FR3113241A1 - COMPOSITION COMPRISING A POLYMER COMPRISING AT LEAST ONE CATIONIC (METH)ACRYLAMIDE MOTIF, A PARTICULAR SILICONE AND A CHEMICAL OXIDIZING AGENT AND/OR AN OXIDATION COLOR - Google Patents

Abstract

Composition comprising a polymer comprising at least one cationic (meth)acrylamide unit, a particular silicone and a chemical oxidizing agent and/or an oxidation dye The present invention relates to a cosmetic composition comprising: has. one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s); b. an oil-in-water emulsion having a D50 particle size of less than 350 nm and comprising: - a mixture of silicones comprising (i) one or more dialkylpolysiloxane(s) terminated by trialkylsilyl having a viscosity of 40,000 to less than 100,000 mPa.s at 25°C and (ii) one or more amino silicone( (s) having a viscosity of 1,000 to 15,000 mPa.s at 25°C and an amine number of 2 to 10 mg of KOH per gram of amino silicone, - an emulsifier blend comprising one or more non-ionic emulsifier(s), wherein the emulsifier blend has an HLB value of 10 to 16, and - some water ; vs. one or more chemical oxidizing agent(s) and/or one or more oxidation tint(s); d. optionally one or more cationic polymer(s) different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s). Figure for abstract: None

Description

COMPOSITION COMPRISING A POLYMER COMPRISING AT LEAST ONE CATIONIC (METH)ACRYLAMIDE MOTIF, A PARTICULAR SILICONE AND A CHEMICAL OXIDIZING AGENT AND/OR AN OXIDATION COLOR

The present invention relates to a cosmetic composition for treating keratin fibres, and in particular human keratin fibers such as hair, which comprises one or more polymers comprising one or more cationic acrylamide and/or methacrylamide unit(s). or quaternized(s), a specific oil-in-water type silicone emulsion, and one or more chemical oxidizing agent(s) and/or one or more oxidation tint(s).

The invention also relates to a cosmetic treatment process, in particular for dyeing and/or lightening keratin fibers using this composition. In particular, the present invention also relates to a particular process for dyeing keratin fibers. The present invention also relates to a particular process for lightening keratin fibres.

The invention also relates to the use of such a composition for dyeing and/or lightening keratin fibers.

Finally, the invention relates to a kit comprising at least two compartments, a first compartment comprising a first composition comprising one or more oxidation shade(s), a second compartment comprising a second composition comprising one or more oxidizing agent(s). s) chemical(s), one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s), which are included in the first and/or second composition, and an emulsion of specific oil-in-water type silicone being included in the first and/or second composition.

It is known practice to dye and/or lighten keratin fibres, and in particular human hair, with oxidizing compositions or tinting compositions containing oxidation tinting precursors, which are generally known as " oxidation bases”, in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic bases.

Oxidation tint precursors are compounds which are initially non-colored or moderately colored, which develop their tinting power on the hair in the presence of oxidizing agents, leading to the formation of colored compounds. The formation of these colored compounds results either from an oxidative condensation of the "oxidation bases" with themselves, or from an oxidative condensation of the "oxidation bases" with compounds modifying the coloration, or "couplers", which are generally present in the dye compositions used in oxidation dyeing and are represented more particularly by meta-phenylenediamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds.

The variety of molecules used, consisting on the one hand of “oxidation bases” and on the other of “couplers”, makes it possible to obtain a very rich palette of colors.

However, these treatments can damage the hair and its cosmetic properties. Also, there is a need to offer consumers hair dyeing and/or lightening products which confer good lightening performance and/or dyeing performance such as intensity, chromaticity, selectivity with a high level of cosmetic properties. of said fibers, such as softness, smoothness, manageability and detangling. These cosmetic properties can also be long lasting.

The compositions should give a satisfactory silicone deposit on the keratin fibres.

The applicant has now discovered that a cosmetic composition comprising one or more polymers comprising at least one cationic or quaternized (meth)acrylamide unit, a specific oil-in-water type silicone emulsion, and one or more oxidizing agent(s) Chemical(s) and/or one or more oxidation tint(s) makes it possible to achieve the objectives outlined above.

Thus, the subject of the invention is a cosmetic composition comprising:

To. one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s);

b. an oil-in-water emulsion having a D50 particle size of less than 350 nm and comprising:

- a mixture of silicones comprising (i) one or more dialkylpolysiloxane(s) terminated by trialkylsilyl having a viscosity of 40,000 to less than 100,000 mPa.s at 25°C and (ii) one or more amino silicone(s) s) having a viscosity of 1,000 to 15,000 mPa.s at 25°C and an amine number of 2 to 10 mg of KOH per gram of amino silicone,

- an emulsifier blend comprising one or more non-ionic emulsifier(s), wherein the emulsifier blend has an HLB value of 10 to 16, and

- some water ;

vs. one or more chemical oxidizing agent(s) and/or one or more oxidation dye(s);

d. optionally one or more cationic polymer(s) different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s).

This cosmetic composition, when applied to keratin fibers, in particular human keratin fibers such as hair, provides good lightening performance and/or good dyeing performance such as intensity, chromaticity, selectivity, and leads to improved hair condition and quality, in terms of hair feel (e.g. smooth feel, soft feel, conditioning feel) and hair manageability (e.g. little or no frizz, styling ability/shaping ability, combing, detangling, desirable volume).

This cosmetic composition allows an increase in the silicone deposit on the hair compared to a similar composition which does not contain the specific polymer a.

The present invention also relates to a cosmetic treatment process, in particular for dyeing and/or lightening keratin fibres, preferably human keratin fibers such as hair, using this composition. In particular, the present invention also relates to a particular process for dyeing keratin fibres. The present invention also relates to a particular process for lightening keratin fibres.

Another subject of the invention is the use of the composition according to the invention for dyeing and/or lightening keratin fibers.

The present invention also relates to a kit comprising at least two compartments, a first compartment comprising a first composition comprising one or more oxidation shade(s), a second compartment comprising a second composition comprising one or more oxidizing agent(s) ) chemical(s), the first and/or second composition comprising one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) as defined above, and the specific oil-in-water emulsion as defined above.

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

In the text below, unless otherwise specified, the limits of a range of values are included within that range, for example in the expressions "between" and "ranging from ... to ...".

In addition, the expression "at least one" used in the present description is equivalent to the expression "one or more".

Polymer(s) comprising at least one pattern ( cationic or quaternized meth)acrylamide

The first essential component of the cosmetic composition according to the present invention is one or more polymer(s) comprising one or more cationic or quaternized (meth)acrylamide unit(s). These polymers are non-silicone, ie they do not contain any silicon (Si) atoms.

The polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s) can be cationic and/or amphoteric polymers.

By “cationic and/or amphoteric polymer(s)”, is meant one or more cationic polymer(s), one or more amphoteric polymers or the mixture of one or more polymer(s) cationic(s), and one or more amphoteric polymers.

The polymer(s) comprising one or more cationic or quaternized (meth)acrylamide units may be chosen from cationic polymers, amphoteric polymers and mixtures thereof. Most preferably, they are chosen from cationic polymers.

The cationic charge density of the polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s) may preferably be less than or equal to 6 meq/g, more preferably less than or equal to 5 meq/g. g, and better still less than or equal to 4 meq/g. This cationic charge density is advantageously from 0.5 to 6 meq/g, more preferably from 1 to 5 meq/g, and even more preferably from 1.5 to 4 meq/g.

The expression “cationic polymer” means any polymer comprising cationic groups and/or groups which can be ionized into cationic groups, and not comprising anionic groups and/or groups which can be ionized into anionic groups. Preferably, the cationic polymer is hydrophilic or amphiphilic. The preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and/or quaternary amine groups which can either form part of the main chain of the polymer or be carried by a side substituent which is directly linked to it.

The polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s) which can be used in the present invention are preferably chosen from homopolymers or copolymers comprising at least one of the units of the formulas following:

(II) (III)

in which :

- the R ₁ s, which may be identical or different, denote a hydrogen atom or a CH ₃ radical;

- the R's, which may be identical or different, denote a linear or branched C ₁ to C ₁₂ alkyl radical, preferably a linear C ₁ to C ₆ alkyl radical, optionally substituted by one or more hydroxyl radicals;

- R ₅ , R ₆ and R ₇ , which may be identical or different, denote a linear or branched C ₁ to C ₁₈ alkyl radical or a benzyl radical, preferably a linear or branched C ₁ to C ₆ alkyl radical;

- R ₈ and R ₉ , which may be identical or different, denote a hydrogen atom or a linear or branched C ₁ to C ₆ alkyl radical, preferably a methyl or ethyl; And

- Y ^- denotes an anion derived from a mineral or organic acid or from a halide, preferably a bromide, chloride, acetate, borate, citrate, tartrate, bisulphate, bisulphite, methosulphate, sulphate or phosphate anion.

The polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s) may also contain one or more units derived from comonomers which may be chosen from the families of acrylamides, methacrylamides, diacetone acrylamides, acids acrylics or methacrylics or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters, preferably chosen from the families of acrylamides and methacrylamides, and more preferably acrylamide or methacrylamide.

Among these homo- or co-polymers, mention may be made of:

- halide homopolymers, preferably acrylamidopropyltrimonium chloride, such as the product N-DURHANCE A-1000 from ASHLAND,

- copolymers of halides, preferably chloride, of acrylamidopropyltrimonium and of acrylamide, such as the product sold under the name Salcare® SC 60 by the company BASF or sold under the name N-Hance SP 100 or N-Durhance AA2000 by the company Ashland, or the product sold under the name N-Hance 4572 (conditioning polymer ex Aqualon aqua 4572) by the company Ashland, i.e. a mixture of

- guar hydroxypropyltrimonium chloride and acrylamidepropyltrimonium chloride/acrylamide copolymer,

- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as those sold under the name STYLEZE CC 10 by ISP,

- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name GAFQUAT HS 100 by the company ISP.

The polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s) which can be used in the present invention can also be chosen from amphoteric polymers.

The expression “amphoteric polymer” means any polymer comprising cationic groups and/or groups which can be ionized into cationic groups, and comprising anionic groups and/or groups which can be ionized into anionic groups.

The amphoteric polymers can be chosen more particularly from amphoteric polymers comprising a repetition of:

(i) one or more units derived from a monomer of the (meth)acrylamide type,

(ii) one or more units derived from a monomer of the (meth)acrylamidoalkyltrialkylammonium type, and

(iii) one or more units derived from an acid monomer of (meth)acrylic acid type.

Preferably, the units derived from a monomer of (meth)acrylamide type (i) are units of structure (VI) below:

(VI)

in which :

- R ₁ denotes a hydrogen atom or a CH ₃ radical; And

- R ₂ denotes an NR ₃ R ₄ radical, in which R ₃ and R ₄ , which may be identical or different, denote a hydrogen atom or a linear or branched C ₁ to C ₁₂ alkyl radical, optionally substituted by a or more hydroxyl radicals, preferably R ₂ denotes an amino, dimethylamino, tert-butylamino, dodecylamino or -NH-CH ₂ OH radical.

Preferably, said amphoteric polymer comprises a repetition of a single unit of formula (VI).

The unit derived from a monomer of (meth)acrylamide type of formula (VI) in which R ₁ denotes a hydrogen atom and R ₂ is an amino radical (NH ₂ ) is particularly preferred. It corresponds to the acrylamide monomer per se.

Preferably, the units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii) are units of structure (VII) below:

(VII)

in which :

- R ₁ denotes a hydrogen atom or a CH ₃ radical;

- R ₅ , R ₆ and R ₇ , which may be identical or different, denote a linear or branched C ₁ to C ₆ alkyl radical, preferably a linear or branched C ₁ to C ₄ alkyl radical;

- n denotes an integer ranging from 1 to 6, preferably from 1 to 4; And

- Y ^- denotes an anion derived from a mineral or organic acid or a halide, preferably a bromide, chloride, acetate, borate, citrate, tartrate, bisulphate, bisulphite, methosulphate, sulphate or phosphate anion.

Preferably, said amphoteric polymer comprises a repetition of a single unit of formula (VII).

Among these units derived from a monomer of the (meth)acrylamidoalkyltrialkylammonium type of formula (VII), those which are preferred are those derived from the monomer methacrylamidopropyltrimethylammonium chloride, for which R ₁ denotes a methyl radical, n is equal to 3, R ₅ , R ₆ and R ₇ denote a methyl radical, and Y ⁻ denotes a chloride anion.

Preferably, the units derived from a monomer of (meth)acrylic acid type (iii) are units of formula (VIII):

(VIII)

in which :

- R ₁ denotes a hydrogen atom or a CH ₃ radical; And

- R ₂ denotes a hydroxyl radical or an NR ₃ R ₄ radical, in which R ₃ and R ₄ , which may be identical or different, denote a hydrogen atom or a linear or branched C ₁ to C ₁₂ alkyl radical, optionally substituted by a sulphonic group (-SO ₃ H), preferably R ₂ denotes an –NH-C(CH ₃ ) ₂ -CH ₂ -SO ₃ H radical.

The preferred units of formula (VIII) correspond to the monomers acrylic acid, methacrylic acid and 2-acrylamino-2-methylpropanesulfonic acid.

Preferably, the unit derived from a monomer of (meth)acrylic acid type of formula (VIII) is that derived from acrylic acid, for which R ₁ denotes a hydrogen atom and R ₂ denotes a hydroxyl radical.

The acidic monomer(s) of (meth)acrylic acid type may be unneutralized or partially or totally neutralized with an organic or inorganic base.

Preferably, said amphoteric polymer comprises a repetition of a single unit of formula (VIII).

According to a preferred embodiment of the invention, the amphoteric polymer(s) of this type comprises (comprises) at least 30% by mol of units derived from a monomer of (meth)acrylamide type ( i). Preferably, they comprise from 30 mol% to 70 mol% and more preferably from 40 mol% to 60 mol% of units derived from a monomer of the (meth)acrylamide type.

The content of units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii) can advantageously be from 10% by mol to 60% by mol and preferentially from 20% by mol to 55% by mol.

The content of units derived from an acid monomer of (meth)acrylic acid type (iii) can advantageously be from 1% by mol to 20% by mol and preferentially from 5% by mol to 15% by mol.

According to a particularly preferred embodiment of the invention, the amphoteric polymer of this type comprises:

- from 30% by mol to 70% by mol and more preferably from 40% by mol to 60% by mol of units derived from a monomer of (meth)acrylamide type (i),

- from 10% by mol to 60% by mol and preferably from 20% by mol to 55% by mol of units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii), and

- from 1% by mol to 20% by mol and preferably from 5% by mol to 15% by mol of units derived from a monomer of (meth)acrylic acid type (iii).

The amphoteric polymers of this type can also comprise additional units, other than the units derived from a monomer of the (meth)acrylamide type, of the (meth)acrylamidoalkyltrialkylammonium type and of the (meth)acrylic acid type as described above.

However, according to a preferred embodiment of the invention, said amphoteric polymers consist only of units derived from monomers (i) of (meth)acrylamide type, (ii) of (meth)acrylamidoalkyltrialkylammonium type and (iii) of acid type. (meth)acrylic.

As examples of amphoteric polymers which are particularly preferred, mention may be made of acrylamide/methacrylamidopropyltrimethylammonium chloride/acrylic acid terpolymers. Such polymers are listed in the CTFA dictionary (International Cosmetic Ingredient Dictionary) under the name Polyquaternium 53. Corresponding products are in particular sold under the names Merquat 2003 and Merquat 2003 PR by the company Nalco.

Another preferred type of amphoteric polymer is the polymer comprising a repetition of:

(i) one or more non-ionic units derived from a monomer of the (meth)acrylate type,

(ii) one or more units derived from a monomer of the (meth)acrylamidoalkyltrialkylammonium type, and

(iii) one or more units derived from an acid monomer of (meth)acrylic acid type.

The (meth)acrylamidoalkyltrialkylammonium type monomer and the (meth)acrylic acid type acid monomer (monomers (ii) and (iii) respectively) are as described above.

The nonionic monomers (i) of (meth)acrylate type are preferably chosen from C ₁ to C ₄ alkyl acrylates and methacrylates. A preferred monomer is methyl acrylate.

As particularly preferred examples of such amphoteric polymers, mention may be made of acrylic acid/methylacrylamidopropyltrimethylammonium chloride/methyl acrylates terpolymers. Such polymers are listed in the International Cosmetic Ingredient Dictionary CTFA under the name polyquaternium 47. Corresponding products are notably sold under the names Merquat 2001 and Merquat 2001N by the company Nalco.

The polymer(s) comprising one or more cationic or quaternized (meth)acrylamide unit(s) is (are) preferably chosen from:

- (meth)acrylamido(C ₁ to C ₆ alkyl)tri(C ₁ to C ₄ alkyl)ammonium/(meth)acrylamide halide copolymers, preferably (meth)acrylamidopropyltrimonium chloride/( meth)acrylamide, and more preferably copolymers of acrylamidopropyltrimonium chloride/acrylamide,

- (meth)acrylamido(C ₁ to C ₆ alkyl)tri(C ₁ to C ₄ alkyl)ammonium/(meth)acrylamide/(meth)acrylic acid halide terpolymers, preferably terpolymers of (meth)acrylamidopropyltrimonium/(meth)acrylamide/(meth)acrylic acid, more preferably acrylamide/methacrylamidopropyltrimethylammonium chloride/acrylic acid terpolymers,

- terpolymers of (meth)acrylamido(C ₁ to C ₆ alkyl)tri(C ₁ to C ₄ alkyl)ammonium halide/(C ₁ to C ₆ alkyl)/acid (meth )acrylic, preferably terpolymers of (meth)acrylamidopropyltrimonium chloride/(meth)acrylate (C ₁ to C ₆ alkyl)/(meth)acrylic acid; more preferably acrylic acid/methylacrylamidopropyltrimethylammonium chloride/methyl acrylates terpolymers,

- and mixtures thereof.

More preferably, the polymer(s) comprising one or more cationic or quaternized (meth)acrylamide unit(s) is (are) preferably chosen from:

- (meth)acrylamido(C ₁ to C ₆ alkyl)tri(C ₁ to C ₄ alkyl)ammonium/(meth)acrylamide halide copolymers, preferably (meth)acrylamidepropyltrimonium chloride/( meth)acrylamide, and most preferably acrylamidopropyltrimonium chloride/acrylamide copolymers.

The total quantity of polymer(s) comprising one or more cationic or quaternized (meth)acrylamide unit(s) present in the cosmetic composition of the present invention advantageously ranges from 0.01 to 5% by weight, preferably from 0.015 to 4% by weight, more preferably from 0.02 to 2% by weight, even more preferably from 0.03 to 1% by weight, and even more preferably from 0.04 to 0 5% by weight, based on the total weight of the cosmetic composition.

