
[0593] Preferably, the alkoxysilane(s) chosen from the compounds of formula (I) or (I’), more preferentially of formula (I), as described above, oligomers thereof and / or mixtures thereof are present in composition A and / or composition C in a total amount ranging from 0.1% to 60% by weight, more preferentially 0.1% to 40% by weight, even more preferentially 0.5% to 30% by weight, better still 0.75% to 25% by weight, better still 1% to 20% by weight and even better still 5% to 15% by weight, relative to the total weight of composition A and / or composition C.
[0594] Preferably, the total content of 3 -aminopropyltri ethoxy silane in composition A ranges from 0.1% to 60% by weight, more preferentially 0.1% to 40% by weight, even more preferentially from 0.5% to 30% by weight, better still from 0.75% to 25% by weight, better still from 1% to 20% by weight and even better still from 5% to 15% by weight, relative to the total weight of composition A.
[0595] Preferably, the total content of 3 -aminopropyltri ethoxy silane in composition C ranges from 0.1% to 60% by weight, more preferentially from 0.1% to 40% by weight, even more preferentially from 0.5% to 30% by weight, better still from 0.75% to 25% by weight, better still from 1% to 20% by weight and ever better still from 5% to 15% by weight, relative to the total weight of composition C. Preferably, when they are present, the non-amino alkoxysilane(s) of formula (II), oligomers thereof and / or mixtures thereof are present in composition A in a total amount ranging from 0.1% to 20% by weight, more preferentially from 0.5% to 15%, even more preferentially from 1% to 10% by weight, better still from 1% to 5% by weight, relative to the total weight of composition A.
[0596] Preferably, when they are present, the non-amino alkoxysilane(s) of formula (II), oligomers thereof and / or mixtures thereof are present in composition C in a total amount ranging from 0.1% to 20% by weight, more preferentially from 0.5% to 15%, even more preferentially from 1% to 10% by weight, better still from 1% to 5% by weight, relative to the total weight of composition C.
[0597] Preferably, when composition A comprises methyltrimethoxysilane (MTMS), octytri ethoxy silane (OTES) and / or methyltriethoxysilane (MTES), the total content of methyltrimethoxysilane (MTMS), octytriethoxysilane (OTES) and / or methyltriethoxysilane (MTES) in composition C ranges from 0.1% to 20% by weight, more preferentially from 0.5% to 15%, even more preferentially from 1% to 10% by weight, better still from 1% to 5% by weight, relative to the total weight of composition A.
[0598] Preferably, when composition C comprises methyltrimethoxysilane (MTMS), octytriethoxysilane (OTES) and / or methyltriethoxysilane (MTES), the total content of methyltrimethoxysilane (MTMS), octytriethoxysilane (OTES) and / or methyltriethoxysilane (MTES) in composition C ranges from 0.1% to 20% by weight, more preferentially from 0.5% to 15%, even more preferentially from 1% to 10% by weight, better still from 1% to 5% by weight, relative to the total weight of composition C.
[0599] Preferably, composition A comprises water.
[0600] Preferably, the total water content of composition A ranges from 10% to 98% by weight, more preferentially from 40% to 95% by weight, even more preferentially from 50% to 92% by weight, better still from 60% to 90% by weight and even better still from 70% to 90% by weight, relative to the total weight of composition A.
[0601] Preferably, composition C comprises water.
[0602] Preferably, the total water content of composition C ranges from 10% to 98% by weight, more preferentially from 40% to 95% by weight, even more preferentially from 50% to 92% by weight, better still from 60% to 90% by weight and even better still from 70% to 90% by weight, relative to the total weight of composition C. Preferably, composition A and / or composition C also comprise at least one alcohol chosen from monoalcohols and polyols; more preferentially from Ci-Ce monoalcohols and C2-C6 polyols; more preferentially from Ci-Ce monoalcohols.
[0603] More preferentially, composition A and / or composition C also comprise ethanol.
