Nail varnish composition comprising a sequenced polymer

Translation of description of equivalent WO 2004028494 A2

Nail varnish composition comprising a block polymer

The present invention relates to a varnish nitrocellulose free nail comprising a block polymer. The invention also relates to a process for making up or caring for the nails. These compositions can be applied to the nails of human beings or alternatively to false nails.

The compositions for application to the nail, of. nail varnish type or care base for nails solvent medium include the customary manner, at least one polymer. film, optionally a plasticizer, pigments, rheological agents and solvents.

Nitrocellulose film is commonly used in varnish solvent based nail to get brilliant compositions and crisp. Nitrocellulose is a polymer consisting of anhydroglucose rings assembly nitrated partly obtained by estérifi cation of a portion of the free hydroxyl functions of cellulose with nitric acid in the presence of sulfuric acid.

Currently, nitrocellulose remained still the most widely used primary film-forming in solvents in nail polish formulations gloss and conducting optimized. However, formulations comprising nitrocellulose have the following disadvantages:

- They allow to obtain films with a proper level of hardness and gloss, but with a resistance over time unsatisfactory, mainly due to the poor resistance of the film to chipping. - They give hard films that lack adhesion to the nail. One can overcome this drawback, by adding plasticizers, but in this case it is necessary to use very large quantities of plasticizers and co-resins, of the order of that of nitrocellulose. In addition, the presence of plasticizers in these formulations is reflected, after film formation and drying, in particular by changes in film properties over time, due both to a slow evaporation of the residual solvents contained in the film after drying and a potential loss of some of the plasticizers, in particular by evaporation, resulting in a curing of the film over time and poor chipping resistance.

Some known formulations comprising nitrocellulose have the disadvantage of yellowing on the nail over time. In addition, the manufacture of nitrocellulose, its transportation and its incorporation in formulations pose safety problems, so we try to substitute it with other film. The search to replace nitrocellulose by other film-forming agents such as polyacrylic and polyurethane in nail varnishes, as for example the aqueous polyurethane dispersions described in the document EP0648485, have not given satisfactory results including terms of dress and resistance to external factors such as water or detergents.

The application US2002 / 18759 discloses a copolymer acrylic acid / butyl methacrylate as film-forming polymer to partially substitute the nitrocellulose. The nail polish containing this polymer does not have an outfit, especially a holding of sufficient brightness and requires the addition of plasticizers.

Applicant has discovered a new way of formulating a nail polish without nitrocellulose, which has good properties of gloss and resistance.

This nail polish also provides a lamination films without rec ourir the addition of large amounts of external plasticizers, while maintaining a good level of film hardness and resistance of varnishes on the nail and shock / or chipping and thus an improvement of the behavior in time of the varnish on the nail and / or wear resistance.

More specifically, the invention relates to a nail varnish composition comprising, in a cosmetically acceptable organic solvent, at least one film-forming linear ethylenic polymer sequence, said composition being free of nitrocellulose, the block polymer being such that when it is present in sufficient amount in the composition, the mean gloss - 20 ° of a deposit of the said composition, once spread onto a support, is greater than or equal to 50 out of 100.

The invention also relates to a nail varnish composition comprising, in a cosmetically acceptable medium, at least one film-forming ethylenic linear block polymer as described below, said composition being free of nitrocellulose.

The term "nitrocellulose" refers to any nitrated cellulose derivative, especially nitrocellulose. According to the present invention, the term. "Forming polymer" a polymer capable, by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to a support, especially on Kerati cal materials.

By "composition free nitrocellulose" in meant a composition containing less than 5%, preferably less than 3%, preferably less than 2%, preferably less than 1%, preferably less than 0.5%; preferably less than 0.1%, preferably less than 0.05% nitrocellulose.

The invention _. also relates to a cosmetic process or for the nontherapeutic care of the nails comprising applying to the nails, at least one layer of nail polish composition as defined above.

The invention further relates to the use of a nail varnish composition comprising at least one ethylenic polymer sequence, linear film-forming, said composition being free of nitrocellulose, to obtain a film, once spread onto a support, 20 ° gloss greater than 50 100, and incidentally that is good holding.

Brilliance average composition

The term "mean gloss" means the gloss as may be measured using a glossmeter, in a conventional manner by the following method.

On a Leneta brand contrast card of reference Form 1A Penopac, is spread a layer between 50 .mu.m and 150 .mu.m thick of the composition using an automatic spreader. The layer covers at least the white background of the card. Allowed to dry the deposit for 24 hours at a temperature of 30 ° C, then proceed to measuring the 20 ° gloss on the white background with a mark of Byk Gardner gloss microTri-GLOSS reference. This measurement (between 0 and 100) is repeated at least three times, and the mean gloss is the mean of at least three measurements taken.

The mean gloss of the composition measured at 20 ° is preferably greater than or equal to 50 out of 100, better still greater than or equal to 55, better still greater than or equal to 60, better still greater than or equal to 65, more preferably, greater than or equal to 70 or better still greater than or equal to 75 out of 100, even greater than or equal to 80 out of 100. Preferably, the mean gloss of the composition, once spread onto a support, measured at 60 ° is greater than or equal to 50, better still greater than or equal to 60, better still greater than or equal to 65, more preferably greater or equal to 70, better still greater than or equal to 75 ° more preferably, greater than or equal to 80, better still greater than or equal to 85 or better still greater than or equal to 90 out of 100.

One proceeds to the measurement of the mean gloss at 60 ° as follows. The gloss may be measured using a glossmeter, in a conventional manner by the following method. On a parte contrast Leneta brand and of reference Form 1A Penopac, is spread a layer between 50 .mu.m and 150 .mu.m thick of the composition using an automatic spreader. The layer covers at least the white background of the card. It is allowed to dry the deposit for 24 hours at a temperature of 30 ° C, then proceed to measuring the 60 ° gloss on the white background with a brand glossmeter Byk Gardner reference microTri-GLOSS .

