CN1700903A - Composition containing block polymer and gelling agent - Google Patents

Abstract

This invention relates to a cosmetic composition comprising at least one non-elastic film-forming linear olefinic block polymer in a cosmetically acceptable liquid medium and a gelling agent for said organic liquid medium. The invention also relates to combining the block polymer with the gelling agent to improve the texture and application of the composition on keratin fibers.

Description

Composition comprising block polymer and gelling agent

The present invention relates to a cosmetic composition for the make-up or care of the skin of the human body and face, including the scalp, human lips or epidermis derivatives such as hair, eyebrows, eyelashes or nails, said cosmetic composition comprising specific block polymers.

The composition can be loose or compact powder, foundation, rouge, eye shadow, concealer, blush, lipstick, lip gloss, lip gloss, lip pencil, eyeliner, mascara, eyeliner, nail polish, or Products for body makeup or skin coloring.

The known compositions have poor adhesion over time, especially in their colour. This poor adhesion is characterized by a change in color (discoloration, fading), usually as a result of interaction with sebum and/or perspiration from the skin (eg, foundation, rouge, or eyeshadow), or as a result of interaction with saliva Results (like lipstick). This variation forces the user to frequently touch up makeup, thereby wasting time.

So-called "non-transferring" cosmetic compositions for the lips and skin are compositions which have the advantage that the deposits formed are not deposited at least partially on the supports with which they come into contact (eg glass, clothing, cigarettes, fabrics).

Known non-transfer compositions are usually based on silicone resins and volatile silicone oils, although they improve adhesion, they have the disadvantage that when the volatile silicone oils evaporate, they leave a film on the skin and lips, which after a period of time Uncomfortable (dry and tight feeling), so some women are reluctant to use these lipsticks.

Known non-transfer compositions comprise a volatile oil and a film-forming polymer which is soluble in the oil in order to limit color transfer. However, the introduction of these polymers in solutions in volatile solvents has the disadvantage that sometimes low viscosity formulations result (particularly because of the use of very low viscosity oils, especially volatile oils). The problem with this low rheology is that application is tricky and unattractive, and drying due to the presence of volatiles can make the deposit uneven.

There continues to be a need for non-transfer cosmetics that have good adhesion and good texture, are easy to apply and give an even deposit.

The composition according to the invention may in particular be a product for the makeup of the human body, lips or epidermis derivatives, especially if the composition has non-therapeutic and/or caring properties. The composition according to the invention may in particular be a lipstick or gloss, rouge, eye shadow, tattoo product, mascara, eyeliner, nail polish, artificial tanning product, hair coloring or hair care product.

The present inventors have surprisingly found that compositions comprising a cosmetically acceptable organic liquid medium, at least one specific block polymer and a gelling agent for said medium exhibit good spreading and lubricating properties, and that uniform makeup effect. Furthermore, the composition is glossy, non-transferring and has good adhesion.

More specifically, the present invention first provides a cosmetic composition comprising at least one non-elastomeric film-forming linear olefinic block polymer in a cosmetically acceptable organic liquid medium and for A film former for the organic liquid medium.

The present invention also provides a cosmetic composition comprising at least one film-forming linear olefinic block polymer free of styrene units in a cosmetically acceptable organic liquid medium and for use in said Film former for organic liquid media.

The invention also relates to a method of making up the skin and/or lips and/or epidermal derivatives, said method comprising applying to the skin and/or lips and/or epidermal derivatives a composition as described above.

The compositions of the present invention may be applied to the skin (face, scalp or body), mucous membranes (eg lips, inner side of the lower eyelids) and epidermal derivatives (eg nails, eyebrows, hair, eyelashes and even body hair).

Preferably the compositions of the present invention are not wash-off compositions.

The present invention also relates to the cosmetic use of a composition as defined above for improving the uniformity of make-up of the skin and/or lips and/or epidermis derivatives.

Finally the invention provides the use of a gelling agent in a composition comprising a block polymer as described above, in order to obtain a good texture, easy application and to obtain a gloss, no transfer and/or a good texture. adhesion and/or uniform deposit composition.

block polymer

The composition of the invention comprises at least one block polymer. The term "block polymer" refers to a polymer comprising at least two different blocks, preferably at least three different blocks.

According to one embodiment, the block polymer of the composition of the invention is an olefinic polymer. The term "olefinic polymer" refers to a polymer obtained by polymerizing monomers containing ethylenic unsaturated bonds.

According to one embodiment, the block polymers of the composition of the invention are linear polymers. On the contrary, polymers with a non-linear structure are branched, starburst or grafted polymers.

According to one embodiment, the block polymer of the composition of the invention is a film-forming polymer. The term "film-forming polymer" refers to a polymer capable of forming a continuous film attached to a support, especially a keratin material, either by itself or in the presence of auxiliary film-forming agents.

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

The term "non-elastomeric polymer" refers to a polymer that, when stretched by a stress (eg, 30% relative to its original length), does not return to a length substantially equal to its original length if the stress is stopped.

More specifically, the term "non-elastomeric polymer" refers to a polymer having an instantaneous recovery R _i < 50% and a delayed recovery R _2h < 70% at an elongation of 30%. Preferably R _i < 30%, R _2h < 50%.

More specifically, the inelastic properties of a polymer are determined as follows:

The polymer solution was poured into a Teflon-coated mold to prepare a polymer film, and then dried for 7 days at a temperature of 23±5° C. and a relative humidity of 50±10%.

A film about 100 [mu]m thick is thus obtained, which is cut (for example using a punch) into rectangular specimens 15 mm wide and 80 mm long.

Tensile stress was applied to the specimen using Zwick's apparatus at the same temperature and humidity as in the drying process.

The specimen is pulled at a rate of 50 mm/min with a distance between the grips of 50 mm, which corresponds to the initial length (l ₀ ) of the specimen.

The instantaneous recovery R _i is determined by the following method:

- Stretch the sample by 30% (ε _max ), i.e. the elongated length is approximately 0.3 times the initial length (l ₀ ),

- Release the coercive force by applying a recovery rate equal to the rate of extension (ie 50 mm/min), after the coercive force has reached zero, determine the remaining percent elongation (ε _i ) of the specimen.

The percentage of instant recovery (R _i ) is obtained by the following formula:

R _i =((ε _max -ε _i )/ε _max )×100

For the determination of delayed recovery, the residual percent elongation (ε _2h ) of the specimen is determined 2 hours after the forcing force has returned to zero.

The delayed response percentage (R _2h ) is obtained by the following formula:

R _2h ＝((ε _max -ε _2h )/ε _max )×100

As a guide only, one embodiment of the invention is a polymer with an immediate recovery R _i of 10% and a delayed recovery R _2h of 30%.

According to another embodiment, the block polymer of the composition of the invention does not comprise any styrene units. "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 of i) the formula -CH(C ₆ H ₅ )-CH ₂ - Polymers of styrene units or ii) substituted styrene units such as methylstyrene, chlorostyrene or chloromethylstyrene.

According to one embodiment, the block polymers of the composition of the invention are derived from aliphatic olefinic monomers. The term "aliphatic monomer" refers to a monomer that does not contain an aromatic group.

According to one embodiment, the block polymer is an olefinic polymer derived from an aliphatic olefinic monomer comprising a carbon-carbon double bond and at least one ester group -COO- or amido- CON-. The ester group may be attached to one of the two unsaturated carbons through a carbon atom or an oxygen atom. The amido group may be attached to one of the two unsaturated carbons through a carbon atom or a nitrogen atom.

According to one embodiment, the block polymer comprises at least one first block and at least one second block.

The term "at least one block" refers to one or more blocks.

In this context, the terms "first" and "second" block are considered in no way the order of said blocks (or segments) in the polymer structure.

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

In this embodiment, the first and second blocks may be linked together by an intermediate block having a glass transition temperature between the glass transition temperatures of the first and second blocks.

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

Preferably the middle block is mainly derived from the constituent monomers of the first block and the second block.

The term "mainly" means in the range of at least 85%, preferably at least 90%, more preferably 95%, even more preferably 100%.

Preferably, the middle block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block is a random polymer.

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

The term "mutually incompatible blocks" means that at room temperature (25°C) and normal pressure (105Pa), the mixture formed by the corresponding polymer of the first block and the corresponding polymer of the second block is in a liquid immiscible, the liquid being the liquid that predominates in the organic liquid medium of the composition, wherein the mixture of polymers is present in an amount greater than or equal to 5% by weight of the total mixture (polymer and principal organic liquid) ,requirement is:

i) the relative weight ratio of said polymers in said mixture ranges from 10/90 to 90/10, and

ii) The average (weight average or number average) molecular weight of each polymer corresponding to the first and second blocks is equal to the average (weight average or number average) molecular weight of the block polymers ± 15%.

When the organic liquid medium contains a mixture of organic liquids, the polymer mixture is immiscible in at least one of the liquid mediums under the condition that the mass ratio of the two or more liquids is the same.

When the organic liquid medium contains only one organic liquid, this liquid is clearly the majority by weight.

The term "organic liquid medium" refers to a medium comprising at least one organic liquid, ie at least one organic compound that is liquid at room temperature (25° C.) and normal pressure (10 ⁵ Pa). According to one embodiment, the main liquid of said liquid medium is a volatile or non-volatile oil (fatty substance). Preferably the organic liquid is a cosmetically acceptable (acceptable tolerance, toxicity and sensory) organic liquid. The organic liquid medium is cosmetically acceptable in the sense that it is compatible with keratin substances, such as oils or organic solvents conventionally used in cosmetic compositions.

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

The term "polymerization solvent" means a solvent or a mixed solvent. The polymerization solvent may be chosen in particular from ethyl acetate, butyl acetate, alcohols such as isopropanol and ethanol, aliphatic alkanes such as isododecane, and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.

Typically, the block polymers can be incorporated into the composition to achieve high solids content, typically greater than 10%, greater than 20%, more preferably greater than 30% and more preferably greater than 45%.

Preferably no silicon atoms are contained in the main chain of the block polymer. The term "backbone" refers to the main backbone of the polymer, as opposed to the pendant side chains.

Preferably, the polymers of the invention are not water-soluble at room temperature (25° C.), without changing the pH, and have an active substance content of at least 1% by weight, i.e. the polymers are insoluble in water or in water with a compound containing 2 to 5 carbon atoms. Mixture of linear or branched lower monohydric alcohols such as ethanol, isopropanol or n-propanol.

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

The polydispersity index I of the block polymers used in the compositions of the invention is preferably greater than 2 (e.g. in the range of 2 to 9), preferably greater than or equal to 2.5 (e.g. in the range of 2.5 to 8), and more preferably greater than or Equal to 2.8, especially in the range 2.8 to 6.

The polydispersity index I of the polymer is equal to the ratio of the weight-average molecular weight Mw to the number-average molecular weight Mn.

The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined by gel permeation liquid chromatography (the solvent was THF, a calibration curve was established with a linear styrene standard substance, and a refractive index detector).

Preferably the block polymer has a weight average molecular weight (Mw) of less than or equal to 300 000, such as a weight average molecular weight of 35 000 to 200 000, more preferably 45 000 to 150 000.

Preferably the block polymer has a number average molecular weight (Mn) of less than or equal to 70 000, such as a number average molecular weight of 10 000 to 60 000, more preferably 12 000 to 50 000.

Each block of the block polymer is derived from one type of monomer or from two or more different types of monomers.

This means that the individual blocks may consist of homopolymers or copolymers, which copolymers making up said blocks may themselves be random or alternating copolymers.

