ACRYLIC POLYMER COMPRISING ALKOXYSILANE GROUPS AND COSMETIC USES THEREOF

Abstract

The invention relates to a cosmetic process for caring for or making up keratin materials, comprising either the topical application to the keratin materials of an (extemporaneous) anhydrous mixture of a cosmetic composition comprising a maleic anhydride acrylic polymer and of an amino alkoxysilane compound (I); or the sequential application to the keratin materials of an anhydrous cosmetic composition comprising a maleic anhydride acrylic polymer and of an amino alkoxysilane compound (I), wherein said maleic anhydride acrylic polymer is obtained by polymerization of:

(a) 50% to 90% by weight, relative to the total weight of monomers, of isobornyl (meth)acrylate
(b) 1% to 50% by weight of maleic anhydride
(c) 0% to 49% by weight of additional (meth)acrylate monomer;
said amino alkoxysilane having the formula (I):

RNHR.sub.1Si(OR.sub.2).sub.z(R.sub.3).sub.x(I)

in which:
R.sub.1 is a C.sub.1-C.sub.20 hydrocarbon-based divalent group,
R=H or a C.sub.1-C.sub.4 alkyl group,
R.sub.2 and R.sub.3 represent an alkyl group 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.

Uses: skin-tensioning agent, makeup, hair fixing.

Claims

1. A process for caring for or making up keratin materials, comprising: either the topical application to the keratin materials of an anhydrous (extemporaneous) mixture of a cosmetic composition comprising a maleic anhydride acrylic polymer and of an amino alkoxysilane compound (I) or of a cosmetic composition containing same; or the sequential application to the keratin materials of an anhydrous cosmetic composition comprising a maleic anhydride acrylic polymer and of an amino alkoxysilane compound (I) or of an anhydrous cosmetic composition containing same, said maleic anhydride acrylic polymer being able to be obtained by polymerization of: (a) 50% to 90% by weight, relative to the total weight of monomers, of isobornyl (meth)acrylate (b) 1% to 50% by weight of maleic anhydride (c) 0 to 49% by weight of additional (meth)acrylate monomer chosen from: (i) linear or branched, saturated or unsaturated C.sub.1-C.sub.20 alkyl (meth)acrylates, optionally interrupted with one or more non-adjacent heteroatoms chosen from O and S or with a group NR, R being a C.sub.1-C.sub.4 alkyl group, optionally substituted with a phenyl or furfuryl group; (ii) saturated C.sub.4-C.sub.8 cycloalkyl (meth)acrylates optionally interrupted with O or NH; said amino alkoxysilane having the formula (I):
RNHR.sub.1Si(OR.sub.2).sub.z(R.sub.3).sub.x(I) in which: R.sub.1 is a linear or branched, saturated or unsaturated, cyclic or acyclic C.sub.1-C.sub.20 hydrocarbon-based divalent group, which may be interrupted in its chain with a heteroatom (O, S, NH) or a carbonyl group (CO), R.sub.1 being linked to the silicon atom directly via a carbon atom; R=H or a C.sub.1-C.sub.4 alkyl group, preferably H; R.sub.2 and R.sub.3, which may be identical or different, represent a linear or branched alkyl group 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.

2. The process as claimed in claim 1, wherein said maleic anhydride acrylic polymer is derived from the polymerization of: (a) 50% to 80% by weight, relative to the total weight of monomers, of isobornyl (meth)acrylate (b) 5% to 30% by weight of maleic anhydride (c) 15% to 30% by weight of said additional (meth)acrylate monomer.

3. The process as claim 1, wherein said maleic anhydride acrylic polymer is derived from the polymerization of: (a) 60% to 80% by weight, relative to the total weight of monomers, of isobornyl (meth)acrylate (b) 5% to 25% by weight of maleic anhydride (c) 15% to 30% by weight of said additional (meth)acrylate monomer.

4. The process as claimed in claim 1, wherein the maleic anhydride acrylic polymer is derived from the polymerization of: (a) 50% to 80% by weight, relative to the total weight of monomers, of isobornyl (meth)acrylate (b) 5% to 15% by weight of maleic anhydride (c) 15% to 30% by weight of said additional (meth)acrylate monomer.

5. The process as claimed in claim 1, wherein the maleic anhydride acrylic polymer is derived from the polymerization of: (a) 60% to 80% by weight, relative to the total weight of monomers, of isobornyl (meth)acrylate (b) 5% to 12% by weight of maleic anhydride (c) 18% to 30% by weight of said additional (meth)acrylate monomer.

