FR3097755A1 - Process for dyeing keratin fibers comprising a step of cold plasma treatment of said fibers - Google Patents

Abstract

The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising a step of cold plasma treatment of said keratin fibers, followed by steps of applying a dispersion to said keratin fibers. particular oily, of a composition comprising at least one amino compound and at least one coloring material. The present application further relates to a kit comprising a cold plasma generator and a device with at least two compartments containing a particular oily dispersion, a composition comprising at least one amino compound, and at least one coloring material.

Description

Process for dyeing keratinous fibers comprising a step of cold plasma treatment of said fibers

The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising a step of treating said keratin fibers with cold plasma, followed by steps of applying to said keratin fibers a dispersion particular oily substance, of a composition comprising at least one amine compound and at least one dyestuff.

The present application also relates to a kit comprising a cold plasma generator and a device with at least two compartments containing a particular oily dispersion, a composition comprising at least one amine compound, and at least one dyestuff.

For a long time, many people have sought to change the color of their hair in order, for example, to hide their white hair.

To color keratin fibers, and in particular human keratin fibers, two types of stains have essentially been developed.

The first type of coloring is so-called permanent or oxidation coloring, which uses dye compositions containing oxidation dye precursors, generally called oxidation bases. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise by a process of oxidative condensation to colored compounds.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers. The variety of molecules involved in oxidation bases and couplers allows a rich palette of colors to be obtained.

The second type of coloring is so-called semi-permanent coloring or direct coloring, which consists in applying direct dyes which are colored and coloring molecules having an affinity for said fibers to the keratin fibers, leaving them to pause, then rinsing them.

This type of process does not require the use of an oxidizing agent to develop the color. However, it is possible to implement such an agent, in order to obtain a lightening effect with coloring. We then speak of a direct or semi-permanent coloring in lightening conditions.

Permanent or semi-permanent coloring processes under lightening conditions therefore require the use, with the dye composition, of an aqueous composition comprising at least one oxidizing agent, under alkaline pH conditions in the vast majority of cases.

These classic coloring processes can damage the integrity of keratin fibres. Softer solutions, also called make-up solutions and based on weak physico-chemical interactions, make it possible to deposit coloring and/or pearlescent agents on the surface without threatening the integrity of the fibers. Among the coloring agents that can be used in these make-up compositions, the pigments and in particular the nacres, such as the mica/iron oxide type nacres, have interesting coloring properties.

It is currently possible to deposit these coloring agents on the fibers to obtain the desired effect. However, the colorations thus obtained are only of short duration. Indeed, given the weak interaction between the coloring agents and the fibers, the colorings tend to fade, or even eliminate, quickly, vis-à-vis external agents, such as light, sweat, mechanical actions (brushing, styling), and especially after a few shampoos.

Added to these drawbacks are the risks of dyeing the hands and clothes of the users during the application of these compositions to the keratin fibres.

Thus, there is a real need to develop a process for coloring keratin fibers, in particular human keratin fibers such as the hair, which makes it possible to obtain a homogeneous and smooth colored coating on the keratin fibers, as well as perfectly individualized fibers. while forming a coating that is resistant to shampoos and to the various attacks that said fibers may undergo, such as brushing and/or rubbing. This process must also protect the integrity of the fibers.

These objects are achieved by the present invention, the subject of which is in particular a process for dyeing keratin fibres, in particular human keratin fibers such as the hair, comprising:
(i) a step consisting in treating said keratin fibers with cold plasma at atmospheric pressure (1.013·10 ⁵ Pa), followed by
(ii) a step consisting in applying to said keratin fibers an oily dispersion (A), preferably anhydrous, comprising:
(1) one or more particles comprising one or more ethylenic polymers chosen from:
a) ethylenic homopolymers of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl,
b) ethylenic copolymers of b1) (C ₁ -C ₄ )(alkyl)acrylate, (C ₁ -C ₄ )alkyl and of b2) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or or aryl, and
c) ethylenic copolymers of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl;
(2) one or more stabilizing agents, different from the said ethylenic polymer(s) (1), chosen from:
d) ethylenic homopolymers of (C ₁ -C ₆ )(alkyl)acrylate of (C ₉ -C ₂₂ )alkyl, and
e) ethylenic copolymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₉ -C ₂₂ )alkyl and of (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, and
(3) one or more hydrocarbon oils,
(iii) a step consisting in applying to said keratin fibers a composition (B) comprising one or more amino compounds chosen from polyamino compounds comprising at least two groups chosen from primary amines, secondary amines and their mixtures, amino alkoxysilanes and mixtures thereof; And
(iv) a step consisting in applying to said keratinous fibers one or more dyestuffs chosen from pigments, direct dyes and mixtures thereof, said dyestuff(s) being present in the oily dispersion (A) and/or in the composition ( B) and/or in a composition (C);
it being understood that steps (ii), (iii) and (iv) can be carried out simultaneously or sequentially.

The combination of the compounds of the invention, and in particular particular ethylenic copolymers with a pigment and/or a direct dye, preceded by a cold plasma treatment, makes it possible to color the keratin fibers without however damaging them, nor staining the hands and user clothing.

The cold plasma treatment, generated in the first step of the process of the invention, improves the deposit of the coloring materials and makes them in particular more resistant to external agents. Thus the colorations obtained have good remanence to shampoos.

The dyes and the treated keratin fibers are also resistant to rubbing and other mechanical aggressions such as brushing and combing. It should also be noted that the treated keratin fibers do not transfer color to the fabrics and do not stain the scalp.

In addition, keratin fibers have improved cosmetic properties, in particular as regards feel and softness. Furthermore, the method of the invention makes it possible to obtain perfectly individualized fibers which can be styled without any problem.

The present invention also relates to a kit comprising:
- a cold plasma generator, and
- a multi-compartment device comprising:
● a first compartment containing an oily dispersion (A) comprising:
(1) one or more particles comprising one or more ethylenic polymers chosen from:
a) ethylenic homopolymers of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl,
b) ethylenic copolymers of b1) (C ₁ -C ₄ )(alkyl)acrylate, (C ₁ -C ₄ )alkyl and of b2) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or or aryl,
c) ethylenic copolymers of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl
(2) one or more stabilizing agents, different from the said ethylenic polymer(s) (1), chosen from:
d) ethylenic homopolymers of (C ₁ -C ₆ )(alkyl)acrylate of (C ₉ -C ₂₂ )alkyl,
e) ethylenic copolymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₉ -C ₂₂ )alkyl and of (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, and
(3) one or more hydrocarbon oils,
● a second compartment containing a composition (B) comprising one or more amino compounds chosen from polyamino compounds comprising at least two groups chosen from primary amines, secondary amines and their mixtures, amino alkoxysilanes and their mixtures, and
● optionally a third compartment containing one or more dyestuffs chosen from pigments, direct dyes and mixtures thereof.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

Within the meaning of the present invention, and unless a different indication is given:
- A "alkyl radicalis a saturated hydrocarbon group at C₁-VS₆, linear or branched, preferably in C₁-VS₄such as methyl, ethyl, isopropyl, and t-butyl;
- a stem "(VS ₉ -VS ₂₂ )alkylis a saturated hydrocarbon group at C₉-VS₂₂, especially in C₁₀-VS_20,preferentially in VS₁₂-VS₁₈, more preferably in VS₁₂-VS_16,linear or branched, such as stearyl, behenyl, isodecyl, lauryl, hexadecyl, or myristyl;
- A "alkylene radicalis a divalent saturated hydrocarbon group at C₁-VS₈, linear or branched, especially in C₁-VS_6,preferably in C₁-VS₄such as methylene, ethylene, or propylene;
- a stem "cycloalkylis a saturated cyclic hydrocarbon group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyle the cycloalkyl radical being able to be substituted by one or more groups (C₁-VS₄)alkyl such as methyl, preferably the cycloalkyl radical is an isobornyl group.
- a stem "cyclic» is a cyclic hydrocarbon group, saturated or unsaturated, aromatic or non-aromatic, comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms such as cyclohexyl or phenyl;
- a stem "aryl» is an aromatic unsaturated cyclic radical, comprising from 6 to 12 carbon atoms, mono or bicyclic, fused or not, preferably the aryl group comprises 1 ring and 6 carbon atoms such as phenyl;
- a stem "aryloxy» is an aryl-oxy radicaliearyl-O- with aryl as previously defined, preferably phenoxy;
- a stem "aryl(C ₁ -VS ₄ )alkoxyis an aryl-(C₁-VS₄)alkyl-O-, preferably benzoxy;
- by keratin fibres”individualized» means keratinous fibres, in particular hair which, after application of the composition and drying, is not stuck together (or is all separated from one another) and therefore does not form clusters of fibres;
- by "insoluble monomer", therefore means any monomer whose homopolymer or copolymer is not in soluble form, that is to say completely dissolved at a concentration greater than 5% by weight at room temperature (20 ° C) in said environment. However, the so-called monomersinsoluble» may, as monomers, be soluble or insoluble in the hydrocarbon oil(s) (3), it being understood that they become insoluble after polymerization in the hydrocarbon oil(s) (3);
- by "ethylenic homopolymer“means a polymer resulting from the polymerization of identical ethylenic monomers;
- by "ethylene copolymer» means a polymer resulting from the polymerization of monomers different from each other, in particular at least 2 monomers different from each other. Preferably, the ethylenic copolymer of the invention is derived from 2 or 3 monomers different from each other, more preferably from 2 monomers different from each other;
- by "ethylenic monomer» means an organic compound comprising one or more unsaturations of the >C=C< types, conjugated or not, capable of polymerizing;
- by "soluble monomer», means any monomer whose homopolymer or copolymer, preferably homopolymer, is soluble at least to 5% by weight, at 20° C., in the hydrocarbon oil(s) (3) of the dispersion. The homopolymer is completely dissolved in the hydrocarbon oil(s) (3), visually at 20°C i.e. there is no visual note of deposit, nor precipitate, nor agglomerate, nor insoluble sediment. However, the so-called monomerssoluble» may, as monomers, be soluble or insoluble in the hydrocarbon oil(s) (3), it being understood that they become soluble after polymerization in the hydrocarbon oil(s) (3);
- by" fat bodyis meant an organic compound that is insoluble in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mm Hg) (solubility less than 5% and preferably 1% even more preferably at 0 ,1%). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as chloroform, ethanol, benzene, vaseline oil or decamethyl cyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids because salified fatty acids constitute soaps that are generally soluble in aqueous media;
- by fat body "liquidis meant in particular a fatty substance that is liquid at 25° C. and 1 atmosphere, preferably said fatty substance has a viscosity less than or equal to 7000 centipoise at 20° C.;
- by fat body "hydrocarbon» means a fatty substance which comprises at least 50% by weight, in particular from 50 to 100% by weight, for example from 60 to 99% by weight, or even from 65 to 95% by weight, or even from 70 to 90% by weight, relative to the total weight of said fatty substance, of carbonaceous compound, liquid at 25°C, having an overall solubility parameter according to HANSEN's solubility space of less than or equal to 20 (MPa)1/2, or d a mixture of such compounds;
The global solubility parameter δ according to the HANSEN solubility space is defined in the article "Solubility parameter values" by Grulke, in the work "Polymer Handbook" 3^thedition, Chapter VII, pages 519-559 by the relationship:
δ = ( d_D ²+d_P ²+d_H ²)^1/2
in which :
-d_Dcharacterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks,
-d_Pcharacterizes the DEBYE interaction forces between permanent dipoles,
-d_Hcharacterizes the specific interaction forces (type hydrogen bonds, acid/base, donor/acceptor, etc.);
The definition of solvents in the three-dimensional solubility space according to HANSEN is described in the article by HANSEN: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967);
- by dispersion or compositionanhydrous“means a dispersion or composition containing less than 2% by weight of water, or even less than 0.5% by weight of water, and in particular free of water; where appropriate, such small amounts of water can in particular be supplied by ingredients of the composition which can contain residual amounts thereof;
- the limits of a range of values are included in this range, in particular in the expressions “between” and “ranging from … to …”. Furthermore, the expression “at least one” used in the present description is equivalent to the expression “one or more”.

cold plasmas

The dyeing process according to the present invention comprises a step consisting in treating said keratin fibers with cold plasma at atmospheric pressure (1.013·10 ⁵ Pa).

By "cold plasma", we mean a plasma at atmospheric pressure which does not cause excessive heating of the substrate exposed to the plasma, that is to say a plasma whose average temperature remains close to the initial temperature of the gas ( temperature before the triggering of the plasma) and/or close to ambient temperature. A "cold plasma" is also called "non-thermal plasma" or "non-equilibrium plasma".

