WO2020002590A1 - Polyurethanes functionalized with an organosilane group and compositions comprising same - Google Patents

Abstract

The present invention relates to a particular polyurethane functionalized with at least one organosilane group and to compositions comprising same. The present invention also relates to a method for treating keratin fibers, in particular human keratin fibers such as hair, comprising the application of one or more particular polyurethanes functionalized with at least one organosilane group or of a composition comprising same.

Description

 Description

Title: Polyurethanes functionalized by an organosilane group and

 compositions including them

The present invention relates to a particular polyurethane functionalized with at least one organosilane group as well as to compositions comprising it.

The present invention also relates to a process for treating keratin fibers, in particular human keratin fibers such as the hair, comprising the application of one or more polyurethane (s) particu Iier (s) functionalized (s) by at least one organosilane group or of a composition I e (s) comprising and optionally one or more pigments.

Many non-invasive technologies exist today to meet the needs of styling / styling. Styling products are usually used to build, structure the hairstyle and give it a lasting hold. These compositions generally comprise one or more fixing film-forming polymers, in a cosmetically acceptable medium. These polymers allow the formation of a sheathing film on the hair, or the formation of microwelds between the hair, thus ensuring the maintenance of the hairstyle.

Styling products are generally in the form of hairsprays, mousse or even gel. In particular, styling gels are often used to achieve high fixations of the hairstyle. Styling gels are compositions of one or more fixing film-forming polymers, thickened or gelled by one or more thickening polymers.

However, the effects brought by these technologies disappear during the first shampoo and it is necessary to reapply the styling products to be able to obtain the desired effect again. This again imposes on the consumer a more or less long and tedious routine. For example, for a brushing product for curly hair, after applying the styling spray, it is necessary to distribute the product evenly over the whole of the hair and then do a brushing, which can range from 5 to 45 minutes depending on the desired result. . Conversely, products in a durable form make it possible to permanently modify the structure of the fiber by breaking (reduction) of the disulphide bonds which impose the original shape of the hair then re-bridging (e.g. oxidation of cysteines to cystine after an action mechanical such as the installation of curlers in the case of perms). These products must however be reapplied at the root upon regrowth to maintain a homogeneous result. The results are irreversible and can cause damage to the hair. The superimposition of hair straightening products for example can cause discomfort and, ultimately, cause real degradation of the fiber which can go as far as breaking.

There is therefore a real need for a semi-permanent styling / styling product, that is to say the effect of which is persistent in at least one shampoo and which does not degrade the treated keratin fibers, which respects their integrity.

The term “styling / styling product” is intended to mean a product which provides performance in terms of discipline, corporalisation, definition of curl, volume control, shine, which facilitates shaping by natural drying, brushing and / or flat tweezers. , styling. In addition, the product must not generate static electricity.

In the field of dyeing keratin fibers, it is already known to color keratin fibers by different techniques from direct dyes for non-permanent dyes or dye precursors for permanent dyes.

Non-permanent coloring or direct coloring consists in dyeing the keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules with an affinity for keratin fibers. They are applied to the keratin fibers for a time necessary to obtain the desired coloration, then rinsed off.

To be visible on dark hair, these coloring techniques very often require a prior or simultaneous bleaching of the keratin fibers. This bleaching step carried out with an oxidizing agent such as hydrogen peroxide or persalts leads to a non-negligible degradation of the keratin fibers, which alters their cosmetic properties. The hair then tends to become coarse, more difficult to disentangle and more fragile.

Another coloring method is to use pigments. Indeed, the use of pigment on the surface of keratinous fibers generally makes it possible to obtain colorings visible on dark hair since the surface pigment masks the natural color of the fiber. The use of pigment for coloring keratin fibers is for example described in patent application FR 2 741 530, which recommends the use for the temporary coloring of keratin fibers of a composition comprising at least one dispersion of particles of film-forming polymer comprising at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion.

The colorings obtained by this mode of coloring have the disadvantage of being eliminated from the first shampoo.

It is also known from patent application FR 2 907 678 to carry out colored sheathings of the hair from a composition comprising a polysiloxane / polyurea block copolymer and a pigment. However, with such a composition, the sheaths obtained are not always very homogeneous and the individualization of the hair is not always very good.

Thus, there is a real need to develop compositions for coloring keratin fibers, in particular human keratin fibers such as the hair, which in particular make it possible to obtain homogeneous colorings, having good resistance to external agents (light, bad weather, brushing), and in particular good afterglow to shampoos.

There is therefore a need for a cosmetic treatment process for fibers

especially human keratin such as the hair which meets the following criteria:

^• Perceptible effect after application and after one or more shampoos,

^• Shaping keratin fibers, in particular human keratin fibers such as the hair, easily and durably,

^• Provides good cosmetic qualities,

^• Easy to use without risk of damaging the hair,

^• Compatible with conventional hair treatments (shampoos, conditioners, colorings) but also with sebum.

There is also a real need to develop compositions for dyeing keratin fibers, in particular human keratin fibers such as the hair, which in particular make it possible to obtain homogeneous dyes, having good resistance to external agents (light, bad weather, brushing), and in particular good afterglow to shampoos, while respecting keratin fibers.

Thus, this object is achieved with the present invention which relates to a process for treating keratin fibers, in particular the hair, from at least one particular polyurethane, functionalized with at least one organosilane group.

The present invention also relates to a functionalized polyurethane resulting from the reaction of:

- at least one prepolymer of formula (A) below:

in which,

 • Ri represents a bivalent radical of a hydrophilic compound chosen from carboxylic acids,

^• R ₂ represents a radical of a polyisocyanate,

^• R ₃ represents a radical of a polyhydroxy compound selected from lactone polyols, their adducts of alkylene oxide and mixtures thereof,

^• n represents an integer ranging from 1 to 5, and

• m is greater than 1,

 - at least one chain extender, and

 - at least one monomer of organosilane type of formula (I) below

R ₄ -NH-R ₅ Si (OR ₆ ) _z (R ₇ ) _x (I)

in which,

^• R ₄ represents a hydrogen atom or a hydrocarbon chain C ₄ to C _4, linear or branched,

^• R ₅ represents a C ₄ to C ₂₂ , in particular C ₄ to C ₂₀ , linear or branched, saturated or unsaturated, cyclic or acyclic hydrocarbon chain, which can be interrupted by a heteroatom (O, S, NH) or a group carbonyl (CO), R ₅ being linked to the silicon atom directly via a carbon atom;

^• R ₆ and R _7, identical or different, represent an alkyl group, linear or branched comprising from 1 to 6 carbon atoms,

^• z denotes an integer ranging from 1 to 3, and

 x denotes an integer ranging from 0 to 2,

with z + x = 3. The present invention also relates to a composition comprising one or more functionalized polyurethanes as defined above, and optionally one or more pigments.