6. The process as claimed in claim 1, wherein said additional (meth)acrylate monomer is chosen from C.sub.6-C.sub.16 alkyl (meth)acrylates and preferably from C.sub.6-C.sub.16 alkyl acrylates.

7. The process as claimed in claim 1, wherein said maleic anhydride acrylic polymer is derived from the polymerization of: (a) 50% to 80% by weight, relative to the total weight of monomers, of isobornyl (meth)acrylate (b) 5% to 30% by weight of maleic anhydride (c) 15% to 30% by weight of C.sub.6-C.sub.16 alkyl acrylate monomer.

8. The process as claimed in claim 1, wherein the maleic anhydride acrylic polymer is derived from the polymerization of: (a) 50% to 80% by weight, relative to the total weight of monomers, of isobornyl (meth)acrylate (b) 5% to 30% by weight of maleic anhydride (c) 15% to 30% by weight of C.sub.6-C.sub.16 alkyl acrylate monomer.

9. The process as claimed in claim 1, wherein the acrylic polymer comprises isobornyl acrylate, 2-ethylhexyl acrylate and maleic anhydride.

10. The process as claimed in claim 1, wherein the acrylic polymer has a weight-average molecular weight ranging from 5000 to 1 000 000 g/mol.

11. The process as claimed in claim 1, wherein, for the amino alkoxysilane (I): R=H; R.sub.1 is a linear saturated C.sub.1-C.sub.6; R.sub.2 represents an alkyl group; R.sub.3 represents an alkyl group.

12. The process as claimed in claim 1, wherein the amino alkoxysilane (I) is chosen from 3-aminopropyltriethoxysilane, 3-aminoethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane and N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane; preferably chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxysilane.

13. The process as claimed in claim 1, wherein the amino alkoxysilane (I) is used in a mole ratio of amino alkoxysilane/maleic anhydride group of the acrylic polymer ranging from 0.01 to 10.

14. The process as claimed in claim 1, wherein the acrylic polymer is present in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition.

15. The process as claimed in claim 1, wherein the composition comprises a hydrocarbon-based oil.

16. The process as claimed in claim 1, wherein a mixture, prepared less than 5 minutes before application to keratin materials, of the composition comprising the maleic anhydride acrylic polymer and of the amino alkoxysilane or of the composition containing same is applied to the keratin materials.

17. The process as claimed in claim 1, wherein the composition comprising the maleic anhydride acrylic polymer is first applied to keratin materials, and the amino alkoxysilane (I) or an anhydrous composition containing same and comprising a physiologically acceptable medium is then applied.

18. The process as claimed in claim 1, wherein the amino alkoxysilane (I), or an anhydrous composition containing same and comprising a physiologically acceptable medium, is first applied to keratin materials, and the composition comprising the maleic anhydride acrylic polymer is then applied.

19. The process as claimed in claim 1, wherein it is applied to the skin, more particularly the facial skin, in particular wrinkled skin.

20. The process as claimed in claim 1, wherein it is intended for attenuating wrinkles.

21. The cosmetic use, as a tensioning agent for the skin, of a maleic anhydride acrylic polymer and as a mixture with an amino alkoxysilane (I), or of an anhydrous composition containing same and comprising a physiologically acceptable medium, wherein said maleic anhydride acrylic polymer and said amino alkoxysilane (I) are defined according to claim 1.

22. A composition obtained by mixing an anhydrous composition comprising a maleic anhydride acrylic polymer and an amino alkoxysilane (I) or an anhydrous composition containing same and comprising a physiologically acceptable medium, wherein said maleic anhydride acrylic polymer and said amino alkoxysilane (I) are defined according to claim 1.

23. The composition as claimed in claim 1, wherein it is a makeup composition comprising a volatile oil and a nonvolatile oil, preferably a hydrocarbon-based volatile oil and a hydrocarbon-based nonvolatile oil.

24. A kit comprising a first anhydrous composition comprising a maleic anhydride acrylic polymer and a second anhydrous composition comprising an amino alkoxysilane (I) wherein said maleic anhydride acrylic polymer and said amino alkoxysilane (I) are defined according to claim 1 and comprising a physiologically acceptable medium, the first and second compositions each being packaged in a separate packaging assembly.

25. A polymer that may be obtained by reacting an amino alkoxysilane (I) with a maleic anhydride acrylic polymer wherein said maleic anhydride acrylic polymer and said amino alkoxysilane (I) are defined according to claim 1.