The cold plasma treatment step is preferably carried out by moving a plasma generator, also called a plasma production device, over said keratin fibres.

The cold plasma is preferably chosen from direct DBD type plasmas generated by dielectric barrier discharges, FE-DBD type plasmas generated by dielectric barrier discharges with floating electrodes, jet plasmas, hybrid plasmas, needle plasmas, plasmas generated by corona effect, and plasmas generated using a piezoelectric generator, and more preferably among direct DBD type plasmas and plasmas generated using a piezoelectric generator.

A DBD plasma generating device is characterized by the presence of an insulating dielectric material between the electrically conductive material of the electrode and the substrate. The presence of this insulating dielectric material prevents the formation of an electric arc during the realization of the electric field leading to the plasma, because otherwise all the energy is dissipated in the electric arc and then affects only a small portion gas occupying the space between the electrode and the substrate. The insulating dielectric material, due to its position between the electrically conductive material of the electrode and the substrate, will, upon application of the potential difference between the electrically conductive material of the electrode and the substrate, present on the surface a electrical charge :
- negative, resulting from the deposition of electrons, if the dielectric material is associated with the positively charged electrode, or,
- positive, resulting from the deposition of positive ions, if the dielectric material is associated with the negatively charged electrode.

Due to this surface electric charge, the dielectric material will reduce the intensity of the electric field initially created to a value causing the extinction of the plasma. The plasma may be present again when a new discharge may occur, that is to say after elimination of these charges adsorbed on the dielectric material, which is usually achieved by reversing the polarity between the electrodes. The DBD type plasma is then not generated continuously but in the form of point discharges whose frequency will depend on the frequency of an alternating voltage applied to the electrode of the generator.

The oily dispersion (A)

The dyeing process according to the present invention further comprises a step consisting in applying to said keratin fibers an oily dispersion (A) as defined previously.

The oily dispersion (A) of the invention comprises (1) one or more particles comprising at least one ethylenic polymer surface-stabilized with (2) at least one stabilizing agent in a preferably anhydrous medium, containing in (3) at least one hydrocarbon oil.

In order to obtain such an oily dispersion (A), it is proposed to polymerize specific monomers capable of forming the polymeric core (1) of the particles in the presence of a polymeric random stabilizing agent (2); the particles mainly comprising a soluble part (2) and a minority insoluble part (1) in the dispersion medium, ie in the hydrocarbon oil(s) (3).

The dispersions according to the invention consist of particles, generally spherical, and of at least one surface-stabilized polymer, in an anhydrous medium.

Preferably, said particles (1) are not, or only slightly, crosslinked.

Ethylene polymer particles

The oily dispersion (A) used in the dyeing process according to the present invention comprises one or more particles comprising one or more ethylenic polymers chosen from:
a) ethylenic homopolymers of (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, preferably ethylenic homopolymers of (meth)acrylate of C ₁ -C ₄ )alkyl,
b) ethylenic copolymers of b1) (C ₁ -C ₄ )(alkyl)acrylate, (C ₁ -C ₄ )alkyl and of b2) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or or aryl, preferably ethylenic copolymers of (meth)acrylate of C ₁ -C ₄ )alkyl and of (meth)acrylic acid, and
c) ethylenic copolymers of (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, preferably ethylenic copolymers of (meth)acrylate of C ₁ -C ₄ )alkyl.

In other words, the particle(s) consist of an ethylenic polymer core derived from homopolymers a) or from copolymers b) or c) as defined above.

According to a first embodiment of the invention, the ethylenic polymer(s) of the particles (1) are chosen from acrylate homopolymers a), resulting from the polymerization of identical monomers of formula (Ia):
H ₂ C=C(R)-C(O)-O-R' (Ia),
formula (Ia) in which
- R represents a hydrogen atom or a C ₁ to C ₄ alkyl group, linear or branched, such as methyl, and
- R' represents a C ₁ to C ₄ alkyl group, linear or branched, such as methyl or ethyl.

Preferably, the monomers of formula (Ia) are C ₁ to C ₄ alkyl acrylates, such as methyl acrylate.

According to a second embodiment of the invention, the ethylenic polymer(s) of the particles (1) are chosen from acrylate copolymers b), resulting from the copolymerization:
- at least one monomer of formula (Ia) as defined above, preferably a C ₁ to C ₄ alkyl (meth)acrylate monomer, more preferably a methyl (meth)acrylate or ethyl acrylate monomer , And
- at least one monomer of formula (Ib)
_H2C =C(R)-C(O)-OH (Ib)
formula (Ib) in which R is as defined previously for formula (Ia), preferably an acrylic acid monomer.

According to this embodiment, the amount of acrylic acid monomer(s) preferably ranges from 0.1 to 15% by weight, relative to the total weight of monomers of particles (1), that is to say monomers constituting the polymer core of the particles (1).

According to this second embodiment, the ethylenic polymer is preferably an ethylenic copolymer resulting from the copolymerization of acrylic acid with one or more C ₁ to C ₄ alkyl (meth)acrylate monomers.

According to a third embodiment of the invention, the ethylenic polymer(s) of the particles (1) are chosen from ethylenic acrylate copolymers c), resulting from the copolymerization:
- of at least two monomers, different from each other, of formula (Ia) as defined previously, preferably of at least two monomers, different from each other, of (meth)acrylate C ₁ to C ₄ alkyl, such as methyl acrylate and ethyl acrylate, and
- optionally at least one monomer of formula (Ib) as defined above.

Preferably, the ethylenic polymer(s) of the particles (1) are copolymers derived from the polymerization of at least one C ₁ to C ₄ alkyl (meth)acrylate monomer. The C ₁ to C ₄ alkyl (meth)acrylate monomer(s) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, and mixtures thereof and more preferably from methyl (meth)acrylate, methyl (meth)acrylate, ethyl and mixtures thereof.

According to a first variant, the C ₁ to C ₄ alkyl (meth)acrylate monomer(s) are C ₁ to C ₄ alkyl acrylate monomers, and more preferably chosen from methyl acrylate, ethyl acrylate and mixtures thereof.

According to a second variant, the C ₁ to C ₄ alkyl (meth)acrylate monomer(s) are C ₁ -C ₄ alkyl methacrylate monomers, more preferably chosen from methyl methacrylate, ethyl, and mixtures thereof, and more preferably methyl methacrylate.

According to a fourth embodiment of the invention, the ethylenic polymer of the particles (1) is a copolymer resulting from the copolymerization b1) of at least one monomer (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ - C ₄ ) alkyl, and b2) of at least one ethylenic monomer comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or aryl groups, such as benzyl.

More particularly, the ethylenic monomer(s) b2) comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or aryl groups are chosen from:
- the compounds of formula R ¹ (R ² )C=C(R ³ )-Acid with R ¹ , R ² and R ³ , which are identical or different, representing a hydrogen atom or a CO ₂ H, H ₂ PO group ₄ , or SO ₃ H, and Acid representing a carboxy group, a phosphoric acid or a sulphonic acid, preferably a carboxy group, it being understood that R ¹ , R ² and R ³ cannot simultaneously represent a hydrogen atom;
- the compounds of formula H ₂ C=C(R)-C(O)-N(R')-Alk-Acid with R and R', which are identical or different, representing a hydrogen atom, or a C alkyl group ₁ to C ₄ , linear or branched; Alk representing a (C ₁ -C ₆ )alkylene group optionally substituted by at least one group chosen from Acid as defined above and hydroxy; and Acid being as defined above, preferably a carboxy group or a sulphonic acid;
- the compounds of formula Ar-(R ^a )C=C(R ^b )-R ^c with R ^a , R ^b and R ^c , identical or different, representing a hydrogen atom or a C ₁ to C alkyl group ₄ , linear or branched, and Ar representing an aryl group, preferably benzyl, optionally substituted by at least one CO ₂ H, H ₂ PO ₄ , or SO ₃ H acid group, preferably substituted by a CO ₂ H group, or SO ₃ H;
- maleic anhydrides of formula (4a) and (4b):

formulas (4b) and (4b) in which R _a , R _b and R _c , which are identical or different, represent a hydrogen atom or a C ₁ to C ₄ alkyl group, linear or branched, preferably R _a , R _b , and R _c are identical and represent a hydrogen atom; And
- the compounds of formula H ₂ C=C(R)-C(O)-OH with R representing a hydrogen atom, or a C ₁ to C ₄ alkyl group, linear or branched, such as methyl.

Preferably, the ethylenic monomer(s) b2) are chosen from (C ₁ -C ₄ )(alkyl)acrylic acids. And advantageously, the ethylenic polymer of particles (1) is chosen from copolymers of (meth)acrylate of (C ₁ -C ₄ )alkyl and of (meth)acrylic acid.

More preferentially, the ethylenic monomer(s) b2) are chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamiopropanesulfonic acid, acrylamidoglycolic acid, acrylic acid, their salts and their mixtures, and better still the ethylenic monomer b2) is acrylic acid.

Preferably, the ethylenic polymer(s) of the particles (1) are copolymers resulting from the copolymerization b1) of at least one C ₁ to C ₄ alkyl (meth)acrylate monomer, preferably chosen from (meth) methyl acrylate, ethyl (meth)acrylate and mixtures thereof and b2) of at least one ethylenic monomer chosen from maleic anhydrides of formula (4a) and (4b) as defined above.

The polymer particle(s) (1) of the dispersion (A) preferably have a number-average size ranging from 5 and 500 nm, more preferably from 10 to 400 nm, and better still from 20 to 300 nm.

The final size of the polymer particles (1) is preferably greater than 100 nm. In particular a number-average size ranging from 100 nm and 500 nm; more particularly ranging from 150 nm to 400 nm, and even more particularly ranging from 160 nm to 300 nm.

The average size of the particles (1) is determined by conventional methods known to those skilled in the art. One can for example cite the particle size method which can be carried out by means of a MALVERN NanoZS device. The method used can be dynamic light scattering (DLS), also called quasi-elastic light scattering (QELS), individual particle tracking analysis (Nanoparticle Tracking Analysis, NTA), laser diffraction (DL), particle size distributions from nanometer to millimeter, and spatial filter velocimetry.

The sample is pipetted into a single-use plastic tank (4 transparent sides, 1 cm side and 4 mL capacity) placed in the measuring cell. The sample is analyzed on the basis of a cumulant method which leads to a unimodal particle size distribution characterized by an average diameter in intensity d(nm) and a polydispersity factor in sizes Q.

Preferably, the monomers capable of forming the polymeric core of the particle i) are chosen from monomers which are insoluble in the hydrocarbon-based oil(s) (3) of the oily dispersion (A). The insoluble monomers preferably represent 100% by weight of the total weight of the monomers forming the polymer core of the particle.

The total content of said ethylenic polymer particle(s), present in the oily dispersion (A), preferably ranges from 20 to 50% by weight, and more preferably from 25 to 50% by weight, relative to the total weight of the oily dispersion (A).

Stabilizing agents

The oily dispersion (A) used in the dyeing process according to the present invention further comprises one or more stabilizing agents (2), different from the said ethylenic polymer(s) defined above, chosen from:
d) ethylenic homopolymers of (C ₁ -C ₆ )(alkyl)acrylate of (C ₉ -C ₂₂ )alkyl, and
e) ethylenic copolymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₉ -C ₂₂ )alkyl and of (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl.

Preferably only one type of stabilizer (2) is used in the process of the invention.

According to a first embodiment of the invention, the stabilizing agent(s) (2) are chosen from d) ethylenic homopolymers of (C ₁ -C ₆ )(alkyl)acrylate of (C ₉ -C ₂₂ )alkyl, in particular from ethylenic (C ₁ -C ₄ )(alkyl)acrylate (C ₉ -C ₁₈ )alkyl homopolymers, preferably from ethylenic (meth)acrylate (C ₉ -C ₂₂ )alkyl homopolymers, and more preferably from ethylenic homopolymers of (C ₉ -C ₁₈ )alkyl (meth)acrylate.

More particularly, the stabilizing agent(s) (2) are chosen from d) ethylenic homopolymers resulting from the polymerization of monomers of formula H ₂ C=C(R)-C(O)-O-R'' with R representing an atom of hydrogen or a C ₁ to C ₆ , preferably C ₁ to C ₄ , linear or branched alkyl group, such as methyl, and R'' representing a C ₉ to C ₂₂ , preferably C ₉ to C ₁₈ , linear or branched. Preferably R'' represents an isodecyl, lauryl, stearyl, hexadecyl or behenyl group.