The glass transition temperatures of the first and second blocks may be theoretical Tg values determined from the theoretical Tg values of the constituent monomers of the respective blocks, as may be found in handbooks (e.g., "The Polymer Handbook (the Polymer Handbook)", Section 3 Edition, 1989, John Wiley), determined according to the following relationship known as Fox's law:

is the mass fraction of monomer i in the considered block, and _Tgi is the glass transition temperature of the homopolymer of monomer i.

Unless otherwise stated, the Tg values of the first and second blocks referred to in the description of the present invention are theoretical Tg values.

Typically the difference between the glass transition temperatures of the first and second blocks is greater than 10°C, preferably greater than 20°C, more preferably greater than 30°C.

In particular said block polymer comprises at least one first block and at least one second block, the first block being selected from:

a) blocks with a Tg higher than or equal to 40°C,

b) blocks with a Tg lower than or equal to 20°C,

c) blocks with a Tg between 20 and 40°C,

And the second block may be selected from blocks of classes a), b) or c) different from the first block.

In the present invention, the expression "between ... and ..." does not include the two endpoints, "... to ..." and "the range is ...to..." The range of values is inclusive.

a) Blocks with a Tg higher than or equal to 40°C

Blocks with a Tg greater than or equal to 40°C have a Tg such as in the range of 40 to 150°C, preferably greater than or equal to 50°C, such as a Tg in the range of 50°C to 120°C, and more preferably greater than or equal to 60°C, such as The range is 60°C to 120°C.

Blocks with a Tg higher than or equal to 40°C can be homopolymers or copolymers.

The blocks with a Tg higher than or equal to 40°C may be derived in whole or in part from one or more monomers from which the homopolymer prepared therefrom has a glass transition temperature higher than or equal to 40°C.

In case the block is a homopolymer, the block is derived from a monomer from which the homopolymer prepared has a glass transition temperature higher than or equal to 40°C. The first block may be a homopolymer consisting of only one monomer (the Tg of the corresponding homopolymer of this monomer is higher than or equal to 40° C.).

Where the first block is a copolymer, this block may be derived in whole or in part from one or more monomers, the nature and concentration of which are selected such that the resulting copolymer has a Tg greater than or equal to 40°C . The copolymer may comprise monomers such as:

- monomers from which the Tg of the homopolymer produced is higher than or equal to 40°C, such as a Tg in the range of 40°C to 150°C, preferably higher than or equal to 50°C, such as in the range of 50°C to 120°C, and more preferably is greater than or equal to 60°C, such as in the range of 60°C to 120°C, and

- monomers from which the Tg of the homopolymer is lower than 40°C, selected from monomers whose homopolymer Tg is between 20°C and 40°C as described below and/or homopolymers thereof Monomers whose Tg is lower than or equal to 20°C, such as a Tg in the range of -100°C to 20°C, preferably lower than 15°C, especially in the range of -80°C to 15°C, and more preferably lower than 10°C, For example, the range is -50°C to 0°C.

The monomers whose glass transition temperature of the corresponding homopolymer is higher than or equal to 40° C. are preferably selected from the following monomers (these monomers are also called main monomers):

- methacrylates of the formula CH ₂ =C(CH ₃ )-COOR ₁ , wherein R ₁ represents an unsubstituted straight-chain or branched alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, propylene or isobutyl, or R ₁ represents C ₄ -C ₁₂ cycloalkyl;

- acrylates of the formula CH ₂ =CH-COOR ₂ , wherein R ₂ represents C ₄ -C ₁₂ cycloalkyl (such as isobornyl acrylate) or tert-butyl;

- (meth)acrylamides of the formula:

Wherein R ₇ and R ₈ can be the same or different, and each represents a hydrogen atom or a straight or branched C ₁ -C ₁₂ alkyl group, such as n-butyl, tert-butyl, isopropyl, isohexyl, isooctyl or isononyl, or _R7 represents H and _R8 represents 1,1-dimethyl-3-oxobutyl, and R' represents H or methyl. Examples of monomers that may be mentioned are: N-butylacrylamide, N-tert-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutyl Acrylamide;

- and mixtures thereof.

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

b) Blocks with a Tg lower than or equal to 20°C

Blocks with a Tg lower than or equal to 20°C have a Tg such as in the range of -100°C to 20°C, preferably lower than or equal to 15°C, especially in the range of -80°C to 15°C, and more preferably lower than or equal to 10°C °C, such as in the range -50 °C to 0 °C.

Blocks with a Tg lower than or equal to 20°C can be homopolymers or copolymers.

The blocks with a Tg of less than or equal to 20°C may be derived in whole or in part from one or more monomers from which the homopolymer produced has a glass transition temperature of less than or equal to 20°C.

Where the block is a homopolymer, the block is derived from a monomer from which the homopolymer made has a glass transition temperature lower than or equal to 20° C. The second block may consist of only one monomer Composition of homopolymers (the Tg of the corresponding homopolymer of this monomer is lower than or equal to 20°C).

Where the block with a Tg lower than or equal to 20°C is a copolymer, the block may be derived in whole or in part from one or more monomers, the nature and concentration of which are selected such that the Tg of the resulting copolymer lower than or equal to 20°C.

The copolymer may comprise monomers such as:

- one or more corresponding homopolymers having a Tg lower than or equal to 20°C, such as a Tg in the range -100°C to 20°C, preferably lower than 15°C, especially in the range -80°C to 15°C , and more preferably below 10°C, such as in the range -50°C to 0°C, and

- one or more monomers as described above whose homopolymers have a Tg higher than 20°C, such as monomers whose homopolymers have a Tg higher than or equal to 40°C, such as whose homopolymers have a Tg in the range of 40 °C to 150°C, preferably greater than or equal to 50°C, such as in the range of 50°C to 120°C, and more preferably greater than or equal to 60°C, such as in the range of 60°C to 120°C monomers and/or homopolymers thereof The Tg of the compound is a monomer between 20°C and 40°C.

Preferably the blocks with a Tg lower than or equal to 20°C are homopolymers.

Monomers whose homopolymer Tg is lower than or equal to 20°C are preferably selected from the following monomers or main monomers:

-Acrylic esters of the formula CH ₂ =CHCOOR ₃ , R ₃ represents unsubstituted straight or branched C ₁ -C ₁₂ alkyl, except for tert-butyl, in which one or more groups selected from O, N and S heteroatoms;

-Methacrylate of the formula CH ₂ ═C(CH ₃ )-COOR ₄ , R ₄ represents an unsubstituted linear or branched C ₆ -C ₁₂ alkyl group, wherein one or more groups selected from O , heteroatoms of N and S;

- Vinyl esters of the formula R ₅ -CO-O-CH=CH ₂ , wherein R ₅ represents straight or branched C ₄ -C ₁₂ alkyl;

-C ₄ -C ₁₂ alkyl vinyl ether;

-N-(C ₄ -C ₁₂ )alkylacrylamides, such as N-octylacrylamide;

- and mixtures thereof.

It is particularly preferred that the main monomer as a block with a Tg lower than or equal to 20°C is an alkyl acrylate containing 1 to 10 carbon atoms (except tert-butyl) on the alkyl chain, such as methyl acrylate, isobutyl acrylate esters and 2-ethylhexyl acrylate and mixtures thereof.

c) Blocks with Tg between 20°C and 40°C

Blocks with a Tg between 20°C and 40°C can be homopolymers or copolymers.

The blocks with a Tg between 20°C and 40°C may be derived in whole or in part from one or more monomers from which the homopolymer prepared therefrom has a glass transition temperature between 20°C and 40°C.

Blocks with a Tg between 20°C and 40°C may be derived in whole or in part from monomers whose corresponding homopolymers have a Tg higher than or equal to 40°C and whose corresponding homopolymers have a Tg lower than or equal to 20°C of monomers.

Where the block is a homopolymer, the block is derived from a monomer (or principal monomer) from which the homopolymer prepared has a glass transition temperature between 20°C and 40°C. The first block may be a homopolymer consisting of only one monomer (the corresponding homopolymer of this monomer has a Tg in the range of 20°C to 40°C).

Monomers whose homopolymers have a glass transition temperature between 20° C. and 40° C. are preferably selected from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate and isodecyl acrylamide and mixtures thereof.

In the case where the block with a Tg between 20°C and 40°C is a copolymer, the block is derived in whole or in part from one or more monomers (or principal monomers), the nature and concentration of which are selected The resulting copolymer has a Tg of between 20°C and 40°C.

Preferably the blocks with a Tg between 20°C and 40°C are copolymers derived wholly or partly from the following monomers:

- main monomers with a Tg of the corresponding homopolymer as described above higher than or equal to 40°C, such as a Tg in the range of 40°C to 150°C, preferably higher than or equal to 50°C, such as in the range of 50°C to 120°C, and more preferably greater than or equal to 60°C, such as in the range of 60°C to 120°C, and/or

- main monomers with a Tg of corresponding homopolymers as described above lower than or equal to 20°C, such as a Tg in the range of -100°C to 20°C, preferably lower than or equal to 15°C, especially in the range of -80°C to 15°C, and more preferably less than or equal to 10°C, such as in the range -50°C to 0°C, the monomers are selected such that the Tg of the copolymer forming the first block is between 20°C and 40°C.

These main monomers are for example selected from methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, butyl acrylate and 2-ethylhexyl acrylate and mixtures thereof.

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

Preferably the first block and the second block each comprise at least one monomer selected from the group consisting of acrylic acid, acrylate esters, (meth)acrylic acid and (meth)acrylate esters, and mixtures thereof.

Preferably the first and second blocks are each entirely derived from at least one monomer selected from the group consisting of acrylic acid, acrylate esters, (meth)acrylic acid and (meth)acrylate esters and mixtures thereof.

However, each of the blocks may contain a small amount of at least one constituent monomer of the other block.

Thus, the first block may comprise at least one constituent monomer of the second block, and vice versa.

In addition to the above-mentioned various monomers, each of the first and/or second blocks may contain one or more other monomers called "other monomers" different from the above-mentioned main monomers.

The nature and amount of other monomers and various other monomers are chosen such that the blocks in which they are located have the desired glass transition temperature.

Such other monomers are for example selected from the following monomers:

a) Hydrophilic monomers, such as:

- Ethylenically unsaturated monomers containing at least one carboxylic or sulfonic acid function, such as acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropyl Sulfonic acid, vinylbenzoic acid, vinylphosphonic acid and their salts;

- Ethylenically unsaturated monomers containing at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylamino Propylmethacrylamide and its salts;

- methacrylates of the formula CH ₂ =C(CH ₃ )-COOR ₆ ,

Wherein R ₆ represents a linear or branched alkyl group comprising 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isobutyl, said alkyl being selected from one or more hydroxyl groups (such as Alkyl substituted with substituents of 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I or F) such as trifluoroethyl methacrylate;

- methacrylates of the formula CH ₂ =C(CH ₃ )-COOR ₉ ,

R ₉ represents a C ₆ -C ₁₂ linear or branched chain alkyl group, wherein one or more heteroatoms selected from O, N and S are optionally inserted, and the alkyl group is replaced by one or more groups selected from hydroxyl and halogen ( Cl, Br, I or F) substituent substitution;

- acrylates of the formula CH ₂ =CHCOOR ₁₀ ,

R ₁₀ represents a linear or branched C ₁ -C ₁₂ alkyl group substituted by one or more substituents selected from hydroxyl and halogen (Cl, Br, I or F) (such as 2-hydroxypropyl acrylate and acrylic acid 2-hydroxyethyl ester), or R ₁₀ represents C ₁ -C ₁₂ alkyl-O-POE (polyoxyethylene) with 5-30 oxyethylene repeating units, such as methoxy-POE, or

R ₁₀ represents a polyoxyethylene group comprising 5 to 30 oxyethylene units,

b) Ethylenically unsaturated monomers containing one or more silicon atoms, such as methacryloxypropyltrimethoxysilane and methacryloxypropyltris(trimethylsiloxy)silane ;

- and mixtures thereof.

