WO2016066613A1

WO2016066613A1 - Polymer comprising alkoxysilane groups and use in cosmetics

Info

Publication number: WO2016066613A1
Application number: PCT/EP2015/074811
Authority: WO
Inventors: Pascal Giustiniani; Sandrine Chodorowski-Kimmes
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2014-10-29
Filing date: 2015-10-27
Publication date: 2016-05-06
Anticipated expiration: 2017-04-29
Also published as: FR3027903B1; FR3027903A1

Abstract

The invention relates to a polymer comprising alkoxysilane groups, obtained by polycondensation of a diisocyanate, of a difunctional compound, of an alkoxysilane and of a monofunctional compound. The invention also relates to a cosmetic composition comprising such a polymer and to a process for caring for or making up keratin materials by application of the composition to the keratin materials.

Description

Polymer comprising alkoxysilane groups and use in cosmetics

The present invention relates to a process for preparing a product containing polymeric compounds comprising an alkoxysilane group and to the use of such a product in a cosmetic composition for treating keratin materials, in particular the nails and the hair.

The use of sol/gel techniques for the purposes of preparing cosmetic compositions is known per se. Such compositions form films after application to keratin materials. After drying, a hybrid material is in fact formed by polycondensation and crosslinking.

For example, patent application WO 98/44906 describes a cosmetic or dermatological composition suitable for forming a coating on keratin materials via a reaction of sol/gel type obtained by mixing (A) at least one organometallic compound with (B) at least one functionalized organic polymer or at least one functionalized silicone polymer other than the first compound, and (C) an amount of water sufficient to hydrolyse the organometallic compound.

There is a need to provide compounds or compositions that have both stability properties before application thereof to keratin materials, and good reactivity.

There is also a need to have compounds which make it possible to obtain, after application thereof to keratin materials, a uniform and smooth deposit. Furthermore, the layer of the composition deposited on the keratin materials is not tacky. It thus has a good appearance and is not degraded on contact with foreign bodies, for instance a glass, a cigarette, clothing or skin.

In addition, properties of persistence on washing with water and with detergents are sought.

It is sought to obtain a film which is resistant in particular to mechanical attacks such as rubbing, and adherent.

Finally, sheen properties of the deposited film may be sought.

The inventors have found that such advantages may be obtained by using a polymeric product comprising particular alkoxysilane groups, as described hereinafter.

After application to keratin materials, the polymeric product, on contact with the moisture in the air, crosslinks to form a film. The film obtained is shiny and has good water resistance. The polymeric product is thus suitable for use as a film-forming agent in a nail varnish composition or a hair composition, in particular for haircare or else for hair shaping (styling), or else in a composition for caring for or making up the skin, in particular for filling the surface irregularities of the skin, such as wrinkles or grooves.

More specifically, a subject of the present invention is a process for preparing a polymer comprising alkoxysilane groups (referred to as Pf) which can be obtained by polycondensation, comprising, in a first step, the reaction between:

(i) a diisocyanate of formula (I): OCN-Z-NCO (I)

in which Z denotes a divalent hydrocarbon-based radical containing from 4 to 20 carbon atoms; and

(ii) a difunctional compound of formula (II): H-T-A-T-H (II)

in which:

T denotes a heteroatom chosen from O or S or an -N(R)- radical, R being H or a CrC₄ alkyl radical, in particular methyl,

A denotes a linear or branched, divalent hydrocarbon-based C₂-Ci₀o radical, optionally interrupted with one or more non-adjacent heteroatoms chosen from O and S, or an -N(R')- group in which R' denotes a hydrogen atom or a C C₄ alkyl radical, in particular methyl; in order to form a prepolymer (P) containing at least one isocyanate function, preferably containing 2 isocyanate functions; followed by a second step in which the prepolymer (P) obtained is reacted with an alkoxysilane of formula (III) and a compound of formula (IV):

(R₁0)(R₂)(R₃)Si-CH₂-(NH-L₁)_p-X₁-H (III)

in which p = 0 or 1 ;

Xi denotes -NRa-, S or O, Ra denoting H or a saturated or unsaturated Ci-C₈ (cyclo)alkyl radical, in particular methyl or cyclohexyl, or a C₆-Ci₀ aryl radical, in particular phenyl; Ri denotes a CrC₆ alkyl radical;

R₂ and R₃, which may be identical or different, preferably identical, are chosen from:

- a Ci-C₆, in particular Ci-C₄, alkoxy radical;

- a linear or branched Ci-C₆ alkyl radical;

U denotes a linear or branched, saturated divalent hydrocarbon-based Ci-C₂₀ radical; R'X₂-H (IV)

in which:

R' denotes a linear or branched, saturated or unsaturated hydrocarbon-based C1-C100 radical, optionally interrupted with one or more non-adjacent heteroatoms or groups chosen from - 0-, -N(Rc)-, -Si-, and -3\[03\(Α^(Α₂)(Α₃)][03\(ΑΊ )(Α·2)(Α )(Α'₂)(Α'₃)]- or with one or more divalent radicals -Si(Re)(Rd)-0-, and/or with a hydrocarbon-based ring having from 5 to 8 ring members, such as a benzene ring, Rc denoting a hydrogen atom or a saturated C1-C4 alkyl radical such as methyl, Rd and Re independently denoting a saturated C1-C4 alkyl radical such as methyl, A-i , A₂, A₃, A'-i , A'₂ and A'₃ independently denoting a saturated C1-C4 alkyl radical such as methyl;

X₂ denotes NH or O or S, preferably NH or O; it being possible for the alkoxysilane (II I) and the compound (IV) to be added either simultaneously or sequentially, for example by first introducing the alkoxysilane (II I) then the compound (IV), or else by first introducing the compound (IV) then the alkoxysilane (I II).

Advantageously, the reagents are used in the preparation process according to the following molar equivalents:

diisocyanate (I): 2 equivalents

difunctional compound (I I): 1 equivalent

alkoxysilane (I I I): u equivalent

compound (IV): v equivalent

with u + v = 2 (u and v other than 0). A subject of the invention is also the product (Pf) which can be obtained according to the preparation process described above.