According to a second embodiment of the invention, the stabilizing agent(s) (2) are chosen from e) ethylenic copolymers of (C ₁ -C ₆ )(alkyl)acrylate of (C ₉ -C ₂₂ )alkyl and of (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, preferably from copolymers of (C ₁ -C ₄ )(alkyl)acrylate (C ₉ -C ₁₈ )alkyl and of ( C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl, and more preferentially among the copolymers of (meth)acrylate of (C ₉ -C ₁₈ )alkyl and of (meth)acrylate of (C ₁ -C ₄ )alkyl.

More preferably, the stabilizing agent(s) (2) are chosen from ethylenic copolymers e) of formula (IIa) and (IIb):
H ₂ C=C(R)-C(O)-O-R' (IIa) H ₂ C=C(R)-C(O)-O-R'' (IIb)
formulas (IIa) and (IIb) in which,
- R, identical or different, represent a hydrogen atom or a C ₁ to C ₄ alkyl group, linear or branched, such as methyl,
- R' represents a C ₁ to C ₄ alkyl group, linear or branched such as methyl or ethyl, and
- R'' represents an alkyl group, linear or branched, C ₉ to C ₂₂ , preferably C ₁₀ to C ₂₀ , and in particular a (C _2n )alkyl group with n representing an integer equal to 5, 6, 7, 8, 9, or 10. Preferably R'' represents an isodecyl, lauryl, stearyl, hexadecyl or behenyl group.

Preferably, the stabilizing agent(s) (2) are chosen from copolymers resulting from the copolymerization of monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, ( hexadecyl meth)acrylates, behenyl (meth)acrylates, and C ₁ to C ₄ alkyl (meth)acrylates, preferably methyl (meth)acrylate.

More preferably, the stabilizing agent(s) (2) are chosen from copolymers resulting from the copolymerization of monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, ( hexadecyl meth)acrylates, and C ₁ to C ₄ alkyl (meth)acrylates, preferably methyl (meth)acrylate or ethyl (meth)acrylate.

More particularly, the stabilizing agent(s) (2) are chosen from homopolymers of isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate, behenyl (meth)acrylate and random copolymers of isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylate behenyl and C ₁ to C ₄ alkyl (meth)acrylate, preferably present in a weight ratio of lauryl, stearyl, hexadecyl, behenyl / C ₁ -alkyl (meth)acrylate C ₄ greater than 4.5.

Advantageously, said weight ratio ranges from 5 to 15, more preferably said weight ratio ranges from 5.5 to 12.

According to another embodiment, the stabilizing agent(s) (2) are chosen from ethylenic copolymers e) resulting from the copolymerization of at least one monomer of formula (IIb) as defined previously and of at least two monomers, different from each other, of formula (IIa) as defined previously.

Preferably, the stabilizing agent(s) (2) are chosen from copolymers resulting from the copolymerization:
- at least one monomer chosen from isodecyl, lauryl, stearyl, hexadecyl and behenyl (meth)acrylates, and
- at least two monomers, different from each other, of C ₁ to C ₄ alkyl (meth)acrylate, preferably at least one methyl acrylate monomer and at least one acrylate monomer d 'ethyl. In particular, the weight ratio of isodecyl, lauryl, stearyl, hexadecyl, behenyl (meth)acrylates/C ₁ to C ₄ alkyl (meth)acrylate is greater than 4. Advantageously, said weight ratio ranges from 5 to 10, more preferably said weight ratio ranges from 5.5 to 7.

For these random copolymers, the defined weight ratio makes it possible to obtain a stable polymer dispersion, in particular after storage for 7 days at room temperature.

According to a particular embodiment of the invention, the oily dispersion (A) comprises from 2 to 40% by weight, in particular from 4 to 25% by weight, and in particular from 5.5 to 20% by weight of monomers ( C ₁ -C ₆ )(alkyl)acrylate of (C ₉ -C ₂₂ )alkyl included in d) or e) soluble in the hydrocarbon oil(s) (3), relative to the total weight of soluble and insoluble polymers contained in the said oily dispersion (A).

Advantageously, the weight ratio between the content of the stabilizing agent(s) (2), different from the ethylenic polymers and the content of the ethylenic polymer particle(s) (1), present in the oily dispersion (A), ranges from 0, 5 to 2, and preferably this weight ratio is equal to 1.

The total content of the stabilizing agent(s) (2), present in the oily dispersion (A) of the invention, preferably ranges from 2 to 40% by weight, more preferably from 3 to 30% by weight, and better still from 4 to 25% by weight, relative to the total weight of the oily dispersion (A).

Preferably, the stabilizing agent(s) (2) and the particle(s) i) have a number-average molecular weight (Mn) of between 1,000 and 1,000,000 g/mol, in particular between 5,000 and 500,000 g/mol and even better between 10,000 and 300,000 g/mol.

The dispersion (A) according to the invention is ultimately formed of polymer particles, of fairly large diameter, i.e. preferably greater than 100 nm, and leads to film-forming, shiny deposits that are resistant to fatty substances at room temperature (25° C.). , which are particularly interesting for make-up applications.

Hydrocarbon oils

The oily dispersion (A) used in the dyeing process according to the present invention further comprises one or more hydrocarbon oils.

This oil can be volatile (vapor pressure greater than or equal to 0.13 Pa measured at 25° C.) or non-volatile (vapor pressure less than 0.13 Pa measured at 25° C.).

Preferably, the hydrocarbon oil is volatile.

Hydrocarbon oil is a liquid hydrocarbon fatty substance at room temperature (25°C) and atmospheric pressure.

The hydrocarbon oil is preferably chosen from:
- branched C ₈ to C ₁₆ alkanes such as C ₈ to C ₁₆ isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and for example the oils sold under the trade names Isopars or Permetyls;
- C ₈ to C ₁₆ linear alkanes, for example such as n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97 , as well that their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (C ₁₁ ) and of n-tridecane (C ₁₃ ) obtained in examples 1 and 2 of application WO2008/155059 from the company Cognis, and their mixtures;
- short chain esters (having 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate;
- hydrocarbon oils of plant origin such as triglycerides consisting of esters of fatty acids and glycerol, the fatty acids of which may have chain lengths varying from C ₆ to C ₂₄ , the latter possibly being linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or alternatively wheat germ, sunflower, grapeseed, sesame, corn, apricot, castor, shea, avocado, olive, soy, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or alternatively caprylic/capric acid triglycerides such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol ^810® , ^812® and ^818® by the company Dynamit Nobel;
- synthetic ethers having 10 to 40 carbon atoms;
- linear or branched hydrocarbons comprising more than 16 carbon atoms, of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as ^Parleam® , squalane, paraffin oils, and mixtures thereof;
- synthetic esters such as the oils of formula R ₁ COOR ₂ in which R ₁ represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain in particular branched containing from 1 to 40 carbon atoms provided that R ₁ + R ₂ is ³ 10, such as Purcellin's oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C ₁₂ alcohol benzoates at C ₁₅ , hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethyl-hexyl palmitate, isostearyl isostearate, 2-hexyl-decyl laurate, palmitate 2-octyl-decyl, 2-octyl-dodecyl myristate, heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate, 2-octyl-dodecyl lactate; polyol esters and pentaerythritol esters;
- fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol; And
- their mixtures.

Advantageously, the hydrocarbon oil is apolar (therefore formed only of carbon and hydrogen atoms), and better, it is chosen by the hydrocarbons.

The hydrocarbon-based oil is preferably chosen from hydrocarbon-based oils having from 8 to 16 carbon atoms, more preferably from 12 to 16 carbon atoms, and better still apolar oils.

Preferably, the hydrocarbon oil is chosen from linear or branched C ₈ to C ₁₆ alkanes, and preferably from C ₁₂ to C ₁₆ , more preferably chosen from branched C ₈ to C ₁₆ alkanes, and preferably from C ₁₂ to _C16 . Particularly preferably, the hydrocarbon oil is isododecane.

Preferably the hydrocarbon oil or oils present in the oily dispersion (A), and more preferably when this oil is isododecane, constitute the only oil or oils in the oily dispersion (A), or are present in a majority content by relative to the additional oils possibly present in the oily dispersion (A).

The total content of the hydrocarbon oil(s), present in the oily dispersion (A) according to the invention, preferably ranges from 20 to 90% by weight, more preferably from 30 to 80% by weight, and better still from 40 to 70% by weight, relative to the total weight of the oily dispersion (A).

Without this being limiting, in general, the oily dispersion (A) according to the invention can be prepared in the following way: the polymerization is carried out in " dispersion ", that is to say by precipitation of the copolymer ethylene in the process of formation, with protection of the particles formed with one or more stabilizing agents, preferably with a stabilizing agent.
In a first step, the stabilizing agent b) is prepared by mixing the monomer or monomers constituting said stabilizing agent with a radical initiator, in a solvent called a synthetic solvent, and by polymerizing said monomers.
In a second stage, the monomers constituting the ethylenic copolymer of the particles a) are added to the stabilizing agent thus formed in the preceding stage and the polymerization of said added monomers is carried out in the presence of the radical initiator.

When the non-aqueous medium is a non-volatile c) hydrocarbon-based oil, the polymerization can be carried out in an apolar organic solvent (synthetic solvent), then add the non-volatile hydrocarbon-based oil (which must be miscible with said synthetic solvent) and selectively distilling the synthesis solvent.

When the dyestuff(s), chosen from pigments, direct dyes and mixtures thereof, are included in the oily dispersion (A), they can be added during the first stage. According to another variant, the said dyestuff(s) is (are) added during the second stage or after the second stage.

A synthetic solvent is therefore preferably chosen in which the monomers of the stabilizing agent and the radical initiator are soluble, while the particles of ethylenic copolymer obtained are insoluble so that they precipitate during their formation.

In particular, a synthetic solvent is chosen which is apolar organic, and preferably chosen from alkanes such as heptane or cyclohexane.

When the non-aqueous medium is a volatile hydrocarbon c) oil, the polymerization can be carried out directly in said oil which therefore also acts as a synthesis solvent. The monomers of the stabilizer and the radical initiator must also be soluble therein, and the ethylenic copolymer of the particles obtained must be insoluble therein.

The monomers of the ethylenic copolymer are preferably present in the synthesis solvent, before polymerization, in a proportion of 5 to 45% by weight, relative to the total weight of the reaction mixture. All of said monomers may be present in the solvent before the start of the reaction, or part of said monomers may be added as the polymerization reaction progresses.

The polymerization is preferably carried out in the presence of one or more radical initiators, in particular of the type:
- peroxide in particular chosen from tert-Butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel; Or
- azo in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2'-azo-bis(2-amidinopropane) dihydrochloride.

The polymerization is preferably carried out at a temperature ranging from 70 to 110° C. and at atmospheric pressure.

The particles of ethylenic copolymer a) are stabilized at the surface, during the polymerization thanks to the stabilizing agent b). The stabilization can be carried out by any known means, and in particular by direct addition of the stabilizing agent b) during the polymerization.

The stabilizer ii) is preferably present in the mixture before polymerization of the monomers of the ethylenic copolymer a). However, it is also possible to add it continuously, in particular when the monomers of the ethylenic copolymer a) are added as the polymerization reaction progresses.

It is possible in particular to use from 10 to 30% by weight of the stabilizing agent(s) a) relative to the total weight of monomers used (stabilizing agents ii) + ethylenic copolymers i)), and preferably from 15 to 25% by weight .

According to a first embodiment, the oily dispersion (A) according to the invention is an anhydrous composition. By “ anhydrous ” composition is meant a composition containing less than 2% by weight of water, or even less than 0.5% of water, and in particular free of water. Where appropriate, such small amounts of water can in particular be supplied by ingredients of the composition which can contain residual amounts thereof.

According to a second embodiment, the dispersion (A) is in an inverse emulsion, i.e. of the water-in-oil (W/O) or “water-in-oil (W/O)” type. In this case the composition comprises one or more surfactants, preferably nonionic.

Composition (B)

The dyeing process according to the present invention further comprises a step consisting in applying to said keratin fibers a composition (B) as defined previously.

Amino compounds

The composition (B) used in the dyeing process according to the present invention comprises one or more amino compounds chosen from polyamino compounds comprising at least two groups chosen from primary amines, secondary amines and their mixtures, amino alkoxysilanes ( also called amino alkoxysilanes), and mixtures thereof.

The amino compound(s) which can be used in composition (B) of the invention are chosen in particular from diamino compounds, triamino compounds, amino alkoxysilane compounds, and mixtures thereof.