[0604] Preferably, the total content of alcohol(s) in composition A ranges from 1% to 25% by weight, preferably from 2% to 20% by weight, more preferentially from 5% to 15% by weight, relative to the total weight of composition A.
[0605] Preferably, the total content of ethanol in composition A ranges from 1% to 25% by weight, preferably from 2% to 20% by weight and more preferentially from 5% 15% by weight, relative to the total weight of composition A.
[0606] Preferably, the total content of alcohol(s) in composition C ranges from 1% to 25% by weight, preferably from 2% to 20% by weight, more preferentially from 5% to 15% by weight, relative to the total weight of composition C.
[0607] Preferably, the total content of ethanol in composition C ranges from 1% to 25% by weight, preferably from 2% to 20% by weight, more preferentially from 5% to 15% by weight, relative to the total weight of composition C.
[0608] Compositions A, B, C and / or D may also contain any adjuvant or additive usually used in cosmetic compositions intended for treating keratin fibres.
[0609] Among the additives that may be contained in compositions A, B, C and / or D, mention may be made of reducing agents, softeners, antifoams, moisturizers, clays, mineral fillers, UV-screening agents, peptizers, fragrances, cationic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers P and CP described previously, preserving agents, amino silicones, and mixtures thereof.
[0610] Compositions A, B, C and D may notably be in the form of a suspension, a dispersion, a gel, an emulsion, notably an oil-in-water (O / W) or water-in-oil (W / O) emulsion, or a multiple emulsion (W / O / W or polyol / O / W or O / W / O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, notably of ionic or nonionic lipids, or a two-phase or multi-phase lotion. Process for treating keratin fibres:
[0611] The process for treating keratin fibres, preferably the hair, according to the invention, comprises at least the following steps: i) a step of applying to the keratin fibres at least one dye composition B comprising at least one colouring agent and at least one polymer P comprising repeating units obtained from at least one monomer of formula (III) as defined above; and then ii) a step of applying to the dyed keratin fibres at least one composition D, different from composition B, comprising:
[0612] - at least one nonionic surfactant,
[0613] - at least one non-silicone fatty substance.
[0614] In this process, step i) of applying the dye composition B is performed before step ii) of applying composition D.
[0615] Advantageously, the keratin fibre treatment process may also optionally comprise:
[0616] - at least one step o) of applying to said keratin fibres a pretreatment composition A as defined above; and / or
[0617] - at least one step i’) of applying to said keratin fibres a post-treatment composition C as defined above.
[0618] According to the invention, if steps o) and i’) are performed in the treatment process, the pretreatment composition A is identical to or different from the posttreatment composition C.
[0619] According to the invention, if steps o) and i’) are performed in the treatment process, composition B preferably does not comprise any alkoxysilane.
[0620] According to the invention, if step o) is performed in the treatment process, step o) is performed before step i).
[0621] According to the invention, if step i’) is performed in the treatment process, step i’) is performed after step i) and before step ii).
[0622] According to the invention, composition B dyes the keratin fibres, and composition D removes the colour deposited by composition B from the keratin fibres. Composition D is similar to a hair “makeup-removing” composition. Preferably, step ii) of applying at least one composition D to the dyed keratin fibres is performed at least 2 hours after step i) of applying at least one dye composition B to the keratin fibres, more preferentially at least 4 hours later, even more preferentially at least 8 hours later, better still at least 12 hours later, and even better still at least 24 hours later.
[0623] The applications of the compositions to keratin fibres may be performed on said fibres, which may be wet or dry.
[0624] Preferably, the keratin fibres are hair. The process according to the invention may be performed on all types of light or dark, natural or dyed, permanent-waved, bleached or relaxed hair.
[0625] The application of the compositions to the keratin fibres may be performed via any standard means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.
[0626] The applications of the compositions to the keratin fibres are generally performed at room temperature (between 15 and 25°C).
[0627] After applying compositions B and / or D, and optionally A and / or C, the keratin fibres may be left to dry or may be dried, for example at a temperature of greater than or equal to 30°C.