(4) (6)

In the structures drawn, the ^* denotes the point of attachment with the isocyanate function. Preferentially, Z denotes the divalent radical isophorone (radical (6)).

For the difunctional compound of formula (II) defined above:

T preferably denotes O or NH and preferentially denotes O;

A preferably denotes a linear or branched hydrocarbon-based C₂-C₅o radical optionally interrupted with one or more non-adjacent oxygen atoms,

in particular, A denotes a divalent radical chosen from:

(i) a divalent radical -[(CH2)_n-0-]_m-(CH2)_n'- with n and n' independently denoting a number between 1 and 10 (limits included), preferably between 1 and 5, m denoting a number between 1 and 30, preferably between 1 and 20, more particularly between 1 and 10;

(ii) a C₂-C₅o, preferably C20-C50, in particular C₃2-C₄₀, alkylene radical, which is in particular non-linear, such as a C₃6 radical;

(iii) a divalent radical -[CH(Me)-CH₂-0-]_x-(CH₂) CH(Me)- with x denoting a number between 2 and 70 (limits included), preferably between 2 and 7; in particular, x = 2.5 or

6.1 or 33 or 68;

(iv) a divalent radical -CH(Me)-CH2-[0-CH2-CH(Me)]_x'-[0-CH2-CH₂]y'-[0-CH2-CH(Me)-]_z' with y' denoting a number between 2 and 50 (limits included), preferably between 2 and 40 and in particular y' = 2 or 9 or 12.5 or 39, x' + z' denoting a number between 1 and 10 (limits included), preferably between 1 and 7; in particular, x' + z' = 1 .2 or 3.6 or 6;

(v) a divalent radical -(CH₂)x"-0-CH2-CH2-0-(CH₂)x"- with x"₂-CH₂-0-(CH₂)x"- with x" denoting a number between 1 and 10 (limits included), preferably between 1 and 5; in particular, x" = 2 or 3.

For the alkoxysilane (III) defined above:

Xi preferably denotes -NRa-, Ra being defined as above.

Preferentially, NRa denotes -NH- or -N-cyclohexyl.

Ri preferably denotes a methyl or ethyl radical;

R₂ and R₃, which may be identical or different, preferably identical, are preferably chosen from:

- methoxy or ethoxy radicals;

- methyl or ethyl, preferably methyl, radicals. Preferably, U represents a linear or branched, saturated hydrocarbon-based C1-C1₀ radical, more particularly a linear, saturated hydrocarbon-based C1-C1₀ radical. According to one preferred embodiment, when p=1 , L represents a saturated divalent d- C₈ radical and in particular a divalent radical chosen from -CH₂-CH₂- and -(CH₂)₆-.

Advantageously, the alkoxysilane (III) can be chosen from those of formula (Ilia) below: (R₁0)(R₂)(R₃)Si-CH₂-(NH-L₁ )p-NRa-H (Ilia)

in which:

p = 0 or 1 ;

Ri denotes a methyl or ethyl radical; R₂ and R₃, which may be identical or different, denote a methoxy, ethoxy, methyl or ethyl radical; when p = 1 , U represents a saturated divalent hydrocarbon-based Ci-C₈ radical;

Ra denotes H or a saturated or unsaturated Ci-C₈ (cyclo)alkyl radical, or a phenyl radical; preferably, Ra denotes H or a cyclohexyl radical.

As examples of an alkoxysilane (III), mention may be made of:

Chemical name CAS No. Chemical structure

1 -(dimethoxymethylsilyl)methanamine (343926-26-1 )

1 -(diethoxymethylsilyl)methanamine (18186-77-1 ) /\

O CH,

H₃C O. I

3 ^ .Si NH,

H₃C ^ ²

1 -(triethoxysilyl)methanamine (18306-83-7)

1 O CH,

O 1

:Si NH₂

H₃C O ^ ²

1 -(trimethoxysilyl)methanamine (71408-48-5) CH,

1 ³

O.

H,C .Si NH,

³ O 1 ²

o

CH₃

1 -(trimethoxysilyl)methanethiol (30817-94-8) CH,

1 ³

O.

H,C .Si SH

³ O 1

o

CH₃

1 -(diethoxymethylsilyl)methanethiol (55161 -63-2)

1 -(triethoxysilyl)methanethiol (60764-83-2)

1 O CH,

O 1

:Si SH

H₃C O ^

As examples of a preferred alkoxysilane (III), mention may be made of:

1 -(diethoxymethylsilyl)methanamine (18186-77-1 )

1 -(triethoxysilyl)methanamine (18306-83-7)

N-[(diethoxymethylsilyl)methyl]cyclohexanamine (27445-54-1 )

N-[(triethoxysilyl)methyl]cyclohexanamine (26495-91 -0)

N-[(triethoxysilyl)methyl]-1 ,6-hexanediamine (15129-36-9) More preferentially, use is made, as first alkoxysilane (III), of

N-[(triethoxysilyl)methyl]-1 ,6-hexanediamine (15129-36-9)

N-[(triethoxysilyl)methyl]cyclohexanamine (26495-91 -0)

For the compound (IV) defined above:

X₂ preferably denotes NH or O.

According to a first embodiment, X₂ denotes NH or O and R' denotes a linear or branched, saturated or unsaturated, preferably saturated, hydrocarbon-based Ci-C₅o radical.

According to this embodiment, R' denotes for example a radical chosen from isopropyl, ethyl, 2-ethylhexyl, 2-butyl-1 -decyl, 2-hexyl-1 -octyl, 2-hexyl-1 -decyl, 2-octyl-1 -decyl, 2- hexyl-1 -dodecyl, 2-octyltetradecyl, 2-dodecyl-1 -hexadecyl, 2-tetradecyl-1 -octadecyl, 2- tetradecyl-1 -eicosyl, 2-hexadecyl-1 -octadecyl and 2-hexadecyl-1 -eicosyl.