The polymer of the invention makes it possible to obtain keratin fibers that are respectful of the fiber. In addition, these compositions make it possible to obtain a residual form of at least one shampoo. In addition, the composition according to the invention makes it possible to space out the shampoos by limiting the regreasing of the treated hair, gives better control of the volume, a reduction in frizz and a gain in discipline.

The hair thus shaped also exhibits good properties of

conditioning, especially in terms of individualization.

When the composition applied to the keratin fibers comprises the functionalized polyurethane (s) as defined above and one or more pigments, the keratin fibers, in particular the hair are dyed in a remanent manner with at least one shampoo , and this without degradation of the keratin fibers.

A coloration is thus obtained which is less insensitive to external aggressions such as washing and which remains tenacious over time.

Hair thus colored also has good conditioning properties, in particular in terms of cladding and individualization.

The invention also relates to a process for treating keratin fibers, in particular human keratin fibers such as the hair, comprising the application of the polyurethane (s) as defined above or of a composition as defined above.

In addition, the method according to the invention can involve a natural drying step and / or optionally a step of applying heat to the keratin fibers using a heating tool, the application of heat being able to intervene. during or after application of the composition, preferably after.

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

The invention is not limited to the examples illustrated. The characteristics of the different examples can in particular be combined within variants not illustrated. In what follows, and unless otherwise indicated, the bounds of a domain of values are included in this domain, in particular in the expressions “included between” and “ranging from to ···”.

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

By “keratin fibers” according to the present application, is meant human keratin fibers such as the hair and the eyelashes, and more particularly the hair.

Unless otherwise indicated, when the compounds are mentioned in the present application, their optical isomers, their geometric isomers, their tautomers, their salts or their solvates, alone or as a mixture, are also understood.

Functionalized polyurethanes

The functionalized polyurethane according to the invention is obtained from at least one prepolymer of formula (A), as defined above, that is to say resulting from the polymerization reaction of at least one polyisocyanate monomer, and at least one polyhydroxylated monomer (or compound) chosen from lactone polyols, their alkylene oxide adducts and their mixtures.

The polyisocyanates, represented by R2 in formula (A) above, are preferably chosen from diisocyanates, and more preferably from those represented by general formula R (NCO) ₂ , in which R represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

The diisocyanate (s) which can be used in the present invention are advantageously chosen from tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, isocyanate 3-isocyanatomethyl-3,5,5- trimethylcyclohexane (isophorone diisocyanate or I PDI), bis- (4-isocyanatocyclohexyl) -methane, 1,3-bis (isocyanatomethyl) -cyclohexane (isocyanatomethyl) -cycloh exan e, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane, isomers of toluene diisocyanate (TDI) such as 2,4-toluene diisocyanate, 2,6- toluene diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures with its isomers 2,4-diphenylmethane diisocyanate and optionally 2,2'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and mixtures thereof.

Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates.

More particularly, the polyisocyanate is 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate.

Preferably, the polyhydroxy compounds, represented by R ₃ in formula (A) above, are chosen from lactone diols, their alkylene oxide adducts and their mixtures.

The term "diol" is intended to include mixtures of diols as well as mixtures containing low levels of triols or tetrols which do not excessively affect the properties of the final product.

As alkylene oxides which can be used according to the present invention, mention may, for example, be made of ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, oxide isobutylene, epichlorohydrin, and mixtures thereof.

Lactone polyols can be prepared by reacting a lactone, such as epsilon-caprolactone or a mixture of epsilon-caprolactone and an alkylene oxide, with a polyfunctional initiator such as a polyhydric alcohol.

The term "lactone polyol" also includes various copolymers such as lactone copolyesters, lactone polyester / polycarbonates, polyester / lactone polyethers, and polyester / polyether / lactone polycarbonate / polycarbonate.

Preferably, the polyhydroxy compound is the caprolactone diol.

The weight ratio between the quantity of the polyhydroxylated compound (s), chosen from lactone polyols, their alkylene oxide adducts and their mixtures, and the quantity of the polyisocyanate (s) is preferably greater than or equal to 1, and more preferably between 1 and 5.

The molar ratio between the isocyanate functions and the sum of the alcohol and amine functions (that is to say alcohol + amine functions) preferably ranges from 0.8 to 1.5. According to a particularly preferred embodiment, the functionalized polyurethane according to the invention is obtained from at least one prepolymer resulting from the polymerization reaction of at least one polyisocyanate chosen from aliphatic diisocyanates, cycloaliphatic diisocyanates and mixtures thereof, and at least one polyhydroxy compound chosen from lactone polyols, their alkylene oxide adducts and their mixtures. In other words, the prepolymer is preferably of formula (A) in which R ₂ represents a polyisocyanate chosen from aliphatic diisocyanates, cycloaliphatic diisocyanates and their mixtures, and R ₃ represents a polyhydroxylated compound chosen from lactone polyols, their alkylene oxide adducts and their mixtures.

More preferably, the prepolymer results from the reaction of 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and of the caprolactone diol. In other words, the prepolymer is more preferably of formula (A) in which R ₂ represents a 3-isocyanatomethyl-3,5,5-trimethylcyclohexane radical and R ₃ represents a diol radical of caprolactone.

Preferably, the hydrophilic compound (or monomer), represented by R _x in the formula (A) above, is chosen from the compounds of formula (II) below:

 R-C (0) -0H (II)

in which, R represents a linear or branched, saturated or unsaturated C _j to Cm alkyl chain, substituted by one or more hydroxy group.

More preferably, R represents a branched alkyl chain, saturated in C 1 to C ₁₀ , better still in C _j to C ₆ , substituted by one or more hydroxy groups.

Preferably, the hydrophilic compound is 2,2-bis (hydroxymethyl) propionic acid.

The prepolymer of formula (A) according to the invention can be neutralized with a base, for example a primary, secondary or tertiary amine, the amine possibly or not containing (hydroxyl) substituents, such as amino-2-methyl- 2-propanol, and the salified or quaternized forms thereof. More particularly, the prepolymer is neutralized with a tertiary amine such as diisopropylethylamine. Other bases can be used such as potash, soda or ammonia.

The carboxylic groups can be neutralized before or after the formation of the prepolymer of formula (A). In other words, the neutralization can be carried out before or after the addition of the polyisocyanate monomer (s). Once formed, the prepolymer of formula (A) is extended with at least one chain extender.

The chain extenders which can be used according to the present invention are preferably chosen from low molecular weight diols.

By "low molecular weight diol" is meant, according to the present invention, a diol having a molecular weight of about 62 to 700, and preferably from 62 to 200. These diols can comprise aliphatic, alicyclic or aromatic groups. Preferably, they only include aliphatic groups.

