POLYMER COMPRISING ALKOXYSILANE GROUPS AND USE IN COSMETICS

Abstract

The invention relates to a polymer comprising alkoxysilane groups, obtained by polycondensation of a diisocyanate, of a difunctional compound and of two different alkoxysilanes.

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.

Claims

1. A 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 and S or an —N(R)— radical, R being H or a C.sub.1-C.sub.4 alkyl radical, A denotes a linear or branched, divalent hydrocarbon-based C.sub.2-C.sub.100 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.sub.1-C.sub.4 alkyl radical; in order to form a prepolymer (P) containing at least one isocyanate function; followed by a second step in which the prepolymer (P) obtained is reacted with a first alkoxysilane of formula (III) and a second alkoxysilane of formula (IV):
(R.sub.1O)(R.sub.2)(R.sub.3)Si—CH.sub.2—(NH-L.sub.1).sub.p-X.sub.1—H   (III) in which p=0 or 1; X.sub.1 denotes —NRa—, S or O, Ra denoting H or a saturated or unsaturated C.sub.1-C.sub.8 (cyclo)alkyl radical, in particular methyl or cyclohexyl, or a C.sub.6-C.sub.10 aryl radical; R.sub.1 denotes a C.sub.1-C.sub.6 alkyl radical; R.sub.2 and R.sub.3, which may be identical or different, preferably identical are chosen from: a C.sub.1-C.sub.6, in particular C.sub.1-C.sub.4, alkoxy radical; a linear or branched C.sub.1-C.sub.6 alkyl radical; L.sub.1 denotes a linear or branched, saturated divalent hydrocarbon-based C.sub.1-C.sub.20 radical;
(R′.sub.1O)(R′.sub.2)(R′.sub.3)Si—CH(R.sub.4)—CH(R.sub.5)-(L.sub.2).sub.q-X.sub.2—H   (IV) in which: q=0 or 1; X.sub.2 denotes —NRb— or S or O or —NHCO—NRc-, Rb denoting H or a saturated or unsaturated C.sub.1-C.sub.8 (cyclo)alkyl radical, or a C.sub.6-C.sub.10 aryl radical; Rc denoting a saturated C.sub.1-C.sub.4 alkyl radical; R′.sub.1 denotes a C.sub.1-C.sub.6 alkyl radical; R′.sub.2 and R′.sub.3, which may be identical or different, are chosen from: a C.sub.1-C.sub.6; a linear or branched C.sub.1-C.sub.6 alkyl radical; R.sub.4 denotes H or a C.sub.1-C.sub.4 alkyl radical; R.sub.5 denotes H or a C.sub.1-C.sub.4 alkyl radical optionally substituted with an —NH.sub.2 group; L.sub.2 denotes a linear or branched, saturated divalent hydrocarbon-based C.sub.1-C.sub.20 radical, optionally interrupted with an —NH— group, optionally substituted with an NH.sub.2 group; it being possible for the first and second alkoxysilanes (III) and (IV) to be added either simultaneously or sequentially by first introducing the first alkoxysiloxane (III) then the second alkoxysilane (IV), or by first introducing the second alkoxysilane (IV) then the first alkoxysilane (III).

2. The process according to claim 1, wherein, for the diisocyanate (I), the Z radical is chosen from the following radicals (1) to (6): ##STR00070##

3. The process according to claim 1, wherein, for the difunctional compound of formula (II): T denotes O or NH; A denotes a linear or branched hydrocarbon-based C.sub.2-C.sub.50 radical optionally interrupted with one or more non-adjacent oxygen atoms.

4. The process according to claim 1, wherein, for the first alkoxysilane (III): X.sub.1 denotes —NRa; R.sub.1 denotes a methyl or ethyl radical; R.sub.2 and R.sub.3, which may be identical or different, are chosen from: methoxy or ethoxy radicals; methyl or ethyl; L.sub.1 represents a linear or branched, saturated hydrocarbon-based C.sub.1-C.sub.10 radical.

5. The process according to claim 1, wherein the first alkoxysilane (III) is chosen from those of formula (IIIa) below:
(R.sub.1O)(R.sub.2)(R.sub.3)Si—CH.sub.2—(NH-L.sub.1).sub.p-NRa—H   (IIIa) in which: p=0 or 1; R.sub.1 denotes a methyl or ethyl radical; R.sub.2 and R.sub.3, which may be identical or different, denote a methoxy, ethoxy, methyl or ethyl radical; when p=1, L.sub.1 represents a saturated divalent hydrocarbon-based C.sub.1-C.sub.8 radical; Ra denotes H or a saturated or unsaturated C.sub.1-C.sub.8 (cyclo)alkyl radical, or a phenyl radical; preferably, Ra denotes H or a cyclohexyl radical.