According to this embodiment, the compounds of formula (IV) can be chosen from:

(i) isopropanol, ethanol, 2-butyl-1 -octanol, 2-butyl-1 -decanol, 2-hexyl-1 -octanol, 2-hexyl-1 - decanol, 2-octyl-1 -decanol, 2-hexyl-1 -dodecanol, 2-octyl-1 -tetradecanol, 2-dodecyl-1 - hexadecanol, 2-tetradecyl-1 -octadecanol, 2-tetradecyl-1 -eicosanol, 2-hexadecyl-1 - octadecanol and 2-hexadecyl-1 -eicosanol. Such alcohols, alone or as a mixture, are for example sold by the company Jarchem under the trade references Jarcol® i12 , Jarcol® i14T, Jarcol® i16 , Jarcol® i18T, Jarcol® i18E, Jarcol® i20, Jarcol® i24, Jarcol® i28, Jarcol® i32, Jarcol® i34T and Jarcol® i36;

(ii) ethyl-2-hexylamine, stearylamine, t-butylamine, dimethyl-1 ,3 butylamine, 2,3- dimethylcyclohexylamine, 4-phenylbutylamine, pentylamine, 1 -ethylpropylamine, 1 ,5- dimethylhexylamine, N-morpholino-3-propylamine and 3-(2-ethylhexyloxy)-3-propylamine.

According to a second embodiment, X₂ denotes NH or O and R' denotes a linear or branched, saturated or unsaturated, preferably saturated, hydrocarbon-based C4-C100 radical, interrupted with one or more non-adjacent oxygen atoms, and/or with a hydrocarbon-based ring having from 5 to 8 ring members, such as a benzene ring.

According to this embodiment, R' denotes for example a radical chosen from the following radicals:

CH₃-(0-CH₂-CH₂)_e-0-CH₂-CH₂-, 1 < e < 100

CH₃-(0-CH₂-CH₂)_h-(0-CH₂-CH(Rg))r with Rg = H or methyl, 0 < h < 45, 0 < i < 33, h+i greater than 1 ;

CH₃-(CH₂)₁₂-0-CH₂-CH(Me)-0-CH₂-CH(Me)- C₉H₁₉-Ph-(0-CH₂-CH(Me))_k- 1 < k < 30

According to this embodiment, the compounds of formula (IV) can be chosen from: methoxypolyethylene glycol amine (Mw= 1000) (CAS No. 80506-64-5; Aldrich reference 767565)

CH₃-(CH₂)₁₂-0-CH₂-CH(CH₃)-0-CH₂-CH(CH₃)-NH₂ (jeffamine ® XTJ-435)

m-C₉H₁₉-phenyl-(0-CH₂-CH(CH₃))_{13 5}-NH₂ (jeffamine ® XTJ-436)

CH₃-0-CH₂CH₂-(0-CH₂-CH(CH₃))₉-NH₂ (jeffamine ® M600)

CH₃-(0-CH₂CH₂)₁₉-(0-CH₂-CH(CH₃))₃-NH₂ (jeffamine ® M1000)

CH₃-(0-CH₂CH₂)₆-(0-CH₂-CH(CH₃))₂₉-NH₂ (jeffamine ® M-2005)

CH₃-(O-CH₂CH₂)₃₁-(O-CH₂-CH(CH₃))₁₀-NH₂ (jeffamine ® M2070)

sold by the company Huntsman.

For these compounds, R'X₂ corresponds to the following radicals:

CH₃-(CH₂)₁₂-0-CH₂-CH(CH₃)-0-CH₂-CH(CH₃)-NH- m-C₉H₁₉-phenyl-(0-CH₂-CH(CH₃))_{13 5}-NH-

CH₃-0-CH₂CH₂-(0-CH₂-CH(CH₃))₉-NH-

CH₃-(0-CH₂CH₂)₁₉-(0-CH₂-CH(CH₃))₃-NH- CH₃-(0-CH₂CH₂)₆-(0-CH₂-CH(CH₃))₂₉-NH- CH₃-(0-CH₂CH₂)3i-(0-CH₂-CH(CH₃))io-NH-.

According to a third embodiment, X₂ denotes NH or O and R' denotes a linear or branched, saturated hydrocarbon-based C4-C1₀₀ radical, interrupted with one or more divalent radicals -Si(Re)(Rd)-0-, Rd and Re independently denoting a saturated C1-C4 alkyl radical such as methyl.

According to this embodiment, X₂ preferably denotes O and R' denotes for example a radical CH3-(CH2)m^,-Si(Me)(Me)-[0-Si(Me)(Me)]n'-0-Si(Me)(Me)-CH2-W- with m' being an integer ranging from 1 to 6, in particular 3, n'3-(CH₂)_m-Si(Me)(Me)-[0-Si(Me)(Me)]_n-0- Si(Me)(Me)-CH₂-W- with m' being an integer ranging from 1 to 6, in particular 3, n' being an integer ranging from 5 to 65, W = hydrocarbon-based chain containing from 1 to 9 carbon atoms, optionally interrupted with one, two or three non-adjacent oxygen atoms, such as the divalent radicals ethoxypropyl or (polyethyleneoxy)propyl.

According to this embodiment, the compounds of formula (IV) can be chosen from:

(i) polymethylsiloxanes comprising a hydroxyethoxypropyl end group, such as those sold under the names MCR-C12, MCR-C18 and MCR-C22 by the company Gelest (CAS

207308-30-3); (ii) symmetrical polydimethylsiloxanes comprising a hydroxypoly(ethyleneoxy)propyl group, such as that sold under the names MCS-C1 1 and MCS-C13 by the company Gelest (CAS 67674-67-3).