Preferably, the chain extenders are chosen from low molecular weight diols having less than 20 carbon atoms, and more preferably chosen from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1 , 3-diol, butane 1,4-diol, pentane 1,5-diol, butylene 1,3-glycol, neopentyl glycol, butethylethylpropane diol, cyclohexane diol, 1,4- cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol A hydrogenated (2,2-bis (4-hydroxycyclohexyl) propane), and mixtures thereof .

After reaction with the chain extender, the polyurethane is functionalized with at least one monomer of the organosilane type of formula (I) as defined above.

Preferably, the organosilane type monomer (s) are chosen from the compounds of formula (I) for which R ₆ represents an alkyl group comprising from 1 to 4 carbon atoms and / or R ₇ represents an alkyl group comprising from 1 to 4 carbon atoms.

According to a particular preferred embodiment, R ₆ represents a linear alkyl group comprising from 1 to 4 carbon atoms. Preferably, R ₆ represents the ethyl group.

According to another preferred embodiment, R ₇ represents a linear alkyl group comprising from 1 to 4 carbon atoms. Preferably, R ₇ represents the methyl or ethyl group.

Preferably, R ₄ represents a hydrogen atom.

Advantageously, R ₅ is a linear or branched, saturated or unsaturated acyclic C _j to C ₆ hydrocarbon chain. More preferably, R ₅ is a linear and saturated C hydrocarbon chain _! to C ₆ , and better yet. R ₅ is a linear and saturated C ₂ to C ₄ hydrocarbon chain. Preferably, R ₅ is a linear and saturated C _j to C ₆ hydrocarbon chain, R ₄ represents a hydrogen atom, R ₆ represents an alkyl group comprising from 1 to 4 carbon atoms, and R ₇ represents an alkyl group comprising from 1 to 4 carbon atoms.

Preferably z is equal to 3.

The organosilane type monomer (s) of formula (I) are advantageously chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3 - aminopropyltriethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, p- aminophenyltrimethoxysilane, N- (2- aminoethylaminomethyphenethyltrimethoxysilane, and their mixtures, and more preferably among 3-aminopropyltriethoxysilane ETTES) , 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane and their mixtures.

More preferably, the organosilane type monomer of formula (I) is 3-aminopropyl triethoxysilane (APTES).

Preferably, the monomer (s) of organosilane type represents (s) from 1 to 20% by weight, and more preferably from 2 to 15% by weight, relative to the total weight of the polyurethane.

The polyurethanes of the invention are preferably obtained by the following process:

(D- The prepolymer of formula (A) is previously synthesized by reaction of the polyisocyanate monomer (s), and of the polyhydroxylated monomer (s) chosen from lactone polyols, their adducts alkylene oxide and their mixtures, in the presence of a catalyst, and preferably a tin-based catalyst such as tin ethyl-2-hexanoate. Hydrophilic monomers are also added to the reaction medium, and their acid functions are neutralized by the addition of at least one organic base as defined above. This polymerization step is preferably carried out in a solvent, and more particularly in acetone or methyl ethyl ketone. This polymerization step is preferably carried out at a temperature between 50 and 90 ° C, and more preferably between 50 and 85 ° C. (2) - The prepolymer thus formed is then lengthened by adding the extender (s) chain before being functionalized using organosilane compounds.

 (3) - Water may be added,

(4) - The solvent can be totally or partially removed by distillation.

(5) - One or more organic solvents can then be added to the composition containing the polymers and optionally water.

Thus, it is possible to obtain an aqueous dispersion of particles of functionalized polyurethane (s) as defined according to the present invention. Preferably, the aqueous dispersion thus obtained is a latex.

The functionalized polyurethane particles can have an average diameter of up to about 1000 nm, for example from about 30 nm to about 500 nm. These particle sizes can be measured with a laser particle sizer (eg Brookhaven B 190).

The content of functionalized polyurethane (dry matter), present in the final solution (acetone, methyl ethyl ketone or aqueous dispersion), preferably ranges from 20 to 70% by weight, relative to the total weight of the solution.

Composition

The composition useful according to the invention is preferably a composition for treating keratin fibers, in particular human keratin fibers such as the hair.

The composition used according to the invention comprises at least one particular polyurethane, functionalized with at least one organosilane group as defined above.

The content of the functionalized polyurethane (s) present in the composition according to the invention preferably ranges from 1 to 30% by weight, and more preferably from 5 to 25% by weight, relative the total weight of the composition.

According to one embodiment, the composition according to the present invention further comprises one or more pigments.

By “pigment -” is meant all the pigments bringing color to the keratin materials. Their solubility in water at 25 ° C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%. The pigments which can be used are in particular chosen from the organic and / or mineral pigments known in the art, in particular those which are described in the encyclopedia of chemical technology of Kirk-Othmer and in the encyclopedia of industrial chemistry of Ullmann.

These pigments can be in the form of powder or pigment paste. They can be coated or uncoated.

The pigments can for example be chosen from mineral pigments, organic pigments, lacquers, pigments with special effects such as nacres or glitter, and mixtures thereof.

The pigment may preferably be an inorganic pigment. "Mineral pigment" means any pigment that meets the definition of the Ullmann encyclopedia in the chapter on inorganic pigment. Mention may be made, among the mineral pigments useful in the present invention, of iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

The pigment may preferably be an organic pigment. By "organic pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the chapter on organic pigment. The organic pigment can in particular be chosen from the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of the metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

In particular, the white or colored organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments coded in the Color Index under the references Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references Cl 12085, 12120 , 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole derivatives , phenolic as they are dec rits in patent FR 2,679,771. The pigments in accordance with the invention may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising an inorganic core, at least one binder ensuring the fixing organic pigments on the core, and at least one organic pigment at least partially covering the core.

The organic pigment can also be a lacquer. By "lacquer" is meant the dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use.

The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

Among the dyes, mention may be made of cochineal carmine. Mention may also be made of the dyes known under the following names: D & C Red 21 (Cl 45 380), D & C Orange 5 (Cl 45 370), D & C Red 27 (Cl 45 410), D & C Orange 10 (Cl 45 425), D & C Red 3 (Cl 45 430), D & C Red 4 (Cl 15 510), D & C Red 33 (Cl 17 200), D & C Yellow 5 (Cl 19 140), D & C Yellow 6 (Cl 15 985), D & C Green (Cl 61 570), D & C Yellow 1 O (Cl 77 002), D & C Green 3 (Cl 42 053), D & C Blue 1 ( Cl 42,090).

Examples of lacquers that may be mentioned include the product known under the following name: D & C Red 7 (Cl 15 850: 1).