Silicon(s) Under the form of one oil in water emulsion

The cosmetic composition according to the invention comprises an oil-in-water (or silicone-in-water) emulsion having a particle size D50 of less than 350 nm and comprising:

- a mixture of silicones comprising (i) a dialkylpolysiloxane terminated by trialkylsilyl having a viscosity of 40,000 to less than 100,000 mPa.s at 25° C. and (ii) an amino silicone having a viscosity of 1,000 to 15,000 mPa. s at 25°C and an amine number of 2 to 10 mg of KOH per gram of amino silicone,

- a mixture of emulsifiers comprising one or more non-ionic emulsifier(s), in which the mixture of emulsifiers has an HLB value of 10 to 16; And

- some water.

In the oil-in-water emulsion, or silicone-in-water emulsion, one liquid phase (the dispersed phase) is dispersed in the other liquid phase (the continuous phase); in the present invention, the mixture of silicones, or silicone phase, is dispersed in the continuous aqueous phase.

The mixture of silicones comprises one or more dialkylpolysiloxanes terminated by trialkylsilyl, which are preferably of formula (IX):

R′ ₃ SiO(R′ ₂ SiO) _p SiR′ ₃ (IX),

in which :

- the R', identical or different, are a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, better still from 1 to 3 carbon atoms, more preferably methyl, And

- p is an integer from 500 to 2000, preferably from 1000 to 2000.

The dialkylpolysiloxane(s) terminated by trialkylsilyl (or blocked at the end or position α, ω) according to the invention have a viscosity of 40,000 to less than 100,000 mPa.s (100,000 excluded ) at 25°C, preferably a viscosity of 40,000 to 70,000 mPa.s at 25°C, more preferably a viscosity of 51,000 to 70,000 mPa.s at 25°C.

The dialkylpolysiloxanes terminated by trialkylsilyl according to the invention are preferably linear but additionally contain R′ ₂ SiO _2/2 units (D units) in formula (IX), RSiO _3/2 units (T units) and/or SiO _4/2 units (Q units), in which the R', identical or different, is a monovalent hydrocarbon radical containing from 1 to 18 carbon atoms.

Preferably, the R′, which are identical or different, are alkyl radicals, preferably C ₁ to C ₁₈ alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2- n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl, hexyl radicals, such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and the isooctyl radicals, such as the 2,2,4-trimethylpentyl radical, the nonyl radicals, such as the n-nonyl radicals, the decyl radicals, such as the n-decyl radical, the dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical; alkenyl radicals such as the vinyl and allyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; radicals, alkaryl; such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals such as the benzyl radical and the a- and b-phenylethyl radical. The methyl radical is most preferred.

Preferably, the dialkylpolysiloxanes terminated by trialkylsilyl are PDMS (polydimethylsiloxanes or dimethicones) terminated by trimethylsilyl.

The mixture of silicones comprises one or more amino silicones, which are preferably of formula (X):

XR ₂ Si(OSiAR) _n (OSiR ₂ ) _m OSiR ₂ X (X),

in which :

- the Rs, which are identical or different, are a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, better still from 1 to 3 carbon atoms, more preferably methyl;

- the Xs, which are identical or different, are R or a hydroxyl (OH) or C ₁ to C ₆ alkoxy group; preferably X is R, i.e. a monovalent hydrocarbon radical having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, more preferably methyl ;

- A is an amino radical of formula -R ¹ -[NR ² -R ³ -] _x NR ² ₂ , or the protonated amino forms of said amino radical, in which R ¹ is a C ₁ to C ₆ alkylene radical, of preferably a radical of formula -CH ₂ CH ₂ CH ₂ - or -CH ₂ CH(CH ₃ )CH ₂ -, the R ² s, which are identical or different, are a hydrogen atom or a C ₁ to C ₄ alkyl radical , preferably a hydrogen atom, R ³ is a C ₁ to C ₆ alkylene radical, preferably a radical of formula -CH ₂ CH ₂ -, and x is 0 or 1;

And

- m + n is an integer from 50 to about 1000, preferably from 50 to 600.

Preferably, A is an amino radical of formula -R ¹ -[NR ² -R ³ -] _x NR ² ₂ , or the protonated amino forms of said amino radical, in which R ¹ is -CH ₂ CH ₂ CH ₂ - or -CH ₂ CH(CH ₃ )CH ₂ -, R ² are hydrogen atoms, R ³ is -CH ₂ CH ₂ -, and x is 1.

Preferably, the Rs, which are identical or different, are alkyl radicals, preferably C ₁ to C ₁₈ alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n -butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl, hexyl radicals, such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and isooctyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as n-nonyl radicals, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical; alkenyl radicals such as the vinyl and allyl radical; cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; aryl radicals, such as phenyl, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the a- and b-phenylethyl radical. The methyl radical is most preferred.

The amino silicones according to the invention have a viscosity of 1,000 to 15,000 mPa.s at 25° C., preferably of 1,500 to 15,000 mPa.s.

The amino silicones according to the invention have an amine value of 2 to 10 mg of KOH per gram of amino silicone, preferably of 3.5 to 8 mg.

The mole percent of amine functionality is preferably in the range of about 0.3 to about 8%.

Examples of amino silicones useful in the silicone blend of the invention include a trialkylsilyl terminated amino silicone.

Most preferably, the amino silicones are trimethylsilyl-terminated aminoethylaminopropylmethylsiloxane, most preferably trimethylsilyl-terminated - aminoethylaminopropylmethylsiloxane - dimethylsiloxane copolymers. The amino radical A can be partially or totally protonated by adding acids to the amino silicone, the salt forms of the amino radical being obtained. Examples of acids are carboxylic acids with 3 to 18 carbon atoms which can be linear or branched, such as formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, sorbic acid, benzoic acid, salicylic acid. The acids are preferably used in amounts of 0.1 to 2.0 mol per 1 mol of amino radical A in the amino silicone of formula (X).

The silicone mixture preferably comprises (i) one or more trialkylsilyl terminated dialkylpolysiloxane(s) having a viscosity of 40,000 to less than 100,000 mPa.s at 25°C in an amount of 70 to 90% by weight, preferably from 75 to 85% by weight, based on the total weight of the mixture of silicones, and (ii) one or more amino silicones having a viscosity of 1,000 to 15,000 mPa.s at 25°C and an index of amine from 2 to 10 mg of KOH per gram of amino silicone, in an amount of 10 to 30% by weight, preferably 15 to 25% by weight, based on the total weight of the mixture of silicones.

The oil-in-water emulsion further comprises an emulsifier mixture which includes one or more non-ionic emulsifiers. It could optionally include one or more cationic surfactants.

The emulsifier blend has an HLB value of 10 to 16.

The nonionic emulsifiers can be chosen from nonionic surfactants as described below.

Mention may be made of alcohols, α-diols and alkylphenols (C ₁ to C ₂₀ ), these compounds being polyethoxylated and/or polypropoxylated and/or polyglycerolated, the number of ethylene oxide and/or propylene oxide groups optionally ranging from 1 to 100, and the number of glycerol groups optionally ranging from 2 to 30; or as a variant, these compounds comprising at least one fatty chain comprising from 8 to 30 carbon atoms and in particular from 16 to 30 carbon atoms.

Mention may also be made of condensates of ethylene oxide and propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5, and in particular from 1.5 to 4, glycerol groups; ethoxylated fatty acid esters of sorbitan preferably containing from 2 to 40 ethylene oxide units, fatty acid esters of sucrose, polyoxyalkylenated and preferably polyoxyethylene fatty acid esters containing from 2 to 150 mol of ethylene oxide, including oxyethylenated vegetable oils, N-(C ₆ -C ₂₄ alkyl)glucamine derivatives, amine oxides such as (C ₁₀ -C ₁₄ alkyl)amine oxides or N-(C ₁₀ -C ₁₄ acyl)aminopropylmorpholine oxides.

Mention may also be made of nonionic surfactants of the alkyl(poly)glycoside type, represented in particular by the following general formula:

R ₁ O-(R ₂ O) _t -(G) _v ,

in which :

- R ₁ represents a linear or branched alkyl or alkenyl radical comprising 6 to 24 carbon atoms and in particular 8 to 18 carbon atoms, or an alkylphenyl radical whose linear or branched alkyl radical comprises 6 to 24 carbon atoms and in particular 8 to 18 carbon atoms;

- R ₂ represents an alkylene radical comprising 2 to 4 carbon atoms,

- G represents a sugar unit comprising 5 to 6 carbon atoms,

- t denotes a value ranging from 0 to 10 and preferably 0 to 4,

- v denotes a value ranging from 1 to 15 and preferably 1 to 4.

Preferably, the alkylpolyglycoside surfactants are compounds of the formula described above in which:

- R ₁ denotes a linear or branched, saturated or unsaturated alkyl radical comprising from 8 to 18 carbon atoms,

- R ₂ represents an alkylene radical comprising 2 to 4 carbon atoms,

- t denotes a value ranging from 0 to 3 and preferably equal to 0,

- G denotes glucose, fructose or galactose, preferably glucose;

- the degree of polymerization, ie the value of v, optionally ranging from 1 to 15 and preferably from 1 to 4; the average degree of polymerization being in particular between 1 and 2.

The glucoside bonds between the sugar units are generally of the 1-6 or 1-4 type and preferably of the 1-4 type. Preferably, the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant. C ₈ /C ₁₆ 1,4-alkyl(poly)glycosides, and in particular decyl glucosides and caprylyl/capryl glucosides, are very particularly preferred.

Among the commercial products, mention may be made of the products sold by the company Cognis under the names PLANTAREN® (600 CS/U, 1200 and 2000) or PLANTACARE® (818, 1200 and 2000); the products sold by SEPPIC under the names ORAMIX CG 110 and ORAMIX NS 10; the products sold by the company BASF under the name LUTENSOL GD 70, or otherwise the products sold by the company CHEM Y under the name AG10 LK.