According to a fourth embodiment, X₂ denotes NH or O and R' denotes a linear or branched, saturated hydrocarbon-based C₃-C₂₀ radical, interrupted with one or more divalent radicals -Si[OSi(A₁)(A₂)(A₃)][OSi(A'₁)(A'₂)(A'₃)]- which may be identical or different, preferably identical, Ai , A₂, A₃, ΑΊ, A'₂ and A'₃ independently denoting a saturated C1-C4 alkyl radical such as methyl. According to this embodiment, X₂ preferably denotes NH and R' preferably denotes a linear, saturated hydrocarbon-based C3-C10 radical, interrupted with a divalent radical -Si[OSiMe3)][OSiMe3]-; in particular, R'₃-Ci₀ radical, interrupted with a divalent radical - Si[OSiMe₃)][OSiMe₃]-; in particular, R' denotes the radical -(CH₂)₃-Si[OSiMe₃)][OSiMe₃]- CH₃.

According to this embodiment, the compound (IV) may be 3-(3- aminopropyl)methylbis(trimethylsiloxy)silane.

As an example of a preferred compound (IV), mention may be made of isopropanol, ethanol, 2-octyl-1 -tetradecanol, methoxypolyethylene glycol amine (Mw = 1000) and 3-(3- aminopropyl)methylbis(trimethylsiloxy)silane. For the compounds (IV) described above, the R' radical corresponds to the radical derived from the compound (IV) without the hydrogen atom of the X₂H function.

In the process according to the invention, the alkoxysilane (III) and the compound (IV) can be used in any relative proportions.

Preferably, the mixture of alkoxysilane (III) and compound (IV) used comprises from 5 to 95 mol% of alkoxysilane (III), relative to the total moles of alkoxysilane (III) and of compound (IV).

Preferentially, the mixture of alkoxysilane (III) and compound (IV) used comprises from 20 to 80 mol% of alkoxysilane (III), relative to the total moles of alkoxysilane (III) and of compound (IV).

In particular, the mixture of alkoxysilane (III) and compound (IV) used comprises from 30 to 70 mol% of alkoxysilane (III), relative to the total moles of alkoxysilane (III) and of compound (IV).

In particular, the mixture of alkoxysilane (III) and compound (IV) used comprises from 50 to 70 mol% of alkoxysilane (III), relative to the total moles of alkoxysilane (III) and of compound (IV).

It is understood that the amount of compound (IV) in these mixtures is the remainder to 100 mol% adding to the molar amount of alkoxysilane (III) indicated.

As indicated above, in the second step of the process, the alkoxysilane (III) and the compound (IV) may be added simultaneously to the prepolymer (P) or else added sequentially by, for example, first adding the alkoxysilane (III) then the compound (IV), or else by first adding the compound (IV) then the alkoxysilane (III). Preferably, the alkoxysilane (III) is first added and, after complete reaction thereof with the prepolymer (P), the compound (IV) is then added.

In the preparation process described above, the first step may be carried out in the presence of a catalyst, in particular a tin-based organic catalyst, such as tin 2- ethylhexanoate, dibutyltin dilaurate, dioctyltin dilaurate, butyltin tris(2-ethylhexanoate), dibutyltin diacetate or dioctyltin diacetate, and preferably tin 2-ethylhexanoate.

Advantageously, the first step of the preparation process is carried out in an aprotic solvent, such as methyltetrahydrofuran, tetrahydrofuran or toluene,

at a temperature of between 40°C and 120°C, in particular between 50°C and 70°C.

The first step may be carried out with a reaction time ranging from 3 to 7 hours.

The second step of the preparation process may be carried out at a temperature of between 20°C and 60°C, in particular at ambient temperature (25°C). This second step may be carried out with a reaction time ranging from 2 to 12 hours. After the second step of the process, it is possible to carry out a solvent exchange, according to the techniques known to those skilled in the art, in particular by elimination of the aprotic solvent (gradual elimination by distillation) and addition of a carrier solvent of the obtained polymer comprising an alkoxysilane group (Pf). The carrier solvent may be an alcohol solvent, in particular a C₂-C₂2 alcohol solvent, such as ethanol, isopropanol, propanol, t-butanol, sec-butanol or 2-octyldodecanol.

When the compound (IV) is an alcohol, in particular a C₂-C₂2 alcohol, the addition step described above can be carried out at the time of the addition of the compound (IV), the latter then being added in excess such that the amount of compound (IV) which has not reacted then constitutes the medium carrying the final polymer (Pf) obtained.

Advantageously, the obtained polymer comprising an alkoxysilane group (Pf) is carried in a carrier solvent, in particular an alcohol solvent as described above. The preparation process described above can be represented schematically according to the following reaction scheme:

First step:

OCN-Z-NCO + H-T-A-T-H ► OCN-Z-NH-CO-T-A-T-CO-NH-Z-NCO

(l) (2 eq) (M) (1 eq) (P)

Second step:

(P) + (RiO)(R₂)(R₃)Si-CH₂-(NH-L₁)_p-X₁-H + R'X₂-H

(III) (u eq) (IV) (v eq) ►

mixture containing the 3 compounds C1 , C2, C3

(C1 )

and

(R₁0)(R₂)(R3)Si-CH2-(NH-L₁)p-X₁-CO-NH-Z-NH-CO-T-A-T-CO-NH-Z-NH-CO-X₂-R'

(C2)

and

R'-X₂-CO-N H-Z-N H-CO-T-A-T-CO-N H-Z-N H-CO-X₂-R'

(C3) u denoting the number of molar equivalents of alkoxysilane (III) placed in reaction v denoting the number of molar equivalents of compound (IV) placed in reaction with u + v = 2 (v and u other than 0). Preferably, u is greater than 1.

According to one preferred embodiment of the preparation process, u is between 0.1 and 1 .9 (limits included). Preferably, u is between 0.4 and 1.6. Preferentially, u is between 0.6 and 1 .4. In particular, u is between 1 and 1 .4.

The final product is obtained at the end of the reaction (total consumption of the isocyanate functions) in the form of a solution in a solvent which may be the reaction solvent or a carrier solvent, such as an alcohol solvent, in particular by solvent exchange, as described above.

The simplified reaction scheme described above is an illustration of the case corresponding to the formation of the pure prepolymer (P). Nevertheless, the prepolymer (P) can be obtained as a mixture with other compounds resulting from the condensation of (I) with (II) and/or (II) with (P); thus, it is possible to obtain, in the final product (Pf), other compounds which are additional to the compounds C1 , C2 and C3, resulting in particular from the polycondensation of the compound (P) with the compound (II), then of these products with the compounds (III) and/or (IV).