The polyamine compounds, comprising at least two groups chosen from primary amines, secondary amines and their mixtures, can be chosen from non-polymeric polyamine compounds, polymeric polyamine compounds and their mixtures.

By “ non-polymeric ” compound is meant a compound which is not directly obtained by a polymerization reaction of monomers. Conversely, “ polymeric ” compound means a compound which is obtained by a polymerization reaction of monomers.

According to a first embodiment of the invention, the amino compound(s) are preferably chosen from nonpolymeric polyamino compounds, comprising at least two groups chosen from primary amines, secondary amines and mixtures thereof, and preferably comprising 2 to 20 carbon atoms.

As nonpolymeric polyamino compounds which can be used, mention may in particular be made of N-methyl-1,3-diaminopropane, N-propyl 1,3-diaminopropane, N-isopropyl 1,3-diaminopropane, N-cyclohexyl 1,3- diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2-aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, methyl bis(3-aminopropyl)amine, N-(3-aminopropyl)- 1,4-diaminobutane, N,N-dimethyldipropylene, triamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, ethylene diamine, 1,3-propylenediamine, 1,4-butylenediamine, lysine, cystamine, xylene diamine, tris(2-aminoethyl)amine and spermidine.

According to a second embodiment of the invention, the amino compound(s) are preferably chosen from amino alkoxysilanes and mixtures thereof, and more preferably from the compounds of formula (III) below:
R' ₁ -Si(OR' ₂ ) _z (R' ₃ ) _x (III)
formula (III) in which:

● R'₁is a C alkyl chain₁to C₁₀, linear or branched, saturated or unsaturated, cyclic or acyclic, substituted by one or more groups chosen from the groups:
- primary amine NH₂or secondary N(H)R with R representing a C alkyl group₁to C₄, linear or ramified,
- aryl or aryloxy substituted by an amino group, a group (C₁-VS₄)alkylamino or by a C aminoalkyl group₁to C₄, And
- amide –C(O)-NH₂or urea –NH-C(O)-NH₂;
R'₁being optionally interrupted in its alkyl chain by one or more heteroatoms (in particular O, S, NH), a carbonyl group (CO), or their combination such as ester –C(O)-O- or amide –C(O)- NH-, R'₁being bonded to the silicon atom directly via a carbon atom,
● R'₂and R'₃, identical or different, represent a C alkyl chain₁to C₆, linear or ramified,
● z denotes an integer ranging from 1 to 3, preferably 3, and
● x denotes an integer ranging from 0 to 2, with z+x =3.

Preferably, R′ ₂ represents a linear or branched C ₁ to C ₄ alkyl chain, more preferably a linear C ₁ to C ₄ alkyl chain, and better still an ethyl group.

Preferably, R′ ₃ represents a linear or branched C ₁ to C ₄ alkyl chain, more preferably a linear C ₁ to C ₄ alkyl chain, and better still a methyl or ethyl group.

Advantageously, R′ ₁ represents an acyclic chain. Preferably, R' ₁ represents an acylcic alkyl chain in C ₁ to C ₆ , linear or branched, saturated or unsaturated, substituted by an amine group NH ₂ or N(H)R with R representing an alkyl group in C ₁ to C ₆ , a C ₃ to C ₆ cycloalkyl group or a C ₆ aromatic group. Preferably, R′ ₁ represents a saturated linear C ₁ to C ₆ , preferably C ₂ to C ₄ , alkyl chain substituted by an amine group NH ₂ .

Preferably, the amino compound(s) are chosen from the compounds of formula (III) for which:
R' ₁ represents a saturated linear C ₁ to C ₆ alkyl chain substituted by an amine group NH ₂ ,
R' ₂ represents a C ₁ to C ₄ alkyl group, linear or branched,
R' ₃ represents C ₁ to C ₄ , linear or branched, and
z is equal to 3.

Preferably, the amino compound(s) are chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropyl methyldiethoxysilane, N-(2-aminoethyl)-3-amino propyltriethoxysilane, 3- (m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane, and mixtures thereof; more preferably from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropyl methyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and mixtures thereof; and more preferably the amino compound is 3-aminopropyl triethoxysilane (APTES).

According to yet another third embodiment of the invention, the amino compound(s) are preferably chosen from polymeric polyamino compounds (also called polyamino polymers), and more preferably from polyamino polymers having a weight-average molecular weight ranging from 500 to 1,000,000, preferably ranging from 500 to 500,000, and preferentially ranging from 500 to 100,000.

As polyamino polymers that can be used according to this other embodiment, mention may be made in particular of:
- poly((C ₂ -C ₅ )alkylene imines), and in particular polyethyleneimines and polypropyleneimines , in particular poly(ethyleneimine) (for example that sold under the reference 46,852-3 by the company Aldrich Chemical);
- poly(allylamine), for example that sold under the reference 47,913-6 by the company Aldrich Chemical);
- polyvinylamines and their copolymers, in particular with vinylamides; mention may in particular be made of vinylamine/vinylformamide copolymers such as those marketed under the name LUPAMIN® 9030 by the company BASF;
- polyamino acids having NH ₂ groups such as polylysine, for example that sold by the company JNC Corporation (formerly Chisso);
- amino dextran, such as that sold by the company CarboMer Inc;
- polyvinyl amino alcohol, such as that sold by the company CarboMer Inc;
- copolymers based on acrylamidopropylamine;
- chitosan;
- polydi(C ₁ -C ₄ )alkylsiloxanes, in particular polydimethylsiloxanes, comprising amine groups at the end of the chain or on the side chains, preferably terminal or lateral amino(C ₁ -C ₆ )alkyl groups such as aminopropyl , and more particularly those of formula (IVa), (IVb) or (IVc):

(IVa)
formula (IVa) in which,
R ^a , and R ^b , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
R ^c and R' ^c , which are identical or different, preferably identical, represent a hydrogen atom, a (C ₁ -C ₄ )alkyl group, an amino(C ₁ -C ₄ )alkyl or (C ₁ -C ₄ ) alkylamino (C ₁ -C ₄ ) alkyl, preferably a hydrogen atom or an amino (C ₁ -C ₄ ) alkyl group such as aminoethyl,
X represents a covalent bond or an oxygen atom, preferably a covalent bond,
ALK and ALK', which are identical or different, preferably identical, represent a (C ₁ -C ₆ )alkylene group, preferably (C ₁ -C ₄ )alkylene group such as propylene;
n representing an integer greater than 2 and more particularly the value of n is such that the weight-average molecular weight of the compound of formula (IVa) is between 500 and 55,000;

Preferably, the polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IVa) are of the following formula (IV'a):

(IV’a)

(IV''a)
formula (IV'a) in which the value of n is such that the weight-average molecular weight of the compound of formula (IV'a) is between 500 and 55,000.
As an example of amino silicone (IVa) or (IV'a), mention may be made of those sold under the names "DMS-A11", "DMS-A12", "DMS-A15", "DMS-A21", "DMS- A31”, “DMS-A32, “DMS-A35” by the company GELEST;
Formula (IV′′a) in which R ^c , R′ ^c , ALK, ALK′, and n are as defined above for (IVa). Preferably ALK and ALK' are identical and represent a (C ₁ -C ₄ )alkylene group such as propylene, and R ^c and R' ^c are identical and represent an amino(C ₁ -C ₄ )alkyl group such as aminoethyl. By way of example, mention may particularly be made of Dimethoxysilyl Ethylenediaminopropyl Dimethicone (RN: 71750-80-6), under the trade name GP-RA-157, marketed by Genesee Polymers.

(IVb)
formula (IVb) in which,
R ^a , R ^b , and R ^d , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl, R ^d can also represent a (C ₁ -C ₆ )alkyl group substituted by a (C ₁ -C ₄ )alkylamino or amino group,
R ^c represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom;
ALK represents a (C ₁ -C ₆ )alkylene group, preferably (C ₁ -C ₄ )alkylene such as propylene;
n and m, which are identical or different, represent an integer greater than 2 and more particularly the values of m and n are such that the weight-average molecular weight of the compound of formula (IVb) is between 1000 and 55,000;

Preferably, the polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IVb) are of the following formula (IV'b)

(IV'b)
formula (IV'b), in which the values of n and m are such that the weight-average molecular weight of the compound of formula (IV'b) is between 1000 and 55,000. As examples of silicone of formula (IVb) mention may be made of those sold under the names “AMS-132”, “AMS-152”, “AMS-162”, “AMS-163”, “AMS-191”, “AMS-1203” by the company GELEST;

(IVc)
formula (IVc) in which,
R ^a and R ^b , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group, such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
R ^d represents a (C ₁ -C ₆ )alkyl group optionally substituted by a (C ₁ -C ₄ )alkylamino or amino group, preferably (C ₁ -C ₄ )alkyl, such as isobutyl, terbutyl or n -butyl,
R ^c represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom;
ALK represents a (C ₁ -C ₆ )alkylene group, preferably (C ₁ -C ₄ )alkylene such as propylene;
n representing an integer greater than 2 and more particularly the value of n is such that the weight-average molecular weight of the compound of formula (IVc) is between 500 and 5000;

Preferably, the polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IVc) are of the following formula (IV'c):

H ₂ NCH ₂ CH ₂ CH ₂ -Si(CH ₃ ) ₂ -O-[Si(CH ₃ ) ₂ -O]n-Si(CH ₃ ) ₂ C ₄ H ₉

(IV'c)
formula (IV'c) in which the value of n is such that the weight-average molecular weight of the compound of formula (IV'c) is between 500 and 3000. As an example of a silicone of formula (IVc), it is possible cite those sold under the names "MCR-A11", "MCR-A12" by the company GELEST;
- amodimethicones, and in particular those of formula (IVd):

(IVd)
formula (IVd) in which,
R ^a , and R ^b , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
R ^c represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom,
R ^e represent a hydroxy, (C ₁ -C ₄ )alkoxy, amino, (C ₁ -C ₄ )alkylamino group,
R ^f , represents a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, a hydroxy group or -O–(SiR ₂ ) _x -R' with R representing a group (C ₁ -C ₄ )alkyl or (C ₁ -C ₄ )alkoxy and R' representing a (C ₁ -C ₄ )alkoxy or hydroxy group, preferably R ^f represents a (C ₁ -C ₄ )alkyl group, (C1-C4)alkoxy, or -O–(SiR ₂ ) _x -R' with R representing a (C ₁ -C ₄ )alkyl group such as methyl and R' a hydroxy or (C ₁ -C ₄ )alkoxy group such as methoxy,
R ^g represents a hydrogen atom, a (C ₁ -C ₆ )alkyl group,
ALK and ALK', identical or different, represent a (C ₁ -C ₆ )alkylene group, preferably (C ₁ -C ₄ )alkylene such as ethylene or propylene; n and m, identical or different, representing an integer greater than 2, p and x are integers greater than or equal to 0, preferably p is between 2 and 20 and more particularly the values of m, n, p and x are such that the weight-average molecular weight of the compound of formula (IVe) is between 2,000 and 700,000, preferably between 5,000 and 500,000;

Preferably, the amodimethicones of formula (IVd) are of the following formula (IV'd), (IV''d) or (IV'''d):

(IV’d)
formula (IV'd) in which,
ALK represents a (C ₁ -C ₆ )alkylene group, preferably ethylene,
ALK' represents a (C ₁ -C ₆ )alkylene group, preferably propylene, and
m, n and p represent integers greater than 2, with m and n and p such that the weight-average molecular mass of the compound of formula (IV'd) is between 5,000 and 500,000 approximately; preferably p represents an integer between 8 and 20;

(IV''d)
formula (IV''d) in which,
R ^a , and R ^b , identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
R ^c represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom,
R ^g represent a hydrogen atom, or a (C ₁ -C ₄ )alkyl group,
R ^f , represents a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, or -O–(SiR ₂ ) _x -R' with R representing a (C ₁ -C ₄ )alkyl such as methyl and R' a hydroxy or (C ₁ -C ₄ )alkoxy group such as methoxy,
R ^g represents a hydrogen atom, a (C ₁ -C ₆ )alkyl group,
ALK represents a (C ₁ -C ₆ )alkylene group, preferably ethylene,
ALK' represents a (C ₁ -C ₆ )alkylene group, preferably propylene,
n and m, identical or different, representing an integer greater than 2, x is an integer greater than or equal to 0, preferably the values of m, n, and x are such that the weight-average molecular weight of the compound of formula ( IV''d) is between 2,000 and 700,000, preferably between 5,000 and 500,000;

formula (IV'''d) in which, R ^f , R ^g , ALK, ALK', m, n as defined for (IV''d).
The amodimethicones and trimethylsiloxyamodimethicones belonging to the formulas (IV''d) and (IV'''d), are for example the amodimethicones and trimethylsiloxyamodimethicones of the ADM type sold by the company Wacker-Belsil ^® , mention may also be made of polydimethylsiloxanes with aminoethylaminopropyl groups , with a methoxy and/or hydroxy and alpha-omega silanol function in 60% cationic aqueous emulsion (Supplier reference: XIAMETER MEM-8299 EMULSION for DOW CORNING or Supplier reference: BELSIL ADM 4000 E for WACKER);
- polydimethylsiloxanes with an aminoethyl iminopropyl group in nonionic microemulsion at 15% preserved (Supplier reference: BELSIL ADM LOG 1);
- polyether amines known in particular under the reference JEFFAMINE from the company HUNSTMAN; and in particular: Polyethylene glycol and/or polypropylene glycol α, ω-diamine (with amine function at the end of the chain) such as those sold under the names JEFFAMINE D-230, D-400, D-2000, D-4000, ED-600, ED-9000, ED-2003;
- polytetrahydrofuran (or polytetramethylene glycol) α, ω-diamine, polybutadienes α, ω-diamine;
- polyamidoamine (PANAM) dendrimers with terminal amine functions;
- poly(meth)acrylates or poly(meth)acrylamides carrying lateral primary or secondary amine functions such as poly(3-aminopropyl)methacrylamide, poly(2-aminoethyl) methacrylate.

