Copolymer obtained by polymerization of at least one particular dicarboxylic ethylenic monomer and at least two particular unsaturated ester monomers.

Abstract

A copolymer obtained from at least one monomer of specified formula (I), at least one ester monomer of specified formula (II), and at least one ester monomer of specified formula (III). A process for obtaining these polymers and their areas of application. A composition, preferably cosmetic, comprising such a copolymer with preferred ingredients.

Description

Title of the invention: Copolymer obtained by polymerization of at least one particular dicarboxylic ethylenic monomer and at least two particular unsaturated ester monomers.

[0001] Film-forming polymers are particularly valued in many fields because they allow active ingredients to adhere to a wide variety of substrates. These substrates can be, for example, metals, alloys, ceramics, plastics, fabrics, leather, or natural human substrates such as skin, hair, and mucous membranes. One of the most sought-after properties for these film-forming polymers is the ability to produce films with high durability on the substrates to which they are deposited. This durability most often results from good resistance to water and friction. For some years now, research has also been underway on polymers that lead to good biodegradability in order to avoid pollution during their disposal. We are also looking for polymers whose manufacture has a low impact on natural resources. These include polymers whose monomers can be bio-based, that is, obtained from renewable resources such as biomass. Finally, for many of the applications mentioned, and in particular for the applications of film-forming polymers on natural human substrates such as skin, hair and mucous membranes, we are looking for polymers that do not present any unpleasant effects on application and after application on the substrates, in particular no greasy or sticky effects. For all these reasons, there is a real need for new film-forming polymers that satisfy these requirements.

[0002] To this end the applicant recommends copolymers obtained from at least one monomer of formula (I), at least one ester monomer of formula (II) and at least one ester monomer of formula (III). CO2 M p< _ pu —- p ■ ix i vn ......... w R2 — CO2 M' Formula (I) Formula (II)

[0003] Formula (III)

[0004] formulas in which: R, R', R1, R'1, R"1 and R"2 independently designate a hydrogen atom or a linear or branched C1-C4 alkyl group. R2 designates a linear or branched C1-C4 alkylene group.

[0005] R'2 designates a methylene group R3 designates a linear, branched or cyclic C4-C20 alkyl group, a tetrahydrofurfuryl group M and M' independently designate a hydrogen atom or a residue of an alkali agent and at least one of the radicals R and R' being different from hydrogen knowing that the monomer(s) of formula (I) represent at least 5% by weight of all the monomers used to obtain said copolymer.