The pigment can also be a special effect pigment. By "special effect pigments" is meant pigments which generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is non-uniform and changeable according to the conditions of observation (light , temperature, angles of observation · · ·) · They therefore oppose the colored pigments which provide a uniform opaque, semi-transparent or transparent classic shade.

There are several types of pigments with special effects, those with a low refractive index such as fluorescent, photochromic or thermochromic pigments, and those with a high refractive index such as nacres or flakes.

Examples of pigments with special effects include pearlescent pigments such as titanium mica coated with an iron oxide, mica coated with an iron oxide, mica coated with bismuth oxychloride, mica titanium coated with chromium oxide, titanium mica coated with an organic dye, in particular of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It can also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic coloring matters.

The nacres can more particularly have a yellow or pink, red, bronze, orange, brown, gold and / or coppery color or reflection.

As an illustration of the nacres which can be used in the context of the present invention, mention may be made in particular of the gold-colored nacres sold in particular by the company ENGELHARD under the name Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold in particular by the company MERCK under the name Fine bronze (17384) (Colorona) and Bronze (17353) (Colorona), by the company Eckart under the

name Prestige Bronze and by ENGELHARD under the name Super bronze (Cloisonne); the orange nacres sold in particular by the company ENGELHARD under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the pearls of brown tint in particular

sold by ENGELHARD under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-reflective nacres sold in particular by ENGELHARD under the name Copper 340A (Timica) and by Eckart under the name Prestige Copper; mother-of-pearl with a red reflection, in particular sold by the company MERCK under the name Sienna fine (17386) (Colorona); the yellow-reflective nacres sold in particular by the company ENGELHARD under the name Yellow (4502) (Chromalite); the red-tinted pearls with a gold reflection, in particular sold by the company ENGELHARD under the name Sunstone G012 (Gemtone); black mother-of-pearl with a gold reflection in particular sold by the company ENGELHARD under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl in particular marketed by the company MERCK under the name Matte blue (17433) (Microna), Dark Blue (117324) (Colorona), the white pearls with a silver reflection in particular marketed by the company MERCK under the name Xirona Silver and the pinkish golden green orange nacres in particular marketed by the company MERCK under the name Indian summer (Xirona) and their mixtures. In addition to nacres on a mica support, one can consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium borosilicate and sodium or calcium borosilicate and aluminum, and aluminum.

Mention may also be made of pigments with an interference effect which are not fixed on a substrate such as liquid crystals (Helicones HC from Wacker), holographic interference flakes (Geometry Pigments or Spectra f / x from Spectratek). Special effect pigments also include fluorescent pigments, whether they are substances which fluoresce in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, pigments

thermochromic and quantum dots, sold for example by the company Quantum Dots Corporation.

The variety of pigments which can be used in the present invention makes it possible to obtain a rich palette of colors, as well as specific optical effects such as metallic, interference effects.

The size of the pigment used in the cosmetic composition according to the present invention is generally between 10 nm and 200 m m, preferably between 20 nm and 80 m m, and more preferably between 30 nm and 50 m m.

The pigments can preferably be dispersed in the product using a dispersing agent.

The dispersing agent serves to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent can be a surfactant, an oligomer, a polymer or a mixture of several of them, carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can physically or chemically cling to the surface of the pigments. These dispersants also have at least one functional group which is compatible or soluble in the continuous medium. In particular, the esters of 12-hydroxy stearic acid in particular and of C ₈ to C ₂₀ fatty acid and of polyol such as glycerol, diglycerin, such as poly (12-hydroxystearic acid stearate) are used. ) of molecular weight of approximately 750 g / mole such as that sold under the name of Solsperse 21,000 by the company Avecia, 2-polygyceryl-dipolyhydroxystearate (name CTFA) sold under the reference Dehymyls PGPH by the company Henkel or else l polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures. As other dispersant which can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17,000 sold by the company Avecia, mixtures of poly dimethylsiloxane / oxypropylene such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C.

The pigments which can be used in the cosmetic composition according to the invention can be surface-treated with an organic agent.

Thus, the pigments previously treated on the surface that can be used in the context of the invention are pigments which have undergone totally or partially a surface treatment of chemical, electronic, electro-chemical, mechanical-chemical or mechanical nature, with an organic agent such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, p. 53-64 before being dispersed in the composition according to the invention. These organic agents can, for example, be chosen from amino acids; waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polysaccharides, for example chitosan, cellulose and its derivatives; polyethylene; polymers

(meth) acrylics, for example polymethylmethacrylates; polymers and

copolymers containing acrylate units; the proteins ; alkanoamines; silicone compounds, for example silicones, polydimethylsiloxanes,

alkoxysilanes, alkylsilanes, siloxy-silicates; fluorinated organic compounds, for example perfluoroalkyl ethers; fluoro-silicone compounds.

The surface-treated pigments usable in the cosmetic composition according to the invention may also have been treated with a mixture of these compounds and / or have undergone several surface treatments.

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

Preferably, the surface-treated pigments are covered with an organic layer. The organic agent with which the pigments are treated can be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments.

The surface treatment can thus be carried out for example by chemical reaction of a surfactant with the surface of the pigments and creation of a covalent bond between the surfactant and the pigments or the fillers. This method is described in particular in US patent 4,578,266.

Preferably, an organic agent linked to the pigments will be used covalently.

The agent for the surface treatment may preferably represent from 0.1 to 50% by weight of the total weight of the pigments treated on the surface, more preferably from 0.5 to 30% by weight, and better still from 1 to 10%. in weight.

Preferably, the surface treatments of the pigments are chosen from the following treatments:

 - PEG-Silicone treatment such as the AQ surface treatment marketed by LCW

- a Chitosan treatment such as the CTS surface treatment marketed by LCW;

- Triethoxycaprylylsilane treatment such as AS surface treatment

marketed by LCW;

 - a methicone treatment such as the IS surface treatment marketed by LCW;

- a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW;

 - a Dimethicone / Trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment sold by LCW;

 - a Lauroyl Lysine treatment such as the LL surface treatment marketed by LCW;

 - a Lauroyl Lysine Dimethicone treatment such as the LL / SI surface treatment marketed by LCW;

 - a Magnesium Myristate treatment such as the surface treatment M M

marketed by LCW;

 - Aluminum Dimyristate treatment such as surface treatment M l

marketed by Miyoshi;

- a Perfluoropolymethyl isopropyl ether treatment such as the FHC surface treatment marketed by LCW; - an Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi;

 - a Disodium Stearoyl Glutamate treatment such as the NAI surface treatment marketed by Miyoshi;

 - a Dimethicone / Disodium Stearoyl Glutamate treatment such as the SA / NAI surface treatment marketed by Miyoshi;

 - a Perfluoroalkyl phosphate treatment such as the PF surface treatment marketed by Daito;