A subject of the invention is the product which is a polymer comprising an alkoxysilane group (Pf), which can be obtained with the preparation process described above.

As indicated above, the preparation process makes it possible to obtain a mixture comprising the compounds C1 , C2 and C3 described above.

Thus, a subject of the invention is the mixture of the compounds C1 , C2 and C3.

A subject of the invention is also the compound C2 as novel compound.

A further subject of the invention is an anhydrous composition comprising, in a physiologically acceptable medium, a product or compound or mixture of compounds as defined above. The term "physiologically acceptable medium" is intended to mean a medium that is compatible with keratin materials such as the skin, the hair or the nails, as a cosmetic medium.

In particular, the composition comprises the product (Pf) obtained according to the preparation process described above. In particular, the composition comprises a mixture of the compounds C1 , C2 and C3 as described above.

The product (Pf) or the mixture of compounds comprising C1 , C2, C3 may be present in the composition according to the invention in a content ranging from 0.1 % to 60% by weight, relative to the total weight of the composition, preferably ranging from 0.1 % to 50% by weight, preferentially ranging from 0.5% to 45% by weight. A further subject of the invention is a process, in particular a cosmetic process, for caring for or making up keratin materials, in particular the nails or the hair or the skin, comprising the application to the keratin materials, in particular to the nails or the hair or the skin, of a composition as described above.

According to one particular embodiment, the composition according to the present invention may also comprise at least one solvent.

The term "volatile organic solvent" denotes, in the present invention, an organic compound which is liquid at ambient temperature (25°C), which comprises at least one group chosen from hydroxyl, ester, ketone, ether or aldehyde groups, and which has a vapour pressure greater than 1 mbar (100 Pa) at 20°C.

Among the volatile organic solvents that may be used in the composition in accordance with the invention, mention may be made of lower monoalcohols containing from 1 to 5 carbon atoms, such as ethanol and isopropanol, C₃-C₄ ketones, C₂-C₄ aldehydes and C₂- C₄ short-chain esters.

The composition according to the invention is anhydrous. The term "anhydrous" is intended to mean a composition comprising a content of less than or equal to 2% and in particular 1 % by weight of water, relative to the total weight of the composition, or is even free of water. It is in particular intended to mean that water is preferably not deliberately added to the compositions, but may be present in trace amounts in the various compounds used in the compositions.

The composition according to the invention may also comprise a cosmetic adjuvant chosen from film-forming polymers, plasticizers, colorants, preservatives, fragrances, fillers, oils, waxes, thickeners, antioxidants, surfactants and skin care active agents. The invention will now be described with reference to the examples that follow, which are given as non-limiting illustrations.

Example 1 : 22.2 g (0.10 mol) of isophorone diisocyanate, 100 μΙ of tin 2-ethylhexanoate catalyst and 300 g of MeTHF (dried over sieve) were introduced into a 500 ml reactor equipped with a dropping funnel, under an argon atmosphere. The solution was heated to 55°C. Then 33 g of poly(tetrahydrofuran) having a mass of 660 (Aldrich CAS:25190-06-1 ) (0.05 mol) diluted in 30 g of MeTHF were added over the course of 40 minutes. At the end of the addition, heating was carried out at 65°C until half the isocyanate functions had been consumed.

23.4 g (0.08 mol) of N-(6-aminohexyl)aminomethyltriethoxysilane in 30 g of MeTHF were introduced into the dropping funnel and then this mixture was added to the reactor at ambient temperature over the course of 30 minutes. Reaction was allowed to take place for 5 hours and then 200 g of isopropanol were added and the resulting mixture was heated for 1 hour at 60°C; the temperature was then increased in order to distil-off the MeTHF. When half the amount of MeTHF had been distilled-off, 100 g of isopropanol were added and the distillation was continued. The operation was repeated until the MeTHF had been totally removed. In the end, an isopropanolic solution containing a mixture (Pf) comprising compounds (1 ), (2) and (3) with a solids content of 42% by weight in the isopropanol was obtained.

The solution obtained contains the following compounds (1 ), (2) and (3):

The solution obtained, comprising the mixture of these compounds, applied to a Teflon® plate, rapidly forms a film. The film obtained is uniform, transparent, shiny and non-tacky. The film obtained was subsequently detached from the plate and then placed in a crystallizer filled with water and kept stirring for 24 hours at 25°C: after this time, it was noted that the film remains in a state that is still transparent and shiny and therefore has good water resistance.

Example 2:

22.2 g (0.10 mol) of isophorone diisocyanate, 100 μΙ of tin 2-ethylhexanoate catalyst and 300 g of MeTHF (dried over sieve) were introduced into a 500 ml reactor equipped with a dropping funnel, under an argon atmosphere. The solution was heated to 55°C. 26.7 g (0.05 mol) of C36 non-linear dimer diol (Pripol® 2033 from Croda) diluted in 30 g of MeTHF were added over the course of 40 minutes. At the end of the addition, heating was carried out at 65°C until half the isocyanate functions had been consumed.

23.4 g (0.08 mol) of N-(6-aminohexyl)aminomethyltriethoxysilane in 30 g of MeTHF were introduced into the dropping funnel and then this mixture was added to the reactor at ambient temperature over the course of 30 min. Reaction was allowed to take place for 5 hours and then 200 g of isopropanol were added and the resulting mixture was heated for 1 hour at 60°C; the temperature was then increased in order to distil-off the MeTHF. When half the amount of MeTHF had been distilled-off, 100 g of isopropanol were added and the distillation was continued. The operation was repeated until the MeTHF had been totally removed. In the end, an isopropanolic solution containing a mixture (Pf) comprising compounds (1 '), (2') and (3') with a solids content of 42% by weight in the isopropanol was obtained. The solution obtained contains the following compounds (1 '), (2') and (3'):

Example 3:

A nail varnish having the following composition (as weight percentage) is prepared: solution obtained according to Example 1 99%

Red 27 pigment 1 %

The solution of Example 1 may be replaced with that of Example 2. The varnish composition, after application to false nails, forms, on contact with the air, a glossy and scratch-resistant film.