This measurement (between 0 and 100) is repeated at least three times, and the mean gloss is the mean of at least three measurements taken.

According to one embodiment, the gloss of the composition measured at 20 ° is preferably greater than or equal to 60, preferably 65, 70 or 75 out of 100, and / or the gloss of the composition measured at 60 ° is preferably greater than or equal to 80, 85 or 90 out of 100.

Polymer sequence:

The composition according to the present invention contains at least a polymer sequence. By "block polymer" means a polymer comprising at least two different blocks and preferably at least three distinct sequences.

According to one embodiment, the block polymer of the composition according to the invention is an ethylene polymer. The term "ethylenic polymer" means a polymer obtained by polymerizing monomers comprising an ethylenic unsaturation.

According to one embodiment, the block polymer of the composition. according to the invention is a linear polymer. In contrast, a non-linear structure polymer is, for example, a polymer of branched structure, star, graft, or otherwise. According to one embodiment, the block polymer of the composition according to the invention is a film forming polymer. By polymer "film" means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to a support, especially to keratin materials.

According to one embodiment, the block polymer of the composition according to the invention is a non-elastomeric polymer.

"Non-elastomeric polymer" means a polymer which, when subjected to a stress intended to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its length initial when the stress.

More specifically, "non-elastomeric polymer" denotes a polymer with an instantaneous recovery R <50% and a delayed recovery R_{2 hours} <70% after having undergone an elongation of 30%. Preferably R_\ is <30%, and R_{2 hours} <50%.

More specifically, the non-elastomeric nature of the polymer is determined according to the following protocol: A polymer film is prepared by pouring a solution of the polymer in a Teflon-coated mold, followed by drying for 7 days in an atmosphere at 23 ± 5 ° C and 50 ± 10

% Relative humidity.

We then obtain a film about 100 microns thick in which are cut rectangular specimens (for example Pemporte-piece) with a width of 15 mm and a length of 80 mm.

It requires that sample to a tensile stress using a machine sold under the reference Zwick, under the same conditions of temperature and humidity for drying. The specimens are pulled at a speed of 50 mm / min and the distance between the jaws is 50 mm, which corresponds to the initial length (l₀) Of the test piece.

It determines the instantaneous recovery Ri as follows: - the specimen is stretched by 30% (ε_max), That is to say about 0.3 times its initial length (l₀) - The stress is released by applying a return speed equal to the tensile speed, ie 50 mm / min and measuring the percentage of the residual elongation of the specimen, after returning to zero constraint (εj). The% instantaneous recovery (R) is given by the following formula:

Ri = (ε_myχ- εi) / ε_max) X 100

To determine the delayed recovery, the residual elongation is measured in percent specimen (ε_2rι), 2 hours after returning to zero stress.

The% delayed recovery (R_{2 hours}) Is given by the following formula:

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Purely as a guide, a polymer according to one embodiment of the invention has an instantaneous recovery R of 10% and a delayed recovery R_{2 hours} 30%.

According to another embodiment, the block polymer of the composition according to the invention does not comprise styrene unit. By polymer free of styrene units, means a polymer comprising less than 10%, preferably less than 5%, preferably less than 2%, more preferably less than 1% by weight i) of styrene of the formula -CH pattern ( C₆H₅) -CH₂- Or ii) of substituted styrene units, for instance methylstyrene, chlorostyrene or chloromethylstyrene.

According to one embodiment, the block polymer of the composition according to the invention is derived from aliphatic ethylenic monomers. Aliphatic monomer means a monomer comprising no aromatic groups.

According to one embodiment, the block polymer is an ethylenic polymer derived from aliphatic ethylenic monomers comprising a carbon-carbon double bond and at least one ester group -COO- or amide -CONk The ester group may be linked to one of the two unsaturated carbons via the carbon atom or the oxygen atom. The amide group may be linked to one of the two unsaturated carbons via the carbon atom or the nitrogen atom.

According to a mode of implementation, the block polymer comprises at least one first block and at least one second sequence.

By "at least one block" means one or more sequences. It was noted that in the above and following the terms "first" and "second" blocks do not in any way condition the order of the said sequences (or blocks) in the polymer structure.

According to one embodiment, the block polymer comprises at least one first block and at least one second block having glass transition temperatures (Tg).

In this implementation mode, the first and second blocks may be linked together via an intermediate segment having a glass transition temperature between the glass transition temperatures of the first and second sequences.

According to one embodiment, the block polymer comprises at least one first block and at least one second block linked together via an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block .

Preferably, the intermediate block is derived essentially from constituent monomers of the first sequence and second sequence.

By "substantially" means 85% at least, preferably at least 90%, more than 95% and even better still 100%.

Advantageously, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.

According to one embodiment, the block polymer comprises at least one first block and at least one second sequence incompatible in the organic liquid medium of the composition of the invention.

"Mutually incompatible blocks with each other" means that the mixture formed from the polymer corresponding to the first block and the polymer corresponding to the second block is not miscible in the organic liquid majority by weight content in the organic liquid medium of the composition at room temperature (25 ° C) and atmospheric pressure (10⁵ Pa), for a content of the upper polymer blend or equal to 5% by weight, relative to the total weight of the mixture (polymers and major organic liquid), it being understood that: i) the said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and ii). each of the polymers corresponding to the first and second blocks has an average molecular weight (weight or number) equal to that of the block polymer +/- 15%.

In the case where the organic liquid medium comprises a mixture of organic liquids, in the hypothesis of two or more liquids present in identical mass proportions, the said polymer mixture is immiscible in at least one of them.