6. The process according to claim 1, wherein 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.

7. The process according to claim 1, wherein, for the second alkoxysilane (IV): X.sub.2 denotes —NRb— or S, Rb denoting H or a saturated or unsaturated C.sub.1-C.sub.8 (cyclo)alkyl radical, or a C.sub.6-C.sub.10 aryl radical; L.sub.2 represents a linear or branched, saturated hydrocarbon-based C.sub.1-C.sub.12 radical, optionally interrupted with an —NH— group; preferably, when q=1, L.sub.2 represents a saturated divalent C.sub.1-C.sub.10 radical, or else a divalent radical —(CH.sub.2).sub.n—NH—(CH.sub.2).sub.m with n and m denoting integers such that 2≦n+m≦4; R′.sub.1 denotes a methyl or ethyl radical, R′.sub.2 and R′.sub.3, which may be identical or different, are chosen from: methoxy or ethoxy radicals; methyl or ethyl; R′.sub.4 and R′.sub.5 denote H.

8. The process according to claim 1, wherein the second alkoxysilane (IV) is chosen from those of formula (IVa) below:
(R′.sub.1O)(R′.sub.2)(R.sub.3)Si—CH.sub.2—CH.sub.2-(L.sub.2).sub.q-NRb—H   (IVa) in which: q=0 or 1; Rb denoting H or a saturated or unsaturated C.sub.1-C.sub.8 (cyclo)alkyl radical; R′.sub.1 denotes a methyl or ethyl radical; R′.sub.2 and R′.sub.3, which may be identical or different, denote a methoxy, ethoxy, methyl or ethyl radical; L.sub.2 denotes a linear or branched, saturated hydrocarbon-based C.sub.1-C.sub.12 radical, optionally interrupted with an —NH— group; when q=1, L.sub.2 represents a saturated divalent C.sub.1-C.sub.10 radical, or else a divalent radical —(CH.sub.2)—NH—(CH.sub.2).sub.m with n and m denoting integers such that 2≦n+m≦4.

9. The process according to claim 1, wherein the second alkoxysilane (IV) is chosen from: 3-(dimethoxymethylsilyl)-1-propanamine 3-(trimethoxysilyl)-1-propanamine 3-(triethoxysilyl)-1-propanamine 3-(diethoxymethoxysilyl)-1-propanamine 2-methyl-3-(trimethoxysilyl)-1-propanamine 3-(triethoxysilyl)-1-propanamine 3-(diethoxymethylsilyl)-1-propanamine 3-(methyldipropoxysilyl)-1-propanamine 3-(diethoxyethylsilyl)-1-propanamine 3-(ethyldimethoxysilyl)-1-propanamine 4-(triethoxysilyl)-1-butanamine 4-(dimethoxymethylsilyl)-1-butanamine 4-(trimethoxysilyl)-1-butanamine 2,2-dimethyl-4-(trimethoxysilyl)-1-butanamine 4-(diethoxymethylsilyl)-1-butanamine 4-(dimethoxymethylsilyl)-2,2-dimethyl-1-butanamine 11-(triethoxysilyl)-1-undecamine 11-(trimethoxysilyl)-1-undecamine 2-[(dimethoxymethylsilyl)methyl]-1,4-butanediamine 2-[(trimethoxysilyl)methyl]-1,4-butanediamine N-(3-(trimethoxysilyl)propyl)butylamine N-ethyl-3-(trimethoxysilyl)-1-propanamine N-methyl-3-(trimethoxysilyl)propylamine N-[3-trimethoxysilyl]propyl]cyclohexylamine N-[3-trimethoxysilyl]propyl]aniline N-[3-trimethoxysilyl]propyl]ethylenediamine N-[3-triethoxysilyl]propyl]ethylenediamine 1-(trimethoxysilyl)-2-propanamine 2-(trimethoxysilyl)ethanamine 2-(triethoxysilyl)-1-propanamine 2-(dimethoxymethylsilyl)ethanamine 2-(diethoxymethylsilyl)-1-propanamine 2-(diethoxymethylsilyl)ethanamine 2-(triethoxysilyl)ethanamine 4-(trimethoxysilyl)-1-butanol 3-(trimethoxysilyl)-1-propanol 11-(trimethoxysilyl)-1-undecanethiol 4-(trimethoxysilyl)-2-butanethiol 2-(triethoxysilyl)ethanethiol 3-(triethoxysilyl)-1-propanethiol 2-(trimethoxysilyl)ethanethiol 3-(trimethoxysilyl)-1-propanethiol 3-(dimethoxymethylsilyl)-1-propanethiol N-[3-(trimethoxysilyl)propyl]acetamide.

10. The process according to claim 1, wherein the mixture of first and second alkoxysilanes (III) and (IV) used comprises from 5 to 95 mol % of alkoxysilane (III), relative to the total moles of alkoxysilanes (III) and (IV).

11. The process according to claim 1, wherein the reagents are used according to the following molar equivalents: diisocyanate (I): 2 equivalents difunctional compound (II): 1 equivalent first alkoxysilane (III): u equivalent second alkoxysilane (IV): v equivalent with u+v=2, u and v not being zero.