Preferably, according to this embodiment, the amino compound(s) are chosen from chitosans, polydi(C ₁ -C ₄ )alkylsiloxanes comprising amine groups at the end of the chain or on the side chains, amodimethicones and their mixtures, more preferably from chitosans, polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IVa), amodimethicones of formula (IVd) and mixtures thereof, and better still from chitosans, polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IV'a), amodimethicones of formula (IV'd) and mixtures thereof. The amino compound(s) are advantageously chosen from chitosans, polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IV''a), amodimethicones of formula (IV''d) and mixtures thereof

The content of said amino compound(s), present in composition (B) according to the invention, preferably ranges from 0.5 to 20% by weight, more preferably from 1 to 20% by weight, and better still from 1 to 10 % by weight, relative to the total weight of the composition.

According to a first embodiment, the composition (B) used in the dyeing process according to the invention may optionally also comprise one or more hydrocarbon oils as defined above.

Preferably, the hydrocarbon-based oil(s) optionally present in composition (B) are advantageously chosen from hydrocarbon-based oils having from 8 to 14 carbon atoms and mixtures thereof, and better still the hydrocarbon-based oil is isododecane.

When the composition (B) comprises one or more hydrocarbon-based oils, the latter are preferably identical to those included in the oily dispersion (A).

According to another embodiment, the composition (B) used in the dyeing process according to the invention is aqueous or aqueous-alcoholic. By “ hydroalcoholic ” composition is meant a composition which comprises a mixture of water and a linear or branched C ₂ to C ₄ alkanol, preferably ethanol.

Dyestuffs

The dyeing process according to the present invention further comprises a step of applying to said keratin fibers one or more coloring matter(s) chosen from pigments, direct dyes and mixtures thereof, the said dyestuffs being present in the oily dispersion (A) and/or in the composition (B) and/or in a composition (C).

Preferably, the dyestuff(s) are chosen from pigments.

By “pigment”, is meant all the pigments providing color 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%. More particularly, the pigment is little or not soluble in hydro-alcoholic media.

Mention may be made, as pigment, of organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 and ibid, " Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim10.1002/14356007.a20_243.pub3.

Mention may in particular be made of azo pigments which contain one or more azo groups AN=NB with A representing an optionally substituted (hetero)aryl, B representing optionally substituted (hetero)aryl or –CH[C(O)-R]-C( O)-X ₁ -A', A' representing an optionally substituted (hetero)aryl and R representing a hydrogen atom or a (C ₁ -C ₆ )alkyl group, with the groups A, A' and B (hetero )aryls that do not contain solubilizing groups such as –SO ₃ H, –COOH.

They can be particularly monoazoic including β-Naphthols, monoazopyrrolone pigments,Benzimidazolone pigments ; diazo pigments such as diazodiarylide pigments and Bis(N-acetoacetarylide), triazo or tetraazo pigments.

Mention may also be made of Azo Pigments with Metal Complexes “azo metal complex pigment”.

Other pigments are also interesting, these are Isoindolinones and Isoindolines pigments, Phthalocyanine pigments; Quinacridone pigments; Perinone pigments; Perylene pigments; Anthraquinone pigments such as Hydroxyanthraquinone Pigments; Aminoanthraquinone pigments including Acylaminoanthraquinones and Azo Anthraquinone pigments; Heterocyclic Anthraquinones; polycarbocyclic Anthraquinone pigments, Pyranthrone Pigments; Anthanthrone pigments; Diketopyrrolopyrrole (DPP) pigments; Thioindigo pigments; dioxazine pigments; triphenylmethane pigments; Quinophthalone pigments; and fluorescent pigments.

When the dyes include one or more solubilizing groups such as –SO ₃ H, -COOH, these dyes are made insoluble and therefore pigmented by formation of lake ie by salification (ex. Na, Ca, St, Ba…) and divided mainly in β-naphthol pigment and 2-hydroxy-3-naphthoic acid “(BON) pigment lakes”.

In the context of the present invention, the pigment can be at least partly organic.

According to one embodiment of the invention, the pigment is an organic pigment.

According to another embodiment of the invention, the pigment is an inorganic pigment.

The microcapsules according to the invention comprise at most 80% by weight of the pigment relative to the weight of the polymer matrix. In particular, they may comprise from 0.5 to 75% by weight, for example from 1 to 70% by weight, in particular from 20 to 65% by weight, or even from 30 to 60% by weight of the pigment relative to the weight of the polymer matrix.

Of course, the encapsulation rate depends on the desired color modulation and can therefore vary significantly depending on the desired effect.

By way of illustration of the pigments which can be used in the present invention, mention may be made of carbon black, titanium oxide, chromium oxide, pigments of the D&C, FD&C type and their lakes, and in particular those known under the names D&C Blue #4, D&C Brown #1, FD&C Green #3, D&C Green #5, D&C Green #6, FD&C Green #8, 20 D&C Orange #4, D&C Orange #5, D&C Orange #10, D&C Orange #11, FD&C Red #4, D&C Red #6, D&C Red #7 (CI 15850), D&C Red #17, D&C Red #21, D&C Red #22, D&C Red #27, D&C Red #28, D&C Red #30, D&C Red #31, D&C Red #33, D&C Red #34, D&C Red #36, FD&C Red #40, FD&C Red 40 lake, D&C Violet n°2, Ext. D&C Violet #2, FD & C Blue #1, D&C Yellow #6, FD&C Yellow #6, D&C Yellow #7, 25 Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10 or D&C Yellow No. 11, it being understood that when said pigment is not naturally insoluble in the hydrophilic and lipophilic phases usually used in cosmetics, it is used in the form of a corresponding lacquer as explained previously.

By way of example of lacquers, mention may in particular be made of lacquers based on barium, strontium, calcium, aluminium, or alternatively diketo pyrrolopyrrole.

As another example of pigments that can be used in the present invention, mention may be made in particular of mineral pigments, optionally surface-treated and/or coated, and in particular titanium dioxide, zirconium or cerium oxides, as well as zinc oxides. , iron (black, yellow or red) or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue, or metal powders such as aluminum powder, copper powder, gold powder and silver powder.

Mention may also be made of optical effect pigments such as particles comprising an organic or mineral, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being coated or not with metallic substances such as aluminium, gold, silver, platinum, copper, bronze, or metallic oxides such as titanium dioxide, iron oxide, or chromium oxide.

It can also be mother-of-pearl.

By “pearls”, we mean iridescent pigments, in particular produced by certain molluscs in their shell or else synthesized.

The mother-of-pearl pigments can be chosen from mica covered with titanium or with bismuth oxychloride, titanium mica covered with iron oxides, titanium mica covered with in particular ferric blue or chromium oxide, titanium mica covered with with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It is also possible to use interference pigments, in particular liquid-crystal or multilayer pigments.

They may also be pigments having a structure which may for example be of the sericite/brown iron oxide/titanium dioxide/silica type.

They may also be pigments having a structure which may for example be of the silica microsphere type containing iron oxide.

By way of examples of pigments most particularly suitable for the implementation of the present invention, mention may in particular be made of D&C Red No. 7, titanium oxide, chromium oxide, lakes of D&C type pigments and FD&C mentioned above, and in particular D&C Red n°22 lake, Yellow n°6 lake, FD&C Blue n°1 lake.

The pigments in accordance with the invention may be in the form of a powder or a pigment paste. They can be coated or uncoated.

The pigments in accordance with the invention may, for example, be chosen from white or colored pigments, lakes, special effect pigments such as mother-of-pearl or glitter, and mixtures thereof.

As examples of white or colored mineral pigments, mention may be made of zirconium or cerium oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue.

As examples of white or colored organic pigments, mention may be made of the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of the metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

In particular, the white or colored organic pigments can be chosen from carmine, carbon blacks such as Black 2, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, pigments blues codified in the Color Index under Cl references 42090, 69800, 69825, 73000, 74100, 74160, yellow pigments codified in the Color Index under Cl references 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the Cl references 61565, 61570, 74260, the orange pigments codified in the Color Index under the CI references 11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the References CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, oxidative polymerization of indole, phenolic derivatives as described in patent FR 2 679 771.

Preferably carbon blacks such as Black 2 or lacquers such as D&C Red 7.

It is possible to use pigment pastes of organic pigment such as the products sold by the company HOECHST under the name:
- YELLOW COSMENYL IOG: Pigment YELLOW 3 (Cl 11710);
- COSMENYL G YELLOW: Pigment YELLOW 1 (Cl 11680);
- ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);
- COSMENYL RED R: Pigment RED 4 (Cl 12085);
- CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);
- VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);
- COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);
- GREEN COSMENYL GG: Pigment GREEN 7 (Cl 74260);
- COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

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 be composed in particular of particles comprising:
- an inorganic core,
- at least one binder ensuring the fixing of the organic pigments on the core, and
- at least one organic pigment at least partially covering the core.

By "lacquer", we mean the dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates on which the dyes are adsorbed are for example alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum. Among the organic dyes, mention may be made of cochineal carmine.

Examples of lacquers include the products 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 7 (CI 15 850:1), 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 (CI 61 570), D & C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42053), D&C Blue 1 (CI 42090).

By "special effect pigments" is meant pigments which generally create a colored appearance (characterized by a certain shade, a certain vividness and a certain clarity) which is not uniform and changes according to the conditions of observation (light , temperature, viewing angles, etc.). They are therefore opposed to white or colored pigments which provide a uniform opaque, semi-transparent or classic transparent hue.

As examples of special effect pigments, mention may be made of white pearlescent pigments such as mica covered with titanium, or bismuth oxychloride, colored pearlescent pigments such as mica covered with titanium and iron oxides , mica covered with titanium and in particular with ferric blue or chromium oxide, mica covered with titanium and an organic pigment as defined above, as well as pearlescent pigments based on bismuth oxychloride.

Mention may also be made of pigments with an interference effect not fixed on a substrate, such as liquid crystals (Helicones HC from Wacker), holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also include fluorescent pigments, whether fluorescent in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by the Quantum Dots Corporation.

Quantum dots are luminescent semiconductor nanoparticles capable of emitting, under light excitation, radiation having a wavelength of between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they can be manufactured according to the methods described for example in US Pat. No. 6,225,198 or US Pat. No. 5,990,479, in the publications cited therein, as well as in the following publications: Dabboussi BO et al "(CdSe)ZnS core -shell quantum dots: synthesis and characterization of a size series of highly luminescent nanocrystallites" Journal of physical chemistry B, vol 101, 1997, pp 9463-9475 . and Peng, Xiaogang et al, "Epitaxial Growth of highly Luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility" Journal of the American Chemical Society, vol 119, N°30, pp 7019-7029 .

The pigments in accordance with the invention are preferably colored pigments.

The variety of pigments involved makes it possible to obtain a rich palette of colors, as well as special optical effects such as metallic and interference effects.