 - an acrylate / dimethicone copolymer and perfluoalkyl phosphate treatment, such as the FSA surface treatment marketed by Daito;

 - a Polymethylhydrogen siloxane / Perfluoroalkyl phosphate treatment such as the FS01 surface treatment marketed by Daito;

 - a Lauryl Lysine / Aluminum Tristearate treatment such as the LL-StAI surface treatment marketed by Daito;

 - an Octyltriethylsilane treatment such as the OTS surface treatment marketed by Daito;

 - an Octyltriethylsilane / Perfluoroalkyl phosphate treatment such as the FOTS surface treatment marketed by Daito;

 - an Acrylate / Dimethicone Copolymer treatment such as the ASC surface treatment marketed by Daito;

 - an Isopropyl Titanium Triisostearate treatment, such as the ITT surface treatment marketed by Daito;

 - a Microcrystalline Cellulose and Carboxymethyl Cellulose treatment such as the AC surface treatment marketed by Daito;

 - a Cellulose treatment such as the C2 surface treatment marketed by Daito;

- an acrylate copolymer treatment such as the APD surface treatment marketed by Daito; and

 -a Perfluoroalkyl phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

The composition according to the present invention can optionally further comprise one or more pigments which are not surface treated.

According to a particular embodiment of the invention, the pigment or pigments are mineral pigments. According to another particular mode of the invention, the pigment or pigments are chosen from pearlescent agents.

The amount of the pigment (s) present in the coloring composition according to the invention preferably ranges from 0.5 to 40% by weight, and more preferably from 1 to 20% by weight, relative to the total weight of the coloring composition.

The weight ratio between the quantity of functionalized polyurethane (s) and the quantity of pigment (s) present in the composition according to the invention is greater than or equal to 1, more preferably greater or equal to 1.5, and better still this weight ratio goes from 1.5 to 10.

The composition according to the invention comprises functionalized polyurethane (s) in solution or in the form of a dispersion.

The composition according to the present invention can comprise water. Preferably, the water content is greater than or equal to 30% by weight, relative to the total weight of the composition.

Preferably, the water content, present in the composition of the invention, ranges from 30 to 80% by weight, and more preferably from 50 to 75% by weight, relative to the total weight of the composition.

The composition according to the present invention can optionally comprise one or more organic solvents, or mixtures thereof.

As organic solvent, there may be mentioned, for example, alkanols, linear or branched, C ₂ to C ₄ , such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols or ethers such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

Other solvents can also be used such as acetone, butyl acetate or methyl ethyl ketone.

According to a preferred form of the invention, the particular polyurethane (s) of the invention are obtained by the following process and then used in the useful composition of the shaping process: (D- The prepolymer of formula (A) is previously synthesized by reaction of the polyisocyanate monomer (s), and of the polyhydroxylated monomer (s) chosen from lactone polyols, their adducts alkylene oxide and their mixtures, in the presence of a catalyst, and preferably a tin-based catalyst such as tin ethyl-2-hexanoate. Hydrophilic monomers are also added to the reaction medium, and their acid functions are neutralized by the addition of at least one organic base as defined above. This polymerization step is preferably carried out in a solvent, and more particularly in acetone or methyl ethyl ketone. This polymerization step is preferably carried out at a temperature between 50 and 90 ° C, and more preferably between 50 and 85 ° C.

(2) - The prepolymer thus formed is then lengthened by adding the chain extender (s) before being functionalized using organosilane compounds.

 (3) - Water is added,

(4) the solvent is completely removed by distillation.

In other words, according to this preferred form of the invention, the particular polyurethane (s) of the invention are obtained in the form of an aqueous dispersion and used as such in the useful composition of the shaping process.

According to another embodiment of the invention, the particular polyurethane (s) of the invention are obtained by the following process and then used in the useful composition of the shaping process:

(D- The prepolymer of formula (A) is previously synthesized by reaction of the polyisocyanate monomer (s), and of the polyhydroxylated monomer (s) chosen from lactone polyols, their adducts alkylene oxide and their mixtures, in the presence of a catalyst, and preferably a tin-based catalyst such as tin ethyl-2-hexanoate. Hydrophilic monomers are also added to the reaction medium, and their acid functions are neutralized by the addition of at least one organic base as defined above. This polymerization step is preferably carried out in a solvent, and more particularly in acetone or methyl ethyl ketone. This polymerization step is preferably carried out at a temperature between 50 and 90 ° C, and more preferably between 50 and 85 ° C. (2) - The prepolymer thus formed is then lengthened by adding the chain extender (s) before being functionalized using organosilane compounds.

(4) the solvent is partially removed by distillation.

In other words, according to this particular form of the invention, the particular polyurethane (s) of the invention are obtained in the form of a solution in a solvent, at a concentration preferably of 20 to 70% by weight, and used as such in the useful composition of the shaping process.

Preferably, the composition is in the form of a dispersion, in particular a dispersion in water.

More preferably, the composition is in the form of a dispersion in water, and may contain an organic solvent (s) chosen from acetone, butyl acetate, methyl ethyl ketone and their mixtures in contents in particular from 0.0001% to 5% by weight relative to the total weight of the composition.

When present, organic solvents usually represent

0.0001% to 40% by weight, more preferably 50 to 85% by weight, relative to the total weight of the composition.

The composition according to the present invention may optionally further comprise one or more additives, different from the compounds of the invention and among which mention may be made of cationic, anionic, nonionic, amphoteric or

zwitterionics, anionic, nonionic, amphoteric polymers or their mixtures, dandruff agents, antiseborrhoeic agents, hair loss and / or regrowth agents, vitamins and pro-vitamins including panthenol, organic sunscreens, dyes direct, dye precursors such as oxidation bases and couplers, sequestering agents, plasticizing agents, solubilizing agents, acidifying agents, mineral or organic thickening agents, in particular polymeric thickening agents, anti-aging agents oxidants, hydroxy acids, fragrances, preservatives and ceramides.

The above additives can generally be present in an amount for each of them between 0 and 20% by weight, relative to the total weight of the composition.

Treatment process The present invention also relates to a method for treating keratin fibers, in particular human keratin fibers such as the hair, comprising (i) the application to the keratin fibers of the polyurethane (s) or of a composition as defined above.

The composition described above can be used on dry or wet keratin fibers as well as on all types of light or dark fibers, natural or colored, permed, discolored or straightened. Preferably, the composition useful in the process according to the invention is used on wet keratin fibers.

According to a particular embodiment of the process of the invention, the fibers are washed before application of the composition described above.

The application of the composition of the invention to keratin fibers can be carried out for example by means of a comb, of a brush, with the aid of a brush or with the fingers.

The application of the composition of the invention to keratin fibers can also be implemented for example by means of a spray.