In the case where the organic liquid medium comprises only one organic liquid, the latter is obviously the majority liquid by weight.

By "organic liquid medium" means a medium containing at least one organic liquid, that is to say, at least one liquid organic compound at room temperature

(25 ° C) and atmospheric pressure (10⁵ Pa). According to one embodiment, the majority liquid of the organic liquid medium is an oil (fat) volatile or nonvolatile. Preferably, the organic liquid is cosmetically acceptable (acceptable tolerance, toxicology and feel). The organic liquid medium is cosmetically acceptable, in that it is compatible with keratin materials, such as oils or organic solvents commonly used in cosmetic compositions.

According to one embodiment, the major liquid of the organic liquid medium is the polymerization solvent or one of the solvents of the block polymer as described below.

By polymerization solvent is meant a solvent or solvent mixture. The polymerization solvent may be chosen especially from ethyl acetate, butyl acetate, alcohols such as isopropanol, ethanol, aliphatic alkanes such as isododecane, and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol, or isododecane.

In general, the block polymer may be incorporated into the composition at a high dry contents, typically greater than 10%, greater than 20% and more preferably greater than 30% and more preferably greater than 45% by weight relative to the total weight of the composition while being easy to formulate.

Preferably, the block polymer comprises no silicon atoms in its skeleton. By. "Skeleton" means the main chain of the polymer, as opposed to the pendent side chains. Preferably, the inventive polymer is not water soluble, i.e. the polymer is not soluble in water or in a mixture of water and of linear or branched lower monoalcohols containing from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without pH modification, at an active material content of at least 1% by weight at room temperature (25 ° C).

According to one embodiment, the block polymer has a polydispersity index I of greater than 2.

Advantageously, the block polymer used in the compositions according to the invention has a polydispersity index I of greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8 and better still greater than or equal to 2.8 and in particular, ranging from 2.8 to 6.

The polydispersity index I of the polymer is equal to the ratio of the weight-average mass

Mw to the number-average mass Mn.

the average molecular weights are determined by weight (Mw) and number (Mn) by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

The weight-average mass (Mw) of the block polymer is preferably less than or equal to 300 000, it is for example from 35 000 to 200 000 and better still from 45 000 to 150 000.

The number-average mass (Mn) of the block polymer is preferably less than or equal to 70 000, it is for example from 10 000 to 60 000 and better still from 12 000 to 50 000.

Each sequence or block of the block polymer is derived from one type of monomer or from several different types of monomer.

This means that each block may consist of a homopolymer or a copolymer; this copolymer constituting the block may be his turn random or alternating.

The glass transition temperatures indicated for the first and second blocks may be theoretical Tg values ​​determined from the theoretical Tg values ​​of the constituent monomers of each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 3^rd ed, 1989, John Wiley, according to the following relationship, known as Fox's law:

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Unless otherwise indicated, the Tg values ​​indicated for the first and second blocks in the present patent application are theoretical Tg.

The difference between the glass transition temperatures of the first and second blocks is generally greater than 10 ° C, preferably greater than 20 ° C and better still greater than 30 ° C.

In particular, the block polymer comprises at least one first block and at least one second sequence such that the first block may be chosen from: a) a block with a Tg of greater than or equal to 40 ° C, b) a block with a Tg less than or equal to 20 ° C, c) a block with a Tg of between 20 and 40 ° C, and the second sequence can be chosen from a category a), b) or c) different from the first sequence.

Is meant in the present invention, the expression "between ... and ...", a range of values ​​which the limits mentioned are excluded, and "from ... to ..." and "going from ... to ... ", a range of values ​​whose terminals are included.

a) Block with a Tg greater than or equal to 40 ° C.

The block with a Tg of greater than or equal to 40 ° C for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example ranging from 50 ° C to 120 ° C and better still greater or¹ equal to 60 ° C, for example ranging from 60 ° C to 120 ° C.

The block with a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer. The block with a Tg of greater than or equal to 40 ° C may be totally or partially derived from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature exceeding 40 ° C.

In the case where this block is a homopolymer, it is derived from monomers which are such (s) that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40 ° C. This first block may be a homopolymer consisting of one type of monomer (for which the Tg of the corresponding homopolymer is greater than or equal to 40 ° C).

In the case where the first block is a copolymer, it may be totally or partially derived from one or more monomers, the nature and concentration are chosen such that the Tg of the resulting copolymer is greater than or equal to 40 ° C. The copolymer can for example include: - monomers which are such (s) that the homopolymers prepared from these monomers have or above Tg 40 ° C, for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example ranging from 50 ° C to 120 ° C and better still greater than or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C, and - of the monomers which are such ( s) that the homopolymers prepared from these monomers have lower Tg at 40 ° C, chosen from monomers with a Tg of between 20 to 40 ° C and / or monomers with a Tg of less than or equal to 20 ° C, for example a Tg ranging from -100 to 20 ° C, preferably below 15 ° C, especially ranging from - 80 ° C to 15 ° C and preferably below 10 ° C, for example ranging from -50 ° C to 0 ° C, as described further.

The monomers whose homopolymers have a glass transition temperature exceeding 40 ° C are preferably chosen from the following monomers, also known as the main monomers:

- Methacrylates of formula CH₂ = C (CH₃) COOR₁ wherein R represents an unsubstituted alkyl group, linear or branched, containing from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isobutyl group or R is cycloalkyl C -C _2ι

- CH formula acrylates₂ = CH-COOR₂ wherein R₂ is cycloalkyl C₄ -C₁₂acrylate such as isobornyl or a tert-butyl group, (meth) acrylamides of formula

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wherein R₇ and R₈ identical or different, each represent a hydrogen atom or an alkyl group C₁ -C₁₂ linear or branched, such as n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl; or R₇ is H and R₈ represents a 1, 1 -dimethyl-3-oxobutyI, and R 'denotes H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide,

- And mixtures thereof.