The size of a pigment other than nacres in solution is generally between 10 nm and 10 μm, preferably between 50 nm and 5 μm, and even more preferably between 100 nm and 3 μm. The size of a nacre in solution is generally between 1 and 200 μm, preferably between 1 and 80 μm, and even more preferably between 1 and 50 μm.

Among the mineral pigments, mention may be made, by way of example, of titanium dioxide (rutile or anastase) optionally surface-treated and codified in the Color Index under the reference CI77891; black, yellow red and brown iron oxides, codified under the references CI77499, 77492, 77491; manganese violet (CI77742); ultramarine blue (CI77007); hydrated chromium oxide (CI77289); ferric blue
(CI77510).

Among the organic pigments, mention may be made, by way of example, of the pigment YELLOW 3 sold in particular under the trade name "JAUNE COVANOR W 1603" by the company WACKHERR (CI 17710), "D & C RED n° 19" ( CI 45170), the "D & C RED n° 9 (CI 15585), the "D & C RED n° 21" (CI 45380), the "D & C ORANGE n° 4" (CI 15510), the " D & C ORANGE No. 5" (CI 45370), "D & C RED No. 27" (CI45410), "D & C RED No. 13 (CI 15630), "D & C RED No. 7 " (CI 15850-1), "D & C RED No. 6 (CI 15850-2), "D & C YELLOW No. 5" (CI 19140), "D & C RED No. 36" ( CI 12085), "D & C ORANGE n° 10" (CI 45425), "D & C YELLOW n° 6" (CI 15985), "D & C RED n° 30" (CI 73360), "D & C RED No. 3" (CI 45430), carbon black (CI 77266), and cochineal carmine lakes (CI 75470).

It is also possible to use pearlescent pigments which can be chosen in particular from white pearlescent pigments such as mica covered with titanium oxide, bismuth oxide; colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment of the precipitate type, as well as those based on oxychloride of bismuth.

More particularly, pigment pastes of organic pigment are used, such as the products sold by the company HOECHST under the name:
- COSMENYL YELLOW 1OG: Pigment YELLOW 3 (CI 11710)
- COSMENYL YELLOW G: Pigment YELLOW 1 (CI 11680)
- ORANGE COSMENYL GR: Pigment ORANGE 43 (CI 71105)
- COSMENYL RED R°: Pigment RED 4 (CI 12085)
- CARMIN COSMENYL FB: Pigment RED 5 (CI 12490)
- VIOLET COSMENYL RL: Pigment VIOLET 23 (CI 51319)
- COSMENYL BLUE A2R: Pigment BLUE 15.1 (CI 74260)
- GREEN COSMENYL GG: Pigment GREEN 7 (CI 74260)
- COSMENYL BLACK R: Pigment BLACK 7 (CI 77266)

The coloring material(s) is (are) advantageously chosen from pigments, preferably from white organic pigments, colored organic pigments, and mixtures thereof, and more preferably carbon blacks, such as such as Black 2, lacquers, such as D&C Red 7, and mixtures thereof.

The dyestuff(s) can be chosen from direct dyes.

By “direct dye”, we mean natural and/or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the fiber.

They can be ionic or nonionic, preferably cationic or nonionic.

These direct dyes are, for example, chosen from neutral, acid or cationic nitrobenzene direct dyes, neutral, acid or cationic azo direct dyes, tetraazapentamethine dyes, quinone and in particular neutral, acid or cationic anthraquinone dyes, azine direct dyes , triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.

Examples of suitable direct dyes include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines, and styryl dyes; carbonyls; azines; nitro (hetero)aryl; tri-(hetero)aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures.

Preferably, the direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group.

According to a particular embodiment of the invention, the direct dyes comprise at least one quaternized cationic chromophore.

By way of direct dye according to the invention, mention may be made of acridine dyes; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azo, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthropes; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis isoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindins; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isovianthrone; lactones; (poly)methines such as dimethines of the stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, in particular nitro(hetero)aromatics; oxadiazoles; oxazines; periones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes/carotenoids; porphyrins; pyranthrone; pyrazolanthrones; pyrazolones; pyrimidinoanthropes; pyronins; quinacridones; quinolines; quinophthalones; squares; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

For cationic azo dyes, particular mention may be made of those derived from the cationic dyes described in the Kirk Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & sons, updated on 04/19/2010.

Among the azo dyes that can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

According to a preferred embodiment of the invention, the direct dye or dyes are chosen from cationic dyes called “basic dyes”.

Mention may be made, among the azo dyes described in the International Color Index 3rd edition, and in particular of the following compounds:
Basic Red 22
Basic Red 76
Basic Yellow 57
Basic Brown 16
Basic Brown 17.

Among the cationic quinone dyes, those mentioned in the aforementioned International Color Index are suitable, and among these, the following dyes may be mentioned, among others:
Basic Blue 22
Basic Blue 99.

Among the azine dyes which are suitable, mention may be made of those listed in the International Color Index and for example the following dyes:
Basic Blue 17
Basic Red 2.

Among the cationic triarylmethane dyes which can be used according to the invention, mention may be made, in addition to those listed in the Color Index, of the following dyes:
Basic Green 1
Basic Purple 3
Basic Purple 14
Basic Blue 7
Basic Blue 26.

Mention may also be made of cationic dyes in documents US 5888252, EP 1133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954. Mention may also be made of those listed in the encyclopedia "The chemistry of synthetic dye" by K. VENKATARAMAN, 1952, Academic press vol 1 to 7, in the encyclopedia "Kirk Othmer" "Chemical technology", chapter "dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of ULLMANN's ENCYCLOPEDIA of Industrial chemistry 7th edition, Wiley and sons.

Preferably, the cationic direct dyes are chosen from those derived from azo and hydrazono type dyes.

According to a particular embodiment, the direct dyes are cationic azo, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 3,53836 2189006, fr 1560664, fr 1540423, fr 1567219, FR 1516943, FR 1221122, of 4220388, of 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 35248413, GB 738585, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh. Obshch. Khim. (1970), 40(1), 195-202; Ann. Chem. (Rome) (1975), 65(5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211; Rev. rum. Chem. (1988), 33(4), 377-83; Text. Res. J. (1984), 54(2), 105-7; Chem. Ind. (Milan) (1974), 56(9), 600-3; Khim. Tekhnol. (1979), 22(5), 548-53; Ger. Monatsh. Chem. (1975), 106(3), 643-8; Mr R. L. Bull. Res. Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Pigment dyes. (1992), 19(1), 69-79; Pigment dyes. (1989), 11(3), 163-72.

Preferably, the cationic direct dye or dyes include a quaternary ammonium group, more preferably the cationic charge is endocyclic.

These cationic radicals are for example a cationic radical:
- with exocyclic charge (di/tri)(C ₁ -C ₈ )alkylammonium, or
- with an endocyclic charge such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phénazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium , quinolium, tétrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium ou xanthylium.

Mention may be made of the hydrazono cationic dyes of formula (V) and (VI), the azo compounds of formulas (VII) and (VIII) below:

formulas (V) to (VIII) in which:
● Het ⁺ represents a cationic heteroaryl radical, preferentially with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferentially by at least one (C ₁ -C ₈ )alkyl group such as methyl;
● Ar ⁺ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(C ₁ -C ₈ )alkyl-ammonium such as trimethylammonium;
● Ar represents an aryl group, in particular phenyl, optionally substituted, preferably by one or more electron-donating groups such as i) (C ₁ -C ₈ )alkyl optionally substituted, ii) (C ₁ -C ₈ )alkoxy optionally substituted, iii) (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(C ₁ -C ₈ )alkylamino, v) N-(C ₁ -C ₈ ) alkyl-N-aryl (C ₁ -C ₈ ) alkylamino optionally substituted or else Ar represents a julolidine group;
● Ar'' represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl optionally substituted, preferably by one or more (C ₁ -C ₈ )alkyl, hydroxyl, (di)(C ₁ -C ₈ )(alkyl )amino, (C ₁ -C ₈ )alkoxy or phenyl;
● R _a and R _b , identical or different, representing a hydrogen atom or a (C ₁ -C ₈ )alkyl group optionally substituted, preferably by a hydroxyl group;
● or else the substituent R _a with a substituent of Het ⁺ and/or R _b with a substituent of Ar form together with the atoms which carry them a (hetero)cycloalkyl; particularly R _a and R _b , representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group optionally substituted by a hydroxyl group;
● Q ^- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

In particular, mention may be made of direct dyes with cationic charge, endocyclic azo and hydrazono of formula (V) to (VIII) as defined above. More particularly the cationic direct dyes of formula (V) to (VIII) with endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferably, the following direct dyes:

formulas (V-1) and (VIII-1) in which:
- R ¹ represents a (C ₁ -C ₄ )alkyl group such as methyl;
- R ² and R ³ , which are identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl; And
- R ⁴ represents a hydrogen atom or an electron-donating group such as (C ₁ -C ₈ )alkyl optionally substituted, (C ₁ -C ₈ )alkoxy optionally substituted, (di)(C ₁ -C ₈ )(alkyl) amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R ⁴ is a hydrogen atom,
- Z represents a CH group or a nitrogen atom, preferably CH,
- Q ^- is an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

In particular, the dyes of formula (III-1) and (V-1) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives:

with Q' an anionic counter ion as defined previously, particularly halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say they contain at least one fluorescent chromophore as defined above.

As fluorescent dyes, mention may be made of the radicals resulting from the dyes acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN) methyl]-1H-pyrrolato-kN}bores (BODIPY ^® ), diketopyrrolo-pyrroles, fluorindines, (poly)methines (including cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines, periones , perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes, xanthenes.

Mention may also be made of the fluorescent dyes described in the documents EP 1133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954 and those listed in the encyclopedia "The chemistry of synthetic dye" by K VENKATARAMAN, 1952, Academic press vol 1 to 7, in the encyclopedia "Kirk Othmer" "Chemical technology", chapter "dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of the encyclopedia "ULLMANN's ENCYCLOPEDIA of Industrial chemistry" 7th edition, Wiley and sons, in The Handbook — A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes/Invitrogen – Oregon 2005 distributed via the Internet or in previous printed editions.

According to a preferred variant of the invention, the fluorescent dye or dyes are cationic and comprise at least one quaternary ammonium radical such as those of formula (IX) below:

W ⁺ –[C(R _c )=C(R _d )] _m' –Ar, Q ^-

(IX)
formula (IX) in which:
● W ⁺ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted by one or more (C ₁ -C ₈ )alkyl groups optionally substituted in particular by one or more hydroxyl groups;
● Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (C ₁ -C ₈ )alkyl groups, preferably C ₁ -C ₄ such as methyl; iii) one or more hydroxyl groups; iv) one or more (C ₁ -C ₈ )alkoxy groups such as methoxy; v) one or more hydroxy(C ₁ -C ₈ )alkyl groups such as hydroxyethyl, vi) one or more amino or (di)(C ₁ -C ₈ )alkylamino groups, preferably with the C ₁ -C alkyl part ₄ optionally substituted by one or more hydroxyl such as (di)hydroxyethylamino, vii) by one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidinyl or 5 or 6 membered heteroaryl such as pyrrolidinyl, pyridinyl and imidazolinyl;
● m' represents an integer between 1 and 4 inclusively, particularly m is 1 or 2; more preferably 1;
● R _c , R _d , identical or different, represent a hydrogen atom or an optionally substituted (C ₁ -C ₈ )alkyl group, preferably C ₁ -C ₄ , or else R _c contiguous to W ⁺ and/or R _d contiguous to Ar form with the atoms which carry them a (hetero)cycloalkyl, particularly R _c is contiguous to W ⁺ and forms a (hetero)cycloalkyl such as cyclohexyl;
● Q ^- is an organic or inorganic anionic counterion as previously defined.

Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine, orceins. It is also possible to use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

Preferably, the dyestuff(s) are chosen from pigments and mixtures thereof, more preferably from carbon black, iron oxides, in particular black, and micas coated with iron oxide, red iron oxides (iron oxide (III), also called ferric oxide), triarylmethane pigments, in particular blue and purple, such as BLUE 1 LAKE, azo pigments, in particular red, such as D&C RED 7, and mixtures thereof.

According to a particular embodiment of the invention, the dyestuff(s) are included in the oily dispersion (A). In other words, according to this embodiment, the oily dispersion (A) comprises:
(1) one or more particles of ethylenic polymers as defined above,
(2) one or more stabilizing agents, different from the said ethylenic polymer(s) a), as defined above
(3) one or more hydrocarbon oils as defined above, and
(4) one or more dyestuffs chosen from pigments, direct dyes and mixtures thereof, and preferably from pigments and mixtures thereof.