[0006] Document CN114426641 A of CHINESE PETROCHEMICAL INDUSTRY LTD COMPANY describes a bio-based demulsifier, characterized in that the bio-based demulsifier comprises a polymer formed by polymerization of itaconic acid, dimethyl itaconate and dibutyl itaconate. Itaconic acid is a monomer of formula (I). Dimethyl itaconate and dibutyl itaconate are monomers of formula (II). No additional monomers are planned for the synthesis of the described copolymer. Therefore, monomers of formula (III) are not mentioned. Document CN105482029 A from SKSHU PAINT CO LTD describes a bio-based, energy-saving and environmentally friendly aqueous emulsion polymer, characterized in that it is composed of the following raw materials in parts by weight: 40-50 parts water, 10-18 parts methyl methacrylate, 10-20 parts n-butyl acrylate, 2-8 parts isooctyl acrylate, 10-25 parts dibutyl itaconate, 0.1-0.3 parts initiator, 0.1-0.2 parts pH buffer, 0.3-1.5 parts anionic emulsifier, 0.4-0.6 parts nonionic emulsifier and 0.1-0.8 parts triisopropanolamine. Isooctyl acrylate is a monomer of formula (III) and dibutyl itaconate is a monomer of formula (II). The addition of formula (I) monomers such as itaconic acid is not planned, the use of which as a monomer is even discouraged in the text of the document. The document GB683465 A from STANDARD OIL DEV CO describes the preparation of copolymers of esters of an alphamethylene dicarboxylic acid with certain copolymerizable monomers containing an ethylenic double bond and oxygen in the form of carboxyl, carbonyl or ether groups, intended for use as viscosity index or pour point depressants for lubricating oils. The examples describe, in particular, a copolymer X dimethylitaconate / octyldecyl methacrylate, that is to say, one composed of monomers of formulas (II) and (III). Itaconic acid alone, a compound of formula (I), is mentioned in this document only in the context of the preparation of decyl itaconate (example VI). Copolymerizations take place in an oily environment. Document JP2006199663 A from GOO CHEMICAL CO LTD describes a base for hair cosmetics, comprising a copolymer characterized in that it is obtained by polymerization in solution in a mixed liquid containing the components A to C below: A denotes an ethylenically unsaturated monomer having one or more carboxyl groups in the molecule (a) and a polymerizable ethylenically unsaturated monomer (b); B denotes at least one compound selected from the group consisting of a polyoxyalkylated ether compound represented by a specific formula and phosphoric acid ester compounds represented by the following general formulas (2) and (3): C denotes a hydrophilic solvent or a mixture of water and a hydrophilic solvent. In the monomers (a) are mentioned (meth)acrylic acid, itaconic acid, maleic acid, crotonic acid, itaconic acid being a compound of formula (I) In the monomers (b) are mentioned esters and in a long list are cited acrylates or methacrylates of formula (III). No compound of formula (II) is mentioned in the description. The document JPH4209677 A from MITSUBISHI RAYON CO describes a coating film formation process in which a thermosetting basecoat paint containing a pigment is applied to a base, then a transparent thermosetting paint is applied to the basecoat by a wet-on-wet method, and the uncured coating film is simultaneously heated and cured. The binder component of the base paint is a) - 10 to 50% by weight of a (meth)acrylic acid ester containing a hydroxyl group b) 0.5 to 20% by weight of a vinyl monomer containing a hydroxyl group other than the monomers of a), (c) 0.2 to 10% by weight of an a,[3] monoethylenic unsaturated carboxylic acid or an acid anhydride thereof, d) 20 to 75% by weight of a (meth)acrylic acid ester of specified formula, e) 0 to 50% by weight of another copolymerizable vinyl monomer. The description indicates that monomer (c) can be, among a list of compounds, itaconic acid, compound of formula (I). Also mentioned in the description are, among other monomers, esters of (meth)acrylic acid having a hydrocarbon substituent with 5 or more carbon atoms. Several compounds are cited, including compounds of formula (III). No monomer of formula (II) is mentioned in the document. Document CN107523242 A from DONGGUAN LIANZHOU INTELLECTUAL PROPERTY OPERATIONS MAN CO LTD describes a process for preparing a pressure-sensitive, thermally conductive polyacrylate adhesive, characterized in that it comprises, among several steps, a step for preparing a mixed monomer emulsion obtained in the following manner: lauryl acrylate, ethyl methacrylate, (3-methacryloxypropyl)trimethylsilane, N-tert-octylacrylamide, N-acryloylmorpholine, sodium methyl tetradecanoate α-sulfonate and sodium dodecyl alcohol polyoxyethylene carboxylate are added sequentially to water, stirred for 30 to 40 minutes, then itaconic acid and acrylic acid are added, and stirring is continued for 20 to 30 minutes. This emulsion therefore comprises a monomer of formula (I), itaconic acid and a monomer of formula (III), lauryl acrylate. No monomer of formula (II) is mentioned in the document. Document CN101974117 A of CHANGZHOU GUANGHUI CHEMICAL CO LTD describes a styrene-acrylic emulsion with carboxylic acid groups, characterized in that its raw materials are composed of the following components in percentage by mass: Styrene 20-25%, Ethyl Acrylate 5-8%, Butyl Acrylate 7-10%, Triethylene Glycol Dimethacrylate 1.5-2.0%, Methylidene Succinic Acid 2-3%, Lauryl Methacrylate 6-8%, Emulsifier MS-1 2-4%, Potassium Persulfate 0.2-0.4%, Sodium Bicarbonate 0.1-0.2%, supplemented with demineralized water. Methylidene succinic acid or itaconic acid is a compound of formula (I). Lauryl methacrylate is a compound of formula (III). This document does not mention any monomer of formula (II). The document JPH07278447 A from the company DAINIPPON INK & CHEMICALS describes a non-aqueous colored resin dispersion comprising: a first group of molecular chains made up of a synthetic resin (A) insoluble in a non-aqueous solvent; and a second group of molecular chains made up of a polymer (B) having a carboxyl group soluble in the non-aqueous solvent, the molecular chains being dispersed in the non-aqueous solvent as entangled chain resin microparticles having an interpenetrating