The nonionic emulsifiers can preferably be chosen from ethoxylated aliphatic alcohols, polyoxyethylenated surfactants, carboxylic esters, polyethylene glycol esters, sorbitol esters and their ethoxylated derivatives, glycol esters of fatty acids, carboxylic amides, monoalkanolamine condensates, amides polyoxyethylene fatty acids.

Preferably, the nonionic emulsifiers are chosen from:

(i) polyoxyalkylenated alkyl ethers, in particular (poly)ethoxylated fatty alcohols of formula:

R ₃ -(OCH ₂ CH ₂ ) _cOH ,

with :

- R ₃ representing a linear or branched C ₈ to C ₄₀ alkyl or alkenyl group, preferably a C ₈ to C ₃₀ alkyl or alkenyl group, optionally substituted by one or more hydroxyl groups, and

- c being an integer between 1 and 200 inclusive, preferably between 2 and 150 and more particularly between 4 and 50, most preferably between 8 and 20.

The (poly)ethoxylated fatty alcohols are more particularly fatty alcohols comprising from 8 to 22 carbon atoms, oxyethylenated with 1 to 30 mol of ethylene oxide (1 to 30 EO);

(ii) polyoxyalkylenated (C ₈ to C ₃₂ ) phenyl ethers,

(iii) polyoxyalkylenated (C ₈ to C ₃₂ ) sorbitan fatty acid esters, in particular polyethoxylated sorbitan fatty acid esters preferably containing from 2 to 40 ethylene oxide units, most preferably of 2 to 20 ethylene oxide units; preferably polyoxyethylene sorbitan (C ₁₀ to C ₂₄ ) fatty acid esters preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; And

(iv) polyoxyethylenated (C ₈ to C ₃₂ ) fatty acid esters containing, for example, from 2 to 150 mol of ethylene oxide; preferably polyoxyethylenated (C ₁₀ to C ₂₄ ) fatty acid esters containing, for example, from 2 to 150 mol of ethylene oxide.

Preferably, the nonionic emulsifiers could be chosen from an alkyl ether of polyalkylene glycol and alkyl esters of polyalkylene glycol; preferably polyethylene glycol (PEG).

Some useful emulsifiers are:

- polyethylene glycol octyl ether; polyethylene glycol lauryl ether; polyethylene glycol tridecyl ether; polyethylene glycol cetyl ether; polyethylene glycol stearyl ether; among these, mention may be made more particularly of trideceth-3, trideceth-10 and steareth-6.

- polyethylene glycol nonylphenyl ether; polyethylene glycol dodecylphenyl ether; polyethylene glycol cetylphenyl ether; polyethylene glycol stearylphenyl ether;

- polyethyleneglycol sorbitan monostearate, polyethyleneglycol sorbitan monooleate.

- polyethylene glycol stearate, and in particular PEG-100 stearate.

Most preferably, the nonionic emulsifiers are selected from steareth-6, PEG-100 stearate, trideceth-3 and trideceth-10 and mixtures thereof; preferably all of these emulsifiers are present in the emulsifier mixture.

The mixture of emulsifiers could comprise one or more cationic emulsifiers which could be chosen from tetraalkylammonium halides, tetraarylammonium halides, tetraalkylarylammonium halides, and their salts; quaternary ammonium compounds including salts; preferably, the cationic emulsifiers could be chosen from cetrimonium halides or behentrimonium halides, such as chloride.

The oil-in-water emulsion preferably comprises the emulsifier mixture in a total amount of 5 to 15 wt%, preferably 8 to 15 wt%, most preferably 10 to 12 wt%. , based on the total weight of the emulsion.

The oil-in-water emulsion preferably comprises nonionic emulsifiers in a total amount of 5 to 15% by weight, preferably 8 to 15% by weight, most preferably 10 to 12% by weight, based on the total weight of the emulsion.

The oil-in-water emulsion preferably comprises cationic emulsifiers, when present, in a total amount of 0.5 to 1.5% by weight, based on the total weight of the emulsion.

The oil-in-water emulsion preferably comprises the mixture of silicones in a total amount of 40 to 60% by weight, preferably 45 to 55% by weight, based on the total weight of the emulsion.

The oil-in-water emulsion preferably comprises the trialkylsilyl-terminated dialkylpolysiloxane(s) in a total amount of 35 to 45% by weight, preferably 38 to 42% by weight, based on the weight total of the emulsion.

The oil-in-water emulsion preferably comprises the amino silicone(s) in a total amount of 5 to 15% by weight, preferably 8 to 12% by weight, based on the total weight of the emulsion.

The oil-in-water emulsion comprises water preferably in an amount of 25 to 50% by weight, preferably 30 to 45% by weight, most preferably 35 to 42% by weight, based to the total weight of the emulsion.

The oil-in-water emulsion could additionally comprise a biocide, such as phenoxyethanol, which could be present in the emulsion in an amount of 0.5 to 1% by weight, based on the total weight of the emulsion.

A process for preparing the oil-in-water emulsion preferably comprises:

- a step of mixing one or more dialkylpolysiloxane(s) terminated by trialkylsilyl with a viscosity of 40,000 to less than 100,000 mPa.s at 25°C and one or more amino silicones with a viscosity of 1,000 to 15 000 mPa.s at 25°C and an amine number of 2 to 10 mg of KOH per gram of amino silicone, at a temperature of 15°C to 40°C, preferably at 25°C, to obtain a mixed silicone fluid, then

- a step of adding an emulsifier mixture comprising one or more nonionic emulsifier(s), the emulsifier mixture having an HLB value of 10 to 16, to the mixed silicone fluid to obtain a mixture silicone-emulsifier, then

- a step of homogenizing the silicone-emulsifier mixture followed by

- a step of adding, preferably by step, water, preferably demineralised water, to obtain an oil-in-water emulsion having a particle size D50 of less than 350 nm.

The process for preparing the oil-in-water emulsion could also comprise an additional step of adding a biocide. The biocide could be added to preserve the emulsion against microbial contamination. The biocide could be added in order to preserve the emulsion from microbial contamination and to obtain said emulsion. The amount of biocide depends on the type of biocide and as recommended by the manufacturer.

The preparation of the mixture of emulsifiers could be carried out by mixing one or more non-ionic emulsifiers.

The pH of the oil-in-water emulsion after neutralization (i.e. after addition of the biocide) is preferably 4 to 6.

The oil-in-water emulsion has a D50 particle size of less than 350 nm, preferably 100-300 nm, more preferably 150-250 nm, more preferably 150-225 nm, and most preferably 160 to 200 nm. It corresponds to the mean hydrodynamic particle diameter. The D50 particle size is expressed in volume. The D50 particle size could be measured using a ZetaSizer device from Malvern, UK, model Nano-ZS, which is based on the Photon Correlation Spectroscopy (PCS) method.

Particle size measurement

The particle size of the emulsion was measured using a ZetaSizer device from Malvern, UK, Nano-ZS model which is based on the method of Photon Correlation Spectroscopy (PCS). The D50 value of the particle size (mean hydrodynamic particle diameter) is measured, the evaluation algorithm being “cumulant analysis”.

Take 0.5 g of the emulsion sample in a 250 mL beaker, pour 100 mL of deionized water into it and mix them well to obtain the sample test solution. The sample test solution is poured into the cuvette cell and placed in the slot of the instrument to measure the particle size of the emulsion. D50 is defined as the value of the 50% particle diameter in the cumulative distribution. For example, if D50 = 170nm, then 50% of the particles in the sample are larger than 170nm, and 50% smaller than 170nm or approximately 50% by volume of all droplets in said emulsion are 170nm .

Viscosity measurement

The viscosity, in particular of the silicones or of the emulsion, is measured at 25° C., at atmospheric pressure .

For viscosities between 1,000 to 40,000 mPa.s at 25°C: the viscosity could be measured with an Anton Paar rheometer; MCR101 model, single-groove cylinder geometry: CC27 spindle and shear rate of 1 s ^-1 for 2 minutes, at 25°C.

For viscosities between 40,000 to 100,000 mPa.s at 25°C: the viscosity could be measured with an Anton Paar rheometer; model MCR101, 25-6 cone (plane-cone geometry: 25 mm diameter/6° cone); the "Zero groove" adjustment being carried out and with a shear rate of 1 s ^-1 for 2 minutes, at 25°C.

Three measurements are made for each sample and the viscosity value is taken at 60 seconds. Products in the MCR Rheometer range operate in accordance with USP (US Pharmacopeia convention) 912 – Rotational Rheometer methods.

Amine number measurement

The amine number is determined by acid-base titration using a potentiometer [Make: Veego; Model: VPT-MG]. Take 0.6 g of sample in a 500 mL beaker and add a 1:1 toluene-butanol mixture and shake to mix the sample completely; then the sample solution is titrated with a 0.1(N) HCl solution. A determination of the blank value is also carried out with the 1:1 toluene-butanol mixture. The calculation of the amine index is carried out by the aforementioned potentiometer.

The amine index is calculated according to the formula:

56.11 × (V - V Blank) × N/W mg KOH/g sample,

where V = Volume of HCl required in mL, VBlank = Volume of HCl for blank value (without sample) with 1:1 toluene-butanol mixture in mL; N = Normality of HCl, i.e. 0.1 N, W = weight of the sample taken in grams.

HLB value

The term HLB is well known to those skilled in the art, and designates the hydrophilic-lipophilic balance of a surfactant or emulsifier. In the present invention, HLB values refer to values at 25°C.

HLB can be measured by experimental determination or can be calculated.

A calculation of the HLB value of nonionic surfactants is made according to the equation: HLB = (E + P)/5, where E is the weight percentage of the oxyethylene content and P is the weight percentage of the alcohol content polyhydric, described in the publication Griffin, J. Soc. Cosm. Chem. 1954 (vol.5, n° 4), pp.249 to 256.