The total content of the dyestuff(s), used in the dyeing process according to the present invention, preferably ranges from 0.5 to 15% by weight, and more preferably from 1 to 10% by weight, relative to the total weight of the composition comprising them.

The oily dispersion (A) and/or the composition (B) and/or optionally the composition (C) used in the dyeing process according to the present invention may optionally also comprise one or more additional compounds different from the compounds defined above. -before, preferably chosen from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof, anionic, cationic, nonionic, amphoteric, zwitterionic polymers and mixtures thereof, inorganic or organic thickening agents, and in particular anionic, cationic, nonionic or amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones volatile, modified or unmodified, film-forming agents, ceramides, preservatives, opacifying agents.

Preferably, when the additional compound(s) above are present in the oily dispersion (A) and/or the composition (B) and/or optionally the composition (C) according to the invention, the additional compound(s) are in generally present in an amount comprised for each of them between 0.01 and 20% by weight relative to the weight of the composition comprising them.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties inherently attached to the compositions of the invention are not, or substantially not, altered by the addition(s) envisaged.

Coloring process

The process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprises:
(i) a step consisting in treating said keratin fibers with cold plasma at atmospheric pressure (1.013·10 ⁵ Pa), followed by
(ii) a step consisting in applying to said keratin fibers an oily dispersion (A) as defined above,
(iii) a step consisting in applying to said keratin fibers a composition (B) as defined above; And
(iv) a step consisting in applying to said keratinous fibers one or more dyestuffs chosen from pigments, direct dyes and mixtures thereof, said dyestuff(s) being present in the oily dispersion (A) and/or in the composition ( B) and/or in a composition (C);
it being understood that steps (ii), (iii) and (iv) can be carried out simultaneously or sequentially.

According to a first particular embodiment of the method of the invention, steps (ii), (iii) and (iv) are carried out simultaneously, that is to say together. In other words, the oily dispersion (A) as defined above, the composition (B) as defined above and the dyestuff(s) as defined above are applied together or else in the form of a ready-to-use composition. the use resulting from the extemporaneous mixing of said oily dispersion (A), of said composition (B) and of said dyestuff(s).

According to this first embodiment, the method according to the invention is a two-step method, comprising:
- a first step consisting in treating said keratin fibers with cold plasma at atmospheric pressure (1.013 10 ⁵ Pa), followed by
- a second step consisting in simultaneously applying to said keratin fibers an oily dispersion (A), as defined above, a composition (B) as defined above and one or more dyestuffs as defined above or a ready-to-use composition job as defined above.

According to a first advantageous variant of this embodiment, the said dyestuff(s) are initially present in the oily dispersion (A). According to this first variant, the oily dispersion (A) and the composition (B) are applied together or the ready-to-use composition applied in the second stage of the process results from the extemporaneous mixing of the oily dispersion (A) and the composition (B).

According to a second advantageous variant of this embodiment, the said dyestuff(s) are initially present in the composition (B). According to this second variant, the oily dispersion (A) and of the composition (B) are applied together or the ready-to-use composition applied in the second stage of the process results from the extemporaneous mixing of the oily dispersion (A) and of the composition (B).

According to a third advantageous variant of this embodiment, the said dyestuff(s) are initially present in a composition (C). According to this first variant, the oily dispersion (A), the composition (B) and the composition (C) are applied together or the ready-to-use composition applied in the second stage of the process results from the extemporaneous mixing of the oily dispersion ( A), composition (B) and composition (C).

According to a second particular embodiment of the method of the invention, steps (ii), (iii) and (iv) are carried out sequentially in no particular order. Thus, according to this embodiment, step (iii) can be carried out after step (ii) and before step (iv) or conversely, step (iii) can be carried out after step (iv). ) and before step (ii).

According to an advantageous variant of this embodiment, steps (ii) and (iv) are carried out simultaneously before step (iii). Thus, according to this variant, the dyestuff(s) as defined above are preferably present in the oily dispersion (A) of the invention. The latter is then applied to the keratin fibers before application of composition (B) as defined previously.

When steps (ii), (iii) and (iv) are carried out sequentially, they are preferably carried out without an intermediate rinsing step between each step.

The bath ratio of the composition(s) applied after the cold plasma treatment step of the process preferably varies from 0.1 to 10, and more preferably from 0.2 to 5. bath, within the meaning of the present invention is meant the ratio between the total weight of the composition applied and the total weight of keratin fibers to be treated.

After the last step of the process, the keratin fibers can optionally be rinsed with water or washed with shampoo. The keratin fibers are then optionally dried using a hair dryer or a helmet or left to dry in the open air.

The kit

The invention also relates to a kit comprising:
- a cold plasma generator, and
- a multi-compartment device comprising:
● a first compartment containing an oily dispersion (A) as defined previously,
● a second compartment containing a composition (B) as defined previously, and
● optionally a third compartment containing one or more dyestuffs chosen from pigments, direct dyes and mixtures thereof.

The contents of each compartment of the kit can be released either sequentially or simultaneously.

The kit may in particular be in the form of a box.

The assembly for packaging the compositions, that is to say the device with several compartments, is in known manner any packaging suitable for storing cosmetic compositions (bottles, tube, spray bottle, aerosol bottle in particular).

Such a kit makes it possible to implement the process for dyeing keratin fibers according to the invention.

The following examples serve to illustrate the invention without, however, being of a limiting nature.

Examples

Example 1:
The oily dispersions (A) are formed as a whole [particles of ethylenic polymers (1) + stabilizing agent (2)] at:
- 70% by weight of ethyl acrylate,
- 10% by weight of maleic anhydride, and at
- 20% by weight of isobornyl acrylate.

The preparation of these oily dispersions was carried out in a 1 liter controlled reactor. The synthesis is carried out in two steps:
During a first step, isobornyl acrylate is polymerized in isododecane / ethyl acetate (60/40) in the presence of a small amount of ethyl acrylate and a radical initiator (T21S). In the first step, the isobornyl acrylate/ethyl acrylate mass ratio is 92/8.
During the second step, the rest of the ethyl acrylate and the maleic anhydride are poured in the presence of isododecane/ethyl acetate (60/40) and Trigonox 21S (T21S) radical initiator.
After stripping, the polymer has a solids content of 52% in isododecane. The ratios used to obtain the stabilizer and the particulate core are summarized in Table 1 below:

Mass percentage
Stabilizing Agent – Particulate Core Monomer Mass percentage in the stabilizer
and the particulate heart Stabilizing agent 22 Isobornyl acrylate 92 Ethyl acrylate 8 Particle heart 78 Maleic anhydride 13

The quantities of reagents are given in the tables below:

Step 1
Reagents Mass (g) Isobornyl Acrylate 50 Ethyl Acrylate 4 T21S 0.54 Isododecane / AcOEt (60/40) 96

Isododecane added between the two steps:
Reagent Mass (g) Isododecane / AcOEt (60/40) 80

2nd step :
Reagents Mass (g) Mass added in beaker for casting (g) Ethyl Acrylate 171 196.65 Maleic Anhydride 25 28.7 T21S 1.96 2.25 Isododecane / AcOEt (60/40) 196 225.4

Experimental protocol :
Isododecane/ethyl acetate (60/40), Isobornyl Acrylate, Ethyl Acrylate and T21S are introduced into a reactor at the bottom of the tank. The medium is heated to 90° C., under argon and with stirring. The dry extract during this first step is 35.9%.
After 2 h of heating, the NMR indicates a consumption of 97% of Isobornyl Acrylate (Consumption of Ethyl Acrylate: 97%).
After 2 h of reaction, isododecane/ethyl acetate (60/40) are introduced into the base stock. Heat to 90°C in the middle.
Once the medium has reached 90° C., ethyl acrylate/maleic anhydride, isododecane/ethyl acetate (60/40), and T21S are introduced over 2 hours by pouring. At the end of the casting the medium is milky. The dry extract is 40%.
After 7 hours of synthesis, traces of the starting monomers remain.
A stripping of 1L of isododecane and ethyl acetate is then carried out (the NMR indicates that there are no more monomers and the ethyl acetate is completely removed from the dispersion). The dry extract is about 52%.

Example 2:

1) Preparation of the compositions
The oily dispersion (A) and the composition (B) according to the invention were prepared from the ingredients mentioned in the tables below, and whose contents are expressed in percentage by weight relative to the total weight of the composition. including.

Ingredients Oily dispersion (A) Ethyl acrylate/maleic anhydride/isobornyl acrylate copolymer (70/10/20) prepared according to Example 1 30 Iron oxide 6 Isododecane 64

Ingredients Membership (B) Chitosan 5 Water 95

2) Protocol
The oily dispersion (A) and the composition (B) thus obtained are then applied according to the following processes:

Process 1 (comparative):
The oily dispersion (A) is applied to locks of 90% white natural hair at the rate of 0.5 grams of dispersion per gram of lock. The locks of hair are then combed, then dried with a hair dryer.

Composition (B) is then applied to said locks of hair at the rate of 0.5 grams of composition per gram of lock. The locks of hair are then combed, then dried with a hair dryer.

Method 2 (invention):
A cold plasma treatment, generated using a piezoelectric generator, is performed on locks of natural hair that are 90% white and dry. The generator is applied for 4min40 on each side of the locks.
At the end of this treatment, the oily dispersion (A) is applied to the locks of hair at the rate of 0.5 grams of dispersion per gram of lock. The locks of hair are then combed, then dried with a hair dryer.

Composition (B) is then applied to said locks of hair at the rate of 0.5 grams of composition per gram of lock. The locks of hair are then combed, then dried with a hair dryer.

Process 3 (invention):
A cold plasma treatment, generated by dielectric barrier discharges, is carried out on locks of natural hair that are 90% white and dry. The generator is applied for 3min on each side of the locks.
At the end of this treatment, the oily dispersion (A) is applied to the locks of hair at the rate of 0.5 grams of dispersion per gram of lock. The locks of hair are then combed, then dried with a hair dryer.

Composition (B) is then applied to said locks of hair at the rate of 0.5 grams of composition per gram of lock. The locks of hair are then combed, then dried with a hair dryer.

At the end of each of the processes mentioned above, the locks of hair are washed according to the following protocol:
The locks are washed with a Garnier Ultra Doux shampoo. The locks are then rinsed under water, before being combed and dried with a hair dryer. This protocol is repeated five times for each of the locks.

The persistence of the color of the locks is then evaluated by colorimetry in the CIE L*a*b* system using a Minolta CM 3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included).

In this L*a*b* system; L* represents the lightness of the color, a* indicates the green/red color axis and b* the blue/yellow color axis. The lower the value of L*, the darker and more powerful the coloration. The lower the value of a* and the greener the color, the higher the value of a* the more red the color. The lower the value of b* and the more blue the color, the higher the value of b* the more yellow the color.

The persistence of the coloring is evaluated by the difference in color ΔE* between the colored locks before shampoo and the locks of the processes 1, 2 and 3 above after having undergone 5 shampoos. ΔE* is defined according to the following equation:

In this equation, L*, a* and b* represent the values measured after coloring the hair and after having undergone 5 shampoos and L ₀ *, a ₀ * and b ₀ * represent the values measured after coloring the hair but without shampooing.

The lower the value of ∆E*, the greater the resistance to shampoo of the colorations.

3) Results
The colorimetric values obtained after coloring the locks (before and after shampooing) with processes 1 to 3 are given in the table below.

I* To* b* ΔE* Colored locks without shampoo 39.44 27.82 20.73 0 Method 1 (comparative) after 5 shampoos 44.73 23.06 18.48 7.46 Method 2 (invention) after 5 shampoos 38.86 27.07 20.42 1.00 Process 3 (invention) after 5 shampoos 37.03 27.87 21.16 2.45

The results obtained above show that the color of the locks treated with the method according to the present invention, that is to say having undergone a cold plasma pre-treatment (methods 2 and 3) has a good remanence to shampoos unlike to the color of locks that have not undergone any pre-treatment (method 1). Indeed, the values of ΔE* measured on the locks colored according to the method of the invention (methods 2 and 3) are much lower than that obtained with the comparative method (method 1).