[0628] Preferably, the process according to the invention may also comprise a step iii) of applying heat to the keratin fibres using a heating device.
[0629] Such a device may be, for example, a hood, a hair dryer, a straightening or curling iron, a Climazon, etc. Preferably, step d) of applying heat is performed using a hair dryer.
[0630] During step iii) of applying heat to the hair, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.
[0631] When step iii) of applying heat to the hair is performed using a hood or a hairdryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.
[0632] Advantageously, the dyeing process according to the invention may optionally also comprise a step iv) of rinsing the keratin fibres.
[0633] The term “rinsing step” refers to the application of water to the keratin fibres.
[0634] Preferably, a rinsing step iv) is performed before step i). According to one embodiment of the invention, after application of composition B to the keratin fibres, it is preferable to observe a leave-on time of 10 seconds to 20 minutes, notably 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes of composition B on said fibres.
[0635] According to a preferred embodiment of the invention, the process for treating keratin fibres, preferably the hair, according to the invention comprises at least the following steps in this order: o) a step of applying to said keratin fibres a pretreatment composition A as defined above comprising at least one amino alkoxysilane chosen from the compounds of formula (I) or (I’) as described previously, oligomers thereof and / or mixtures thereof; iv) optionally a step of rinsing the keratin fibres; i) a step of applying to the keratin fibres at least one dye composition B comprising at least one colouring agent and at least one polymer P comprising repeating units obtained from at least one monomer of formula (III) as defined above; and then ii) a step of applying to the dyed keratin fibres at least one composition D, different from composition B, comprising:
[0636] - at least one nonionic surfactant,
[0637] - at least one non-silicone fatty substance.
[0638] According to another preferred embodiment of the invention, the process for treating keratin fibres, preferably the hair, according to the invention comprises at least the following steps in this order: o) a step of applying to said keratin fibres a pretreatment composition A as defined above comprising at least one alkoxysilane chosen from the compounds of formula (I) or (I’) as described previously, oligomers thereof and / or mixtures thereof; iv) optionally a step of rinsing the keratin fibres; i) a step of applying to the keratin fibres at least one dye composition B comprising at least one colouring agent and at least one polymer P comprising repeating units obtained from at least one monomer of formula (III) as defined above; i’) a step of applying to said keratin fibres a post-treatment composition C as defined above comprising at least one alkoxysilane chosen from the compounds of formula (I) or (I’) as described previously, oligomers thereof and / or mixtures thereof; and then ii) a step of applying to the dyed keratin fibres at least one composition D, different from composition B, comprising:
[0639] - at least one nonionic surfactant,
[0640] - at least one non-silicone fatty substance.
[0641] Another subject of the present invention is a multi -compartment device comprising a first compartment containing a composition B comprising at least one colouring agent and at least one polymer P as described previously, and a second compartment containing a composition D different from composition B, comprising at least one nonionic surfactant and at least one non-silicone fatty substance as described previously.
[0642] Preferably, composition B also comprises at least one non-amino silicone, at least one hydrocarbon-based oil and / or at least one alkoxysilane as described previously.
[0643] The device according to the invention is intended for treating keratin fibres, such as the hair.
[0644] The present invention will now be described more specifically by means of examples, which do not in any way limit the scope of the invention. However, the examples make it possible to support specific characteristics, variants and preferred embodiments of the invention.
[0645] Examples:
[0646] In the examples below, the temperature is given in degrees Celsius and corresponds to room temperature (20-25°C), unless otherwise indicated, and the pressure is atmospheric pressure, unless otherwise indicated.