It can also be determined experimentally according to the book by F. Puisieux and M. Seiller, entitled “Galenica 5: Dispersed systems – Volume I – Surface agents and emulsions – Chapter IV – Notions of HLB and critical HLB, pp. 153 to 194 paragraph 1.1.2. Determination of HLB experimentally, pp. 164 to 180”.

The calculated HLB is the preferred HLB values that should be considered.

Said calculated HLB could be defined as follows:

"Calculated HLB = 20 × molar mass of hydrophilic part/total molar mass".

For an oxyethylenated fatty alcohol, the hydrophilic part corresponds to the oxyethylene units condensed on the fatty alcohol and the “calculated HLB” then corresponds to the “Griffin HLB” as defined above.

For an ester or an amide, the hydrophilic part is naturally defined as being beyond the carbonyl group, starting from the fatty chain(s).

For ionic surfactants/emulsifiers, the HLB value of an individual surfactant/emulsifier can be calculated by applying Davies' formula as described in Davies JT (1957), "A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent”, Gas/Liquid and Liquid/Liquid Interface (Proceedings of the International Congress of Surface Activity): 426 to 438.

According to the formula, the HLB is derived by summing the hydrophilic/hydrophobic contribution allowed by the structural components of the emulsifier: HLB = (number of hydrophilic groups) – n(number of groups per CH ₂ group) + 7.

Approximate HLB values for some cationic emulsifiers are given in Table IV, in "Cationic emulsifiers in cosmetics", GODFREY, J. Soc. Cosmetic Chemists (1966) 17, pp17-27.

When two emulsifiers A and B of known HLB are mixed for use, the HLB _Mix is said to be the required HLB for the mixture. This is expressed by the equation (W _A HLB _A + W _B HLB _B )/(W _A + W _B ) = HLB _Mix , where W _A = the quantity (weight) of the first emulsifier (A) used, and W _B = the amount (weight) of the second emulsifier (B); HLB _A , HLB _B = assigned HLB values for emulsifiers A and B; HLB _Mix = the HLB of the mixture.

Said oil-in-water emulsion is for example described in WO 2017/108824.

The cosmetic composition according to the invention may comprise the oil-in-water emulsion b in an amount ranging from 0.1% to 20% by weight, preferably from 0.3% to 10% by weight and better still from 0 4% to 10% by weight, better still from 0.5 to 8%, even more preferentially from 1 to 5% by weight relative to the total weight of the composition.

The composition according to the invention preferably comprises the dialkylpolysiloxane(s) terminated by trialkylsilyl having a viscosity of 40,000 to less than 100,000 mPa.s at 25° C. in a total quantity ranging from 0.05 % to 8% by weight, more preferably 0.1% to 5% by weight, even more preferably 0.2% to 4% by weight, more preferably 0.3 to 3% by weight, reported to the total weight of the composition.

The composition according to the invention preferably comprises the amino silicone(s) having a viscosity of 1,000 to 15,000 mPa.s at 25° C. and an amine number of 2 to 10 mg of KOH per gram. of amino silicone, in a total amount ranging from 0.01% to 5% by weight, more preferably from 0.05% to 3% by weight, even more preferably from 0.075% to 2% by weight, better still from 0.1 to 1% by weight, based on the total weight of the composition.

The composition according to the invention comprises one or more chemical oxidizing agents and/or one or more oxidation dyes.

Chemical oxidizing agent

The term "chemical oxidizing agent" is intended to denote an oxidizing agent other than atmospheric oxygen.

Preferably, the chemical oxidizing agent(s) is (are) chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates , in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids and oxidase enzymes (with possible co-factors) such as peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof .

More preferably, the chemical oxidizing agent(s) is (are) selected from hydrogen peroxide, persalts, and mixtures thereof, and more preferably is hydrogen peroxide. hydrogen.

When it is present in the cosmetic composition according to the present invention, said chemical oxidizing agent is advantageously present in an amount ranging from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight, of more preferably from 1% to 15% by weight, more preferably from 2% to 10% by weight, based on the total weight of the cosmetic composition.

When it is present in the cosmetic composition according to the present invention, the hydrogen peroxide is advantageously present in an amount ranging from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight, more preferably from 1% to 15% by weight, more preferably from 2% to 10% by weight based on the total weight of the cosmetic composition.

Oxidation shades

The oxidation tints can be chosen from one or more oxidation bases, optionally in combination with one or more couplers. Preferably, the oxidation tints comprise at least one oxidation base and at least one coupler.

By way of example, the oxidation bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and their addition salts.

Among para-phenylenediamines, examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine , 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine , 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4- N,N–bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)- para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl )-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hyd roxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and their addition salts with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6 -dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines, examples which may be mentioned include N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)1,3-diaminopropanol, N,N '-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(β-hydroxyethyl)-N, N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl )ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane and their addition salts.

Among para-aminophenols, examples that can be mentioned include para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol , 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino- 2-fluorophenol, and their addition salts with an acid.

Among the ortho-aminophenols, examples which may be mentioned include 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts.

Among the heterocyclic bases, examples that can be mentioned include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, for example 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and their addition salts.

Other pyridine oxidation bases which are useful in the present invention are the 3-aminopyrazolo[1,5-a] pyridine oxidation bases or their addition salts described, for example, in patent application FR 2 801,308. Examples which may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin- 4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine , (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1, 5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo [1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, pyrazolo[ 1,5-a]pyridin-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a ]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopy razolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin -4-ol, 3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol and their addition salts.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399, JP 88-169571, JP 05-63124 and EP 0770375 or patent application WO 96/15765, such as 2.4 ,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts, and their tautomeric forms, when a tautomeric equilibrium exists.

Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3843892, DE 4133957 and patent application WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4, 5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5- hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3- methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-tria minopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and their salts addition. It is also possible to use 4,5-diamino-1-(β-methoxyethyl)pyrazole.

A 4,5-diaminopyrazole will preferably be used, and even more preferably 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or a salt thereof.

The pyrazole derivatives which may also be mentioned include diamino-N,N-dihydropyrazolopyrazolones and in particular those described in patent application FR-A-2 886 136, such as the following compounds and their addition salts: 2 ,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1 ,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-( pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3 -one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3- one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-dimethylamino-6,7 -dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol -1-one, 4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolid ine-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a ]pyrazol-1-one.

Use will preferably be made of 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a salt thereof.

Heterocyclic bases which will preferably be used include 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol -1-one and/or a salt thereof.

Preferably, the oxidation bases are chosen from para-phenylenediamine, 1-methyl-2,5-diaminobenzene, para-aminophenol, 1-hydroxyethyl-4,5-diaminopyrazole sulfate and 2,3-diaminodihydroxypyrazolone dimethosulfonate, their salts of addition and mixtures thereof.

When it is present in the cosmetic composition according to the present invention, said oxidation base is advantageously present in an amount ranging from 0.001% to 10% by weight, preferably from 0.005% to 10% by weight, based on the total weight of the cosmetic composition.

The coupler(s) is (are) advantageously chosen from those conventionally used for dyeing keratin fibres.

Among these couplers, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, couplers based on naphthalene and heterocyclic couplers, and also their addition salts.

Examples that may be mentioned include 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2- methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol , 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl) amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl- 3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, their addition salts with an acid of, and mixtures thereof.

In general, the addition salts of oxidation bases and couplers which can be used in the context of the invention are chosen in particular from addition salts with an acid, such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

Preferably, the coupler(s) are chosen from resorcinol, 2-methylresorcinol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 2-methyl-5-aminophenol, 1-β-hydroxyethyloxy dihydrochloride -2,4-diaminobenzene and 3-aminophenol, their addition salts, and mixtures thereof.

When it is present in the cosmetic composition according to the present invention, said coupler is advantageously present in an amount ranging from 0.001% to 10% by weight, preferably from 0.005% to 10% by weight, based on the total weight of the composition cosmetic.

When it is present in the cosmetic composition according to the present invention, said oxidizing tint is advantageously present in an amount ranging from 0.001% to 20% by weight, preferably from 0.01% to 5% by weight, based on the total weight of the cosmetic composition.

The cosmetic composition can optionally also comprise one or more alkaline agents.

The alkaline agents can be chosen from carbonates, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and their derivatives, oxyethylenated and/or oxypropylene ethylenediamines, mineral or organic hydroxides, alkali metal silicates such as sodium metasilicates, amino acids, preferably acids basic amines such as arginine, lysine, ornithine, citrulline and histidine, and the compounds of formula (I) below:

(I)

in which :

- W is a divalent (C ₁ to C ₈ ) alkylene group, preferably a propylene group, optionally substituted in particular by a hydroxyl group or a C ₁ to C ₄ alkyl radical;

- Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom or a C ₁ to C ₄ alkyl radical or a C ₁ to C ₄ hydroxy alkyl radical.

The inorganic or organic hydroxides, in particular the inorganic or organic hydroxides are preferably chosen from i) the hydroxides of an alkali metal, ii) the hydroxides of an alkaline-earth metal, for example sodium hydroxide or potassium hydroxide, iii) hydroxides of a transition metal, such as hydroxides of metals of groups III, IV, V and VI, iv) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide.

The hydroxide can be formed in situ , for example guanidine hydroxide, formed by reacting calcium hydroxide with guanidine carbonate.

Preferably, the alkaline agents are chosen from alkanolamines, in particular monoethanolamine, diethanolamine and triethanolamine, and ammonium hydroxide, and mixtures thereof.

Said cosmetic composition may optionally also comprise one or more organic solvents.