Particularly preferred main monomers are methyl methacrylate, (meth) acrylate, isobutyl (meth) isobornyl acrylate and mixtures thereof.

b) Séguence before a Tg less than or equal to 20 ° C.

The block with a Tg less than or equal to 20 ° C for example a Tg ranging from -100 to 20 ° C, preferably less than or equal to 15 ° C, especially ranging from -80 ° C to 15 ° C and preferably less or equal to 10 ° C, for example ranging from -50 ° C to 0 ° C.

The block with a Tg less than or equal to 20 ° C may be a homopolymer or a copolymer.

The block with a Tg less than or equal to 20 ° C may be totally or partially derived from one or more monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature or equal to 20 ° C. In the case where this block is a homopolymer, it is derived from monomers which are such (s) that the homopolymers prepared from these monomers have glass transition temperatures less than or equal to 20 ° C. This second block may be a homopolymer consisting of one type of monomer (for which the Tg of the corresponding homopolymer is less than or equal to 20 ° C).

In the case where the block with a lower or Tg at 20 ° C is a copolymer, it may be totally or partially derived from one or more monomers, the nature and concentration are chosen such that the Tg of the resulting copolymer is less than or equal to 20 ° C.

It may for example comprise

- One or more monomers whose corresponding homopolymer has a Tg of less than or equal to 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, preferably below 15 ° C, especially ranging from - 80 ° C to 15 ° C and preferably below 10 ° C, for example ranging from -50 ° C to 0 ° C and

- One or more monomers whose corresponding homopolymer has a Tg greater than 20 ° C, such as monomers with a Tg of greater than or equal to 40 ° C, for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example ranging from 50 ° C to 120 ° C and better still greater than or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C and / or monomers with a Tg of between 20 and 40 ° C, as described above.

Preferably, the block with a Tg less than or equal to 20 ° C is a homopolymer.

The monomers whose homopolymer has a Tg of less than or equal to 20 ° C are preferably chosen from the following monomers, or main monomer:

- CH formula acrylates₂ = CHCOOR₃,

R₃ representing a substituted alkyl group at C_12, linear or branched, with the exception of tert-butyl group, in which is (are) optionally intercalated (s) one or more heteroatoms selected from O, N, S,

- Methacrylates of formula CH₂ = C (CH₃) COOR₄,

R₄ representing a substituted alkyl C₆ -C ₂ linear or branched, in which is (are) optionally intercalated (s) one or more heteroatoms selected from 0, N and S;

- A formula of vinyl esters₅-CO-O-CH = CH₂ wherein R₅ is alkyl C₄ to Cι₂ straight or branched;

- Vinyl ethers of C₄ -C₁₂,

- N-alkyl C₄ -C₁₂ acrylamides, such as N-octylacrylamide,

- And mixtures thereof.

Particularly preferred main monomers for the block with a Tg less than or equal to 20 ° C are alkyl acrylates whose alkyl chain contains from 1 to 10 carbon atoms, except the tert-butyl group, such as acrylate methyl acrylate, isobutyl acrylate and 2-ethylhexyl and mixtures thereof.

c) Block with a Tg of between 20 and 40 ° C.

The sequence which has a Tg of between 20 and 40 ° C may be a homopolymer or a copolymer.

The block with a Tg of between 20 and 40 ° C may be totally or partially derived from one or more monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature between 20 and 40 ° C.

The block with a Tg of between 20 and 40 ° C may be totally or partly from monomers which are such (s) that the corresponding homopolymer has a Tg of greater than or equal to 40 ° C and from monomers which are such ( s) that the corresponding homopolymer has a Tg less than or equal to 20 ° C.

In the case where this block is a homopolymer, it is derived from monomers (or main monomer) which are such (s) that the homopolymers prepared from these monomers have glass transition temperatures between 20 and 40 ° C. This first block may be a homopolymer consisting of one type of monomer (for which the Tg of the corresponding homopolymer ranges from 20 ° C to 40 ° C).

The monomers whose homopolymer has a glass transition temperature between 20 and 40 ° C are preferably chosen from methacrylate, n-butyl acrylate, cyclodecyl acrylate, neopentyl, Pisodécylacrylamide and mixtures thereof. In the case where the block with a Tg of between 20 and 40 ° C is a copolymer, it is totally or partially derived from one or more monomers (or main monomer) whose nature and concentration are chosen such that the Tg of the resulting copolymer is between 20 and 40 ° C.

Advantageously, the block with a Tg of between 20 and 40 ° C is a copolymer outcome in whole or in part:

- Main monomers whose corresponding homopolymer has a Tg of greater than or equal to 40 ° C, for example a Tg ranging from 40 ° C to 150 ° C, preferably greater than or equal to 50 ° C, for example ranging from 50 to 120 ° C and better still greater than or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C, as described above, and / or

- Main monomers whose corresponding homopolymer has a Tg less than or equal to 20 ° C, for example a Tg ranging from -100 to 20 ° C, preferably less than or equal to 15 ° C, especially ranging from -80 ° C at 15 ° C and preferably less than or equal to 10 ° C, for example ranging from -50 ° C to 0 ° C, as described above, the said monomers being chosen such that the Tg of the copolymer forming the first block is between 20 and 40 ° C.

Such main monomers are chosen, for example methyl methacrylate, acrylate and methacrylate, isobornyl acrylate, butyl acrylate and 2-ethylhexyl and mixtures thereof.

Preferably, the proportion of the second block with a Tg less than or equal to 20 ° C is from 10 to 85% by weight of the polymer, more preferably from 20 to 70% and more preferably 20 to 50%.