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

According to one embodiment, the first and second blocks of the block polymer each comprise at least one monomer selected from (meth)acrylates and optionally at least one other monomer (such as (meth)acrylate ) acrylic acid) and mixtures thereof.

According to another embodiment, the first and second blocks of the block polymer are each entirely derived from at least one monomer selected from (meth)acrylates and optionally at least one other monomer such as ( (meth)acrylic acid) and mixtures thereof.

According to a preferred embodiment, said block polymer is a non-silicone polymer, ie a polymer that does not contain silicon atoms.

The content of this or these other monomers is usually less than or equal to 30% by weight of the total weight of the first and/or second block, such as 1% to 30% by weight, preferably 5% to 20% by weight, more preferably 7% to 15% by weight.

The block polymer can be obtained by radical solution polymerization according to the following preparation method:

- introducing part of the polymerization solvent into a suitable reactor and heating up to a temperature suitable for the polymerization reaction (typically between 60°C and 120°C),

- once this temperature has been reached, the constituent monomers of the first block are introduced in the presence of part of the polymerization initiator,

- after a time T corresponding to a maximum conversion of 90%, the introduction of the constituent monomers of the second block and the remaining initiator,

- continue to react the mixture for a period of time T' (ranging from 3 to 6 hours), then cool the mixture to room temperature,

- Obtaining a polymer dissolved in a polymerization solvent.

The first implementation plan

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

Preferably the first block with a Tg higher than or equal to 40°C is a copolymer derived from a monomer (such as the above-mentioned monomers) from which the homopolymer prepared has a glass transition temperature higher than or equal to 40°C.

Preferably the second block having a Tg lower than or equal to 20°C is a homopolymer of a monomer from which the homopolymer prepared has a glass transition temperature lower than or equal to 20°C, such as the monomers described above.

Preferably, the content of blocks with a Tg higher than or equal to 40° C. ranges from 20% to 90% by weight of the polymer, more preferably from 30% to 80%, even more preferably from 50% to 70%.

Preferably the content of blocks having a Tg lower than or equal to 20°C ranges from 5% to 75%, preferably from 15% to 50%, and more preferably from 25% to 45% by weight of the polymer.

Thus, according to a first variant, the polymers of the invention may comprise:

- a first block having a Tg higher than or equal to 40°C, such as a Tg in the range of 70°C to 110°C, said first block being a methyl methacrylate/acrylic acid copolymer,

- a second block having a Tg lower than or equal to 20°C, such as a Tg ranging from 0°C to 20°C, said second block being a homopolymer of methyl acrylate, and

- A middle block which is a methyl methacrylate/acrylic acid/methyl acrylate copolymer.

According to a second variant, the polymers of the invention may comprise:

- a first block having a Tg higher than or equal to 40°C, such as in the range of 70°C to 100°C, said first block being a methyl methacrylate/acrylic acid/trifluoroethyl methacrylate copolymer,

- a second block having a Tg lower than or equal to 20°C, such as in the range of 0°C to 20°C, said second block being a homopolymer of methyl acrylate, and

- A middle block which is a methyl methacrylate/acrylic acid/methyl acrylate/trifluoroethyl methacrylate random copolymer.

According to a third variant, the polymers of the invention may comprise:

- a first block having a Tg higher than or equal to 40°C, such as in the range of 85°C to 115°C, said first block being an isobornyl acrylate/isobutyl methacrylate copolymer,

- a second block having a Tg lower than or equal to 20°C, such as in the range -85°C to -55°C, said second block being a homopolymer of 2-ethylhexyl acrylate, and

- A middle block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer.

According to a fourth variant, the polymers of the invention may comprise:

- a first block having a Tg higher than or equal to 40°C, such as in the range of 85°C to 115°C, said first block being an isobornyl acrylate/methyl methacrylate copolymer,

- a second block having a Tg lower than or equal to 20°C, such as in the range -85°C to -55°C, said second block being a homopolymer of 2-ethylhexyl acrylate, and

- A middle block which is an isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate random copolymer.

According to a fifth program variant, the polymers of the invention may comprise:

- a first block having a Tg higher than or equal to 40°C, such as in the range of 95°C to 125°C, said first block being an isobornyl acrylate/isobornyl methacrylate copolymer,

- a second block having a Tg lower than or equal to 20°C, such as in the range -85°C to -55°C, said second block being a homopolymer of 2-ethylhexyl acrylate, and

- A middle block which is an isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random copolymer.

According to a sixth variant, the polymer of the invention may comprise:

- a first block having a Tg higher than or equal to 40°C, such as in the range of 85°C to 115°C, said first block being an isobornyl methacrylate/isobutyl methacrylate copolymer,

- a second block having a Tg lower than or equal to 20°C, such as in the range -35°C to -5°C, said second block being an isobutyl acrylate homopolymer, and

- A middle block which is an isobornyl methacrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.

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

- a first block having a Tg higher than or equal to 40°C, such as in the range of 95°C to 125°C, said first block being an isobornyl acrylate/isobornyl methacrylate copolymer,

- a second block having a Tg lower than or equal to 20°C, such as in the range -35°C to -5°C, said second block being an isobutyl acrylate homopolymer, and

- A middle block which is an isobornyl acrylate/isobornyl methacrylate/isobutyl acrylate random copolymer.

According to an eighth variant, the polymers of the invention may comprise:

- a first block having a Tg higher than or equal to 40°C, such as in the range of 60°C to 90°C, said first block being an isobornyl acrylate/isobutyl methacrylate copolymer,

- a second block having a Tg lower than or equal to 20°C, such as in the range -35°C to -5°C, said second block being an isobutyl acrylate homopolymer, and

- A middle block which is an isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.

The following examples illustrate the corresponding polymers of this first embodiment in a non-limiting manner.

Quantities are expressed in grams.

Example 1: Preparation of poly(methyl methacrylate/acrylic acid/methyl acrylate) polymer 100 g of butyl acetate was added to a 1 liter reactor, followed by raising the temperature from room temperature (25° C.) over 1 hour to 90°C.

Subsequently at 90° C., 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-ethylhexanoylperoxy)-2 were added within 1 hour, 5-Dimethylhexane (Trigonox® 141 from Akzo Nobel).

The mixture was kept at 90°C for 1 hour.

Then, still at 90°C, 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-dimethyl Hexane was added to the above mixture.

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

A solution comprising 40% of polymer active substance in a butyl acetate/isopropanol mixture was obtained.

A polymer comprising a first block of poly(methyl methacrylate/acrylic acid) with a Tg of 100°C, a second block of polymethylacrylate with a Tg of 10°C and a middle block of formazan methyl acrylate/acrylic acid/polymethyl acrylate random polymer.

The polymer had a weight-average molecular weight of 52 000 and a number-average molecular weight of 18 000, ie a polydispersity index I of 2.89.

Example 2: Poly(isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate)

Preparation of polymers

100 g of isododecane were added to a 1 liter reactor, followed by raising the temperature from room temperature (25° C.) to 90° C. within 1 hour.

Subsequently at 90°C, 120 g of isobornyl acrylate, 90 g of isobutyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2 , 5-Dimethylhexane (Trigonox® 141 from Akzo Nobel).

The mixture was maintained at 90°C for 1 hour and 30 minutes.

Then, still at 90°C, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-bis Methyl hexane was added to the above mixture.

The mixture was kept at 90°C for 3 hours, then cooled.

A solution comprising 50% of polymer active substance in isododecane was obtained.

Polymerization comprising a first block of poly(isobornyl acrylate/isobutyl methacrylate) with a Tg of 80°C, a second block of poly(2-ethylhexylacrylate) with a Tg of -70°C and a middle block material, the middle block is isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random polymer.

The polymer had a weight-average molecular weight of 77 000 and a number-average molecular weight of 19 000, ie a polydispersity index I of 4.05.

Example 3: Poly(isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate)

Preparation of Copolymer

100 g of isododecane were added to a 1 liter reactor, followed by raising the temperature from room temperature (25° C.) to 90° C. within 1 hour.

Subsequently at 90° C., 150 g of isobornyl acrylate, 60 g of methyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2 were added within 1 hour, 5-Dimethylhexane (Trigonox® 141 from Akzo Nobel).

The mixture was maintained at 90°C for 1 hour and 30 minutes.

Subsequently, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-bis(2-ethylhexanoylperoxy)-2,5-bis Methyl hexane was added to the above mixture.

The mixture was kept at 90° C. for 3 hours, then cooled throughout.

A solution comprising 50% of polymer active substance in isododecane was obtained.

A polymer comprising a first block of poly(isobornyl acrylate/methyl methacrylate) with a Tg of 100°C, a second block of poly(2-ethylhexylacrylate) with a Tg of -70°C and a middle block is obtained , the middle block is isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate random polymer.

The polymer had a weight-average molecular weight of 76 500, a number-average molecular weight of 22 000, and a polydispersity index I of 3.48.

Embodiment 4: Poly(isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate

Preparation of ester) polymer

100 g of isododecane were added to a 1 liter reactor, followed by raising the temperature from room temperature (25° C.) to 90° C. within 1 hour.

Subsequently at 90°C, 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2 , 5-Dimethylhexane (Trigonox® 141 from Akzo Nobel).

The mixture was maintained at 90°C for 1 hour and 30 minutes.

Then, still at 90°C, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-bis Methyl hexane was added to the above mixture.

The mixture was kept at 90°C for 3 hours, then cooled.

A solution comprising 50% of polymer active substance in isododecane was obtained.

Polymerization comprising a first block of poly(isobornyl acrylate/isobornyl methacrylate) with a Tg of 110°C, a second block of poly(2-ethylhexylacrylate) with a Tg of -70°C and a middle block material, the middle block is isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random polymer.

The polymer had a weight average molecular weight of 103 900 and a number average molecular weight of 21 300, i.e. a polydispersity index I of 4.89.

The second implementation plan

According to a second embodiment, the block polymer comprises a first block having a glass transition temperature (Tg) between 20°C and 40°C as described in c) above and a glass transition temperature (Tg) as described in b) above. A second block with a transition temperature lower than or equal to 20°C or a second block with a glass transition temperature higher than or equal to 40°C as described in a) above.

Preferably the content of the first block having a Tg between 20°C and 40°C ranges from 10% to 85% by weight of the polymer, more preferably from 30% to 80%, even more preferably from 50% to 70%.

When the second block is a block with a Tg higher than or equal to 40°C, it is preferred that its content ranges from 10% to 85% by weight of the polymer, more preferably from 20% to 70%, even more preferably from 30% to 70%.

When the second block is a block with a Tg lower than or equal to 20°C, it is preferably present in an amount ranging from 10% to 85% by weight of the polymer, more preferably from 20% to 70%, even more preferably 20% up to 50%

Preferably the first block with a Tg between 20°C and 40°C is derived from a monomer having a Tg of the corresponding homopolymer higher than or equal to 40°C and a monomer having a Tg of the corresponding homopolymer lower than or equal to 20°C. solid copolymers.

Preferably the second block with a Tg lower than or equal to 20°C or a Tg higher than or equal to 40°C is a homopolymer.