network structure due to the entanglement between the molecular chains of the first group and the molecular chains of the second group; and a dye (D), in which the mesh size of the matrix of the interpenetrating network structure of the entangled chain resin microparticles dispersed in the non-aqueous solvent is less than the diameter of the dye particles (D), and the dye (D) is physically trapped in the matrix. Itaconic acid of formula (I) is mentioned as being among the possible acid monomers for polymer B. Higher alkylacrylates (therefore potentially of formula (III)) can be used in associations with these acid monomers. An ester of formula (II) appears only in example 2 where a complex colored resin dispersion is mentioned in which lauryl methacrylate (compound of formula III) and monobutyl itaconate (compound of formula (II)) appear as monomers of the dispersant, but not itaconic acid. BASF SE's US2011282000 Al document describes a composition comprising a copolymer derived from monomers including: a vinylaromatic monomer; a second monomer selected from the group consisting of butadiene, alkyl acrylates, alkyl methacrylates and mixtures thereof; and a bio-based monomer comprising isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, or mixtures thereof. Isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate are monomers of formula (III). In the alkyl acrylates of the second monomer can be included esters of itaconic acid but also acrylates or methacrylates of formula (III). Optional monomers can be added, and among the many options are α,[3-monoethylenic] unsaturated mono- and dicarboxylic acids, including itaconic acid, compound of formula (I), also described in the section on bio-based monomers. Composition example 1 includes itaconic acid and isobornyl acrylate among the monomers used. Composition example 51 includes itaconic acid and lauryl methacrylate among the monomers used. None of the monomers of formula (II) are mentioned in this document. Document JPH03206024 A from GOO KAGAKU KOGYO KK describes a hair styling resin composition obtained by polymerizing polymerizable monomers a to e and neutralizing the following monomers with a water-soluble basic organic substance: a. 6 to 35% by weight of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid; b. 15 to 50% by weight of at least one monomer consisting of an ester of acrylic acid and / or methacrylic acid with an aliphatic alcohol having 10 to 18 carbon atoms; c. 15 to 50% by weight of at least one monomer comprising an ester of acrylic acid and / or methacrylic acid with an aliphatic alcohol having 4 to 8 carbon atoms; d. 5 to 50% by weight of at least one monomer selected from the N-alkyl-substituted acrylamide of specific formula e additional monomer. Itaconic acid is a compound of formula (I) The compounds (b) are monomers of formula (III). No compound of formula (II) is mentioned in the description of this document. Document CN108329788 A from DONGGUAN JIAQIAN NEW MAT TECH CO LTD describes a water-based styrene acrylic emulsion interior decorative wall paint, characterized in that it comprises the following components by weight: 100 parts modified styrene acrylic emulsion, 15 to 23 parts eucalyptus essential oil, 20 to 30 parts diatomaceous earth, 8 to 12 parts polyethylene glycol-400, 4 to 7 parts dispersant, 2 to 5 parts film-forming agent, 4 to 9 parts anti-sedimentation agent, 3 to 5 parts leveling agent, 1 to 2 parts anti-foaming agent, 3 to 6 parts pigment, and 30 to 40 parts water. The method for preparing the modified styrene-acrylic emulsion is specified and implements the styrene monomers, methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, itaconic acid and lauryl methacrylate. Itaconic acid is a monomer of formula (I), 2-ethylhexyl acrylate and lauryl methacrylate are monomers of formula (III). No monomer of formula (II) is mentioned in the description of this document. Document WO2022185578 A1 from DAINICHISEIKA COLOR CHEM describes an aqueous pigment dispersion comprising a pigment, water, a water-soluble organic solvent, and a polymer dispersant for dispersing the pigment, wherein the polymer dispersant contains a structural unit (i) derived from at least one compound selected from (meth)acrylic acid and itaconic acid, and a structural unit (ii) derived from a (meth)acrylate derived from a biological material, the polymer dispersant having an acidity index of 30 to 250 mg KOH / g, a content of structural unit (ii) equal to or greater than 50% by mass, a number-average molecular weight of 1,000 to 30,000, and a molecular weight distribution (weight-average molecular weight / number-average molecular weight) of 2.5 or less, and a polymer in which at least some of the carboxy groups are neutralized by an alkali,and the (meth)acrylate derived from biological material is at least one element selected from the group consisting of ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate and octadecyl (meth)acrylate. Itaconic acid is a monomer with formula (I). The monomers leading to the structural units (ii) are monomers of formula (III). Examples of formulations using itaconic acid and formula (III) monomers (dispersants D-3 and D-4). No monomer of formula (II) is mentioned in the description of this document. The document WO2016075498 Al from the company REVOLYMER UK LTD describes the use of a polymer comprising: a) 10 to 100% monomer fragments formed from the polymerization of itaconic acid salts; b) 0 to 90% monomer fragments formed from the polymerization of itaconic acid, itaconic acid esters, itaconic acid amides and / or itaconic anhydride, as a film-forming agent in a cosmetic or personal care product. Itaconic acid salts are monomers of formula (I) Esters of itaconic acid, mono or diesters, are mentioned as monomers (b) such as monomethyl ester, dimethyl ester, monoethyl ester, and diethyl ester. These are monomers of formula (II). The only examples of copolymers with monomers of formulas (B) and (II) are Examples 25, 26, 27, and 28. The ester in question is monoethyl itaconate. Optional monomers are not considered. Therefore, no monomer of formula (III) is mentioned. None of the prior art documents describe the simultaneous presence of monomers belonging to all three formulas (I), (II) and (III).