Preferably, each of the first and second blocks comprises at least one monomer selected from acrylic acid, acrylic acid esters, (meth) acrylic acid, esters of (meth) acrylic acid and mixtures thereof.

Advantageously, each of the first and second blocks is totally derived from at least one monomer selected from acrylic acid, acrylic acid esters, (meth) acrylic acid, esters of (meth) acrylic acid and mixtures thereof.

Each of the blocks may contain in small proportion at least one constituent monomer of the other sequence. Thus, the first block may contain at least one constituent monomer of the second block, and vice versa.

Each of the first and / or second blocks (Fri) comprise, in addition to the monomers indicated above, one or more other monomers known as additional monomers, different from the main monomers mentioned above.

The nature and amount of this or these additional monomer are chosen so that the sequence in which they are present has the desired glass transition temperature.

This additional monomer is chosen, for example: hydrophilic monomers such as:

- Unsaturated monomers (s) ethylenic (s) comprising at least one carboxylic or sulfonic acid function, for instance: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and the salts thereof,

- Unsaturated monomers (s) ethylenic (s) comprising at least one tertiary amine function, for instance 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylamide dimethylaminopropylmethacrylamide, and salts thereof ,

- Methacrylates of formula CH₂ = C (CH₃) COOR₆ wherein R₆ represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups (such as methacrylate 2-hydroxypropyl methacrylate 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate,

- Methacrylates of formula CH₂ = C (CH₃) COOR₉,

R₉ Representative alkyl C₆ -C₁₂ linear or branched, in which is (are) optionally intercalated (s) one or more heteroatoms selected from 0, N and S, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups and halogen atoms ( Cl, Br, I, F);

- CH formula acrylates₂ = CHCOOR₁₀,

R₁₀ Representative alkyl C, to C₁₂ linear or branched substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl,

Br, I and F), such as acrylate and 2-hydroxypropyl acrylate, 2-hydroxyethyl, or R₁₀ represents an alkyl (CC₁₂) -O-POE (polyoxyethylene) with repetition of the oxyethylene unit from 5 to 30 times, for example methoxy-POE, or R₁₀represents a polyoxyethylenated group comprising from 5 to 30 ethylene oxide units

b) ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloxypropyltrimethoxysilane trimethoxy silane, methacryloxypropyl tris (trimethylsiloxy) silane, - and mixtures thereof.

Particularly preferred additional monomers are acrylic acid, methacrylic acid, trifluoroethyl methacrylate and mixtures thereof.

According to one embodiment, each first and second block of the block polymer comprises at least one monomer selected from esters of (meth) acrylic acid and optionally at least one additional monomer such as (meth) acrylic acid, and mixtures thereof.

According to another embodiment, each first and second block of the block polymer is totally derived from at least one monomer selected from esters of (meth) acrylic acid and optionally at least one additional monomer such as the (meth) acrylic acid, and mixtures thereof.

According to a preferred embodiment, the block polymer is a non-silicone polymer, i.e. a polymer free of silicon atoms.

This or these additional monomers represent (s) generally a less than or equal to 30% by weight, for example from 1 to 30% by weight, preferably 5 to 20% by weight and, more preferably, from 7 to 15 % by weight of the total weight of the first and / or second blocks.

The block polymer is obtainable by radical solution polymerization according to the following preparation process: a portion of the polymerization solvent is introduced into a suitable reactor and heated until the adequate temperature for the polymerization (typically between 60 and

120 ° C), once this temperature is reached, the constituent monomers of the first block are introduced in the presence of a portion of the polymerization initiator, after a time T corresponding to a maximum conversion of 90%, the constituent monomers of the second block and the rest of the initiator are introduced, are allowed to react for a time T '(ranging from 3-6 h) after which the mixture is cooled to room temperature, the polymer is obtained in solution in the polymerization solvent.

First Embodiment

According to a first embodiment, the block polymer comprises a first block having an equal or higher Tg to 40 ° C, as described above in a) and a second block with a Tg of less than or equal to 20 ° C as described above in b).

Preferably, the first block with a Tg of greater than or equal to 40 ° C is a copolymer derived from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature exceeding 40 ° C, such as the monomers described above. Advantageously, the second block with a Tg of less than or equal to 20 ° C is a homopolymer derived from monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature not exceeding 20 ° C. such as the monomers described above.

Preferably, the proportion of the block with a Tg greater than or equal to 40 ° C is from 20 to 90% by weight of polymer, preferably from 30 to 80% and more preferably 50 to 70%. Preferably, the proportion of the block with a Tg less than or equal to 20 ° C is from 5 to 75% by weight of polymer, preferably from 15 to 50% and better still from 25 to 45%.

Thus, in a first variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example having a Tg ranging from 70 to 110 ° C, which is a methacrylate copolymer, methyl methacrylate / acrylic acid,

- A second sequence of less than or equal to Tg 20 ° C, for example ranging from 0 to 20 ° C, which is a methyl acrylate homopolymer, and - an intermediate block which is a methyl methacrylate copolymer / acrylic acid / acrylate methyl. In a second variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 70 to 100 ° C, which is a methacrylate copolymer, methyl methacrylate / acrylic acid / trifluoroethyl methacrylate, - a second lower Tg sequence or equal to 20 ° C, for example ranging from 0 to 20 ° C, which is a methyl acrylate homopolymer, and '

- An intermediate block which is a random copolymer of methyl methacrylate / acrylic acid / methyl acrylate / trifluoroethyl methacrylate.

According to a third variant, the. polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an isobornyl acrylate / isobutyl methacrylate,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -85 to - 55 ° C, which is a homopolymer of 2-ethylhexyl acrylate, and - an intermediate block which is an acrylate random copolymer isobornyl acrylate / isobutyl methacrylate / acrylate, 2-ethylhexyl.