Thus, according to a first variant of this second embodiment, said block polymer may comprise:

- a first block with a Tg between 20°C and 40°C, such as a Tg of 25°C to 39°C, said first block comprising at least one methyl acrylate monomer, at least one methyl methacrylate a copolymer of monomers and at least one acrylic monomer,

- a second block having a Tg greater than or equal to 40°C, such as in the range of 85°C to 125°C, said second block being a homopolymer consisting of methyl methacrylate monomer, and

- a middle block comprising at least one methyl acrylate, methyl methacrylate monomer, and

- A middle block comprising methyl methacrylate, at least one acrylic monomer and at least one methyl acrylate monomer.

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

- a first block with a Tg of between 20°C and 40°C, such as a Tg of 21°C to 39°C, said first block comprising isobornyl acrylate/isobutyl methacrylate/2-ethyl acrylate Copolymers of hexyl esters,

- a second block having a Tg lower than or equal to 20°C, such as in the range -65°C to -35°C, said second block being a homopolymer of methyl methacrylate, and

- A middle block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer.

According to a third scheme variant of this second embodiment, said block polymer may comprise:

- a first block having a Tg between 20°C and 40°C, such as a Tg of 21°C to 39°C, said first block being an isobornyl acrylate/methyl acrylate/acrylic acid copolymer,

- a second block having a Tg greater than or equal to 40°C, such as in the range of 85°C to 115°C, said second block being an isobornyl acrylate homopolymer, and

- A middle block which is an isobornyl acrylate/methyl acrylate/acrylic acid random copolymer.

By way of illustration, but not limitation, the polymer corresponding to this second embodiment may be considered to be a polymer as follows:

Embodiment 5: the preparation of poly(methyl methacrylate/methyl acrylate/acrylic acid) polymer

100 g of butyl acetate were added to a 1 liter reactor, followed by raising the temperature from room temperature (25° C.) to 90° C. within 1 hour.

Subsequently at 90°C, 504 g methyl methacrylate, 21 g acrylic acid, 138.6 g methyl acrylate, 40 g butyl acetate, 70 g isopropanol and 1.8 g 2,5-bis(2-ethylhexanoyl) were added within 1 hour peroxy)-2,5-dimethylhexane (Trigonox(R) 141 from AkzoNobel).

The mixture was kept at 90°C for 1 hour.

Then, still at 90°C, 90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2,5-bis(2-ethylhexanoyl peroxy)-2,5- Dimethylhexane was added to the above mixture.

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

A solution comprising 40% of polymer active substance in a butyl acetate/isopropanol mixture was obtained.

A polymer comprising a first block of poly(methyl acrylate/methyl methacrylate/acrylic acid) with a Tg of 35°C, a second block of poly(methyl methacrylate) with a Tg of 100°C and a middle block is obtained , the middle block is methyl methacrylate/acrylic acid/polymethyl acrylate random polymer.

Example 6: Poly(isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate)

Preparation of polymers

100 g of isododecane were added to a 1 liter reactor, followed by raising the temperature from room temperature (25° C.) to 90° C. within 1 hour.

Subsequently at 90° C., 54 g of isobornyl acrylate, 75.6 g of isobutyl methacrylate, 50.4 g of 2-ethylhexyl acrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2 -Ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox(R) 141 from AkzoNobel).

The mixture was maintained at 90°C for 1 hour and 30 minutes.

Then, still at 90°C, 120 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-bis Methyl hexane was added to the above mixture.

The mixture was kept at 90°C for 3 hours, then diluted and cooled throughout.

A solution comprising 50% of polymer active substance in isododecane was obtained.

A first block comprising poly(isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate) with a Tg of 25°C and a second block of poly(2-ethylhexylacrylate) with a Tg of -50°C was obtained. Block and middle block polymers, said middle block being isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random polymer.

The compositions according to the invention comprise preferably 0.1% to 60% by weight, preferably 0.5% to 50% by weight, more preferably 1% to 40% by weight of polymer active substance (solid polymer).

gelling agent

The composition of the invention may also comprise at least one agent for gelling the organic liquid medium of said composition. When the gelling agent is added to the organic liquid medium, the viscosity of the organic liquid medium can be increased and a solid or flowable composition can be obtained.

The gelling agent may be selected from gelling agents in polymeric form and gelling agents in inorganic form.

In one embodiment, the gelling agent is insoluble in the aqueous phase or water.

The gelling agent of the present invention is preferably selected from agents that effect gelation by chemical crosslinking and agents that effect gelation by physical crosslinking.

Gelling agents that achieve gelation by chemical crosslinking

According to one embodiment, crosslinked elastic polyorganosiloxanes with a three-dimensional structure are preferred, such as MQ silicones, polyalkylsesquioxanes (in particular polymethylsesquioxanes) and Resin crosslinked by hydrosilylation. These silicones can have hydrophilic groups such as polyethylene oxide or ethylene oxide/propylene oxide copolymers.

As polyorganosiloxanes which may be used in the present invention there may be mentioned the crosslinked elastic polyorganosiloxanes described in patent application EP-A-0,295,886, the disclosure of which is incorporated herein by reference. According to this application, said crosslinked elastic polyorganosiloxane is obtained by subjecting at least the following to an addition reaction and crosslinking in the presence of a platinum-based catalyst:

-(a) a polyorganosiloxane having at least two C ₂ -C ₆ lower alkenyl groups per molecule; and

- (b) polyorganosiloxanes having at least two hydrogen atoms bonded to silicon atoms per molecule. The polyorganosiloxanes described in U.S. Patent No. 5,266,321, the disclosure of which is incorporated herein by reference, may also be used. According to this patent, said polyorganosiloxane is specifically selected from:

-i) polyorganosiloxanes comprising R ₂ SiO and RSiO _1.5 units and optionally R ₃ SiO _0.5 and/or SiO ₂ units, wherein the groups R ₁ are each independently selected from hydrogen, alkyl (such as methyl, ethyl or propyl), aryl (such as phenyl or tolyl), unsaturated aliphatic groups (such as vinyl), the weight ratio of units R ₂ SiO to units RSiO _1.5 ranges from 1/1 to 30/1 ;

-ii) polyorganosiloxanes which are insoluble in silicone oil but swellable in silicone oil, said polyorganosiloxanes having polyorganohydrogensiloxanes (1) and polyorganosiloxanes having unsaturated aliphatic groups ( The addition reaction of 2) is obtained, such that the amount of hydrogen or unsaturated aliphatic groups in (1) and (2) is 1-20 mole% respectively when the polyorganosiloxane is acyclic, when the When the polyorganosiloxane is cyclic, it is respectively 1-50% by mole. Optionally these polyorganosiloxanes may contain 1 to 40 oxyalkylene groups, such as oxypropylene and/or oxyethylene groups.

As examples of polyorganosiloxanes that can be used in the present invention, mention may be made of the products sold or manufactured under the names: KSG6 from Shin-Etsu, Trefil E-505C or Trefil E-506C from Dow-Corning, Grant Industries Gransil (SR-CYC, SRDMF10, SR-DC556) or those sold as preconstituted gels (KSG15, KSG17, KSG16, KSG18, KSG21 from Shin-Etsu, Gransil SR 5CYC from General Electric gel, Gransil SR DMF 10 gel, Gransil SR DC556 gel, SF 1204, and JK 113). Mixtures of these commercial products may also be used.

Gelling agents that achieve gelation by physical crosslinking

Gelation is preferably achieved by physical crosslinking, in particular gelling agents crosslinked by molecular agitation, hydrogen bonding or dipolar interactions, and liposoluble polymers with liquid crystal groups.

Gelling agents that achieve gelling by molecular mixing are polymers with a high molecular weight, preferably higher than 500,000, such as silicone rubber.

Silicone rubber can have the structure of the formula:

in:

R ₇ , R ₈ , R ₁₁ and R ₁₂ are the same or different, and are each selected from alkyl groups having 1 to 6 carbon atoms,

R ₉ and R ₁₀ are the same or different, and are each selected from alkyl and aryl groups containing 1 to 6 carbon atoms,

X is selected from alkyl, hydroxyl and vinyl groups containing 1 to 6 carbon atoms,

The selection of n and p makes the viscosity of the silicone rubber greater than 100 000mPa.s, such as greater than 500 000mPa.s.

Typically, n and p may each be 0 to 5000, such as 0 to 3000.

Among the silicone rubbers which can be used as gelling agents in the present invention, mention may be made of those in which the groups are defined as follows:

- substituents R ₇ -R ₁₂ and X represent methyl, p=0 and n=2700, such as SE30 sold or produced by General Electric,

- Substituents R ₇ -R ₁₂ and X represent methyl, p=0 and n=2300, such as AK 500 000 sold or produced by Wacker,

- Substituents R ₇ -R ₁₂ represent methyl, substituent X represents hydroxyl, p=0 and n=2700, is a 13% solution in cyclopentasiloxane, such as Q2 sold or produced by Dow Corning Company- 1401,

- Substituents R ₇ -R ₁₂ represent methyl, substituent X represents hydroxyl, p=0 and n=2700, as a 13% solution in polydimethylsiloxane, as sold or produced by Dow Corning Q2-1403,

- Substituents R ₇ , R ₈ , R ₁₁ , R ₁₂ and X represent methyl groups and substituents R ₉ and R ₁₀ represent aryl groups, such that the molecular weight of the silicone rubber is about 600,000, as described by Rhöne-Poulenc (Rhodia Chimie ) company sold or produced by 761.

The gelling agent effecting the gelation of the organic liquid medium by hydrogen bonding is preferably selected from:

- aminopolysiloxane polymers having triazinyl or pyrimidinyl groups bonded to amino groups therein, as described in patent application EP 0 751 170, the disclosure of which is incorporated herein by reference,

- Non-polysiloxane polyamides with ester or triamide functional groups at their ends, such as compounds described in the following patents and patent applications: US 5 783 657, US 6 268 466, WO01/95871, WO00/40216, US 2002/0035237 and EP 1 068 856, the publications of which are incorporated herein by reference,

- polyurethanes, such as compounds described in patent applications DE 10022247 and FR 2 814 365, the publications of which are incorporated herein by reference, and

- Vinyl and/or (meth)acrylic polymers with side groups capable of hydrogen bonding with each other, such as the compounds described in patent application WO93/01797, the disclosure of which is incorporated herein by reference.

Gelling agents can also be selected from the following:

- Copolymers, such as polystyrene-polysiloxane or polyethylene-polysiloxane described in patents US 6 225 390, US 6 160 054, US 6 174 968 and US 6 225 390, the disclosures of which Incorporated herein by reference,

- copolymers comprising polysiloxane blocks and another polyvinyl or poly(meth)acrylic block or grafted chains, such as those described in patents US 5468 477 and US 5 725882, The disclosures of these patents are incorporated herein by reference,

- polymers or copolymers obtained by polymerization or copolymerization of ethylenic monomers containing one or more ethylenic bonds, preferably conjugated bonds (or dienes),

- Polymers or copolymers obtained by polymerization or copolymerization of olefinic monomers, particularly vinyl, acrylic or methacrylic copolymers. The olefinic gelling agent may contain, for example, styrene blocks (S), alkylstyrene blocks (AS), ethylene/butylene blocks (EB), ethylene/propylene blocks (EP), butadiene Block (B), isoprene block (I), acrylate block (A), methacrylate block (MA) or a combination of these blocks.