Example 4:

A hair composition as follows, packaged in a pump dispenser bottle, is prepared:

solution obtained according to Example 1 % AM ethanol qs 100%

The solution of Example 1 may be replaced with that of Example 2. After the application of the composition to the hair, the latter is shiny and

also has more body (it is not lank). It is easier to style.

Example 5:

A skincare composition as follows, packaged in a pump dispenser bottle, is prepared: solution obtained according to Example 1 3% AM

2-octyldodecanol qs 100% a few drops of the composition are deposited on the finger and the product is then applied to the wrinkled area of the face. After application, the deposit formed fills the relief of the treated skin, and the area treated appears smoother.

Claims

1. Process for preparing a polymer comprising alkoxysilane groups which can be obtained by polycondensation, comprising, in a first step, the reaction between:

(i) a diisocyanate of formula (I): OCN-Z-NCO (I)

in which Z denotes a divalent hydrocarbon-based radical containing from 4 to 20 carbon atoms; and (ii) a difunctional compound of formula (II): H-T-A-T-H (II)

in which:

T denotes a heteroatom chosen from O or S or an -N(R)- radical, R being H or a CrC₄ alkyl radical, in particular methyl, A denotes a linear or branched, divalent hydrocarbon-based C₂-Ci₀o radical, optionally interrupted with one or more non-adjacent heteroatoms chosen from O and S, or an -N(R')- group in which R' denotes a hydrogen atom or a C C₄ alkyl radical, in particular methyl; in order to form a prepolymer (P) containing at least one isocyanate function, preferably containing 2 isocyanate functions; followed by a second step in which the prepolymer (P) obtained is reacted with an alkoxysilane of formula (III): (RiO)(R₂)(R₃)Si-CH₂-(NH-L₁)_p-X₁-H (III)

in which p = 0 or 1 ; Xi denotes -NRa-, S or O, Ra denoting H or a saturated or unsaturated CrC₈ (cyclo)alkyl radical, in particular methyl or cyclohexyl, or a C₆-Ci₀ aryl radical, in particular phenyl;

Ri denotes a Ci-C₆ alkyl radical; R₂ and R₃, which may be identical or different, preferably identical, are chosen from:

- a Ci-C₆, in particular Ci-C₄, alkoxy radical;

- a linear or branched Ci-C₆ alkyl radical;

U denotes a linear or branched, saturated divalent hydrocarbon-based Ci-C₂₀ radical; and a compound of formula (IV):

R'X₂-H (IV)

in which:

R' denotes a linear or branched, saturated or unsaturated hydrocarbon-based C1-C100 radical, optionally interrupted with one or more non-adjacent heteroatoms or groups chosen from - 0-, -N(Rc)-, -Si-, and

or with one or more divalent radicals -Si(Re)(Rd)-0-, and/or with a hydrocarbon-based ring having from 5 to 8 ring members, such as a benzene ring, Rc denoting a hydrogen atom or a saturated C1-C4 alkyl radical such as methyl, Rd and Re independently denoting a saturated C1-C4 alkyl radical such as methyl, A-i , A₂, A₃, A'-i , A'₂ and A'₃ independently denoting a saturated C1-C4 alkyl radical such as methyl;

X₂ denotes NH or O or S, preferably NH or O; the alkoxysilane (III) and the compound (IV) being added either simultaneously or sequentially, by first introducing the alkoxysilane (III) then the compound (IV), or else by first introducing the compound (IV) then the alkoxysilane (III).

2. Process according to the preceding claim, characterized in that, for the diisocyanate (I), the Z radical is chosen from the following radicals (1 ) to (6):

preferably Z denotes the divalent radical isophorone (radical (6)).

3. Process according to either of the preceding claims, characterized in that, for the difunctional compound of formula (II):

T denotes O or NH;

A denotes a linear or branched hydrocarbon-based C₂-C₅o radical optionally interrupted with one or more non-adjacent oxygen atoms,

preferably, A denotes a divalent radical chosen from: (i) a divalent radical -[(CH2)_n-0-]_m-(CH2)_n'- with n and n' independently denoting a number between 1 and 10, preferably between 1 and 5, m denoting a number between 1 and 30, preferably between 1 and 20, more particularly between 1 and 10;

(ii) a C₂-C₅o, preferably C20-C50, in particular C₃₂-C₄₀, alkylene radical, which is in particular non-linear, such as a C₃6 radical;

(iii) a divalent radical -[CH(Me)-CH₂-0-]_x-(CH₂) CH(Me)- with x denoting a number between 2 and 70, preferably between 2 and 7;

(iv) a divalent radical -CH(Me)-CH2-[0-CH2-CH(Me)]_x'-[0-CH2-CH₂]y'-[0-CH2-CH(Me)-]_z' with y' denoting a number between 2 and 50, preferably 2 and 40, x' + z' denoting a number between 1 and 10, preferably between 1 and 7;

(v) a divalent radical -(CH₂)x"-0-CH2-CH2-0-(CH₂)x"- with x"₂-CH₂-0-(CH₂)x"- with x" denoting a number between 1 and 10, preferably between 1 and 5.

4. Process according to one of the preceding claims, characterized in that, for the first alkoxysilane (III):

Xi denotes -NRa-, preferably -NRa- denotes -NH- or -N-cyclohexyl;

- Ri denotes a methyl or ethyl radical;

- R₂ and R₃, which may be identical or different, are chosen from:

- methoxy or ethoxy radicals;

- methyl or ethyl, preferably methyl, radicals;

U represents a linear or branched, saturated hydrocarbon-based C1-C10 radical, preferably a linear, saturated hydrocarbon-based C1-C10 radical; preferably, when p=1 , U represents a saturated divalent Ci-C₈ radical, preferably a divalent radical chosen from -CH2-CH2- and -(CH₂)₆-.