In a fourth variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an isobornyl acrylate / methyl methacrylate,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -85 to - 55 ° C, which is a homopolymer of acrylate 2-ethylhexyl and

- An intermediate block which is an isobornyl acrylate random copolymer / methyl methacrylate / acrylate, 2-ethylhexyl.

According to a fifth variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -85 to - 55 ° C, which is a homopolymer of acrylate 2-ethylhexyl and

- An intermediate block which is a random copolymer of isobornyl acrylate / isobornyl methacrylate / acrylate, 2-ethylhexyl.

According to a sixth variant, the polymer according to the invention may comprise: - a first Tg of greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is a copolymer of isobornyl methacrylate / methacrylate isobutyl, - A second sequence Tg of less than or equal to 20 ° C, for example ranging from -35 to - 5 ° C, which is an isobutyl acrylate homopolymer and

- An intermediate block which is a random copolymer of isobornyl methacrylate / isobutyl methacrylate / isobutyl acrylate.

According to a seventh variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -35 to - 5 ° C, which is an isobutyl acrylate homopolymer and

- An intermediate block which is a random copolymer of isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate.

According to an eighth variant, the polymer according to the invention may comprise: - a first Tg of greater than or equal to 40 ° C, for example ranging from 60 to 90 ° C, which is an isobornyl acrylate / methacrylate isobutyl,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from -35 to - 5 ° C, which is an isobutyl acrylate homopolymer and

- An intermediate block which is an isobornyl acrylate random copolymer / isobutyl methacrylate / isobutyl acrylate.

The following examples illustrate without limitation polymers corresponding to this first embodiment. The amounts are expressed in grams.

Example 1: Preparation of methyl poly.méthacrylate polymer / acrylic acid / methyl acrylate)

100 g of butyl acetate are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and in 1 hour, 180 g of methyl methacrylate, 30 g of acrylic acid, 40 g of butyl acetate, 70 g of isopropanol and 1, 8 g of 2.5- Bis ( 2- ethyl! hexanoylperoxy) -2.5-dimethyl hexane (Trigonox^® 141 Akzo Nobel). The mixture is kept 1 hour at 90 ° C. then introduced into the above mixture, still at 90 ° C in 1 hour, 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2.5- Bis (2- ethylhexanoylperoxy) 2,5-dimethylhexane.

The mixture is kept 3 hours at 90 ° C, then diluted with 105 g of butyl acetate and 45 g of isopropanol and then the whole is cooled.

This gives a 40% solution of polymer active material in the mixture of butyl acetate / isopropanol.

A polymer comprising a first sequence or the poly (methyl methacrylate / acrylic acid) having a Tg of 100 ° C a second sequence or methyl polyacrylate block having a Tg of 10 ° C and an intermediate block which is a random polymer methyl methacrylate / acrylic acid / polymethyl acrylate.

This polymer has a weight-average mass of 52 000 and an average weight of 18000, a polydispersity index I of 2.89

Second Embodiment

According to a second embodiment, the block polymer comprises a first block having a glass transition temperature (Tg) of between 20 and 40 ° C, according to the blocks described in c) and a second block having a glass transition temperature or equal to 20 ° C, as described above in b) or a glass transition temperature exceeding 40 ° C, as described in a) above.

Preferably, the proportion of the first block with a Tg of between 20 and 40 ° C is from 10 to 85% by weight of polymer, preferably from 30 to 80% and even better still from 50 to 70%.

When the second sequence is a sequence having greater than or equal to Tg 40 ° C, it is preferably present in a proportion ranging from 10 to 85% by weight of polymer, preferably from 20 to 70% and better still from 30 to 70 %.

When the second sequence is a sequence having less than or equal to Tg 20 ° C, it is preferably present in a proportion ranging from 10 to 85% by weight of polymer, preferably from 20 to 70% and better still from 20 to 50 %. Preferably, the first block with a Tg of between 20 and 40 ° C is a copolymer derived from monomers which are such (s) that the corresponding homopolymer has a Tg of greater than or equal to 40 ° C and from monomers which are such ( s) that the corresponding homopolymer has a Tg less than or equal to 20 ° C. Advantageously, the second block with a Tg less than or equal to 20 ° C or having a Tg greater than or equal to 40 ° C is a homopolymer.

Thus, according to first variant of this second embodiment, the block polymer may comprise: - a first Tg sequence comprised between 20 and 40 ° C, for example having a Tg from 25 to 39 ° C, which is a copolymer comprising at least one methyl acrylate monomer, at least one methyl methacrylate monomer and at least one acrylic acid monomer,

- A second Tg of greater than or equal to 40 ° C, for example ranging from 85 to 125 ° C, which is a homopolymer composed of methyl methacrylate monomers and

- An intermediate block comprising at least one methyl acrylate monomer, methyl methacrylate and

- An intermediate block comprising methyl methacrylate, at least one acrylic acid monomer and at least one methyl acrylate monomer.

According to a second variant of this second embodiment, the block polymer may comprise:

- A first sequence Tg of between 20 and 40 ° C, for example with a Tg from 21 to 39 ° C, which is a copolymer comprising isobornyl acrylate / isobutyl methacrylate / acrylate, 2-ethylhexyl,

- A second sequence of less than or equal to Tg 20 ° C, for example ranging from -65 to - 35 ° C, which is a methyl methacrylate homopolymer and

- An intermediate block which is an isobornyl acrylate random copolymer / isobutyl methacrylate / acrylate, 2-ethylhexyl.

In a third variant of this second embodiment, the block polymer may comprise:

- A first sequence Tg of between 20 and 40 ° C, for example with a Tg from 21 to 39 ° C, which is a copolymer isobornyl acrylate / methyl acrylate / acrylic acid, - a second Tg of greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an acrylate homopolymer of isobornyl - An intermediate block which is an isobornyl acrylate random copolymer / methyl acrylate / acrylic acid.