In one embodiment, copolymers containing at least one styrene block are used as gelling agents. Triblock copolymers can be used, specifically polystyrene/polyisoprene or polystyrene/polybutadiene types such as Luvitol HSB and polystyrene/ethylene-propylene copolymers sold or produced by BASF Corporation Or polystyrene/ethylene-butylene copolymers, such as Kraton sold or produced by Shell Chemical Co. or GelledPermethyl 99A from Penreco. Styrene-methacrylate copolymers can also be used.

Olefinic gelling agents which may be mentioned for use in the composition according to the invention are, for example: Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (SEP), Kraton G1702X (SEP), KratonG1726X(SEB), Kraton D-1101(SBS), Kraton D-1102(SBS), Kraton D-1107(SIS), GeUed Permethyl 99A-750, Gelled Permethyl99A-753-58, Gelled Permethyl 99A- 753-59, Versagel 5970 and Versagel 5960 from Penreco, and OS 129880, OS 129881 and OS 84383 (styrene-methacrylate copolymers) from Lubrizol.

Diblock or triblock copolymers, such as polystyrene-ethylene/propylene copolymers or polystyrene-ethylene/butylene copolymers, such as those described in patent applications WO 98/38981 and US2002/0055562 can also be included in the present invention.

The gelling agent which achieves gelation by dipolar interaction is preferably selected from the compounds described in documents WO 01/30886 and US 6228967, the disclosures of which are incorporated herein by reference. Ionizing groups (eg, zwitterionic groups) in the compound create the dipole interaction.

The present invention is also preferably used as a gelling agent with a liposoluble polymer having a liquid crystal group, especially a liposoluble polymer whose main chain is polysiloxane, vinyl and/or (meth)acrylic and has a liquid crystal side group. Polymers, in particular compounds described in patent application FR 2 816 503, the disclosure of which is incorporated herein by reference.

In another embodiment, the gelling agent may be in inorganic form.

The gelling agent can be a modified clay. Possible modified clays that may be mentioned are: hectorite modified with _C10 - _C22 fatty acid ammonium chloride, such as hectorite modified with distearyldimethylammonium chloride (also known as quatermium-18 bentonite), such as Bentone 34 sold or produced by Rheox, Claytone XL, Claytone 34 and Claytone 40 sold or produced by Southern Clay; modified clays known as quaternium-18 bentonite and benzalkonium bentonite, Claytone HT, Claytone GR, and Claytone PS such as those sold or manufactured by Southern Clay; clays modified with stearyl dimethylbenzoyl ammonium chloride (known as steralkonium bentonite), such as Claytone sold or manufactured by Southern Clay APA and Claytone AF and Baragel 24 sold or produced by Rheox Corporation.

Other inorganic gelling agents which may be mentioned for use in the present invention are silicas, such as fumed silicas. The particle size of the fumed silica can be nanoscale or microscale, such as about 5 nm to 200 nm.

Fumed silica can be produced by pyrolysis of volatile silicon compounds in an oxyhydrogen flame to obtain finely dispersed silica. By this method, hydrophilic silica having a large number of silanol groups on its surface can be obtained. The silanol groups can be replaced, for example, by hydrophobic groups, so that hydrophobic silicas are obtained. Hydrophobic groups can be:

- trimethylsilyloxy groups obtained in particular by treatment of fumed silica in the presence of hexamethyldisilylamine. Silicas thus treated are called "silica silylate" according to the CTFA (6th edition, 1995). Examples of them are Aerosil ^R812 sold or produced by Degussa and CAB-O-SIL TS-530 sold or produced by Cabot ^;

- dimethylsiloxy or polydimethylsiloxy groups, which groups are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. According to the CTFA (6th Edition, 1995), the silica thus treated is called "silica dimethylsilylate". Their examples are Aerosil ^R972® and Aerosil ^R974® sold or produced by Degussa, and CAB-O-SIL TS-610® ^and CAB-O-SIL TS- ^720® sold or produced by Cabot;

- groups derived from the reaction of fumed silica and silane alkoxylates or siloxanes. Examples of such treated silicas are Aerosil R805 ^(R) sold or produced by the company Degussa.

According to the invention, hydrophobic silica, such as fumed silica, can be used as gelling agent.

The concentration of these gelling agents may range from 0.05% to 35%, for example 0.5 to 20% or 1 to 10%, of the total weight of the composition.

The composition of the present invention may comprise a hydrophilic medium comprising water or a mixture of water and a hydrophilic organic solvent such as an alcohol (especially a straight chain containing 2 to 5 carbon atoms or branched lower monohydric alcohols (such as ethanol, isopropanol or n-propanol) and polyols (such as glycerol, diglycerol, propylene glycol, sorbitol, pentanediol and polyethylene glycol)) or _C2 ethers and C ₂ - _C4 aldehyde.

The content of water or the mixture of water and hydrophilic organic solvent in the composition of the present invention may range from 0.1% to 99%, preferably from 10% to 80%, of the total weight of the composition.

The compositions of the present invention comprise a cosmetically acceptable organic liquid vehicle (acceptable tolerability, toxicity and sensory).

According to a particularly preferred embodiment, the organic liquid medium of the composition comprises at least one organic solvent which is the polymerisation solvent of the block polymer as described above or one of the polymerisation solvents therein. Preferably, the organic solvent is the liquid that constitutes the majority (by weight) of the organic liquid medium of the cosmetic composition.

According to one embodiment, said organic liquid medium comprises a fatty substance which is liquid at room temperature (typically 25° C.). This liquid fatty substance can be of animal, vegetable, mineral or synthetic origin.

Fatty substances (commonly referred to as "oils") that are liquid at room temperature that can be used in the present invention are: hydrocarbon-based oils of animal origin, such as perhydrosqualene; hydrocarbon-based oils of vegetable origin, such as those containing 4 to Liquid triglycerides of 10-carbon fatty acids (such as triheptanoin or tricaprylin), sunflower oil, corn oil, soybean oil, grapeseed oil, sesame oil, almond oil, macadamia nut oil, castor Sesame oil, avocado oil, tricaprylic/tricaprin, jojoba oil, shea butter; straight or branched chain hydrocarbons of mineral origin or synthetic, such as liquid paraffin and its derivatives, petrolatum, polydecene and hydrogenated Polyisobutenes (such as parleam); synthetic esters and ethers, especially of fatty acids, such as purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecane stearate esters, 2-octyldodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, Diisostearyl malate, triisocetyl citrate and heptanoic, caprylic or capric esters of fatty alcohols; polyol esters such as propylene glycol dicaprylate, neopentyl glycol diheptanoate and diisononyl Diethylene glycol esters and pentaerythritol esters; fatty alcohols containing 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecane alcohols and oleyl alcohols; partially hydrocarbyl and/or partially polysiloxane-based fluoro oils; silicone oils, such as volatile or non-volatile, linear or cyclic polymethylsiloxanes (PDMS), such as cyclomethicone ( methicone), dimethicones optionally containing phenyl groups (such as phenyltrimethicone, phenyltrimethylsiloxydiphenylsiloxane, diphenylmethyldimethyltrisiloxane alkanes, diphenyldimethylsiloxanes, phenyldimethylsiloxanes, and polymethylphenylsiloxanes); and mixtures thereof.

These oils may be present in amounts ranging from 0.01% to 90%, and more preferably from 0.1% to 85%, by weight of the total composition.

The organic liquid medium of the compositions of the present invention may also comprise one or more cosmetically acceptable organic solvents (acceptable tolerability, toxicity and sensory).

Typically these solvents may be present in amounts ranging from 0.1% to 90%, preferably from 10% to 90%, and more preferably from 30% to 90% by weight of the total composition.

In addition to the aforementioned hydrophilic organic solvents, solvents that may be mentioned for use in the composition of the present invention are the following substances that are liquid at room temperature: ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, Butyl ketone, isophorone, cyclohexanone, and acetone; propylene glycol ethers, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and dipropylene glycol mono-n-butyl ether; short-chain esters (comprising 3 to 8 carbons in total atoms), such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate and isoamyl acetate; ethers such as diethyl ether, methyl ether or dichlorodiethyl ether; alkanes such as decane, heptane, dodecane alkanes, isododecane, and cyclohexane; aromatic ring compounds, such as toluene and xylene; aldehydes, such as benzaldehyde and acetaldehyde; and mixtures thereof.

In addition to the block polymers described above, the composition may also comprise other polymers (eg, film-forming polymers). According to the invention, the term "film-forming polymer" means a polymer capable of forming, by itself or in the presence of auxiliary film-forming agents, a continuous film attached to a support, in particular a keratin material.

Film-forming polymers that may be used in the composition according to the invention are synthetic polymers of the free-radical type or polycondensate type, polymers of natural origin and mixtures thereof. Film-forming polymers that may be mentioned include in particular acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and cellulose-based polymers such as nitrocellulose.

The polymers may be used in combination with one or more auxiliary film formers. Such film formers may be chosen from any compound known to the person skilled in the art to perform the desired function, and may be chosen in particular from plasticizers and coalescents.

The composition of the invention may comprise at least one wax. For the purposes of the present invention, the term "wax" refers to a lipophilic compound that is solid at room temperature (25°C), exhibits a reversible solid/liquid phase change, and has a melting point greater than or equal to 30°C and up to up to 120°C.

The melting point of the wax can be determined by differential scanning calorimetry (DSC), such as the DSC 30 calorimeter sold by the company Mettler.

The waxes may be hydrocarbon-based, fluorine and/or silicone waxes and may be of vegetable, mineral, animal and/or synthetic origin. In particular the wax has a melting point above 25°C, and more preferably above 45°C.

Waxes that may be mentioned that may be used in the composition according to the invention are: beeswax, carnauba wax, candelilla wax, paraffin wax, microcrystalline wax, ceresin or ozokerite, synthetic waxes such as polyethylene Waxes or Fischer-Tropsch waxes and silicone waxes (such as alkyl or alkoxydimethicones containing 16 to 45 carbon atoms).

The nature and amount of the solid fatty substance depends on the desired mechanical properties and texture. As a guide, the composition may comprise from 0% to 50%, and more preferably from 1% to 30%, of wax by its total weight.

The composition of the invention may also comprise one or more dyes selected from water-soluble dyes and pulverulent dyes, such as pigments, nacres and scales well known to those skilled in the art. The colorant is present in the composition in an amount ranging from 0.01% to 50%, preferably from 0.01% to 30%, by weight of the composition.

The term "pigment" is understood to mean white or coloured, inorganic or organic particles of any shape which are insoluble in the physiological medium and which are capable of coloring the composition in question.

It should be understood that the term "nacre" refers to glitter particles of any shape, especially prepared from the shells of certain molluscs or synthetically.

The pigments may be white or coloured, inorganic and/or organic. Inorganic pigments that may be mentioned are titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide (iron oxide black, iron oxide yellow or iron oxide red), chromium oxide, manganese violet, ultramarine blue, optionally surface-treated , chromium hydroxide and iron blue (ferric blue), and metal powders (such as aluminum powder or copper powder).

Organic pigments that may be mentioned are carbon black, pigments of the D&C type, barium, strontium, calcium or aluminum lakes based on cochineal carmine.

Mention may also be made of effect pigments such as particles comprising inorganic or organic, natural or synthetic substrates such as glass, acrylic resins, polyesters, polyurethanes, polyethylene terephthalate, ceramics or aluminum oxide , the substrate is uncoated or coated with metal substances (such as aluminum, gold, silver, platinum, copper or bronze) or metal oxides (such as titanium dioxide, iron oxide or chromium oxide) and mixtures thereof.