The organic solvents which may be mentioned include linear or branched and preferably saturated monoalcohols or diols, comprising 2 to 6 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4- pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as benzyl alcohol or phenylethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; polyol ethers, for example ethylene glycol or propylene glycol monomethyl, monoethyl or monobutyl ethers; and also diethylene glycol alkyl ethers, in particular C ₁ to C ₄ alkyl ethers, for example diethylene glycol monoethyl ether or monobutyl ether.

The composition according to the invention may also comprise one or more cationic polymers different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) described above. These optional additional cationic polymers do not contain any cationic/quaternized acrylamide and/or methacrylamide units. Preferably, these optional additional cationic polymers are non-silicone polymers.

The additional cationic polymers which can be used preferably have a weight average molecular weight (Mw) between 500 and 5×10 ⁶ approximately and preferably between 10 ³ and 3×10 ⁶ approximately.

Among the additional cationic polymers, mention may be made more particularly of:

(1) cationic polysaccharides, in particular cationic celluloses and galactomannan gums. Among the cationic polysaccharides, mention may more particularly be made of cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and gums of cationic galactomannan.

Cellulose ether derivatives comprising quaternary ammonium groups are described in particular in French patent 1,492,597, and mention may be made of the polymers sold under the name UCARE POLYMER "JR" (JR 400 LT, JR 125 and JR 30M) or “LR” (LR 400 or LR 30M) by Amerchol. These polymers are also defined in the CTFA dictionary as hydroxyethylcellulose quaternary ammoniums that have been reacted with an epoxide substituted with a trimethylammonium group.

Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described in particular in US Pat. No. 4,131,576, and mention may be made of hydroxyalkylcelluloses, for example hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a [(meth)acrylic] dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names CELQUAT L 200 and CELQUAT H 100 by the company National Starch.

Cationic galactomannan gums are described more particularly in US Patents 3,589,578 and 4,031,307, and mention may be made of guar gums comprising cationic trialkylammonium groups. Use may be made, for example, of guar gums modified with a 2,3-epoxypropyltrimethylammonium salt (eg chloride). Such products are notably sold under the names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by Rhodia.

(2) polymers formed by piperazinyl units and divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers.

(3) water-soluble polyamino amides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyamino amides can be cross-linked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; these polyamino amides can be alkylated or, if they include one or more tertiary amine functions, they can be quaternized.

(4) polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with bifunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical comprises from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Among these derivatives, mention may be made more particularly of the polymers of adipic acid/dimethylaminohydroxypropyl/diethylenetriamine sold under the name CARTARETINE F, F4 or F8 by the company Sandoz.

(5) polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 8 carbon atoms; the molar ratio between the polyalkylene polyamine and the dicarboxylic acid preferably being between 0.8:1 and 1.4:1; the resulting polyamino amide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine group of the polyamino amide preferably between 0.5:1 and 1.8:1. Polymers of this type are sold in particular under the name HERCOSETT 57 by the company Hercules Inc. or as a variant under the name PD 170 or DELSETTE 101 by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer.

(6) alkyldiallylamine or dialkyldiallylammonium cyclopolymers, such as homopolymers or copolymers containing, as the main constituent of the chain, units corresponding to formula (XXX) or (XXXI):

(XXX)

(XXXI)

in which :

- k and t are equal to 0 or 1, the sum k + t being equal to 1;

- R ₁₂ denotes a hydrogen atom or a methyl radical;

- R ₁₀ and R ₁₁ , independently of one another, denote a C ₁ to C ₆ alkyl group, a hydroxyl alkyl group (C ₁ to C ₅ ), a C ₁ to C ₄ amidoalkyl group; or as a variant R ₁₀ and R ₁₁ can denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R ₁₀ and R ₁₁ , independently of one another, preferably denote a C ₁ to C ₄ alkyl group; And

- Y ^- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.

Mention may be made more particularly of homo or copolymers of dimethyldiallylammonium halides, preferably of homo or copolymers of dimethyldiallylammonium chloride, better still of a homopolymer of dimethyldiallylammonium chloride, such as a homopolymer of dimethyldiallylammonium chloride of corresponding INCI name Polyquaternium-6 sold for example under the name MERQUAT 100 by the company Nalco.

(7) quaternary diammonium polymers comprising repeating units of formula:

(XXXII)

in which :

- R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms, or C ₁ to C ₁₂ hydroxyalkylaliphatic radicals,

or else R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second non-nitrogen heteroatom,

or else R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent a linear or branched C ₁ to C ₆ alkyl radical substituted by a nitrile, ester, acyl, amide or -CO-OR ₁₇ -D or -CO-NH group -R ₁₇ -D in which R ₁₇ is an alkylene and D is a quaternary ammonium group;

- A1 and B1 represent divalent polymethylene groups comprising from 2 to 20 carbon atoms, linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more rings aromatics or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

- X ^- denotes an anion derived from a mineral or organic acid;

knowing that A ₁ , R ₁₃ and R ₁₅ can form, with the two nitrogen atoms to which they are attached, a piperazine ring;

moreover, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 can also denote a group (CH ₂ ) _n -CO-D-OC-(CH ₂ ) _p - in which n and p, which may be identical or different, denote an integer from 2 to 20, and in which D denotes:

a) a glycol residue of formula -OZO-, in which Z denotes a radical based on a linear or branched hydrocarbon, or a group corresponding to one of the following formulas: -(CH ₂ -CH ₂ -O) _x - CH ₂ -CH ₂ - and -[CH ₂ -CH(CH ₃ )-O] _y -CH ₂ -CH(CH ₃ )-, where x and y denote an integer from 1 to 4, representing a defined degree of polymerization and single or any number from 1 to 4 representing an average degree of polymerization;

b) a secondary bis-diamine residue such as a piperazine derivative;

c) a primary bis-diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon-based radical, or otherwise the divalent radical -CH ₂ -CH ₂ -SS-CH ₂ - CH ₂ -;

d) a ureylene group of formula: -NH-CO-NH-;

Preferably, X ^- is an anion such as chloride or bromide. These polymers have a number average molecular weight (Mn) generally between 1,000 and 100,000.

Mention may more particularly be made of polymers which are composed of repeating units corresponding to the formula:

(XXXIII),

in which R ₁ , R ₂ , R ₃ and R ₄ , which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X ^- is an anion derived from an organic or mineral acid.

A particularly preferred compound of formula (XXXIII) is that for which R ₁ , R ₂ , R ₃ and R ₄ represent a methyl radical and n = 3, p = 6 and X = Cl, known under the name of Hexadimethrine chloride according to the INCI nomenclature (CTFA).

(8) polyquaternary ammonium polymers comprising units of formula (XXXIV):

(XXXIV)

in which :

- R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _p OH, in which p is equal to 0 or to an integer between 1 and 6, provided that R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ do not simultaneously represent a hydrogen atom,

- r and s, which can be identical or different, are integers between 1 and 6,

- q is equal to 0 or an integer between 1 and 34,

- X ^- denotes an anion such as a halide,

- A denotes a dihalide radical or preferably represents --CH ₂ --CH _{2 ---} O-CH ₂ --CH ₂ --.

Examples which may be mentioned include the products ^Mirapol® A15, ^Mirapol® AD1, ^Mirapol® AZ1 and ^Mirapol® 175 sold by the company Miranol.

(9) quaternary polymers of vinylpyrrolidone and vinylimidazole, for example the products sold under the names Luviquat ^® FC 905, FC 550 and FC 370 by the company BASF.

(10) polyamines such as Polyquart ^® H sold by Cognis, designated under the name Polyethylene glycol (15) tallow polyamine in the CTFA dictionary.

(11) polymers comprising in their structure:

(a) one or more units corresponding to formula (A) below:

(b) optionally, one or more units corresponding to formula (B) below:

In other words, these polymers can be chosen in particular from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.

Preferably, these cationic polymers are chosen from polymers comprising, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferably from 10 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B).

These polymers can be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis can be carried out in an acidic or basic medium.

The weight-average molecular mass of said polymer, measured by light scattering, can range from 1,000 to 3,000,000 g/mol, preferably from 10,000 to 1,000,000 g/mol and more particularly from 100,000 to 500,000 g /mol.

The polymers comprising units of formula (A) and optionally units of formula (B) are sold in particular under the name Lupamin by the company BASF, for example, and in a non-limiting manner, the products sold under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.

Other additional cationic polymers which can be used in the context of the invention are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular polyethyleneimines, polymers comprising vinylpyridine or vinylpyridinium units, condensates of polyamines and epichlorohydrin, quaternary polyureylenes and chitin derivatives.

The additional cationic polymers, different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) described above, are preferably chosen from cyclopolymers of alkyldiallylamine or dialkyldiallylammonium corresponding to the general family (6).

More preferentially, the additional cationic polymers are chosen from homo or copolymers of dimethyldiallylammonium halides, preferably homo or copolymers of dimethyldiallylammonium chloride, better still a homopolymer of dimethyldiallylammonium chloride, such as a homopolymer of dimethyldiallylammonium chloride of corresponding INCI name Polyquaternium-6.

According to a preferred embodiment of the present invention, the composition may comprise:

- one or more polymer(s) comprising one or more cationic or quaternized (meth)acrylamide unit(s), preferably chosen from (meth)acrylamido (C-C alkyl) halide copolymers₁to C₆)tri(C-alkyl₁to C₄) ammonium/(meth)acrylamide, (meth)acrylamido (C-12 alkyl) halide terpolymers₁to C₆)tri(C-alkyl₁to C₄) ammonium/(meth)acrylamide/(meth)acrylic acid, (meth)acrylamido (C-12 alkyl) halide terpolymers₁to C₆)tri(C-alkyl₁to C₄) ammonium/(meth)acrylate (C-alkyl₁to C₆)/(meth)acrylic acid; and their mixtures, And

- one or more additional cationic polymers, different from the polymers comprising one or more cationic or quaternized (meth)acrylamide units described above, preferably chosen from alkyldiallylamine or dialkyldiallylammonium cyclopolymers corresponding to general family (6); more preferably chosen from homo or copolymers of dimethyldiallylammonium halides, preferably homo or copolymers of dimethyldiallylammonium chloride, better still a homopolymer of dimethyldiallylammonium chloride with the corresponding INCI name Polyquaternium-6.