5. Process according to one of the preceding claims, characterized in that the first alkoxysilane (III) is chosen from those of formula (Ilia) below:

(R₁0)(R₂)(R₃)Si-CH2-(NH-L₁ )p-NRa-H (Ilia)

in which:

p = 0 or 1 ;

Ri denotes a methyl or ethyl radical; R₂ and R₃, which may be identical or different, denote a methoxy, ethoxy, methyl or ethyl radical;

when p = 1 , U represents a saturated divalent hydrocarbon-based Ci-C₈ radical;

Ra denotes H or a saturated or unsaturated Ci-C₈ (cyclo)alkyl radical, or a phenyl radical; preferably, Ra denotes H or a cyclohexyl radical. 6. Process according to one of the preceding claims, characterized in that the first alkoxysilane (III) is chosen from:

1 -(dimethoxymethylsilyl)methanamine 1 -(diethoxymethylsilyl)methanamine

1 -(triethoxysilyl)methanamine

1 -(trimethoxysilyl)methanamine

1 -(trimethoxysilyl)methanethiol

1 -(diethoxymethylsilyl)methanethiol

1 -(triethoxysilyl)methanethiol

1 -(triethoxysilyl)methanol

N-[(triethoxysilyl)methyl]benzenamine

N-[(trimethoxysilyl)methyl]benzenamine

N-[(diethoxymethylsilyl)methyl]cyclohexanamine

N-[(triethoxysilyl)methyl]cyclohexanamine

N-[(dimethoxymethylsilyl)methyl]cyclohexanamine

N-(diethoxymethylsilyl)-N-methylmethanamine

N-methyl-1 -(trimethoxysilyl)methanamine

N-methyl-1 -(triethoxysilyl)methanamine

N-[(dimethoxy(methyl)silyl)methyl]benzenamine

N-[(triethoxysilyl)methyl]-1 ,6-hexanediamine

N-[(trimethoxysilyl)methyl]-1 ,6-hexanediamine

N-[(diethoxymethylsilyl)methyl]-1 ,6-hexanediamine

N-[(trimethoxysilyl)methyl]-1 ,2-ethanediamine,

and preferably from:

1 -(diethoxymethylsilyl)methanamine

1 -(triethoxysilyl)methanamine

N-[(diethoxymethylsilyl)methyl]cyclohexanamine

N-[(triethoxysilyl)methyl]cyclohexanamine

N-[(triethoxysilyl)methyl]-1 ,6-hexanediamine,

and preferentially from:

N-[(triethoxysilyl)methyl]-1 ,

6-hexanediamine

N-[(triethoxysilyl)methyl]cyclohexanamine.

7. Process according to one of the preceding claims, characterized in that, for the compound (IV):

X₂ denotes NH or O;

R' denotes a linear or branched, saturated or unsaturated, preferably saturated, hydrocarbon-based C C₅o radical; preferably, R' denotes a radical chosen from isopropyl, ethyl, 2-ethylhexyl, 2-butyl-1 -decyl, 2-hexyl-1 -octyl, 2-hexyl-1 -decyl, 2-octyl-1 -decyl, 2- hexyl-1 -dodecyl, 2-octyltetradecyl, 2-dodecyl-1 -hexadecyl, 2-tetradecyl-1 -octadecyl, 2- tetradecyl-1 -eicosyl, 2-hexadecyl-1 -octadecyl and 2-hexadecyl-1 -eicosyl.

8. Process according to one of the preceding claims, characterized in that the compound (IV) is chosen from isopropanol, ethanol, 2-butyl-1 -octanol, 2-butyl-1 -decanol, 2-hexyl-1 - octanol, 2-hexyl-1 -decanol, 2-octyl-1 -decanol, 2-hexyl-1 -dodecanol, 2-octyl-1 - tetradecanol, 2-dodecyl-1 -hexadecanol, 2-tetradecyl-1 -octadecanol, 2 -tetrad ecy 1-1 - eicosanol, 2-hexadecyl-1 -octadecanol, 2-hexadecyl-1 -eicosanol, ethyl-2-hexylamine, stearylamine, t-butylamine, dimethyl-1 ,3 butylamine, 2,3-dimethylcyclohexylamine, 4- phenylbutylamine, pentylamine, 1 -ethylpropylamine, 1 ,5-dimethylhexylamine, N- morpholino-3-propylamine and 3-(2-ethylhexyloxy)-3-propylamine.

9. Process according to one of Claims 1 to 6, characterized in that, for the compound (IV): X₂ denotes NH or O and R' denotes a linear or branched, saturated or unsaturated, preferably saturated, hydrocarbon-based C4-C100 radical, interrupted with one or more non-adjacent oxygen atoms, and/or with a hydrocarbon-based ring having from 5 to 8 ring members; R' preferably denotes a radical chosen from the following radicals:

CH₃-(0-CH₂-CH₂)_e-0-CH₂-CH₂-, 1 < e < 100

10. Process according to the preceding claim, characterized in that the compound (IV) is chosen from:

methoxypolyethylene glycol amine (Mw= 1000)

CH₃-(CH₂)₁₂-0-CH₂-CH(CH₃)-0-CH₂-CH(CH₃)-NH₂

m-C₉H₁₉-phenyl-(0-CH₂-CH(CH₃))_{13 5}-NH₂

CH₃-0-CH₂CH₂-(0-CH₂-CH(CH₃))₉-NH₂

CH₃-(0-CH₂CH₂)₁₉-(0-CH₂-CH(CH₃))₃-NH₂

CH₃-(0-CH₂CH₂)₆-(0-CH₂-CH(CH₃))₂₉-NH₂

CH₃-(O-CH₂CH₂)₃₁-(O-CH₂-CH(CH₃))₁₀-NH₂

and is preferably methoxypolyethylene glycol amine (Mw= 1000).