The process of the invention may contain a step (ii) of shaping the keratin fibers. According to this step, the keratin fibers can be shaped for example with a comb, a brush or with a finger, or even be held by pliers, curlers or any other means intended to maintain the fibers in a particular form or to their give a particular shape.

When the composition of the invention contains one or more pigments, the process of the invention is a process for dyeing keratin fibers, in particular the hair.

In addition, the method according to the invention may involve a natural drying step and / or optionally a step of applying heat to the keratin fibers using a heating tool.

The step of applying heat can take place during or after the step of applying the composition. Preferably, the heat application stage occurs after the application of the composition or of the polyurethane (s) particu I i er (s) of the invention.

According to a particular embodiment of the invention, the application of the composition is then followed by drying at a temperature preferably above 40 ° C., more preferably greater than 45 ° C, and better still, this temperature is greater than 45 ° C and less than 220 ° C.

This drying can be carried out immediately after the application of the composition or after an exposure time which can range from 1 to 30 minutes, without an intermediate rinsing step.

Preferably, the keratin fibers are dried, in addition to providing heat, with a flow of air. This air flow during drying improves the individualization of keratin fibers, in particular human keratin fibers such as the hair.

The drying step of the process of the invention can optionally be carried out with a helmet, a hair dryer, a straightening iron or a climazon.

The heat application step can be performed using any heating device.

One or more heating tools can be applied individually or successively to the hair.

The heating tool can be a straightening iron, a curling iron, a crimping iron, a stirring iron, a helmet, a hair dryer, an infrared heating system, a heated curler.

Preferably, the heating tool is a straightening iron or a hair dryer.

When the drying step is carried out with a helmet or a hairdryer, the drying temperature is preferably between 40 and 110 ° C, and more preferably between 50 and 90 ° C.

A straightening iron can also be used, the drying temperature is then preferably between 110 and 220 ° C, and more preferably between 140 and 200 ° C.

Once the drying is finished, a final rinse or shampoo can possibly be carried out.

During drying, the fibers can be shaped by a mechanical action exerted on the fibers such as combing, brushing, or the passage of the fingers. The present invention also relates to the use of one or more polyurethane (s) as defined above for the shaping of keratin fibers, in particular human keratin fibers such as the hair.

The present invention further relates to the use of a composition as defined above for the shaping of keratin fibers, in particular human keratin fibers such as the hair.

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

Examples

- Example 1: synthesis of polyurethane-f-APTES containing 6% by weight of APTES monomers, dispersed in water

Acetone (90g), caprolactone diol (CAPA 2200 - 82g), 2,2-bis (hydroxymethyl) propionic acid (8g) are introduced into a 1 liter reactor, under an argon atmosphere. , diisopropyl ethylamine (7g), in order to neutralize 90% of the acid units, and a catalyst (2-ethyl tin hexanoate - 25 ppm). The medium is heated to a temperature between 55 and 60 ° C.

 When the temperature is reached and the solution is homogeneous, 38.9 g of isophorone diisocyanate are added little by little. After 2 h 30 of reaction, 3.5 g of 1,5-pentane diol are added. Leave to react for 3 hours before lowering the temperature to 40 ° C.

 9g of (3-aminopropyl) triethoxysilane are then added to the medium and stirring is continued for 2 hours.

 The dispersion in water is carried out the following day by adding drop by drop 345 g of water to the synthesis solution with stirring at 350 rpm. The acetone is then removed by distillation and a pale pale yellow solution is obtained.

 The polyurethane-f-APTES thus formed is found in a dry extract of 30% by weight in water.

- Example 2: synthesis of polyurethane-f-APTES containing 14% by weight of APTES monomers, dispersed in water

Acetone (90g), caprolactone diol (CAPA 2200 - 82g), 2,2-bis (hydroxymethyl) propionic acid (8g) are introduced into a 1 liter reactor, under an argon atmosphere. , diisopropyl ethylamine (7g), in order to neutralize 90% of the acid units, and a catalyst (2-ethyl tin hexanoate - 25 ppm). The medium is heated to a temperature between 55 and 60 ° C.

 When the temperature is reached and the solution is homogeneous, 48g of isophorone diisocyanate are added little by little. After 2 h 30 of reaction, 1.5 g of 1,5-pentane diol are added. Leave to react for 3 hours before lowering the temperature to 40 ° C.

 22.5 g of (3-aminopropyl) triethoxysilane are then added to the medium and stirring is continued for 2 hours.

 The dispersion in water is carried out the next day by adding 400 g of water drop by drop to the synthesis solution with stirring at 350 rpm. The acetone is then removed by distillation and a turbid white solution is obtained.

 The polyurethane-f-APTES thus formed is found in a dry extract of 30% by weight in water.

- Example 3: synthesis of polyurethane-f-APTES containing 6% by weight of APTES monomers, dispersed in water

In a 1 liter reactor, under an argon atmosphere,

methyl ethyl ketone (90g), caprolactone diol (CAPA 2200 - 80g), 2,2-bis (hydroxymethyl) propionic acid (8g), diisopropyl ethylamine (7g), in order to neutralize 90% of the acid units, and a catalyst (2 ethyl ethyl hexanoate - 25ppm). The medium is heated to a temperature between 80 and 85 ° C.

 When the temperature is reached and the solution is homogeneous, 47 g of isophorone diisocyanate are added little by little. After 2 h 30 of reaction, 2 g of 1,5-pentane diol are added. Leave to react for 3 hours before lowering the temperature to 40 ° C.

 9g of (3-aminopropyl) triethoxysilane are then added to the medium and stirring is continued for 2 hours.

 Dispersion in water is carried out the next day by adding 200g of the

methyl ethyl ketone then, drop by drop 542g of water in the synthesis solution with stirring at 350 rpm. The acetone is then removed by distillation and a bluish, bluish solution is obtained.

 The polyurethane-f-APTES thus formed is found in a dry extract of 24% by weight in water.

- Example 4: synthesis of polyurethane-f-APTES containing 14% by weight of APTES monomers, dispersed in water In a 1 liter reactor, under an argon atmosphere, is introduced

methyl ethyl ketone (90g), caprolactone diol (CAPA 2200 - 50g), 2,2-bis (hydroxymethyl) propionic acid (7g), diisopropyl ethylamine (6.2g), in order to neutralize 90% of the motifs acids, and a catalyst (2 ethyl ethyl hexanoate - 25ppm). The medium is heated to a temperature between 80 and 85 ° C.

 When the temperature is reached and the solution is homogeneous, 44.4 g of isophorone diisocyanate are added little by little. After 2 h 30 of reaction, 3.1 g of 1,5-pentane diol are added. Leave to react for 3 hours before lowering the temperature to 40 ° C.

 17.2 g of (3-aminopropyl) triethoxysilane are then added to the medium and stirring is continued for 2 hours.