The quantity of additional cationic polymer(s), different from the polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s), when they are present in the cosmetic composition of the present invention, preferably ranges from 0.01 to 10% by weight, more preferably from 0.02 to 5% by weight, and even better from 0.04 to 1% by weight, and even more more preferably from 0.05 to 0.5% by weight, based on the total weight of the cosmetic composition.

Optional additive(s)

The cosmetic composition of the invention may also contain various additives conventionally used in hair compositions.

As additives which can be used in accordance with the invention, mention can be made of anionic or nonionic polymers, additional amphoteric polymers different from polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s). (s) previously described, anti-dandruff agents, anti-seborrhoea agents, agents for preventing hair loss and/or promoting hair regrowth, fatty substances, vitamins and provitamins including panthenol, sunscreens, mineral pigments or organic, sequestrants, plasticizers, solubilizers, acidifying agents, inorganic or organic thickeners, in particular polymeric thickeners, opacifiers or pearlescent agents, antioxidants, hydroxy acids, perfumes and preservatives, and mixtures thereof.

The above additives are generally present in an amount for each of them between 0.01% and 40% by weight, and preferably between 0.1% and 20% by weight, based on the weight of the cosmetic composition of the 'invention.

It goes without saying that a person skilled in the art will take care to select this (these) optional additive(s) so that the advantageous properties intrinsically associated with the cosmetic composition in accordance with the invention are not not, or substantially not, be adversely affected by the contemplated addition(s).

The present invention also relates to a cosmetic treatment process, in particular for dyeing and/or lightening keratin fibres, and in particular human keratin fibres, in which a composition as described above is applied to said keratin fibres, and after an optional exposure time, it is optionally removed by rinsing.

The exposure time of the composition on the keratin fibers can range from 1 minute to 60 minutes, better still from 5 minutes to 45 minutes and even better from 10 minutes to 30 minutes.

The composition can be applied to wet or dry keratin fibers.

Preferably, the composition as described above is obtained from the mixture of at least two compositions:

- a first composition comprising one or more oxidation shade(s) as described previously;

- a second composition comprising one or more chemical oxidizing agent(s) as defined above,

one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) as defined above, which are included in the first and/or second composition;

at least one oil-in-water emulsion as defined above, which is included in the first and/or second composition,

said polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) and said oil-in-water emulsion preferably being in the second composition.

The present invention may also relate to a process for dyeing keratin fibers, which consists in applying to said keratin fibers a composition comprising:

To. one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s);

b. an oil-in-water emulsion having a D50 particle size of less than 350 nm and comprising:

- a mixture of silicones comprising (i) one or more dialkylpolysiloxane(s) terminated by trialkylsilyl having a viscosity of 40,000 to less than 100,000 mPa.s at 25°C and (ii) one or more amino silicone(s) s) having a viscosity of 1,000 to 15,000 mPa.s at 25°C and an amine number of 2 to 10 mg of KOH per gram of amino silicone,

- an emulsifier blend comprising one or more non-ionic emulsifier(s), wherein the emulsifier blend has an HLB value of 10 to 16, and

- some water ;

vs. one or more chemical oxidizing agent(s) and/or one or more oxidation dye(s);

d. optionally one or more cationic polymer(s) different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s).

The invention may also relate to a process for lightening keratin fibers, which consists in applying to said keratin fibers a composition comprising:

To. one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s);

b. an oil-in-water emulsion having a D50 particle size of less than 350 nm and comprising:

- a mixture of silicones comprising (i) one or more dialkylpolysiloxane(s) terminated by trialkylsilyl having a viscosity of 40,000 to less than 100,000 mPa.s at 25°C and (ii) one or more amino silicone(s) s) having a viscosity of 1,000 to 15,000 mPa.s at 25°C and an amine number of 2 to 10 mg of KOH per gram of amino silicone,

- an emulsifier blend comprising one or more non-ionic emulsifier(s), wherein the emulsifier blend has an HLB value of 10 to 16, and

- some water ;

vs. one or more chemical oxidizing agent(s);

d. optionally one or more cationic polymer(s) different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s).

The present invention also relates to the use of the composition according to the invention as described above for the cosmetic treatment of keratin fibers, in particular for dyeing and/or lightening keratin fibers, and in particular keratin fibers human.

Finally, the invention relates to a kit comprising at least two compartments:

- a first compartment comprising a first composition comprising one or more oxidation shade(s) as defined above;

- a second compartment comprising a second composition comprising one or more chemical oxidizing agent(s) as defined above;

one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) as defined above, which are included in the first and/or second composition ;

at least one oil-in-water emulsion as defined above which is included in the first and/or the second composition,

said polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) and said oil-in-water emulsion preferably being in the second composition.

In the present invention, the expression “keratin fibers” designates human keratin fibers, and in particular human hair such as human hair.

In the description above, all of the preferred component embodiments may be used individually or in combination.

The following examples serve to illustrate the invention.

Examples

In the examples which follow and unless otherwise indicated, the amounts are given in percentages by weight of active ingredient (AM) based on the total weight of the composition.

Example 1 : Preparation of an oil-in-water emulsion

450 g of an amino silicone fluid (copolymer of aminoethyl-aminopropylmethylsiloxane - dimethylsiloxane terminated by trimethylsilyl with an amine number of 7.2 mg of KOH/g of sample) were introduced into an emulsion tank, and a viscosity of 5,600 mPa.s at 25°C). Stirring was started and 1,800 g of trimethylsilyl-terminated dimethylsiloxane polymer fluid with a viscosity of 61,500 mPa.s at 25° C. was introduced into the same tank with stirring. The two fluids were mixed for 2 hours at room temperature.

In a separate tank, 49 g of steareth-6 and 62 g of PEG-100 stearate were introduced and heated to 60° C. The temperature was maintained until both emulsifiers became liquid. Then, 31 g of trideceth-3 and 350 g of trideceth-10 (80% active ingredient) were added. This mixture of non-ionic emulsifiers had an HLB value = 11.25.

Then, 80 g of water and 6.2 g of glacial acetic acid were added to the tank and mixing was started. We continued mixing until the whole mass became a creamy paste. All the paste was added to the emulsion tank. Homogenization was carried out for 30 minutes at room temperature. 79.6 g of deionized water were added and homogenization was carried out for 60 minutes. 72.7 g of deionized water were added and homogenization was carried out for 50 minutes. 197.4 g of deionized water was added and homogenization was carried out for 5 minutes. 294.3 g of deionized water was added and homogenization was carried out for 5 minutes. 180 g of deionized water were added and homogenization was carried out for 5 minutes. 180 g of deionized water were added and homogenization was carried out for 5 minutes. 197.4 g of deionized water was added and homogenization was carried out for 5 minutes. 197.4 g of deionized water were added and homogenized for 3 minutes. 228.5 g of deionized water was added and homogenization was carried out for 3 minutes. Finally, 40.5 g of 2-phenoxyethanol as a biocide was added and homogenization was carried out for 3 minutes.

A stable oil-in-water emulsion with a D50 particle size of 170 nm was obtained.

Example 2

The following composition A was prepared from the ingredients indicated in Table 1 below (% by weight of AM).

Composition AT p-Phenylenediamine 2 Resorcinol 1.71 m-Aminophenol 0.15 2,4-Diaminophenoxyethanol HCl 0.54 Sodium metabisulphite 0.5 Ascorbic acid 0.25 Ethanolamine 4.7 sodium laureth sulphate 1.4 Prunus amygdalus dulcis (sweet almond)/Prunus dulcis oil 0.01 Carbomer 1 Glycerin 5 EDTA 0.1 Argania spinosa kernel oil 0.01 Beheneth-25 acrylates/methacrylate copolymer 0.33 Perfume/ Fragrance 0.5 Water Qs 100

Next, the following comparative compositions 1 and 2 and composition 3 according to the invention were prepared from the ingredients indicated in Table 2 below (% by weight of AM).

Composition 1
(Comparative) 2
(Comparative) 3
(Invention) Cetearyl alcohol (and) ceteareth-25 2.85 2.85 2.85 Trideceth-2 carboxamide mea 0.85 0.85 0.85 Glycerin 0.5 0.5 0.5 Tetrasodium pyrophosphate 0.02 0.02 0.02 sodium stannate 0.04 0.04 0.04 pentasodium pentetate 0.06 0.06 0.06 Hydrogen peroxide 6 6 6 Phosphoric acid Qs pH 2 ± 0.2 Qs pH 2 ± 0.2 Qs pH 2 ± 0.2 Acrylamidopropyltrimonium chloride/acrylamide copolymer (=APTAC/AA) - - 0.09 Poly(diallyldimethylammonium chloride) (in 40% water) (Polyquaternium-6) - 0.12 0.12 Dimethicone (and) Amodimethicone (and) Trideceth-10 (and) PEG-100 Stearate (and) Steareth-6 (and) Trideceth-3
(from example 1) 3% emulsion, i.e. 0.3% AM SiA + 1.2% AM Si 3% emulsion, i.e. 0.3% AM SiA + 1.2% AM Si 3% emulsion, i.e. 0.3% AM SiA + 1.2% AM Si Water Qs 100 100 100

*AM = active ingredient

SiA: amodimethicone

If: PDMS

The compositions were applied to the hair.