[0647] Example 1: Preparation of polymer P - Isobutyl acrylate / tert-butyl acrylate / acetoacetoxyethyl methacrylate (25 / 65 / 10)
[0648] 62.5 g of isobutyl acrylate, 162.5 g of tert-butyl acrylate, 25 g of acetoacetoxyethyl methacrylate, 2.5 g of Trigonox T21S radical initiator and 360 g of an isododecane / ethyl acetate (50 / 50) solvent are introduced into a 1 L pilot reactor. The medium is degassed with argon and then heated to 90°C with stirring. The reaction medium is maintained for 7 hours at 90°C. Stripping with 300 ml of isododecane is then performed to remove the residual monomers.
[0649] On conclusion of the reaction, a polymer P dissolved in isododecane is obtained.
[0650] Example 2:
[0651] The following compositions are prepared (in g / 100 g of starting material in unmodified form).
[0652] [Table 1] [Table 2]
[0653] (1) isobutyl acrylate / tert-butyl acrylate / acetoacetoxyethyl methacrylate statistical copolymer (25 / 65 / 10) obtained according to the preparation process described above in Example 1, as a 58.8% by weight solution in isododecane;
[0654] (2) sold under the name Tarox Iron Oxide R-516 HP by the company Titan Kogyo;
[0655] (3) sold under the name Xiameter PMX-1501 Fluid by the company Dow.
[0656] Protocols:
[0657] Protocol Pl:
[0658] The dye composition B according to the invention is applied by finger to a lock of dry natural chestnut-brown hair (tone height 4), at a rate of 0.6 g of composition per gram of hair.
[0659] The lock of hair is left for 2 minutes at room temperature. The lock of hair is not rinsed.
[0660] The lock of hair is then dried with a hairdryer for 2 minutes.
[0661] The colouring obtained (at To) is then evaluated according to the protocol below.
[0662] The lock of hair thus dyed is then subjected to shampoo washing in order to evaluate the fastness (persistence, resistance) of the colouring obtained, according to the following shampoo washing protocol, repeated three times: The lock of hair is washed using a standard shampoo (Garnier Ultra Doux), at a rate of 0.4 g of shampoo per gram of hair. The lock of hair is then rinsed, combed and dried with a hairdryer.
[0663] The colouring obtained after the three shampoo washes (at Tss) is then evaluated according to the protocol below.
[0664] Protocol P2:
[0665] The dye composition B according to the invention is applied by finger to another lock of dry natural chestnut-brown hair (tone height 4), at a rate of 0.6 g of composition per gram of hair.
[0666] The lock of hair is left for 2 minutes at room temperature. The lock of hair is not rinsed.
[0667] The lock of hair is then dried with a hairdryer for 2 minutes.
[0668] The colouring obtained (at To) is then evaluated according to the protocol below.
[0669] 30 minutes after applying the dye composition, and once the colouring at To has been evaluated, composition Di is applied to the entire lock of hair using a brush, at a rate of 2 g of composition D per gram of hair.
[0670] The lock of hair is left for 5 min at room temperature, and is then rinsed.
[0671] Finally, the lock of hair is washed using a standard shampoo (Garnier Ultra Doux), at a rate of 0.4 g of shampoo per gram of hair. The lock of hair is then rinsed, combed and dried with a hairdryer.
[0672] The removal of the colouring after application of composition DI ( at TDI) is then evaluated according to the protocol hereinbelow.
[0673] Results:
[0674] The persistence of the colour of the locks with respect to shampoo washing was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).
[0675] In this L*a*b* system, L* represents the intensity of the colour, a* indicates the green / red colour axis and b* the blue / yellow colour axis. The persistence of the colouring is evaluated by the colour difference AE between the dyed locks before shampoo washing, then after having undergone three shampoo washes according to the protocol described above. The lower the AE value, the more persistent / resistant the colour with respect to shampoo washing.
[0676] The AE value is calculated according to the following equation:
[0677] In this equation, for the persistence of the colouring with respect to shampoo washing, L*, a* and b* represent the values measured at Tss after dyeing the hair and after performing the three shampoo washes, and Lo*, ao* and bo* represent the values measured at To after dyeing the hair but before the three shampoo washes.