 The dispersion in water is carried out the following day by adding drop by drop 490g of water to the synthesis solution with stirring at 350 rpm. The methyl ethyl ketone is then removed by distillation and a bluish, bluish solution is obtained.

 The polyurethane-f-APTES thus formed is found in a dry extract of 30% by weight in water.

- Example 5: synthesis of polyurethane-f-APTES containing 6% by weight of APTES monomers, soluble in acetone

In a one liter reactor, under an argon atmosphere, acetone (61g), caprolactone diol (CAPA 2200 - 55.2g), 2.2-bis (hydroxymethyl) propionic acid ( 5.4 g), diisopropyl ethylamine (4.7 g), in order to neutralize 90% of the acid units, and a catalyst (2-ethyl tin hexanoate - 25 ppm). The medium is heated to a temperature between 55 and 60 ° C.

 When the temperature is reached and the solution is homogeneous, 26.3 g of isophorone diisocyanate are added little by little. After 2 h 30 of reaction, 2.4 g of 1,5-pentane diol are added. Leave to react for 3 hours before lowering the temperature to 40 ° C.

 6.1 g of (3-aminopropyl) triethoxysilane are then added to the medium and stirring is continued for 2 hours.

 At the end of the reaction, the polyurethane-f-APTES thus formed is in a dry extract of 60% by weight in acetone.

- Example 6: _synthesis of polyurethane-f-APTES containing 6% by weight of APTES monomers, dispersed in water In a one liter reactor, under an argon atmosphere, acetone (61g), caprolactone diol (CAPA 2200 - 55.2g), 2.2-bis (hydroxymethyl) propionic acid ( 5.4 g), diisopropyl ethylamine (4.7 g), in order to neutralize 90% of the acid units, and a catalyst (2-ethyl tin hexanoate - 25 ppm). The medium is heated to a temperature between 55 and 60 ° C.

 When the temperature is reached and the solution is homogeneous, 26.3 g of isophorone diisocyanate are added little by little. After 2 h 30 of reaction, 2.4 g of 1,5-pentane diol are added. Leave to react for 3 hours before lowering the temperature to 40 ° C.

 6.1 g of (3-aminopropyl) triethoxysilane are then added to the medium and stirring is continued for 2 hours.

 The dispersion in water is carried out the next day by adding drop by drop 232 g of water to the synthesis solution with stirring at 350 rpm. The acetone is then removed by distillation and a turbid white solution is obtained.

 The polyurethane-f-APTES thus formed is found in a dry extract of 30% by weight in water.

- Example 7: _synthesis of polyurethane-f-APTES containing 13% by weight of APTES monomers, dispersed in water

Acetone (61g), caprolactone diol (CAPA 2200 - 48.5g), 2,2-bis (hydroxymethyl) propionic acid (in a argon atmosphere, under an argon atmosphere) are introduced. 4.7 g), diisopropyl ethylamine (4.1 g), in order to neutralize 90% of the acid units, and a catalyst (2-ethyl tin hexanoate - 22 ppm). The medium is heated to a temperature between 55 and 60 ° C.

 When the temperature is reached and the solution is homogeneous, 28.4 g of isophorone diisocyanate are added little by little. After 2 h 30 of reaction, 0.9 g of 1,5-pentane diol are added. Leave to react for 3 hours before lowering the temperature to 40 ° C.

 13.3 g of (3-aminopropyl) triethoxysilane are then added to the medium and stirring is continued for 2 hours.

 The dispersion in water is carried out the following day by adding drop by drop 237 g of water to the synthesis solution with stirring at 350 rpm. The acetone is then removed by distillation and a turbid white solution is obtained.

The polyurethane-f-APTES thus formed is found in a dry extract of 30% by weight in water. - Example 8: Effect of polyurethane-f-APTES dispersed in water on the shaping of the hair

(a) The compositions

The compositions (A1) to (A8) according to the invention were prepared from the ingredients, the contents of which, expressed as a percentage by mass of active material, relative to the total weight of each composition, are mentioned in the table below.

[Table 1]

(b) Procedure The compositions (A1) to (A8) thus obtained were applied to locks of hair at 90% natural, previously washed and dried, in an amount of 0.5 g of composition per lock of hair (from 2, 7g). The locks were then dried either in the open air or using a hair dryer with brushing. The remanence of the shaping was evaluated after a shampoo according to the following protocol: the locks were rinsed with lukewarm water by rubbing them 5 times from root to tip; then washed with Garnier UltraDoux shampoo, rubbing them 10 times from root to tip; then rinsed with lukewarm water, rubbing them 15 times from root to tip; then wrung in absorbent paper; then dried in the open air.

The fixation is evaluated at the end of each protocol by a score of 0 to 5 (0: no fixation; 5: very fixing).

(c) Results

The values of the scores for each of the compositions (A1) to (A8) are given in the table below.

[Table 2]

The above results show that the compositions according to the invention (A1) to (A8) comprising a polyurethane according to the invention make it possible to obtain keratin fiber shaping.

[Table 3]

In addition, the above results show that the compositions (A2), (A5) and (A6) make it possible to obtain a residual form after shampooing.

- Example 9: Composition of polyurethane-f-APTES dispersed in water and containing pigments

(a) The compositions

The compositions (A9) and (A10) according to the invention were prepared from the ingredients, the contents of which, expressed as a percentage by mass, relative to the total weight of each composition, are mentioned in the table below. [Table 4]

ma: active ingredient (b) Procedure

The compositions (A9), (A10) thus obtained were applied to locks of hair containing 90% natural hair at the rate of 0.5 g of composition per lock of hair. The locks were then dried with a hair dryer, then left to stand for 24 hours at room temperature.

After 24 hours, the wicks were rinsed with water.

The tenacity of the staining was evaluated with a Konica Minolta CL-3610A ^® spectrophotometer in the L * a * b * system. In this system, L * represents the intensity, the lower the value of L *, the more intense the coloration obtained. Chromaticity is measured by the values a * and b *, a * representing the red / green axis and b * the yellow / blue axis

DE allows to measure the color variation at the time of application and after 24 hours and rinsing with water according to the formula:

in which, L * represents the intensity a * and b *, the chromaticity of the hair after rinsing and L ₀ * represents the intensity and a ₀ * and b ₀ * the chromaticity of the hair before rinsing. The resistance of the color is higher the lower the DE.

(c) Results

The colorimetric values obtained for each of the compositions (A9) and (A10) are given in the table below. [Table 5]

Les résultats ci-dessus montrent que les colorations obtenues à partir des compositions (A9) et (A10), sont résistantes à l’eau.

The above results show that the colors obtained from compositions (A9) and (A10) are resistant to water.