The pearlescent pigments can be selected from white pearlescent pigments (such as mica coated with titanium or bismuth oxychloride), colored pearlescent pigments (such as titanium mica coated with iron oxides, especially titanium coated with iron blue or chromium oxide). mica, titanium mica coated with organic pigments of the type mentioned above, and pearlescent pigments based on bismuth oxychloride). It is also possible to use interference pigments, in particular liquid crystal pigments or multilayer pigments.

Such water-soluble dyes are, for example, beetroot juice and methylene blue.

The composition of the present invention may also contain one or more fillers, the specific content ranges from 0.01% to 50% of the total weight of the composition, preferably from 0.01% to 30%. The term "filler" is understood to mean colorless or white, inorganic or synthetic particles of any shape which are insoluble in the medium of the composition, whatever the temperature at which the composition is prepared. These fillers serve in particular to improve the flow or texture of the composition.

The filler can be any form of flake, spherical or rectangular inorganic or organic filler regardless of crystallization form (such as leaf, cube, hexagon, orthorhombic, etc.). Mention may be made of: talc, mica, quartz, kaolin, polyamide ( ^Nylon® ) powder ( ^Orgasol® from Atochem), poly-β-alanine powder and polyethylene powder, polytetrafluoroethylene powder ( Teflon ^® ), lauroyl lysine, starch, boron nitride, hollow polymer microspheres (such as polyvinylidene chloride/acrylonitrile microspheres, such as Exapancel ^® (Nobel Industrie)), copolymerization of acrylic acid ( ^Polytrap® from Dow Corning) and silicone beads (such as ^Tospearls® from Toshiba), elastic polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate, magnesium bicarbonate, hydroxyapatite Silica, hollow silica microspheres (Silica ^Beads® from Maprecos), ceramic or glass microcapsules and metal soaps derived from organic carboxylic acids containing 8 to 22 carbon atoms (preferably 12 to 18 carbon atoms) ( such as zinc stearate, manganese stearate, lithium stearate, zinc laurate and magnesium myristate).

The compositions of the present invention may be in particular in the form of sticks, suspensions, dispersions, solutions, gels, emulsions, especially oil-in-water (O/W) emulsions, water-in-oil (W/O) emulsions or complex emulsions (W /O/W or polyols/O/W or O/W/O emulsions), or in the form of dispersions in creams, pastes, mousses, capsules, especially ionic or nonionic liposomes, biphasic Or multiphase lotions, sprays, powders, pastes (especially soft pastes, specifically 25C, a shear rate of 200s ^-1 , the dynamic viscosity measured in a cone-plate viscometer after 10 minutes is about 0.1 to 40Pa. s soft paste). The composition may be an anhydrous composition, such as an anhydrous soft paste.

Those skilled in the art can select a suitable formulation form and its preparation method based on their conventional knowledge, firstly considering the properties of the components used, especially their solubility in the carrier, and secondly considering the intended use of the composition.

The composition of the present invention may be a cosmetic composition such as a product for skin tone (foundation), lipstick, eye shadow, lipstick, concealer, rouge, mascara, eyeliner, eyebrow makeup product, lip pencil, eyeliner , Products for nails (such as nail varnish), products for body makeup or products for hair makeup (hair oil or pomade).

The composition of the invention may also be a product for facial or body skin care, in particular a sunscreen product or a skin coloring product (eg a self-tanning product).

The present invention also provides a cosmetic kit, which includes:

i) a container defining at least one compartment, said container being closed by a closing element, and

ii) A composition as described above placed within said compartment.

The container can be in any suitable form. Said container may be in particular in the form of a bottle, tube, can, box, box, sachet or carton.

Said closure element may be in the form of a removable stopper, cap, cap, peel-off strip or bottle cap, in particular of the type comprising an object attached to the container and a covering cap associated with this object. It can also be an element which selectively closes the container, in particular a pump, a valve or a flap valve.

Said container may be combined with an applicator comprising, in particular, the form of a brush whose bristles are kept aligned by twisted wires. Such twisted brushes are described in detail in US 4 887 622. The applicator may also be a comb comprising a plurality of application elements, in particular obtained by moulding. Such a comb is described in FR 2 796 529. The applicator may also be in the form of a delicate brush as described in FR 2 722 380. The applicator may be in the form of a foam or elastomer block, a felt or a doctor blade. As described in US 5 492 426, the applicator can be free (wool or sponge) or firmly fixed on a rod with a closing element. As described in FR 2 761 959, the applicator is a part of the container.

The product may be contained directly or indirectly in the container. For example, the product may be placed on an impregnated carrier, in particular in the form of a wipe or pad, and the impregnated carriers containing the product individually or in plurality subsequently placed in a box or sachet. Such carriers incorporating said products are described, for example, in patent application WO 01/03538.

The closure element can be screwed to the container. Alternatively, the closure element and the container are connected not only by screwing, but also in particular by a bayonet connection mechanism, by snap-fastening, clamping, welding, gluing or magnetic attraction. The term "snap fastening" refers in particular to any system in which a connection is achieved by elastically deforming a part (in particular a closure element) to allow a bead or strip to pass through a bayonet, followed by the return of the part to its non-elastically deformed position. Location.

The container may be manufactured at least partly from thermoplastic material. Examples of thermoplastic materials that may be mentioned include polypropylene and polyethylene.

Alternatively, the container is made of a non-thermoplastic material, in particular glass or metal (or alloys).

The container may have rigid walls or deformable walls, in particular in the form of a tube or vial.

The container may contain means for dispensing or facilitating dispensing of the composition. For example the container may have deformable walls such that positive pressure within the container by elastic (or inelastic) compression of the container walls causes the composition to extrude. Alternatively, particularly when said product is in the form of a stick, the product may be expelled by a piston mechanism. In the case of a stick, in particular a cosmetic stick (eg lipstick, foundation, etc.), the container may contain a mechanism enabling the stick to be replaced in the direction of the opening, in particular a slide rail mechanism, or a threaded stick, or a Spiral groove. Mechanisms of this type are described, for example, in patents FR 2 806 273 or FR 2 775 566. A mechanism of this type for liquid products is described in patent FR 2 727 609.

Said container may also consist of a carton with a base defining at least one compartment containing said composition, and a lid capable of at least partially covering said base, in particular a lid associated with the base. Such cartons are as described in patent application WO 03/018423 or patent FR 2 791 042.

The container may be fitted with a drain located in the crevice area of the container. This drain makes it possible to wipe the applicator and the wand with which the applicator is tightly connected. This is described, for example, in patent FR 2 792 618.

The composition in the container may be atmospheric (at room temperature) or pressurized (in particular by a propellant (aerosol)). In the latter case, the container is fitted with a valve (of the type used for aerosols).

The content of the above-mentioned invention or invention application is incorporated by reference in the present application.

The following examples illustrate the compositions of the present invention in a non-limiting manner.

Example 7: Liquid Lipstick components %quality Polymer of Example 4 50.0 Silica (Aerosil ^R972® , Degussa) 5.0 Isododecane gelled with ethylene/propylene/styrene copolymer and butene/ethylene/styrene copolymer ( ^Versagel® MD 970, Penreco) 7.0 hydrogenated polyisobutylene 2.1 Octyldodecanol 0.9 Phenyltrimethylsiloxane (DC 556, 20cSt, Dow Corning) 2.1 Isododecane 28.3 Vinylpyrrolidone/1-Eicosene Copolymer (Antaron V-220 ^® , ISP) 1.2 pigment 3.0 spices Appropriate amount

The viscosity of this formulation is much higher than that of formulations without gelling agent. It can also be applied effortlessly with a foam applicator and yields a uniform deposit.

Example 8: Sunscreen Compositions components %weight glycerin 6 Propylene Glycol 6 Acrylates/C ₁₀ -C ₃₀ Alkyl Acrylate Copolymer PEMULEN TR-2 (Noveon) 0.3 Ammonium polyacryloyldimethyltaurate polymer (HOSTACERIN AMPS, Clariant) 0.3 Cyclohexasiloxane (DOW CORNING 246 FLUID, Dow Corning) 6 Xanthan Gum RHODICARE XC (Rhodia) 0.1 Terephthalidene Dicamphorone Sulfonic Acid (MEXORYL SX, Chimex) 1.5 Triethanolamine Appropriate amount 2-Cyano-3,3-diphenylacrylate-2-ethylhexyl (UVINUL N539, BASF) 10 Butylmethoxydibenzoylmethane (Parsol 1789, Roche Vitamins) 2.5 2-(2'-Hydroxy-5'-methylphenyl)benzotriazoletrisiloxane (MEXORYL XL, Chimex) 1.5 C ₁₂ -C ₁₅ Alkyl Benzoate (FINSOLV TN, Witco) 4 Polymer of Example 3 1 Triethanolamine 0.35 Preservatives and Chelating Agents Appropriate amount water add up to 100

Embodiment 9: nail polish Polymer of Example 1 23.8g (calculated as active substance) Butyl acetate 24.99g Isopropanol 10.71g Hexylene glycol 2.5g DC RED 7 Lake 1g Hectorite modified with stearyl dimethyl benzyl ammonium chloride (Bentone 27V, Elementis) 1.3g

Example 10: Mascara Composition beeswax 8g paraffin 3g carnauba wax 6g Hectorite modified with distearyldimethylbenzyl ammonium chloride (Bentone38V, Elementis) 5.3g Propylene carbonate 1.7g filler 1g pigment 5g Polymer of Example 2 12g, calculated as active substance Isododecane add up to 100

Example 11: Mascara Composition beeswax 8g paraffin 3g carnauba wax 6g Hectorite modified with distearyldimethylbenzyl ammonium chloride (Bentone 38V, Elementis) 5.3g Propylene carbonate 1.7g filler lg pigment 5g Polymer of Example 4 12g, calculated as active substance Isododecane add up to 100

Example 12: Nail polish Polymer of Example 5 23.8g, calculated as active substance Butyl acetate 24.99g Isopropanol 10.71g Hexylene glycol 2.5g DC RED 7 Lake 1g Hectorite modified with stearyl dimethyl benzyl ammonium chloride (Bentone 27V, Elementis) 1.3g ethyl acetate Add to 100g

Example 13: Mascara Composition beeswax 8g paraffin 3g carnauba wax 6g Hectorite modified with distearyldimethylbenzyl ammonium chloride (Bentone38V, Elementis) 5.3g Propylene carbonate 1.7g filler 1g pigment 5g Polymer of Example 6 12g, calculated as active substance Isododecane Add to 100g

Claims (84)