Description

EXAMPLE 1: ISOBORNYL ACRYLATE/2-ETHYLHEXYL ACRYLATE/MALEIC ANHYDRIDE COPOLYMER (70/20/10 BY WEIGHT)

[0109] 70 g of isobornyl acrylate, 20 g of 2-ethylhexyl acrylate and 10 g of maleic anhydride were placed in a jacketed 1-liter reactor equipped with a stirring anchor. A mixture of 70 g of isododecane and 30 g of ethyl acetate was then added. The medium was brought to a temperature of 40 C. with stirring (150 rpm) and was sparged with argon for 10 minutes, followed by addition of 0.5 g of initiator tert-butyl peroxy-2-ethylhexanoate Trigonox 21S (Trigonox 21S from AkzoNobel).

[0110] The heating of the jacket was set at 90 C. for 7 hours at 150 rpm.

[0111] The medium was then diluted with 300 g of isododecane, and then concentrated by distillation to remove the ethyl acetate and the unreacted maleic anhydride.

[0112] A solution containing 30% by weight of the copolymer in isododecane (yield of greater than 90%) was finally obtained.

[0113] The polymer obtained has a molecular weight (Mw) of close to 200 000 g/mol.

EXAMPLE 2: ISOBORNYL ACRYLATE/2-ETHYLHEXYL ACRYLATE/MALEIC ANHYDRIDE COPOLYMER (65/25/10 BY WEIGHT)

[0114] The polymer was prepared according to the procedure of example 1, using 65 g of isobornyl acrylate, 25 g of 2-ethylhexyl acrylate and 10 g of maleic anhydride. A solution containing 30% by weight of the copolymer in isododecane (yield of greater than 90%) was finally obtained.

[0115] The polymer obtained has a molecular weight (Mw) of close to 200 000 g/mol.

EXAMPLE 3: ISOBORNYL ACRYLATE/2-ETHYLHEXYL ACRYLATE/MALEIC ANHYDRIDE COPOLYMER (75/20/5 BY WEIGHT)

[0116] The polymer was prepared according to the procedure of example 1, using 75 g of isobornyl acrylate, 20 g of 2-ethylhexyl acrylate and 10 g of maleic anhydride. A solution containing 30% by weight of the copolymer in isododecane (yield of greater than 90%) was finally obtained.

[0117] The polymer obtained has a molecular weight (Mw) of close to 200 000 g/mol.

EXAMPLE 4: ISOBORNYL ACRYLATE/2-ETHYLHEXYL ACRYLATE/MALEIC ANHYDRIDE COPOLYMER (60/20/20 BY WEIGHT)

[0118] The polymer was prepared according to the procedure of example 1, using 60 g of isobornyl acrylate, 20 g of 2-ethylhexyl acrylate and 20 g of maleic anhydride. A solution containing 36% by weight of the copolymer in isododecane (yield of greater than 90%) was finally obtained.

[0119] The polymer obtained has a molecular weight (Mw) of close to 200 000 g/mol.

EXAMPLE 5

[0120] Demonstration of the Tensioning Effect of the Polymers Used According to the Invention

[0121] This test consists in comparing, in vitro, the tensioning capacity of the polymer to be evaluated, relative to a reference tensioning polymer: Hybridur 875 polymer dispersion from Air Products (aqueous dispersion at 40% by weight of particles of an interpenetrated network of polyurethane and acrylic polymers). The polymer to be evaluated was deposited on a nitrile rubber strip cut from a glove sold under the reference Safeskin Nitrile Criticial No. 038846 by the company Dominique Dutscher SA, having a surface area of 3.5 cm.sup.2, stretched taut beforehand on a support. An aqueous solution containing the polymer to be evaluated is therefore deposited on the elastomer strip, by depositing 1.8 mg (of solids) of polymer.

[0122] 26 l of an aqueous solution containing 7% AM of Hybridur 875 polymer were thus placed on a nitrile rubber strip so as thus to obtain a reference tensioning strip, and 26 l of a solution containing 7% AM of acrylic polymer to be evaluated in an isododecane/ethanol mixture (70/30 weight/weight) were placed on another strip.

[0123] After drying for 24 hours at room temperature (25 C.), the curving (retraction) of the strip treated with the acrylic polymer is observed in comparison with that obtained with the control (Hybridur 875).

[0124] The tensioning effect of the acrylic polymer was also evaluated in the presence of 3-aminopropyltriethoxysilane (APTES). The solution of acrylic polymer (at 1.75% AM) and the APTES were then mixed in the proportions indicated in the table hereinafter, and then an amount of the prepared mixture was deposited on the nitrile rubber strips.