[0678] Respectively, the elimination of the colouring from the hair is evaluated by the colour difference AE between the dyed locks before application of composition Di, and then after application of composition Di according to the protocol described above. The greater the AE value, the more the colouring obtained by applying composition B has been eliminated.
[0679] The AE value is calculated according to the following equation:
[0680] In this equation, for the persistence of the colouring with respect to composition DI, L*, a* and b* represent the values measured at TDI after applying composition Di, and Lo*, ao* and bo* represent the values measured at To after dyeing the hair but before applying composition Di.
[0681] The colour difference AE’ between the hair before dyeing, and then after application of composition Di, is also evaluated: the lower the AE’ value, the more effective the “makeup removal” (i.e. composition B has been eliminated), and the more the hair regains its natural colour.
[0682] The AE’ value is calculated according to the following equation:
[0683] In this equation, L*, a* and b* represent the values measured at TDI after application of composition Di, and Lo*, ao* and bo* represent the values measured before application of composition B (i.e. control).
[0684] The results obtained with protocols Pl and P2 are collated in the table below: [Table 3]
[0685] The lock of hair treated according to protocol Pl has a low AE value. The coloured keratin fibre coating obtained via the application of dye composition B of the process according to the present invention, thus displays good persistence with respect to shampoo washing.
[0686] In addition, the lock of hair treated according to protocol P2 has a high AE value showing very good colour removal, and a very low AE’ value showing a return to the natural colouring. Thus, the coloured keratin fibre coating obtained by applying dye composition B has indeed been eliminated by applying composition DI of the process according to the invention.
[0687] Example 3:
[0688] The following compositions B2 and B3 are prepared (in g / 100 g of starting material in unmodified form).
[0689] [Table 4]
[0690] (1) isobutyl acrylate / tert-butyl acrylate / acetoacetoxyethyl methacrylate statistical copolymer (25 / 65 / 10) obtained according to the preparation process described above in Example 1, as a 58.8% by weight solution in isododecane;
[0691] (2) sold under the name Tarox Iron Oxide R-516 HP by the company Titan Kogyo;
[0692] Evaluation of the compositions B2 and B3
[0693] The compositions B2 and B3 were evaluated on 1 g locks of natural hair containing 90% white hair.
[0694] The application protocol is as follows:
[0695] Each composition is applied to a lock of dry hair in a proportion of 0.6 g of composition (bath ratio of 0.6 g per g of hair). It is spread with a finger over the lock.
[0696] After a leave-on time of 2 minutes, the lock is dried using a thermal brush and a hair dryer.
[0697] Evaluations in terms of resistance of the colouring to shampoo washing were then carried out 24 hours after applying the composition. The resistance to shampoo washing was evaluated by measuring the colorimetric data of each of the locks. The colorimetric measurements were performed using a Konica Minolta 3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.
[0698] In this L*a*b* system, L* represents the lightness of the colour, a* indicates the green / red colour axis and b* the blue / yellow colour axis.
[0699] The smaller the value of L*, the stronger the colouring obtained.
[0700] The persistence of the colouring is evaluated by the colour difference AE between the coloured locks before shampoo washing, then after having undergone 5 successive shampoo washes. The lower the AE value, the more persistent the colour with respect to shampoo washing.
[0701] The AE value is calculated according to the following equation:
[0702] In this equation, L*, a* and b* represent the values measured after colouring the hair and after having undergone 5 shampoo washes, and Lo*, ao* and bo* represent the values measured after colouring the hair but before the 5 shampoo washes.
[0703] The results obtained are collated in Table 5 below.
[0704] [Table 5]
Claims
CLAIMS1. Process for treating keratin fibres, comprising at least the following steps: i) a step of applying to the keratin fibres at least one dye composition B comprising at least one colouring agent and at least one polymer P comprising repeating units obtained from at least one monomer of formula (III):in which:- Rarepresents a hydrogen atom or a linear or branched (Ci-C4)alkyl group,- Rband Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group,- Rdrepresents a linear or branched (Ci-C4)alkyl group, and- L represents a linear or branched (Ci-Ce)alkylene, or cycloalkylene, group; and then ii) a step of applying to the dyed keratin fibres at least one composition D, different from composition B, comprising:- at least one nonionic surfactant, and- at least one non-silicone fatty substance.