- Example 10: composition of polyurethane-f-APTES solubilized in acetone and pigments

(a) The compositions

The composition (Garlic) according to the invention was prepared from the ingredients, the contents of which, expressed as a percentage by mass, relative to the total weight of each composition, are mentioned in the table below. [Table 6]

 ma: active ingredient

(b) Procedure

The composition (Garlic) thus obtained in the form of a solution was applied to locks of hair containing 90% natural hair at the rate of 0.5 g of composition per lock of hair. The locks were then dried with a hair dryer and disentangled, before being left to stand for 24 hours at room temperature.

After 24 hours, the locks were rinsed with water and then washed with shampoo.

The tenacity of the coloration was evaluated in the L * a * b * system according to the procedure of Example 9. In this example 10, L * represents the intensity a * and b *, the chromaticity of the hair after rinsing or after washing and L ₀ * represents the intensity and a ₀ * and b ₀ * the chromaticity of the hair before rinsing and washing .

The color resistance is higher the lower the DE. (c) Results

The colorimetric values obtained for the composition (Ail) are given in the table below.

[Table 7]

Les résultats ci-dessus montrent que la composition (Ail), comprenant le polyuréthane fonctionnalisé de l’invention, conduit à des colorations qui sont non seulement résistantes à l’eau, mais également rémanentes à au moins cinq shampoings.

The above results show that the composition (Garlic), comprising the functionalized polyurethane of the invention, results in colorings which are not only resistant to water, but also persistent in at least five shampoos.

Claims

claims [Claim 1] Functionalized polyurethane resulting from the reaction of: - at least one prepolymer of formula (A) below:

 in which,  • Ri represents a bivalent radical of a hydrophilic compound chosen from carboxylic acids, R ₂ represents a radical of a polyisocyanate, R ₃ represents a radical of a polyhydroxy compound chosen from lactone polyols, their alkylene oxide adducts and their mixtures,  • n represents an integer ranging from 1 to 5, and  • m is greater than 1,  - at least one chain extender, and  - at least one monomer of organosilane type of formula (I) below R ₄ -NH-R ₅ Si (OR ₆ ) _z (R ₇ ) _x (I)  in which, ^• R ₄ represents a hydrogen atom or a hydrocarbon chain C ₄ to C _4, linear or branched, ^• R ₅ represents a C ₄ to C ₂₂ , in particular C ₄ to C ₂₀ , linear or branched, saturated or unsaturated, cyclic or acyclic hydrocarbon chain, which can be interrupted by a heteroatom (O, S, NH) or a group carbonyl (CO), R ₅ being linked to the silicon atom directly via a carbon atom; ^• R ₆ and R _7, identical or different, represent an alkyl group, linear or branched comprising from 1 to 6 carbon atoms, ^• z denotes an integer ranging from 1 to 3, and  • x denotes an integer ranging from 0 to 2,  with z + x = 3. [Claim 2] Polyurethane according to the preceding claim, characterized in that the polyisocyanate is chosen from diisocyanates [Claim 3] Composition according to claim 1 or 2, characterized in that the polyisocyanate is chosen from the diisocyanates represented by the general formula R (NCO) ₂ , in which R represents a hydrocarbon group  divalent aliphatic having 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms carbon. [Claim 4] Polyurethane according to any one of the claims  above, characterized in that the polyisocyanate is 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate. [Claim 5] Polyurethane according to any one of the claims  above, characterized in that the polyhydroxy compound is chosen from lactone diols, their alkylene oxide adducts and their mixtures. [Claim 6] Polyurethane according to any one of the claims  above, characterized in that the polyhydroxylated compound is the caprolactone diol. [Claim 7] Polyurethane according to any one of the claims  above, characterized in that the weight ratio between the quantity of the polyhydroxylated compound (s), chosen from lactone polyols, their alkylene oxide adducts and their mixtures, and the quantity of or some  polyisocyanate (s) is greater than or equal to 1, and preferably between 1 and 5. [Claim 8] Polyurethane according to any one of the claims  above, characterized in that the hydrophilic compound is chosen from the compounds of formula (II) below:  R-C (0) -0H (II) in which, R represents a linear or branched alkyl chain, saturated or unsaturated at C _j to C ₁₀ , substituted by one or more hydroxy group, preferably R represents a branched alkFyle chain, saturated at C 1 to C ₁₀ , better still at C 1 to C ₆ , substituted by one or more hydroxy groups. [Claim 9] Polyurethane according to any one of the claims above, characterized in that the chain extender (s) are chosen from low molecular weight diols having less than 20 carbon atoms, and preferably from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1,3-diol, butane 1,4-diol, pentane 1,5-diol, butylene 1,3- glycol, neopentyl glycol, butethyl-ethyl-propane diol, cyclohexane diol, 1,4-cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2- bis (4-hydroxyphenyl) propane ), hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), and mixtures thereof. [Claim 10] Polyurethane according to any one of the claims  above, characterized in that the monomer (s) of organosilane type are chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3 -aminopropyltriethoxysilane, 3- (m-aminophenoxy)  propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N- (2- aminoethylaminomethyphenethyltrimethoxysilane, and their mixtures, preferably among 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropyl- aminoethyl) -3-aminopropyltriethoxysilane and mixtures thereof, and more  preferably the organosilane type monomer is 3-aminopropyl triethoxysilane. [Claim 1 1] Polyurethane according to any one of the claims  above, characterized in that the organosilane type monomer (s) represents (s) from 1 to 20% by weight, and preferably from 2 to 15% by weight, relative to the total weight of the polyurethane. [Claim 12] Composition comprising one or more functionalized polyurethane (s) as defined in any one of claims 1 to 11. [Claim 13] Composition according to claim 12 comprising one or more pigment (s). [Claim 14] Composition according to claims 12 or 13, characterized in that the total amount of the functionalized polyurethane (s) ranges from 1 to 30% by weight, and preferably from 5 to 25% by weight, relative to the total weight of the composition. [Claim 15] Composition according to claim 13 or 14, characterized in that the total amount of the pigment (s) ranges from 0.5 to 40% by weight, and more preferably from 1 to 20% by weight, relative to the total weight of the composition. [Claim 16] Composition according to any one of claims 12 to 15, in the form of a dispersion in water. [Claim 17] Process for treating keratin fibers comprising (i.) the application to keratin fibers of the polyurethane (s) as defined in any one of claims 1 to 11 or of a composition as defined in any one of claims 12 to 16 above. [Claim 18] Method according to the preceding claim, which comprises (ii.) The shaping of keratin fibers. [Claim 19] Method according to any one of the claims  above, characterized in that it involves a natural drying step and / or optionally a step of applying heat to the keratin fibers using a heating tool. [Claim 20] A method according to any one of claims 17 to 19 which is a hair coloring method in which the applied composition contains one or more pigments.