Polymer of Example 1

[0125]

TABLE-US-00001 Proportion of APTES (molar equivalent) Volume relative to the Amount of Amount of of the anhydride APTES solution of the mixture to groups of the added polymer of ex 1 be taken Example polymer (in g) (g) for a strip 1a 0.5 0.0355 1 26 l 1b 1 0.0711 1 26 l

[0126] The tensioning effect obtained was measured according to the protocol previously described. The water resistance of the tensioning effect was then evaluated by immersing the rubber strips treated with the polymer to be evaluated in water at room temperature (25 C.) for 10 minutes, followed by evaluating the tensioning effect after 1 hour of drying.

[0127] The following results were obtained:

TABLE-US-00002 Tensioning effect after immersion in Polymer tested Tensioning effect water Hybridure 875 reference correct Correct Example 1 greater than the greater than the reference reference Example 1a greater than the greater than the reference reference Example 1b greater than the greater than the reference reference

[0128] The results obtained show that the polymer of example 1 used alone forms a film which has a good tensioning effect, including after immersion in water. The tensioning performance is improved in the presence of APTES according to examples 1 a and 1 b.

Polymer of Example 2

[0129]

TABLE-US-00003 Proportion of APTES (molar equivalent) Volume relative to the Amount of Amount of of the anhydride APTES solution of the mixture to groups of the added polymer of ex 2 be taken Example polymer (in g) (g) for a strip 2a 0.5 0.0261 1 26 l 2b 1 0.0521 1 26 l 2c 2 0.1043 1 26 l

[0130] The following results were obtained:

TABLE-US-00004 Tensioning effect after immersion in Polymer tested Tensioning effect water Hybridure 875 reference correct Correct Example 2 comparable to the greater than the reference reference Example 2a greater than the greater than the reference reference Example 2b greater than the greater than the reference reference Example 2c comparable to the comparable to the reference reference

[0131] The results obtained show that the polymer of example 2 used alone forms a film which has a good tensioning effect, including after immersion in water. The tensioning performance is improved in the presence of APTES according to examples 2 a, 2 b and 2 c.

Polymer of Example 3

[0132]

TABLE-US-00005 Proportion of APTES (molar equivalent) Volume relative to the Amount of Amount of of the anhydride APTES solution of the mixture to groups of the added polymer of ex 3 be taken Example polymer (in g) (g) for a strip 3a 0.5 0.0263 1 26 l 3b 1 0.0526 1 26 l 3c 2 0.1052 1 26 l

[0133] The following results were obtained:

TABLE-US-00006 Tensioning effect after immersion in Polymer tested Tensioning effect water Hybridure 875 reference correct Correct Example 3 comparable to the greater than the reference reference Example 3a comparable to the greater than the reference reference Example 3b comparable to the greater than the reference reference Example 3c comparable to the greater than the reference reference

[0134] The results obtained show that the polymer of example 3 used alone forms a film which has a good tensioning effect, including after immersion in water. The tensioning performance, after immersion in water, is improved in the presence of APTES according to examples 3 a, 3 b and 3 c.

EXAMPLE 6

[0135] An Anti-Wrinkle Gel Having the Following Composition is Prepared:

TABLE-US-00007 polymer of example 1 as a 30% by weight solution in 7 g AM isododecane disteardimonium hectorite/propylene carbonate in 3 g isododecane (bentone gel ISDV from Elementis) Preservatives qs Isododecane/ethanol (80/20 w/w) qs 100 g

[0136] Just before application to the skin, 1.58 g of 3-aminopropyltriethoxysilane (APTES) are added to the gel.

[0137] A similar composition is also prepared using the polymer of example 2 or 3 or 4. The composition obtained, applied to the face, makes it possible to effectively smooth out wrinkles.

EXAMPLES 7 to 14: COSMETIC EVALUATION OF MAKEUP COMPOSITIONS

[0138] The 8 makeup compositions of base coat and of top coat described below (examples 8, 10, 12, 14 according to the invention: top coat with APTES; examples 7, 9, 11, 13 outside the invention: topcoat without APTES) were prepared.

[0139] Each base coat composition was applied onto a skin equivalent support made of elastomer by producing a deposit with a wet thickness of 100 m, which was left to dry at room temperature (25 C.) for 24 hours.

[0140] The top coat composition was then applied onto each dry base coat deposit by producing a deposit with a wet thickness of 100 m, which was left to dry at room temperature (25 C.) for 24 hours.

[0141] The state of the film obtained was then observed.