Illustrative but not limiting polymers corresponding to this second embodiment can be made as follows.

Example 2 Preparation of a poly (methyl methacrylate / methyl acrylate / acrylic acid)

100 g of butyl acetate are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and in 1 hour, 50.4 g of methyl methacrylate, 21 g of acrylic acid, 138.6 g of methyl acrylate, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g of 2.5-Bis (2-ethylhexanoylperoxy) 2,5-dimethylhexane (Trigonox^® 141 Akzo Nobel). The mixture is kept 1 hour at 90 ° C.

then introduced into the above mixture, still at 90 ° C in 1 hour, 90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of isopropanol and 1, 2 g of 2.5-Bis (2- ethylhexanoylperoxy ) 2,5-dimethylhexane.

The mixture is kept 3 hours at 90 ° C, then diluted with 105 g of butyl acetate and 45 g of isopropanol and then the whole is cooled.

This gives a 40% solution of polymer active material in the mixture of butyl acetate / isopropanol.

The polymer obtained comprises a first block or the poly (methyl acrylate / methyl methacrylate / acrylic acid) having a Tg of 35 ° C a second block or the poly (methyl methacrylate) having a Tg of 100 ° C and a sequence intermediate which is a methacrylate random polymer of methylmethacrylate / acrylic acid / polymethyl acrylate.

Generally, the compositions of the invention contain from 0.1 to 60% by weight, preferably from 0.5 to 50% by weight, and preferably 1 to 40% by weight of the block polymer according to the invention.

solvent medium

The cosmetic composition may comprise an organic solvent or mixture of organic solvents. organic solvent may be chosen from: ketones that are liquid at room temperature such as methyl ethyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; - Alcohols that are liquid at room temperature, such as ethanol, isopropanol, diacetone alcohol, 2-butoxyethanol or cyclohexanol; glycols that are liquid at room temperature such as ethylene glycol, propylene glycol, pentylene glycol or glycerol; liquid propylene glycol ethers at room temperature, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, mono-n-butyl ether of dipropylene glycol; cyclic ethers such as γ-butyrolactone; short-chain esters (having 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, isopropyl acetate, n -butyl, isopentyl acetate, methoxypropyl acetate, butyl lactate; ethers that are liquid at room temperature such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes that are liquid at room temperature, such as decane, heptane, dodecane or cyclohexane; alkyl sulfoxides such as dimethyl sulfoxide; aldehydes that are liquid at room temperature, such as benzaldehyde or acetaldehyde; heterocycles, such as tetrahydrofuran; propylene carbonate, ethyl 3-ethoxypropionate; mixtures thereof.

Preferably, the organic solvent medium has a polarity P of from .442 to .725.

The polarity is defined in terms of solubility parameter according to the Hansen solubility space according to the following relationship:

P = V (Ap² + .DELTA.h²) / .delta.t

- .DELTA.h Characterizes the specific interaction forces (such as hydrogen bonding, acid / base, donor / acceptor, etc. ..); - Ap characterizes the forces of Debye interactions between permanent dipoles and the forces Keesom interaction between induced dipoles and permanent dipoles.

- And .delta.t = V (Ap² + .DELTA.h²Dd +²), Dd characterizes the London dispersion forces arising from the formation of dipoles induced during molecular impacts.

The definition and calculation of solubility parameters in the Hansen three-dimensional solubility space are described in the article by CM Hansen: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967);

When the solvent medium comprises a mixture of solvents, the polarity is determined from the solubility parameters of the mixture which are themselves determined from those of the compounds taken separately, according to the following relationships:

δdmel = Σ xi δdi; δpmel = Σ xi δpi and δhmel = Σ xi δhi

where xi represents the volume fraction of component i in the mixture.

As the organic solvent having a polarity of from 0.442 to 0.725, there may be mentioned in particular methyl acetate, isopropyl acetate, methoxypropyl acetate, butyl lactate, acetone, methyl ethyl ketone, diacetone alcohol, D-butyrolactone, tetrahydrofuran, propylene carbonate, ethyl 3-ethoxypropionate, dimethylsulfoxide, and mixtures thereof.

The organic solvent medium may represent from 10 to 95% by weight, relative to the total weight of the composition, preferably from 15% to 80% by weight and better still from 20 to 60% by weight.

forming additional polymer

The composition may comprise, besides the block polymer of the composition according to the invention, an additional polymer such as a film-forming polymer.

Among the film-forming polymers used in the composition of the present invention, synthetic polymers include, of radical type or of polycondensate type, natural polymers and mixtures thereof. The film forming polymer may be chosen in particular from cellulose polymers such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, ethyl cellulose, or alternatively polyurethanes, acrylic polymers, vinyl polymers , polyvinyl butyrals, alkyd resins, resins derived from aldehyde condensation products, such as arylsulfonamide-formaldehyde resins, for instance toluene sulfonamide formaldehyde resin, epoxy resins aryl sulfonamide.

Film-forming polymers that may especially use toluene sulfonamide formaldehyde resin "Ketjentflex MS80" from Akzo or "Santolite MHP", "Santolite MS 80" from the company Faconnier or "Resimpol 80" from the company Pan Americana, the alkyd resin "Beckosol ODE 230-70-E" from the company Dainippon, acrylic resin "ACRYLOID B66" from the company Rohm &amp; Haas, the polyurethane resin "Trixene PR 4127" from the company Baxenden.