1. A cosmetic composition characterized in that said composition comprises at least one non-elastomeric film-forming linear olefinic block polymer in a cosmetically acceptable organic liquid medium and for said organic liquid medium Gelling agent. 2. A cosmetic composition characterized in that said composition comprises at least one film-forming linear olefinic block polymer free of styrene units in a cosmetically acceptable organic liquid medium and for said Gelling agent for organic liquid media. 3. Cosmetic composition according to claim 1 or 2, characterized in that said block polymer is an olefinic polymer obtained from an aliphatic olefinic monomer comprising carbon-carbon double bonds and at least An ester group -COO- or amido group -CON-. 4. Cosmetic composition according to any one of the preceding claims, characterized in that said polymer is insoluble in water or Mixture of water and straight-chain or branched-chain lower monohydric alcohols containing 2 to 5 carbon atoms. 5. Cosmetic composition according to any one of the preceding claims, characterized in that the block polymer comprises first and second blocks interconnected by an intermediate block comprising at least one first The constituent monomers of the block and at least one constituent monomer of the second block. 6. Cosmetic composition according to any one of the preceding claims, characterized in that the block polymer comprises first and second blocks having different glass transition temperatures (Tg). 7. The composition according to any one of the preceding claims, characterized in that the first and second blocks interact with each other by an intermediate block with a glass transition temperature between the glass transition temperatures of the first and second blocks. connect. 8. Cosmetic composition according to any one of the preceding claims, characterized in that said block polymer comprises a first and a second block which are incompatible in said organic liquid medium. 9. Cosmetic composition according to any one of the preceding claims, characterized in that the polydispersity index I of the block polymer is greater than 2. 10. The composition of claim 6, characterized in that the first block of the polymer is selected from: a) blocks with a Tg higher than or equal to 40°C, b) blocks with a Tg lower than or equal to 20°C, c) Tg is a block between 20°C and 40°C, and The second block is selected from blocks of the class a), b) or c) different from the first block. 11. Composition according to claim 10, characterized in that the blocks with a Tg higher than or equal to 40°C are obtained wholly or partly from one or more homopolymers prepared therefrom with a glass transition temperature higher than or equal to 40°C of monomers. 12. Composition according to any one of the preceding claims, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is higher than or equal to 40° C. are selected from the following monomers: - methacrylates of the formula CH ₂ =C(CH ₃ )-COOR ₁ , wherein R ₁ represents an unsubstituted straight-chain or branched alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, propylene or isobutyl, or R ₁ represents C ₄ -C ₁₂ cycloalkyl; - acrylates of the formula CH ₂ =CH-COOR ₂ , wherein R ₂ represents C ₄ -C ₁₂ cycloalkyl, such as isobornyl acrylate, or tert-butyl; - (meth)acrylamides of the formula: Wherein R ₇ and R ₈ can be the same or different, and each represents a hydrogen atom or a straight or branched C ₁ -C ₁₂ alkyl group, such as n-butyl, tert-butyl, isopropyl, isohexyl, isooctyl or isononyl, or R ₇ represents H and R ₈ represents 1,1-dimethyl-3-oxobutyl, and R' represents H or methyl; - and mixtures thereof. 13. The composition according to claim 11 or 12, characterized in that the monomer whose glass transition temperature of the corresponding homopolymer is higher than or equal to 40° C. is selected from methyl methacrylate, isobutyl (meth)acrylate, Isobornyl (meth)acrylate and mixtures thereof. 14. Composition according to claim 10, characterized in that the blocks with a Tg lower than or equal to 20°C are derived wholly or partly from monomers from which the homopolymers prepared therefrom have a glass transition temperature lower than or equal to 20°C. 15. Composition according to claim 14, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is lower than or equal to 20° C. are selected from the following monomers: -Acrylic esters of the formula CH ₂ =CHCOOR ₃ , R ₃ represents unsubstituted straight or branched C ₁ -C ₁₂ alkyl, except for tert-butyl, in which one or more groups selected from O, N and S heteroatoms; -Methacrylate of the formula CH ₂ ═C(CH ₃ )-COOR ₄ , R ₄ represents an unsubstituted linear or branched C ₆ -C ₁₂ alkyl group, wherein one or more groups selected from O , heteroatoms of N and S; - Vinyl esters of the formula R ₅ -CO-O-CH=CH ₂ , wherein R ₅ represents straight or branched C ₄ -C ₁₂ alkyl; -C ₄ -C ₁₂ alkyl vinyl ether; -N-(C ₄ -C ₁₂ )alkylacrylamides, such as N-octylacrylamide; - and mixtures thereof. 16. The composition according to claim 14 or 15, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is lower than or equal to 20° C. are selected from the group consisting of 1 to 10 carbon atoms in the alkyl chain, except tert-butyl Alkyl acrylates outside the base. 17. Composition according to claim 10, characterized in that the blocks with a Tg between 20°C and 40°C are wholly or partly derived from monomers with a glass transition temperature between 20°C and 40°C of the homopolymer prepared therefrom. body. 18. Composition according to claim 10, characterized in that the blocks with a Tg between 20°C and 40°C are obtained wholly or partly from monomers and corresponding homopolymers whose Tg is higher than or equal to 40°C Monomers whose Tg is lower than or equal to 20°C. 19. Composition according to claim 17 or 18, characterized in that the blocks with a Tg between 20°C and 40°C are obtained wholly or partly from monomers selected from the group consisting of methyl methacrylate, isobornyl acrylate, methyl Isobornyl acrylate, butyl acrylate and 2-ethylhexyl acrylate and mixtures thereof. 20. Composition according to any one of claims 10-19, characterized in that the composition comprises a block polymer comprising at least one first block and at least one second block , the glass transition temperature (Tg) of the first block is higher than or equal to 40°C, and the glass transition temperature of the second block is lower than or equal to 20°C. 21. Composition according to any one of the preceding claims, characterized in that said first block is obtained in whole or in part from one or more homopolymers prepared therefrom having a glass transition temperature higher than or equal to 40°C of monomers. 22. Composition according to claim 21, characterized in that said first block is a copolymer derived from a monomer whose glass transition temperature of the homopolymer prepared therefrom is higher than or equal to 40°C. 23. Composition according to claim 21 or 22, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is higher than or equal to 40° C. are selected from the following monomers: - methacrylates of the formula CH ₂ =C(CH ₃ )-COOR ₁ , wherein R ₁ represents an unsubstituted straight-chain or branched alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, propylene or isobutyl, or R ₁ represents C ₄ -C ₁₂ cycloalkyl; - acrylates of the formula CH ₂ =CH-COOR ₂ , wherein R ₂ represents C ₄ -C ₁₂ cycloalkyl, such as isobornyl acrylate, or tert-butyl; - (meth)acrylamides of the formula: Wherein R ₇ and R ₈ are the same or different, and each represents a hydrogen atom or a straight or branched C ₁ -C ₁₂ alkyl group, such as n-butyl, tert-butyl, isopropyl, isohexyl, isooctyl or iso Nonyl, or R ₇ represents H and R ₈ represents 1,1-dimethyl-3-oxobutyl, and R' represents H or methyl; - and mixtures thereof. 24. The composition according to any one of claims 21-23, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is higher than or equal to 40° C. are selected from the group consisting of methyl methacrylate, isobutyl methacrylate esters and isobornyl (meth)acrylate and mixtures thereof. 25. The composition according to any one of claims 21-24, characterized in that the proportion of the first block ranges from 20% to 90% by weight of the polymer, preferably from 30% to 80%, and more Preferably it is 50%-70%. 26. Composition according to any one of claims 20-25, characterized in that said second block is obtained wholly or partly from one or more homopolymers prepared therefrom having a glass transition temperature lower than or equal to Monomer at 20°C. 27. Composition according to any one of claims 20-26, characterized in that said second block is a homopolymer derived from a monomer whose glass transition temperature of the homopolymer prepared therefrom is lower than or equal to 20°C thing. 28. Composition according to claim 26 or 27, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is lower than or equal to 20° C. are selected from the following monomers: -Acrylic esters of the formula CH ₂ =CHCOOR ₃ , R ₃ represents unsubstituted straight or branched C ₁ -C ₁₂ alkyl, except for tert-butyl, in which one or more groups selected from O, N and S heteroatoms; -Methacrylate of the formula CH ₂ ═C(CH ₃ )-COOR ₄ , R ₄ represents an unsubstituted linear or branched C ₆ -C ₁₂ alkyl group, wherein one or more groups selected from O , heteroatoms of N and S; - Vinyl esters of the formula R ₅ -CO-O-CH=CH ₂ , wherein R ₅ represents straight or branched C ₄ -C ₁₂ alkyl; -C ₄ -C ₁₂ alkyl vinyl ether; -N-(C ₄ -C ₁₂ )alkylacrylamides, such as N-octylacrylamide; - and mixtures thereof. 29. Composition according to any one of claims 26-28, characterized in that the corresponding homopolymers have a glass transition temperature lower than or equal to 20° C. and are selected from monomers comprising 1 to 10 carbon atoms in the alkyl chain , Alkyl acrylates other than tert-butyl. 30. Composition according to any one of claims 20-29, characterized in that the proportion of the second block with a Tg lower than or equal to 20° C. ranges from 5% to 75% by weight of the polymer, more preferably 15% %-50%, and even more preferably 25%-45%. 31. Composition according to any one of claims 10-19, characterized in that the composition comprises a block polymer comprising at least one first block and at least one second block , the glass transition temperature (Tg) of the first block is between 20°C and 40°C, the glass transition temperature of the second block is lower than or equal to 20°C or the glass transition temperature is higher than or equal to 40°C. 32. Composition according to any one of the preceding claims, characterized in that the first block with a Tg between 20°C and 40°C results wholly or partly from the vitrification of one or more homopolymers prepared therefrom Monomers with a transition temperature between 20°C and 40°C. 33. Composition according to claim 31 or 32, characterized in that the first block with a Tg between 20°C and 40°C is derived from a monomer having a Tg higher than or equal to 40°C of the corresponding homopolymer and the corresponding A copolymer of monomers whose homopolymer Tg is lower than or equal to 20°C. 34. Composition according to any one of claims 31-33, characterized in that the first block with a Tg between 20°C and 40°C is obtained from a monomer selected from the group consisting of methyl methacrylate, isobornyl acrylate , isobornyl methacrylate, butyl acrylate and 2-ethylhexyl acrylate and mixtures thereof. 35. Composition according to any one of claims 31-34, characterized in that the proportion of the first block with a Tg between 20°C and 40°C ranges from 10% to 85% by weight of the polymer, more preferably From 30% to 80%, and even more preferably from 50% to 70%. 36. Composition according to any one of claims 31-34, characterized in that said second block has a Tg higher than or equal to 40° C. and is obtained in whole or in part from one or more homopolymers prepared therefrom A monomer whose glass transition temperature is higher than or equal to 40°C. 37. The composition of any one of claims 31-36, characterized in that the Tg of the second block is higher than or equal to 40° C. and is obtained from a homopolymer prepared therefrom with a glass transition temperature higher than Or a homopolymer of monomers equal to 40°C. 38. Composition according to any one of claims 36 and 37, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is higher than or equal to 40° C. are selected from the following monomers: - methacrylates of the formula CH ₂ =C(CH ₃ )-COOR ₁ , wherein R ₁ represents an unsubstituted straight-chain or branched alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, propylene or isobutyl, or R ₁ represents C ₄ -C ₁₂ cycloalkyl; - acrylates of the formula CH ₂ =CH-COOR ₂ , wherein R ₂ represents C ₄ -C ₁₂ cycloalkyl, such as isobornyl acrylate, or tert-butyl; - (meth)acrylamides of the formula:

Wherein R ₇ and R ₈ are the same or different, and each represents a hydrogen atom or a straight or branched C ₁ -C ₁₂ alkyl group, such as n-butyl, tert-butyl, isopropyl, isohexyl, isooctyl or iso Nonyl, or R ₇ represents H and R ₈ represents 1,1-dimethyl-3-oxobutyl, and R' represents H or methyl; - and mixtures thereof. 39. The composition according to any one of claims 35-38, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is higher than or equal to 40° C. are selected from the group consisting of methyl methacrylate, isobutyl methacrylate esters, isobornyl (meth)acrylate and mixtures thereof. 40. Composition according to any one of claims 36-39, characterized in that the proportion of the second block with a Tg higher than or equal to 40° C. ranges from 10% to 85% by weight of the polymer, preferably 20% -70%, and more preferably 30%-70%. 41. Composition according to any one of claims 31-40, characterized in that said second block has a Tg lower than or equal to 20°C and is derived wholly or partly from one or more homopolymeric compounds prepared therefrom Monomers whose glass transition temperature is lower than or equal to 20°C. 42. The composition of any one of claims 31-40, characterized in that the Tg of the second block is lower than or equal to 20° C. and is obtained from a homopolymer prepared therefrom with a glass transition temperature lower than Or a homopolymer of monomers equal to 20°C. 43. Composition according to claim 41 or 42, characterized in that the monomers whose glass transition temperature of the corresponding homopolymer is lower than or equal to 20° C. are selected from the following monomers: -Acrylic esters of the formula CH ₂ =CHCOOR ₃ , R ₃ represents unsubstituted straight or branched C ₁ -C ₁₂ alkyl, except for tert-butyl, in which one or more groups selected from O, N and S heteroatoms; -Methacrylate of the formula CH ₂ ═C(CH ₃ )-COOR ₄ , R ₄ represents an unsubstituted linear or branched C ₆ -C ₁₂ alkyl group, wherein one or more groups selected from O , heteroatoms of N and S; - Vinyl esters of the formula R ₅ -CO-O-CH=CH ₂ , wherein R ₅ represents straight or branched C ₄ -C ₁₂ alkyl; -C ₄ -C ₁₂ alkyl vinyl ether; -N-(C ₄ -C ₁₂ )alkylacrylamides, such as N-octylacrylamide; - and mixtures thereof. 44. Composition according to any one of claims 41-43, characterized in that the corresponding homopolymers have a glass transition temperature lower than or equal to 20° C. and are selected from monomers comprising 1 to 10 carbon atoms in the alkyl chain , Alkyl acrylates other than tert-butyl. 45. Composition according to any one of claims 41-44, characterized in that the proportion of blocks with a glass transition temperature higher than or equal to 40° C. ranges from 20% to 90% by weight of the polymer, more preferably from 30%-80%, and even more preferably 50%-70%. 46. Cosmetic composition according to any one of claims 5-8 or any one of the preceding claims dependent thereon, characterized in that said first block and/or second block comprise at least one other monomer. 47. Composition according to any one of the preceding claims, characterized in that the further monomers are selected from the group consisting of hydrophilic monomers and ethylenically unsaturated monomers comprising one or more silicon atoms and mixtures thereof. 48. Composition according to claim 46 or 47, characterized in that the other monomers are selected from: a) Hydrophilic monomers, such as: - Ethylenically unsaturated monomers containing at least one carboxylic acid or sulfonic acid functional group, such as acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonate acid, vinylbenzoic acid, vinylphosphonic acid and their salts; - ethylenically unsaturated monomers containing at least one tertiary amine functionality, such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylaminopropyl methacrylamide and its salts; - methacrylates of the formula CH ₂ =C(CH ₃ )-COOR ₆ , Wherein R ₆ represents a straight chain or branched chain alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isobutyl, and the alkyl group is selected from one or more groups selected from hydroxyl and halogen atoms (Cl, Br, I or F) substituent substituted alkyl, examples of hydroxyl substitution include 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate, examples of halogen atom substitution include trimethacrylate Fluoroethyl ester; - methacrylates of the formula CH ₂ =C(CH ₃ )-COOR ₉ , R ₉ represents C ₆ -C ₁₂ straight chain or branched chain alkyl, wherein one or more heteroatoms selected from O, N and S are optionally inserted, and the alkyl group is replaced by one or more selected from hydroxyl and halogen ( Cl, Br, I or F) substituent substitution; - acrylates of the formula CH ₂ =CHCOOR ₁₀ , R ₁₀ represents a linear or branched C ₁ -C ₁₂ alkyl group substituted by one or more substituents selected from hydroxyl and halogen (Cl, Br, I or F) (such as 2-hydroxypropyl acrylate and acrylic acid 2-hydroxyethyl ester), or R ₁₀ represents C ₁ -C ₁₂ alkyl-O-POE (polyoxyethylene) with 5-30 oxyethylene repeating units, such as methoxy-POE, or R ₁₀ represents a polyoxyethylene group comprising 5 to 30 oxyethylene units; and b) Ethylenically unsaturated monomers containing one or more silicon atoms, such as methacryloxypropyltrimethoxysilane and methacryloxypropyltris(trimethylsiloxy)silane ; - and mixtures thereof. 49. The composition according to any one of claims 46 and 47, characterized in that the first and second blocks each comprise at least one other monomer selected from the group consisting of acrylic acid, (meth)acrylic acid and trifluoroethyl methacrylate bodies and mixtures thereof. 50. The composition according to any one of claims 46 and 47, characterized in that the first and second blocks each comprise at least one monomer selected from (meth)acrylates and optionally at least one other monomer Body such as (meth)acrylic acid, and mixtures thereof. 51. Composition according to any one of claims 46 and 47, characterized in that the first and second blocks are each entirely derived from at least one monomer selected from (meth)acrylates and optionally at least one Other monomers such as (meth)acrylic acid, and mixtures thereof. 52. Composition according to any one of claims 46 to 51, characterized in that said other monomer or monomers constitute from 1% to 30% of the total weight of the first and/or second block. 53. Composition according to claim 6 or any one of the preceding claims dependent thereon, characterized in that the difference between the glass transition temperatures (Tg) of said first and second blocks is greater than 10°C, preferably greater than 20°C °C, very preferably greater than 30 °C, and more preferably greater than 40 °C. 54. Composition according to claim 9, characterized in that said block polymer has a polydispersity index greater than or equal to 2.5, preferably greater than or equal to 2.8. 55. Composition according to claim 54, characterized in that the polydispersity index of said block polymer is between 2.8 and 6. 56. Composition according to any one of the preceding claims, characterized in that said block polymer has a weight average molecular weight (Mw) less than or equal to 300,000. 57. Composition according to claim 56, characterized in that the weight average molecular weight (Mw) ranges from 35,000 to 200,000, and more preferably from 45,000 to 150,000. 58. Composition according to claim 57, characterized in that the weight average molecular weight (Mw) is less than or equal to 70000. 59. Composition according to any one of claims 56-58, characterized in that the weight average molecular weight (Mw) ranges from 10000 to 60000, and more preferably from 12000 to 50000. 60. Composition according to any one of the preceding claims, characterized in that the composition comprises 0.1% to 60% by weight, preferably 5% to 50% by weight, and more preferably 10% to 40% by weight of polymeric active substances . 61. Composition according to any one of the preceding claims, characterized in that said at least one gelling agent is selected from gelling agents in polymeric form. 62. Composition according to claim 60, characterized in that the polymeric gelling agent is selected from the group consisting of crosslinked elastic polyorganosiloxanes with a three-dimensional structure, such as MQ silicones, polyalkylsilsesquioxanes and by Hydrosilylation crosslinked resin. 63. Composition according to claim 62, characterized in that the polymeric gelling agent comprises hydrophilic groups, such as polyethylene oxide or ethylene oxide/propylene oxide copolymers. 64. Composition according to claim 61, characterized in that said agent effecting gelation by molecular mixing is a silicone rubber of the formula: in: R ₇ , R ₈ , R ₁₁ and R ₁₂ are the same or different, and are each selected from alkyl groups having 1 to 6 carbon atoms, R ₉ and R ₁₀ are the same or different, and are each selected from alkyl and aryl groups containing 1 to 6 carbon atoms, X is selected from alkyl, hydroxyl and vinyl groups containing 1 to 6 carbon atoms, The selection of n and p makes the viscosity of the silicone rubber greater than 100000 mPa·s, such as greater than 500000 mPa·s. 65. The composition of claim 61, characterized in that the polymeric gelling agent is selected from the group consisting of aminopolysiloxane polymers having triazine or pyrimidinyl groups bonded to amino groups therein, end-end ester or Triamide functional non-silicone polyamides, polyurethanes and vinyl and/or (meth)acrylic polymers with pendant groups capable of hydrogen bonding interactions. 66. The composition of claim 61, characterized in that said polymeric gelling agent is selected from: - polystyrene-polysiloxane or polyethylene-polysiloxane copolymers, - copolymers comprising polysiloxane blocks and another polyvinyl or poly(meth)acrylic block or grafted chain, - polymers or copolymers obtained by polymerization or copolymerization of ethylenic monomers containing one or more ethylenic bonds, preferably conjugated bonds (or dienes), - Polymers or copolymers obtained by polymerization or copolymerization of olefinic monomers comprising styrene or alkylstyrene blocks. 67. Composition according to any one of claims 1-60, characterized in that the gelling agent is fumed silica. 68. A cosmetic composition characterized in that said composition comprises in a cosmetically acceptable organic liquid medium a) at least one film-forming linear olefinic block polymer, and b) at least one for The gelling agent of the liquid medium, the gelling agent is selected from: - fumed silica, - polystyrene-polysiloxane or polyethylene-polysiloxane copolymers, - copolymers comprising polysiloxane blocks and another polyvinyl or poly(meth)acrylic block or grafted chain, - polymers or copolymers obtained by polymerization or copolymerization of ethylenic monomers containing one or more ethylenic bonds, preferably conjugated bonds (or dienes), - Polymers or copolymers obtained by polymerization or copolymerization of olefinic monomers comprising styrene or alkylstyrene blocks. 69. Cosmetic composition according to any one of the preceding claims, wherein said at least one gelling agent comprises from 0.05% to 35% of the total weight of said composition, such as from 0.5% to 20% or from 1% to 10%. 70. Cosmetic composition according to any one of the preceding claims, characterized in that said composition also comprises one or more dyes selected from water-soluble dyes and pulverulent dyes, such as pigments, nacres and scales. 71. Cosmetic composition according to any one of the preceding claims, characterized in that the composition is in the form of a suspension, dispersion, solution, gel, emulsion, in particular an oil-in-water (O/W) emulsion, an oil-in- Water (W/O) emulsions, complex emulsions (W/O/W or polyols/O/W or O/W/O emulsions), or as creams, sticks, pastes or mousses, or vehicle dispersions forms, especially ionic or nonionic liposomes, biphasic or multiphasic lotions, sprays, powders or pastes, especially soft or anhydrous pastes. 72. Cosmetic composition according to any one of the preceding claims, characterized in that said composition is a composition for the make-up or care of keratin materials. 73. Cosmetic composition according to any one of the preceding claims, characterized in that said composition is a lip makeup product. 74. Cosmetic composition according to any one of the preceding claims, characterized in that said composition is an ophthalmic cosmetic product. 75. Cosmetic composition according to any one of the preceding claims, characterized in that said composition is a complexion cosmetic product. 76. Cosmetic composition according to any one of the preceding claims, characterized in that said composition is a cosmetic product for nails. 77. A cosmetic kit comprising: a) a container defining at least one compartment, said container being closed by a closing element; and b) a composition placed in said compartment, The composition is a composition according to any one of the preceding claims. 78. The cosmetic kit of claim 77, wherein said container is at least partially formed of at least one thermoplastic material. 79. Cosmetic kit according to claim 77, characterized in that said container is at least partially formed of at least one non-thermoplastic material, in particular glass or metal. 80. A kit according to any one of claims 77-79, characterized in that in the closed position of the container, the closure element is screw-connected to the container. 81. Kit according to any one of claims 77-79, characterized in that in the closed position of the container, the closure element is fastened, glued, in addition to being screwed to the container. Fitted or welded to the container. 82. The kit of any one of claims 77-81, wherein said composition is at substantially atmospheric pressure within said chamber. 83. A kit according to any one of claims 77-81, characterized in that said composition is pressurized within said container. 84. A cosmetic method for the make-up or care of keratinous materials, said method comprising applying to keratinous materials a cosmetic composition according to any one of claims 1-76.