[0142] The resistance of the film obtained was evaluated by separately applying 0.5 ml of olive oil and 0.5 ml of sebum; after 5 minutes of contact, the surface of the film was rubbed with cotton wool and the state of the film was then observed.

[0143] The tackiness of the film and its capacity for transferring or not transferring on touching the film with a finger were also evaluated.

[0144] The evaluation was made in the following manner:

+++: very efficient evaluated cosmetic property
++: moderately efficient evaluated cosmetic property
+: sparingly efficient evaluated cosmetic property
: inefficient evaluated cosmetic property

[0145] The following results were obtained:

TABLE-US-00008 Example 8 Example 10 Example 7 (invention) Example 9 (invention) Base Coat Polymer of example 4 20 g 20 g 20 g 20 g Pigmentary paste 5 g with DC 5 g with DC 5 g with DC 5 g with DC containing 40% by Red 7 Red 7 Red 7 Red 7 weight of pigment in isododecane Disteardimonium 10 g 10 g 10 g 10 g hectorite (Bentone Gel ISD V from Elementis) Isododecane 65 g 65 g 45 g 45 g 2-Octyldodecanol 20 g 20 g Top Coat APTES 10 g 10 g Isododecane 90 g 90 g Appearance of the Homogeneous Homogeneous Homogeneous Homogeneous film film film film film Olive oil resistance + +++ + +++ Sebum resistance + +++ + +++ Non-tacky +++ +++ +++ +++ Transfer-resistant +++ +++ +++ +++ Example 12 Example 14 Example 11 (invention) Example 13 (invention) Base Coat Polymer of example 4 20 g 20 g 20 g 20 g Pigmentary paste 5 g with 5 g with 5 g with 5 g with containing 40% by black iron black iron black iron black iron weight of pigment in oxide oxide oxide oxide isododecane Disteardimonium 10 g 10 g 10 g 10 g hectorite (Bentone Gel ISD V from Elementis) Isododecane 65 g 65 g 45 g 45 g 2-Octyldodecanol 20 g 20 g Top Coat APTES 10 g 10 g Isododecane 90 g 90 g Appearance of the Homogeneous Homogeneous Homogeneous Homogeneous film film film film film Olive oil resistance + +++ + +++ Sebum resistance + +++ + +++ Non-tacky +++ +++ +++ +++ Transfer-resistant +++ +++ +++ +++

[0146] The results obtained show that the deposits resulting from the application of polymer 4, with or without 2-octyldodecanol, followed by APTES (examples 8, 10; 12, 14) form a non-tacky homogeneous film that does not transfer to the finger, and that is resistant to oil and to sebum, whereas the application of polymer 4 alone (examples 7, 9; 11,13) forms a deposit that has poorer resistance to oil and to sebum.

[0147] Thus, the resistance of the film to contact with olive oil and sebum is markedly improved by the application of the top coat composition comprising the APTES.

EXAMPLE 15: COSMETIC EVALUATION OF HAIR COMPOSITION

[0148] 0.5 g of a base coat composition containing 10% AM of the polymer of example 1 in isododecane was applied to a 2.7 g lock of washed and dried hair (lock No. 1). The treated lock was left to dry naturally (25 C.) for 24 hours. 0.5 g of a top coat composition containing 10% AM of APTES in isododecane was then applied to the lock, which was then left to dry naturally for 24 hours.

[0149] The persistence with respect to water and the fixing property of the treated lock were then evaluated by immersing the treated lock in water for 5 minutes. The lock was then dried manually, followed by drying under a hood. The rigidity of the lock was observed by comparison with a nontreated lock.

[0150] It was found that the lock treated before and after immersion in water has a rigid form with good hair fixing. The fixing of the hair thus shows good persistence with respect to water.

EXAMPLE 16: COSMETIC EVALUATION OF MASCARA COMPOSITION

[0151] A base coat composition containing 20% AM of polymer of example 4, 5% of red iron oxide, 10% of disteardimonium hectorite (Bentone Gel ISD V from Elementis) and 65% of isododecane was applied to a false eyelash specimen. The treated eyelashes were left to dry naturally (25 C.) for 24 hours.

[0152] 0.5 g of a top coat composition containing 10% AM of APTES in isododecane was then applied to the lock, which was then left to dry naturally for 24 hours.

[0153] The persistence with respect to sebum of the deposit formed on the treated eyelashes was then evaluated by immersing the treated eyelashes in artificial sebum for 5 minutes. The eyelashes were then left to dry naturally and were rubbed on blotting paper. No trace of deposit was observed on the paper: the deposit formed on the eyelashes is thus sebum-resistant.