The additional film-forming polymer 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 2% to 40% by weight, and from 5% to 25% by weight.

plasticizer

The composition may further comprise at least one plasticizer. In particular, mention may be made, alone or as a mixture, the usual plasticizers such as: glycols and derivatives thereof such as diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether or diethylene glycol hexyl ether, ethylene glycol ethyl ether , ethylene glycol butyl ether, ethylene glycol hexyl ether; glycerol esters, propylene glycol derivatives and in particular propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol butyl ether, esters, in particular carboxylic acids, such as citrates, phthalates, adipates, carbonates, tartrates, phosphates and sebacates, oxyethylenated derivatives such as oxyethylenated oils, in particular vegetable oils such as castor oil; mixtures thereof. The amount of plasticizer may be chosen by the skilled person based on his general knowledge, so as to obtain a composition with cosmetically acceptable properties. Preferably, the plasticizer is present in an amount less than 20%, preferably less than 15% and preferably less than 10%, more preferably less than 5% by weight relative to the total weight of the composition.

Preferably, the composition according to the invention is free of plasticizer.

colourant

The composition according to the invention may further comprise one or more dyestuffs chosen from water-soluble dyes and pulverulent coloring materials such as pigments, pearlescent agents and glitter well known in the art. The dyestuffs may be present in the composition in a content ranging from 0.01% to 50% by weight, based on the weight of the composition, preferably from 0.01% to 30% by weight.

Pigments should be understood particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.

Pearlescent agents should be understood to mean iridescent particles of any form, especially produced by certain mollusks in their shell or synthesized.

The pigments can be white or colored, inorganic and / or organic. These include, among inorganic pigments, titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium, violet manganese, ultramarine blue, chromium hydrate and ferric blue, and metal powders such as aluminum powder, copper powder. Among the organic pigments, carbon black include, pigments of D &amp; C typed, and lakes based on cochineal carmine, barium, strontium, calcium and aluminum. The pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, titanium mica coated especially with blue iron or chromium oxide, titanium mica coated with an organic pigment of the abovementioned type, and pearlescent pigments based on bismuth oxychloride. Water-soluble dyes are for example beetroot juice, methylene blue. The composition according to the invention may further comprise, in addition, one or more fillers, especially in a content ranging from 0.01% to 50% by weight, based on the total weight of the composition, preferably from 0.01 % to 30 wt%. By fillers are meant particles of any shape, colorless or white, inorganic or synthetic, insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve especially to modify the rheology or texture of the composition.

The fillers may be mineral or organic of any shape, platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorom goat, etc). Include talc, mica, silica, kaolin, polyamide powders (Nylon®) (Orgasol® from Atochem), poly-β-alanine and polyethylene, tetrafluoroethylene polymer powders (Teflon® ) lauroyllysine, starch, boron nitride, hollow polymer microspheres such as those of polyvinylidene chloride / acrylonitrile, Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® of Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba, for example), polyorganosiloxane elastomer particles, precipitated calcium carbonate, and magnesium Phydro carbonate, hydroxyapatite, silica microspheres hollow (Silica Beads® from Maprecos), glass microcapsules or ceramic, and metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example stearate zinc, magnesium or lithium, zinc laurate or magnesium myristate.

other Additives

The composition may further comprise other ingredients commonly used in cosmetic compositions. Such ingredients can be chosen from spreading agents, wetting agents, dispersing agents, defoamers, preservatives, UV filters, active agents, surfactants, moisturizers, fragrances, neutralizers, stabilizers, antioxidants.

Of course the skilled care to select this or these optional additional compounds and / or their amounts so that the advantageous properties of the composition according to the invention are not, or not substantially, altered by the addition considered. Of course, the skilled care to select this or these optional additional compounds and / or their quantity, such that the advantageous properties of the composition for use according to the invention are not, or not substantially, altered by the addition envisaged.

The present invention also relates to a cosmetic assembly comprising:

- A container delimiting at least one compartment, said container being closed by a closing member; and

- A composition placed inside said compartment, the composition being in accordance with the invention.

The container can be in any suitable form. It may especially be in the form of a bottle, a box or tube.

The closing member may be in the form of a removable stopper.

The container is preferably equipped with an applicator for the application of the product on the nails. Such an applicator may be in the form of a brush consisting of at least one tuft of bristles. The tuft of bristles may be implanted at the end of a rod borne by the closing member. Preferably, the bristles are oriented along the axis of the rod. The bristles may be implanted by means of a clip, glued or obtained by molding.

Alternatively, the applicator is in the form of an end piece of porous material, in particular open-cell foam or felt.

Further alternatively, the applicator may be in the form of a spatula, in particular elastomeric material.

The closing member may be coupled to the container by screwing. Alternatively, the coupling between the closing element and the container is done other than by screwing, especially via a bayonet mechanism, or by snap-fastening. "Snapping" in particular means any system involving the crossing of a bead or cord of material by elastic deformation of a portion, including the closing member, followed by return elastically unstressed position of the said portion after the crossing of the bead or cord. The container is preferably made of glass. However, other materials than glass can be used. By way of example, we mention: certain thermoplastic materials adequately chosen to be compatible with the composition. Alternatively still, the container may be made of metal.

The following examples are not limited to illustrate the invention.

Example 3: Nail Polish

Polymer of Example 1 23.8 g AM

Butyl Acetate 24.99 g

Isopropanol 0.71 g 1

Hexylene glycol 2.5 g

DC RED 7 Lake 1 g Hectorite modified chloride 1, 3 g of distearyl methyl benzyl ammonium (Bentone^® 27V from Elementis)

Example 4: Nail Polish

Polymer of Example 2 2 3.8 g AM

Butyl Acetate 24.99 g

Isopropanol 10.71 g

hexylene Glycol ^' 2.5 g DC RED 7 g Lake 1

Hectorite modified chloride 1, 3 g of distearyl methyl benzyl ammonium (Bentone^® 27V from Elementis)

Ethyl acetate qs 100 g