[0007] For the purposes of this invention, the residue of an alkali metal is understood to be the portion of the alkali metal bound to the carboxylic group after the salification reaction. This is often an entity carrying at least one positive charge bound to the negative charge of the carboxylate ion. For mineral alkali metals, for example, such as hydroxides or carbonates, this is the positive metallic counter ion. M and / or M' can therefore be, in particular, an ionized metallic residue such as an ionized magnesium or manganese atom, or an ionized sodium, potassium, or lithium atom derived from sodium hydroxide, potassium hydroxide, lithium, or sodium or potassium bicarbonate. It can also be an ammonium ion derived from ammonia. Finally, it can be a residue from an organic base such as monoethanolamine or triethanolamine. When M and / or M' denote a hydrogen atom, it can be ionized. M and / or M' preferably denote a hydrogen atom or an ionized metallic residue. In one variant of the invention, M and M' are identical. Preferably, R2 designates a methylene group CH2 or ethylene CH2-CH2. Even more preferably, R2 designates a methylene group. Preferably in formula (I), RI denotes a hydrogen atom or a methyl group. Even more preferably, RI denotes a hydrogen atom. Preferably in formula (II), R'1 denotes a hydrogen atom or a methyl group. Even more preferably, R'1 denotes a hydrogen atom. Preferably in formula (II), at least one of the radicals R or R' designates an n-butyl group or an isobutyl group. Preferably in formula (III), R"1 denotes a hydrogen atom or a methyl group and R"2 denotes a hydrogen atom. Better R"1 designates a methyl group. Preferably in formula (III), R3 denotes a linear, branched or cyclic C8-C20 alkyl group. More preferably the monomer of formula (I) is itaconic acid or one of its salts. More preferably the monomer of formula (II) is an ester of itaconic acid, preferably an itaconic acid diester, more preferably dibutylitaconate. Preferably the monomer of formula (III) is chosen from lauryl methacrylate or 2-octyl methacrylate (Imethyheptyl methacrylate). A minimum level of formula (I) monomers is introduced to promote film formation and the properties of the resulting film. Preferably the monomers of formula (I) represent from 10 to 60%, better from 20 to 50% by weight of all the monomers used to obtain the copolymer of the invention. Preferably the monomers of formula (II) represent from 1 to 30% by weight of all the monomers used to obtain the copolymer of the invention. Preferably the monomers of formula (III) represent from 20 to 70% by weight of all the monomers used to obtain the copolymer of the invention. Monomers of formulas (I), (II) and (III) are advantageously bio-based.