Claims (18)

Process for dyeing keratin fibres, in particular human keratin fibers such as the hair, comprising:
(i) a step consisting in treating said keratin fibers with cold plasma at atmospheric pressure (1.013·10 ⁵ Pa), followed by
(ii) a step consisting in applying to said keratin fibers an oily dispersion (A), preferably anhydrous, comprising:
(1) one or more particles comprising one or more ethylenic polymers chosen from:
a) ethylenic homopolymers of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl,
b) ethylenic copolymers of b1) (C ₁ -C ₄ )(alkyl)acrylate, (C ₁ -C ₄ )alkyl and of b2) ethylenic monomers comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or or aryl, and
c) ethylenic copolymers of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl;
(2) one or more stabilizing agents, different from the said ethylenic polymer(s) (1), chosen from:
d) ethylenic homopolymers of (C ₁ -C ₆ )(alkyl)acrylate of (C ₉ -C ₂₂ )alkyl, and
e) ethylenic copolymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₉ -C ₂₂ )alkyl and of (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, and
(3) one or more hydrocarbon oils,
(iii) a step consisting in applying to said keratin fibers a composition (B) comprising one or more amino compounds chosen from polyamino compounds comprising at least two groups chosen from primary amines, secondary amines and their mixtures, amino alkoxysilanes and mixtures thereof; And
(iv) a step consisting in applying to said keratinous fibers one or more dyestuffs chosen from pigments, direct dyes and mixtures thereof, said dyestuff(s) being present in the oily dispersion (A) and/or in the composition ( B) and/or in a composition (C);
it being understood that steps (ii), (iii) and (iv) can be carried out simultaneously or sequentially. Process according to the preceding claim, characterized in that the cold plasma is chosen from direct DBD type plasmas generated by dielectric barrier discharges, FE-DBD type plasmas generated by dielectric barrier discharges with floating electrodes, jet plasmas, hybrid plasmas, plasma needle , plasmas generated by corona effect, and plasmas generated using a piezoelectric generator. Process according to any one of the preceding claims, characterized in that the ethylenic polymer(s) (1) are chosen from acrylate homopolymers a), resulting from the polymerization of identical monomers of formula (Ia):
H ₂ C=C(R)-C(O)-O-R' (Ia)
formula (Ia) in which
- R represents a hydrogen atom or a C ₁ to C ₄ alkyl group, linear or branched, such as methyl, and
- R' represents a C ₁ to C ₄ alkyl group, linear or branched, such as methyl or ethyl. Process according to either of Claims 1 and 2, characterized in that the ethylenic polymer or polymers (1) are chosen from acrylate copolymers c), resulting from the copolymerization:
- of at least two monomers, different from each other, of formula (Ia) as defined in claim 3, preferably of at least two monomers, different from each other, of ( C ₁ -C ₄ alkyl meth)acrylate, such as methyl acrylate and ethyl acrylate, and
- optionally at least one monomer of formula (Ib)
_H2C =C(R)-C(O)-OH (Ib)
formula (Ib) in which R is as defined in claim 3 for formula (Ia), preferably an acrylic acid monomer. Process according to the preceding claim, characterized in that the ethylenic polymer or polymers (1) are copolymers resulting from the polymerization of at least one C ₁ to C ₄ alkyl (meth)acrylate monomer, preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate tert-butyl, and mixtures thereof and more preferably from methyl (meth)acrylate, ethyl (meth)acrylate and mixtures thereof. Process according to any one of Claims 1 or 2, characterized in that the ethylenic monomer(s) b2) comprising one or more carboxy, anhydride, phosphoric acid, sulphonic acid and/or aryl groups are chosen from:
- the compounds of formula R ¹ (R ² )C=C(R ³ )-Acid with R ¹ , R ² and R ³ , which are identical or different, representing a hydrogen atom or a CO ₂ H, H ₂ PO group ₄ , or SO ₃ H, and Acid representing a carboxy group, a phosphoric acid or a sulphonic acid, it being understood that R ¹ , R ² and R ³ cannot simultaneously represent a hydrogen atom;
- the compounds of formula H ₂ C=C(R)-C(O)-N(R')-Alk-Acid with R and R', which are identical or different, representing a hydrogen atom, or a C alkyl group ₁ to C ₄ , linear or branched; Alk representing a (C ₁ -C ₆ )alkylene group optionally substituted by at least one group chosen from Acid as defined above and hydroxy; and Acid being as defined above, preferably a carboxy group or a sulphonic acid;
- the compounds of formula Ar-(R ^a )C=C(R ^b )-R ^c with R ^a , R ^b and R ^c , identical or different, representing a hydrogen atom or a C ₁ to C alkyl group ₄ , linear or branched, and Ar representing an aryl group, optionally substituted by at least one CO ₂ H, H ₂ PO ₄ or SO ₃ H acid group;
- maleic anhydrides of formula (4a) and (4b):

formulas (4b) and (4b) in which R _a , R _b and R _c , which are identical or different, represent a hydrogen atom or a linear or branched C ₁ to C ₄ alkyl group; And
- the compounds of formula H ₂ C=C(R)-C(O)-OH with R representing a hydrogen atom, or a C ₁ to C ₄ alkyl group, linear or branched. Process according to the preceding claim, characterized in that the ethylenic polymer(s) of the particles (1) are copolymers resulting from the copolymerization b1) of at least one C ₁ to C ₄ alkyl (meth)acrylate monomer, of preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate and mixtures thereof, and b2) from at least one ethylenic monomer chosen from maleic anhydrides of formula (4a) and (4b) . Process according to any one of the preceding claims, characterized in that the total content of the said ethylenic polymer particle(s) ranges from 20 to 50% by weight, and preferably from 25 to 50% by weight, relative to the total weight oily dispersion (A). Process according to any one of the preceding claims, characterized in that the said stabilizing agent or agents (2) are chosen from d) ethylenic homopolymers of (C ₁ -C ₆ )(alkyl)acrylate of (C ₉ -C ₂₂ ) alkyl, preferably from ethylenic homopolymers of (C ₁ -C ₄ )(alkyl)acrylate of (C ₉ -C ₁₈ )alkyl, and more preferably from ethylenic homopolymers resulting from the polymerization of monomers of formula H ₂ C=C (R)-C(O)-O-R'' with R representing a hydrogen atom or a C ₁ to C ₆ , preferably C ₁ to C ₄ , linear or branched alkyl group, and R'' representing a C ₉ to C ₂₂ , preferably C ₉ to C ₁₈ , linear or branched alkyl group. Process according to any one of Claims 1 to 8, characterized in that the said stabilizing agent or agents (2) are chosen from the ethylenic copolymers e) of formula (IIa) and (IIb):
H ₂ C=C(R)-C(O)-O-R' (IIa) H ₂ C=C(R)-C(O)-O-R'' (IIb)
formulas (IIa) and (IIb) in which,
- R, which are identical or different, represent a hydrogen atom or a C ₁ to C ₄ alkyl group, linear or branched,
- R' represents a C ₁ to C ₄ alkyl group, linear or branched, and
- R'' represents an alkyl group, linear or branched, C ₉ to C ₂₂ , preferably C ₁₀ to C ₂₀ , and in particular a (C _2n )alkyl group with n representing an integer equal to 5, 6, 7, 8, 9, or 10. Process according to any one of the preceding claims, characterized in that the weight ratio between the content of the stabilizer(s) (2), other than the ethylenic polymers and the content of the particle(s) of ethylenic polymers (1) ranges from 0 .5 to 2, and preferably this weight ratio is equal to 1 Process according to any one of the preceding claims, characterized in that the said hydrocarbon-based oil or oils (3) are chosen from branched C ₈ to C ₁₆ alkanes, linear C ₈ to C ₁₆ alkanes, short-chain esters , having 3 to 8 carbon atoms, hydrocarbon oils of vegetable origin, synthetic ethers having 10 to 40 carbon atoms, linear or branched hydrocarbons with more than 16 carbon atoms, of mineral or synthetic origin , synthetic esters, fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having from 12 to 26 carbon atoms, and mixtures thereof. Process according to any one of the preceding claims, characterized in that the oily dispersion (A) is anhydrous. Process according to any one of the preceding claims, characterized in that the said amino compound or compounds are chosen from amino alkoxysilanes and mixtures thereof, preferably from the compounds of formula (III) below:
R'₁-If(OR’₂)_z(R'₃)_x(III)
formula (III) in which:
● R'₁is a C alkyl chain₁to C₁₀, linear or branched, saturated or unsaturated, cyclic or acyclic, substituted by one or more groups chosen from the groups:
- primary amine NH₂or secondary N(H)R with R representing a C alkyl group₁to C₄, linear or ramified,
- aryl or aryloxy substituted by an amino group, a group (C₁-VS₄)alkylamino or by a C aminoalkyl group₁to C₄, And
- amide –C(O)-NH₂or urea –NH-C(O)-NH₂;
R'₁being optionally interrupted in its alkyl chain by one or more heteroatoms (in particular O, S, NH), a carbonyl group (CO), or their combination such as ester –C(O)-O- or amide –C(O)- NH-, R'₁being bonded to the silicon atom directly via a carbon atom,
● R'₂and R'₃, identical or different, represent a C alkyl chain₁to C₆, linear or ramified,
● z denotes an integer ranging from 1 to 3, and
● x denotes an integer ranging from 0 to 2, with z+x =3;
and more preferably from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropyl methyldiethoxysilane, N-(2-aminoethyl)-3-amino propyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N-(2-aminoethylaminomethyl) phenethyltrimethoxysilane, and mixtures thereof. Process according to any one of Claims 1 to 13, characterized in that the said amino compound or compounds are chosen from polyamino polymers, and preferably from:
- poly((C ₂ -C ₅ )alkylene imines);
- poly(allylamine);
- polyvinylamines and their copolymers, in particular with vinylamides;
- polyamino acids having NH ₂ groups;
- amino dextran;
- polyvinyl amino alcohol;
- copolymers based on acrylamidopropylamine;
- chitosan;
- polydi(C ₁ -C ₄ )alkylsiloxanes;
- amodimethicones;
- polydimethylsiloxane containing aminoethyl iminopropyl group in nonionic microemulsion at 15% preserved;
- polyether amines;
- polytetrahydrofuran (or polytetramethylene glycol) α, ω-diamine, polybutadienes α, ω-diamine;
- polyamidoamine (PANAM) dendrimers with terminal amine functions;
- poly(meth)acrylates or poly(meth)acrylamides carrying lateral primary or secondary amine functions; And
- their mixtures. Process according to the preceding claim, characterized in that the amino compound or compounds are chosen from
- chitosan,
- polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IVa):
(IVa)
formula (IVa) in which,
R ^a , and R ^b , which are identical or different, represent a (C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )alkoxy, aryl, aryloxy, aryl(C ₁ -C ₄ )alkyl, or aryl(C ₁ -C ₄ )alkoxy,
R ^c and R' ^c , which are identical or different, represent a hydrogen atom, a (C ₁ -C ₄ )alkyl group, an amino(C ₁ -C ₄ )alkyl or (C ₁ -C ₄ )alkylamino( C ₁ -C ₄ )alkyl,
X represents a covalent bond or an oxygen atom,
ALK and ALK', identical or different, represent a (C ₁ -C ₆ )alkylene group,
n represents an integer greater than 2 and more particularly the value of n is such that the weight-average molecular weight of the compound of formula (IVa) is between 500 and 55,000;
- amodimethicones of formula (IVd):
(IVd)
formula (IVd) in which,
R ^a , and R ^b , which are identical or different, represent a (C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )alkoxy, aryl, aryloxy, aryl(C ₁ -C ₄ )alkyl group, or aryl(C ₁ -C ₄ )alkoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
R ^c represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group,
R ^e represent a hydroxy, (C ₁ -C ₄ )alkoxy, amino, or (C ₁ -C ₄ )alkylamino group,
R ^f , represents a (C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )alkoxy group, a hydroxy group or -O–(SiR ₂ ) _x -R' with R representing a (C ₁ -C ₄ ) group )alkyl or (C ₁ -C ₄ )alkoxy and R' representing a (C ₁ -C ₄ )alkoxy or hydroxy group,
R ^g represents a hydrogen atom or a (C ₁ -C ₆ )alkyl group,
ALK and ALK', identical or different, represent a (C ₁ -C ₆ )alkylene group,
n and m, identical or different, represent an integer greater than 2,
p and x represent integers greater than or equal to 0; And
- their mixtures. Process according to any one of the preceding claims, characterized in that the dyestuff(s) are chosen from pigments, and preferably from white organic pigments, colored organic pigments, and mixtures thereof. Kit including:
- a cold plasma generator as defined in claim 2, and
- a multi-compartment device comprising:
● a first compartment containing an oily dispersion (A) as defined in any one of claims 1 to 13,
● a second compartment containing a composition (B) as defined in any one of claims 1 and 14 to 16, and
● optionally a third compartment containing one or more dyestuffs as defined in any one of claims 1 and 17.