At the time of use, composition A was mixed with oxidizing compositions 1, 2 and 3, respectively, at a mixing ratio of 1:1.

Each mixture was then applied to locks of 90% natural gray hair with 10 g of mixture per 1 g of hair.

After 15 minutes at room temperature (about 27°C), the locks were rinsed, shampooed and dried.

The locks of hair showed very good color rendition and very good conditioning.

The silicone deposit of the above product, namely composition A with compositions 1, 2 and 3, respectively, was evaluated on locks of natural hair.

The evaluation was carried out with a WDXRF Optim Thermofisher XRF system (wavelength dispersion). The principle is based on the radiation emission characteristic of the chemical element, produced by the impact of high energy photons distributed by an X-ray tube.

The operating parameters are as follows:

- Helium gas flow - Argon/Methane (90/10)

- X-ray tube (Rh), PET crystal and FPC detector

- Voltage 25 kv — 2 mA

- 3 measurements/wick = 60 s/measurement

- apply 10 g of product per lock from root to tip

- minimum sample size 250 mg (2 mm pieces)

The results appear in Table 3 below:

Blend Average silicone deposit (ppm) A+1 (comparative) Not detectable A + 2 (comparative) Not detectable A+3 (invention) 451

The mixture according to the invention allows a significant deposit on the hair in comparison with the comparative mixtures.

Claims (10)

Cosmetic composition comprising:
To. one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s);
b. an oil-in-water emulsion having a D50 particle size of less than 350 nm and comprising:
- a mixture of silicones comprising (i) one or more dialkylpolysiloxane(s) terminated by trialkylsilyl having a viscosity of 40,000 to less than 100,000 mPa.s at 25°C and (ii) one or more amino silicone(s) s) having a viscosity of 1,000 to 15,000 mPa.s at 25°C and an amine number of 2 to 10 mg of KOH per gram of amino silicone,
- an emulsifier blend comprising one or more non-ionic emulsifier(s), wherein the emulsifier blend has an HLB value of 10 to 16, and
- some water ;
vs. one or more chemical oxidizing agent(s) and/or one or more oxidation tint(s);
d. optionally one or more cationic polymer(s) different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s). Cosmetic composition according to Claim 1, in which the polymer(s) comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) is (are) chosen from homopolymers or copolymers comprising at least one of the units of the following formulas:
(II) (III)
in which :
- the R's₁, which may be identical or different, denote a hydrogen atom or a CH radical₃;
- the Rs, which may be identical or different, denote a C alkyl radical₁to C₁₂linear or branched, preferably a C alkyl radical₁to C₆linear, optionally substituted with one or more hydroxyl radicals;
-R₅, R₆and R₇, which may be identical or different, denote a C alkyl radical₁to C₁₈linear or branched or a benzyl radical, preferably a C alkyl radical₁to C₆linear or branched;
-R₈and R₉, which may be identical or different, denote a hydrogen atom or a C alkyl radical₁to C₆linear or branched, preferably methyl or ethyl; And
- Y^-means an anion derived from a mineral or organic acid or a halide, preferably a bromide, chloride, acetate, borate, citrate, tartrate, bisulphate, bisulphite, methosulphate, sulphate or phosphate anion. Cosmetic composition according to Claim 1 or 2, in which the polymer(s) comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) additionally contain(s) one or more unit(s) derived from comonomers which are chosen from the families of acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters, preferably chosen from the families acrylamides and methacrylamides, and more preferably acrylamide or methacrylamide. Cosmetic composition according to any one of the preceding claims, in which the polymer(s) comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) is (are) chosen ) from amphoteric polymers, and preferably from amphoteric polymers comprising a repetition of:
(i) one or more units derived from a monomer of (meth)acrylamide type,
(ii) one or more units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type, and
(iii) one or more units derived from an acid monomer of (meth)acrylic acid type. Cosmetic composition according to any one of the preceding claims, in which the polymer(s) comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) is (are) chosen ) among :
- halide copolymers of (meth)acrylamido (alkyl in C₁to C₆)tri(C-alkyl₁to C₄) ammonium/(meth)acrylamide, preferably copolymers of (meth)acrylamidopropyltrimonium chloride/(meth)acrylamide, and more preferably copolymers of acrylamidopropyltrimonium chloride/acrylamide,
- THE (meth)acrylamido(C-alkyl)halide terpolymers₁to C₆)tri(C-alkyl₁to C₄) ammonium/(meth)acrylamide/(meth)acrylic acid, preferably (meth)acrylamidopropyltrimonium chloride/(meth)acrylamide/(meth)acrylic acid terpolymers, more preferably acrylamide/methacrylamidopropyltrimethylammonium chloride terpolymers /acrylic acid,
- (meth)acrylamido(C-C alkyl) halide terpolymers₁to C₆)tri(C-alkyl₁to C₄) ammonium/(meth)acrylate (C-C₁to C₆)/(meth)acrylic acid, preferably the terpolymers of (meth)acrylamidopropyltrimonium chloride/(meth)acrylate (C₁to C₆)/(meth)acrylic acid; more preferably acrylic acid/methylacrylamidopropyltrimethylammonium chloride/methyl acrylates terpolymers,
- and mixtures thereof. Cosmetic composition according to any one of the preceding claims, in which the dialkylpolysiloxanes terminated by trialkylsilyl are of formula (IX): R' ₃ SiO(R' ₂ SiO) _p SiR' ₃ (IX),
in which :
- the R', which are identical or different, are a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, and
- p is an integer from 500 to 2000, preferably from 1000 to 2000;
and preferably are PDMSs (polydimethylsiloxanes or dimethicones) terminated by trimethylsilyl. Cosmetic composition according to any one of the preceding claims, in which the amino silicones are of formula (X): XR ₂ Si(OSiAR) _n (OSiR ₂ ) _m OSiR ₂ X (X),
in which :
- the Rs, which are identical or different, are a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms,
- the Xs, which are identical or different, are R or a hydroxyl group (OH) or a C ₁ to C ₆ alkoxy; preferably X is R,
- A is an amino radical of formula -R ¹ -[NR ² -R ³ -] _x NR ² ₂ , or protonated amino forms of said amino radical, in which R ¹ is a C ₁ to C ₆ alkylene radical, of preferably a radical of formula -CH ₂ CH ₂ CH ₂ - or -CH ₂ CH(CH ₃ )CH ₂ -, R ² , which are identical or different, are a hydrogen atom or a C ₁ to C ₄ alkyl radical , preferably a hydrogen atom, R ³ is a C ₁ to C ₆ alkylene radical, preferably a radical of formula -CH ₂ CH ₂ -, and x is 0 or 1;
And
- m+n is an integer from 50 to approximately 1000, preferably from 50 to 600;
preferably A is an amino radical of formula -R ¹ -[NR ² -R ³ -] _x NR ² ₂ , or protonated amino forms of said amino radical, in which R ¹ is -CH ₂ CH ₂ CH ₂ - or - CH ₂ CH(CH ₃ )CH ₂ -, the R ² are hydrogen atoms, R ³ is -CH ₂ CH ₂ -, and x is 1. Cosmetic composition according to any one of the preceding claims, in which the mixture of emulsifiers comprises one or more emulsifiers chosen from:
(i) polyoxyalkylenated alkyl ethers, in particular (poly)ethoxylated fatty alcohols of formula: R₃-(OCH₂CH₂)_vsOh with:
-R₃representing a C alkyl or alkenyl group₈to C₄₀ linear or branched, preferably a C alkyl or alkenyl group₈to C₃₀, optionally substituted with one or more hydroxyl groups, and
- c being an integer between 1 and 200 inclusive, preferably between 2 and 150;
and more particularly fatty alcohols comprising from 8 to 22 carbon atoms, oxyethylenated with 1 to 30 mol of ethylene oxide (1 to 30 EO);
(ii) (C₈to C₃₂) polyoxyalkylenated phenyl ether;
(iii) fatty acid esters (C₈to C₃₂) polyoxyalkylenated sorbitan, in particular polyethoxylated fatty acid esters of sorbitan preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; preferably fatty acid esters (in C₁₀to C₂₄) polyoxyethylene sorbitans preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; And
(iv) fatty acid esters (in C₈to C₃₂) polyoxyethylene containing for example from 2 to 150 mol of ethylene oxide; preferably fatty acid esters (in C₁₀to C₂₄) polyoxyethylene containing for example from 2 to 150 mol of ethylene oxide. Cosmetic composition according to any one of the preceding claims, in which the cationic polymer(s) different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) (s) is (are) chosen from homo or copolymers of dimethyldiallylammonium halides, preferably homo or copolymers of dimethyldiallylammonium chloride, better still a homopolymer of dimethyldiallylammonium chloride. Process for dyeing and/or lightening keratin fibres, consisting in applying to said keratin fibres, a composition comprising:
To. one or more polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s);
b. an oil-in-water emulsion having a D50 particle size of less than 350 nm and comprising:
- a mixture of silicones comprising (i) one or more dialkylpolysiloxane(s) terminated by trialkylsilyl having a viscosity of 40,000 to less than 100,000 mPa.s at 25°C and (ii) one or more amino silicone(s) s) having a viscosity of 1,000 to 15,000 mPa.s at 25°C and an amine number of 2 to 10 mg of KOH per gram of amino silicone,
- an emulsifier blend comprising one or more non-ionic emulsifier(s), wherein the emulsifier blend has an HLB value of 10 to 16, and
- some water ;
vs. one or more chemical oxidizing agent(s) and/or one or more oxidation tint(s);
d. optionally one or more cationic polymer(s) different from the polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s).