1 1 . Process according to one of Claims 1 to 6, characterized in that, for the compound (IV): X₂ denotes NH or O and R' denotes a linear or branched, saturated hydrocarbon- based C4-C100 radical, interrupted with one or more divalent radicals -Si(Re)(Rd)-0-, Rd and Re independently denoting a saturated C1-C4 alkyl radical, preferably methyl;

X₂ preferably denotes O and R' denotes a radical CH3-(CH2)m'-Si(Me)(Me)-[0- Si(Me)(Me)]n'-0-Si(Me)(Me)-CH2-W- with m' being an integer ranging from 1 to 6, in particular 3, n'₃-(CH₂)_m.-Si(Me)(Me)-[0-Si(Me)(Me)]n_'-0-Si(Me)(Me)-CH₂-VV- with m' being an integer ranging from 1 to 6, in particular 3, n' being an integer ranging from 5 to 65, W = hydrocarbon-based chain containing from 1 to 9 carbon atoms, optionally interrupted with one, two or three non-adjacent oxygen atoms, such as the divalent radicals ethoxypropyl or (polyethyleneoxy)propyl.

12. Process according to the preceding claim, characterized in that the compound (IV) is chosen from:

(i) polymethylsiloxanes comprising a hydroxyethoxypropyl end group;

(ii) symmetrical polydimethylsiloxanes comprising a hydroxypoly(ethyleneoxy)propyl group.

13. Process according to one of Claims 1 to 6, characterized in that, for the compound (IV): X₂ denotes NH or O and R' denotes a linear or branched, saturated hydrocarbon- based C3-C2₀ radical, interrupted with one or more divalent radicals

-Si[OSi(Ai)(A₂)(A₃)][OSi(A^,i)(A^,2)(A^,3)]- which may be identical or different, preferably identical, A^ A₂, A₃, ΑΊ, A'₂ and A'₃ independently denoting a saturated C1-C4 alkyl radical, preferably methyl;

X₂ preferably denotes NH and R' preferably denotes a linear, saturated hydrocarbon- based C3-C10 radical, interrupted with a divalent radical -Si[OSiMe3)][OSiMe3]-; in particular, R 3-C1₀ radical, interrupted with a divalent radical -Si[OSiMe₃)][OSiMe₃]-; in particular, R' denotes the radical -(CH₂)₃-Si[OSiMe₃)][OSiMe₃]-CH₃.

14. Process according to the preceding claim, characterized in that the compound (IV) is 3-(3-aminopropyl)methylbis(trimethylsiloxy)silane.

15. Process according to one of Claims 1 to 6, characterized in that the compound (IV) is chosen from isopropanol, ethanol, 2-octyl-1 -tetradecanol, methoxypolyethylene glycol amine (Mw = 1000) and 3-(3-aminopropyl)methylbis(trimethylsiloxy)silane.

16. Process according to one of the preceding claims, characterized in that the

alkoxysilane (III) and compound (IV) used comprises from 5 to 95 mol% of alkoxysilane (III), relative to the total moles of alkoxysilane (III) and of compound (IV), preferably from 20 to 80 mol%, preferentially from 30 to 70 mol%, and more preferentially from 50 to 70 mol%.

17. Process according to one of the preceding claims, characterized in that the reagents are used according to the following molar equivalents:

diisocyanate (I): 2 equivalents

difunctional compound (II): 1 equivalent

alkoxysilane (III): u equivalent

compound (IV): v equivalent

with u + v = 2, u and v not being zero.

18. Process according to one of the preceding claims, characterized in that the first step is carried out in the presence of a catalyst, in particular a tin-based organic catalyst, such as tin 2-ethylhexanoate, dibutyltin dilaurate, dioctyltin dilaurate, butyltin tris(2- ethylhexanoate), dibutyltin diacetate or dioctyltin diacetate, and preferably tin 2- ethylhexanoate.

19. Process according to one of the preceding claims, characterized in that the first step is carried out in an aprotic solvent, preferably chosen from methyltetrahydrofuran, tetrahydrofuran and toluene, at a temperature of between 40°C and 120°C, preferably between 50°C and 70°C.

20. Process according to one of the preceding claims, characterized in that the second step is carried out at a temperature of between 20°C and 60°C.

21. Process according to one of the preceding claims, characterized in that the second step is followed by a step of solvent exchange by elimination of the aprotic solvent and addition of a carrier solvent, such as an alcohol solvent, in particular a C₂-C₂2 alcohol solvent, preferably chosen from ethanol, isopropanol, propanol, t-butanol, sec-butanol and 2-octyldodecanol.

22. Process according to one of the preceding claims, characterized in that the obtained polymer comprising an alkoxysilane group is carried in a carrier solvent, in particular an alcohol solvent as defined in the preceding claim.

23. Product which is a polymer comprising an alkoxysilane group (Pf), which can be obtained with the preparation process according to any one of the preceding claims.

24. Mixture of compounds C1 , C2 and C3:

(C1 )

and

(C2)

and

R'-X₂-CO-N H-Z-N H-CO-T-A-T-CO-N H-Z-N H-CO-X₂-R'

(C3) in which Z, T, A, R-i , R₂, R3, R', L-i , X-i , X₂ and p have the meanings defined in Claims 1 to 5, 7, 9, 1 1 and 13.

25. Compounds of formula C2:

(C2) in which Z, T, A, R-i , R₂, R3, R', L-i , X₂ and p have the meanings defined in Claims 1 to 5, 7, 9, 1 1 and 13.

26. Anhydrous composition comprising, in a physiologically acceptable medium, a product or compound(s) as defined according to one of Claims 23 to 25.

27. Composition according to the preceding claim, characterized in that the product or the compounds are present in a content ranging from 0.1 % to 60% by weight, relative to the total weight of the composition, preferably ranging from 0.1 % to 50% by weight, preferentially ranging from 0.5% to 45% by weight.

28. Composition according to Claim 26 or 27, characterized in that it comprises at least one volatile organic solvent.

29. Cosmetic process for caring for or making up keratin materials, in particular the nails or the hair or the skin, comprising the application to the keratin materials, in particular to the nails or the hair or the skin, of a composition according to either of Claims 27 and 28.