12. The process according to claim 1, wherein the first step is carried out in the presence of a catalyst, in particular a tin-based organic catalyst.

13. The process according to claim 1, wherein the first step is carried out in an aprotic solvent at a temperature of between 40° C. and 120° C.

14. The process according to claim 1, wherein the second step is carried out at a temperature of between 20° C. and 60° C.

15. The process according to claim 1, wherein the second step is followed by a step of solvent exchange by elimination of the aprotic solvent and addition of a carrier solvent.

16. The process according to claim 1, wherein the obtained polymer comprising an alkoxysilane group is carried in a carrier solvent.

17. A product which is a polymer comprising an alkoxysilane group (Pf), which can be obtained with the preparation process according to claim 1.

18. A mixture of compounds C1, C2 and C3:
(R.sub.1O)(R.sub.2)(R.sub.3)Si—CH.sub.2—(NH-L.sub.1).sub.p-X.sub.1—CO—NH—Z—NH—CO-T-A-T-CO—NH—Z—NH—CO—X.sub.1-(L.sub.1-NH—).sub.p—CH.sub.2—Si(R.sub.1O)(R.sub.2)(R.sub.3)   (C1)
(R.sub.1O)(R.sub.2)(R.sub.3)Si—CH.sub.2—(NH-L.sub.1).sub.p-X.sub.1—CO—NH—Z—NH—CO-T-A-T-CO—NH—Z—NH—CO—X.sub.2-(L.sub.2).sub.q-CH(R.sub.5)—CH(R.sub.4)— . . . Si(R′.sub.1O)(R′.sub.2)(R′.sub.3)   (C2)
(R′.sub.1O)(R′.sub.2)(R′.sub.3)Si—CH(R.sub.4)—CH(R.sub.5)-(L.sub.2).sub.q-X.sub.2—CO—NH—Z—NH—CO-T-A-T-CO—NH—Z—NH—CO—X.sub.2-(L.sub.2).sub.q-CH(R.sub.5)—CH(R.sub.4)— . . . —Si(R′.sub.1O)(R′.sub.2)(R′.sub.3)   (C3)

19. A compound of formula C2:
(R.sub.1O)(R.sub.2)(R.sub.3)Si—CH.sub.2—(NH-L.sub.1).sub.p-X.sub.1—CO—NH—Z—NH—CO-T-A-T-CO—NH—Z—NH—CO—X.sub.2-(L.sub.2).sub.q-CH(R.sub.5)—CH(R.sub.4)— . . . Si(R′.sub.1O)(R′.sub.2)(R′.sub.3)   (C2) in which Z, R.sub.1, R.sub.2, R.sub.3, R′.sub.1, R′.sub.2, R′.sub.3, R.sub.4, R.sub.5, L.sub.1, L.sub.2, X.sub.1, X.sub.2, p and q have the meanings defined in claim 1, and T denotes O or NH; A denotes a linear or branched hydrocarbon-based C.sub.2-C.sub.50 radical optionally interrupted with one or more non-adjacent oxygen atoms.

20. An anhydrous composition comprising, in a physiologically acceptable medium, a product or compound(s) as defined according to claim 17.

21. A composition according to claim 20, wherein 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.

22. The composition according to claim 20, wherein it comprises at least one volatile organic solvent.

23. 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 according to claim 21.

Description

EXAMPLE 1

[0154] 22.2 g (0.10 mol) of isophorone diisocyanate, 100 μl of tin 2-ethylhexanoate catalyst and 270 g of methyltetrahydrofuran (MeTHF) (dried over sieve) are 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 C.sub.36 non-linear diol dimer (Pripol® 2033 from Croda) diluted in 20 g of MeTHF were then 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.

[0155] 20.5 g (0.07 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. 6.6 g (0.03 mol) of (3-aminopropyl) triethoxysilane diluted in 10 g of MeTHF were then added dropwise. Reaction was allowed to take place for 4 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 distill 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, a solution containing a mixture of compounds (Pf) with a solids content of 60% by weight in isopropanol was obtained.

[0156] The solution obtained contains the following compounds:

##STR00069##

with Pripol denoting the non-linear divalent C.sub.36 radical of the dimer diol Pripol 2033.

[0157] 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 with 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

[0158] A nail varnish having the following composition (as weight percentage) is prepared:

TABLE-US-00003 solution obtained according to Example 1 99% Red 27 pigment  1%

[0159] The varnish composition, after application to false nails, forms, on contact with the air, a uniform, glossy and water- and scratch-resistant film.

EXAMPLE 3

[0160] A hair composition as follows, packaged in a pump dispenser bottle, is prepared:

TABLE-US-00004 solution obtained according to Example 1 1% AM ethanol qs 100%

[0161] 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 4

[0162] A skincare composition as follows, packaged in a pump dispenser bottle, is prepared:

TABLE-US-00005 solution obtained according to Example 1 3% AM 2-octyldodecanol qs 100%

[0163] 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.