2. Process according to the preceding claim, characterized in that the colouring agent(s) in composition B are chosen from pigments, direct dyes and mixtures thereof; more preferentially from pigments.
3. Process according to either of the preceding claims, characterized in that the total content of colouring agent(s) in composition B ranges from 0.001% to 20% by weight, more preferentially from 0.01% to 15% by weight, even more preferentially from 0.1% to 10% by weight, better still from 0.5% to 10% by weight and even better still from 1% to 10% by weight, relative to the total weight of composition B.
4. Process according to any one of the preceding claims, characterized in that the polymer(s) P in composition B are chosen from copolymers CP comprising obtained by the polymerization of:- 0% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (1) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobomyl acrylate, isobornyl methacrylate, and mixtures thereof;- 1% to 20% by weight, relative to the total weight of the monomers, at least one monomer (2) of formula (III); and- 0% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (3) chosen from C1-C4 alkyl acrylates, C1-C4 alkyl methacrylates, silicone macromonomers and mixtures thereof, it being understood that said copolymers CP are obtained by polymerization of at least one monomer (2) with at least one monomer (1) and / or at least one monomer (3); more preferentially, the copolymer CP comprises from 80% to 99% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates, and better still the copolymer CP comprises from 80% to 99% by weight of at least one monomer (3) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers, and no monomer (1).
5. Process according to any one of the preceding claims, characterized in that the total content of polymer(s) P in composition B ranges from 1% to 30% by weight, preferably from 2% to 20% by weight and more preferentially from 5% to 15% by weight relative to the total weight of composition B.
6. Process according to any one of the preceding claims, characterized in that composition B is anhydrous.
7. Process according to any one of the preceding claims, characterized in that composition B further comprises at least one hydrocarbon-based oil, preferably chosen from:- Cs-Cie hydrocarbon-based oils, and more preferentially branched Cs-Ci4 alkanes such as isododecane or isodecane;- C3-C8 short-chain esters such as ethyl acetate, methyl acetate, propyl acetate or butyl acetate;- and mixtures thereof; and even more preferentially in a total content ranging from 5% to 80% by weight, better still from 10% to 75%, even better still from 20% to 70% by weight, or even from 35% to 65% by weight, relative to the total weight of the composition.
8. Process according to Claim 7, characterized in that composition B comprises a) at least one C3-C8 short-chain ester and optionally b) at least one C2-C6 polyol; preferably composition B comprises a) at least one C3-C8 short-chain ester and b) at least one C2-C6 polyol.
9. Process according to any one of the preceding claims, characterized in that composition B further comprises at least one non-amino silicone, preferably chosen from polydialkylsiloxanes, notably cyclic polydialkylsiloxanes containing from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols); silicone resins, notably MQ-type resins and T-type resins, notably polymethylsilsesquioxane resins; and mixtures thereof.
10. Process according to any one of the preceding claims, characterized in that composition B further comprises at least one alkoxysilane chosen from the compounds of formula (I), (!') or (II) below, oligomers thereof and / or mixtures thereof:in which:- Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms;- Rb and Rc, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms, notably an ethyl group, it being understood that if Ra does not represent an alkoxy group, then Rb and Rc cannot simultaneously represent a hydrogen atom;- Rd and Re, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms; a cycloalkyl group containing from 3 to 20 carbon atoms; an aryl group containing from 6 to 12 carbon atoms; an aminoalkyl group containing from 1 to 20 carbon atoms;- A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;- Q represents a carbonyl group (CO);- r denotes an integer ranging from 0 to 1;in which:- Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms;- Rb represents a hydrogen atom or an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms, notably an ethyl group;- Re represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms; it being understood that if Ra and Rc do not represent an alkoxy group, then Rb cannot represent a hydrogen atom;- k denotes an integer ranging from 0 to 5, preferably ranging from 0 to 3;- Rf represents a hydrogen atom; an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms; or a group of formula (Ila) below:in which Rn represents a hydroxyl group (OH); an alkyl group containing from 1 to 10 carbon atoms, preferably a methyl.
11. Process according to any one of the preceding claims, also comprising:- at least one step o) of applying to said keratin fibres a pretreatment composition A comprising at least one alkoxysilane, preferably chosen from the compounds of formula (I), (I’) or (II) as defined in Claim 10, oligomers thereof and / or mixtures thereof; and / or- at least one step i’) of applying to said keratin fibres a post-treatment composition C comprising at least one alkoxysilane, preferably chosen from the compounds of formula (I), (I’) or (II) as defined in Claim 10, oligomers thereof and / or mixtures thereof; it being understood that:* compositions A and C are different from compositions B and D;* if steps o) and i’) are performed, the pretreatment composition A is identical to or different from the post-treatment composition C;* if steps o) and i’) are performed, composition B preferably does not comprise any alkoxysilane;* if step o) is performed, step o) is performed before step i);* if step i’) is performed, step i’) is performed after step i) and before step ii).
12. Process according to any one of the preceding claims, characterized in that the nonionic surfactant(s) in composition D are chosen from polyoxyethylenated fatty alcohols, alkyl(poly)glycosides, ethoxylated fatty acid esters of sorbitan containing from 2 to 30 ethylene oxide units, and mixtures thereof; more preferentially chosen from ethoxylated fatty acid esters of sorbitan containing from 2 to 30 ethylene oxide units; and even more preferentially Cs-Cso fatty acid esters of sorbitan containing from 4 to 30 mol of ethylene oxide.
13. Process according to any one of the preceding claims, characterized in that the non-silicone fatty substance(s) in composition D are chosen from liquid fatty esters, solid fatty esters, and mixtures thereof; preferably from liquid fatty esters of Cs- C24 monocarboxylic acid and of C2-C10 monoalcohol; better still from liquid fatty esters of C8-C24 monocarboxylic acid and of C2-C10 monoalcohol, at least one from among the alcohol or the acid of the ester being branched.
14. Process according to any one of the preceding claims, characterized in that the water content in composition D is less than or equal to 15% by weight, preferably ranges from 0% to 13% by weight, more preferentially less than or equal to 12% by weight, better still ranges from 0% to 11% by weight, even better still ranges from 2% to 10% by weight, relative to the total weight of composition D.
15. Process according to any one of the preceding claims, characterized in that composition D also comprises at least one alcohol chosen from monoalcohols and polyols; even more preferentially Ci-Ce monoalcohols and C2-C6 polyols; and better still from ethanol, caprylyl glycol, and mixtures thereof.
16. Process according to any one of the preceding claims, characterized in that the sum of the total contents of nonionic surfactant(s) and non-silicone fatty substance(s) in composition D ranges from 50% to 99% by weight, preferably from 60% to 98% by weight, more preferentially ranging from 70% to 97% by weight, even more preferentially from 80% to 95% by weight, and better still from 85% to 92% by weight, relative to the total weight of composition D.
17. Process according to any one of the preceding claims, characterized in that step ii) of applying at least one composition D to the dyed keratin fibres is performed at least 2 hours after step i) of applying at least one dye composition B to the keratin fibres, preferably at least 4 hours later, more preferentially at least 8 hours later, even more preferentially at least 12 hours later, better still at least 24 hours later.
18. Multi-compartment device comprising a first compartment containing a composition B comprising at least one colouring agent and at least one polymer P as defined in any one of Claims 1 to 10, and a second compartment containing a composition D different from composition B, comprising at least one nonionic surfactant and at least one non-silicone fatty substance as defined in any one of Claims 1 and 12 to 16.
Citation Information
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