[0008] The copolymer of the invention may comprise monomers other than the monomers of formulas (I), (II) and (III). Preferably these additional monomers represent less than 25% by weight, better less than 10% by weight, of the total quantity of monomers in the copolymer.

[0009] Preferably the copolymer of the invention is obtained from at least two monomers of formula (III). In a preferred embodiment of the invention the copolymer does not comprise any monomers other than those of formulas (I), (II) and (III).

[0010] Preferably the copolymer of the invention is non-crosslinked. Preferably the copolymer of the invention is a block copolymer. A block copolymer is a copolymer whose chemical structure is characterized by the juxtaposition of monomer sequences, at least one sequence being made up of the repetition of the same monomer and two juxtaposed sequences comprising at least one different monomer. A block copolymer is distinguished in particular from a statistical copolymer which has a random sequence of monomers. Advantageously, the copolymers of the invention are obtained from an emulsion polymerization process, that is to say, a polymerization process carried out in the presence of water and at least one surfactant. Even more advantageously, the polymerization process is a micellar polymerization. In water, surfactant molecules tend to assemble into micelles above a certain concentration (known as the critical micelle concentration, CMC) to minimize their surface energy. Within these micelles, the hydrophilic heads of the surfactant are positioned on the outside, protecting the hydrophobic core from water. The monomer molecules used for polymerization can be either adsorbed by the micelles, dispersed as droplets stabilized by the adsorbed surfactant molecules, or soluble in the aqueous phase, albeit in small fractions. The surfactant(s) can be anionic, non-ionic, cationic or amphoteric. Preferably the surfactant(s) are anionic or non-ionic. In one embodiment of the invention the surfactant has one or more sulfate or sulfonate groups. In another embodiment of the invention the surfactant has one or more carboxylate groups. Finally, also in another variant of the invention the surfactant has one or more saccharide groups, preferably one or more alkyl glucoside groups.

[0011] Preferably the copolymer is obtained from a process implementing at least the following steps: (a) preparation of a mixture comprising at least some of the monomers with at least one polymerization initiator. (b) heating and then possibly (b') addition of other monomers and / or the remaining weight of monomers already introduced into the mixture, this in one or more steps (b'i) with (b"i) continuation of heating after any further addition of monomers. (c) cooling and recovery of the copolymer. By part of the monomers we mean either a weight fraction of all the monomers of formulas (I), (II) and (III) or one or more monomers of one or two formulas (I) or (II) or (III) in total or fractional weight quantity. In a first variant of the process of the invention, the total weight of all the monomers of formulas (I), (II) and (III) is implemented in step (a). In a second variant of the process of the invention only the total weight of the monomers of formula (I) is implemented in step (a). In this second variant, step (a) is preferably carried out with a weight fraction of at least one monomer of formula (III). The addition of the remaining weight fraction of the monomer(s) of formula (III) and the addition of the monomer(s) of formula (II) can then be done in a single substep (bl)' or in several substeps (b'i). Preferably, the mixture in step (a) includes water. Even more preferably, the mixture includes more than 20% water by weight. Better still, it includes more than 30% water by weight, and even better, more than 40% water by weight relative to the total weight of the mixture. Preferably, the mixture in step (a) comprises at least one surfactant. The surfactant(s) are preferably anionic or non-ionic. The surfactant(s) are present in the mixture of step (a) preferably at a concentration of 0.1 to 10% by weight, better 0.2 to 5% by weight, even better 0.5 to 2% by weight relative to the weight of the mixture. The mixture in step (a) contains at least one polymerization initiator. The initiators are preferably thermal or photochemical initiators. Photoinitiators can be chosen from among benzoin ethers, dialkyl acetophenones, hydroxyalkyl alkyl acetophenones, phenyl glyoxylate, benzyl dimethyl ketal, acyl phosphines and α amino ketones. Preferably, the initiator(s) will be chosen from thermal initiators such as sodium, potassium, or ammonium persulfates, azo initiators such as 2,2-azobis-(2-amidinopropane) dihydrochloride, (2,2-azobis(2-amidinopropane) dihydrochloride, 2,2-azobis-(N,N-dimethylene)isobutyramidine dihydrochloride, 2-carbamoylazoisobutyronitrile, 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobisisobutyroni trile, 4,4-azobis-(4-cyanovaleric acid). Even more preferably, the initiator(s) will be chosen from among the persulfates. In a preferred embodiment of the invention, a single initiator will be used, preferably a thermal initiator and more preferably a persulfate. The initiator(s) generally represent 0.01 to 10% by weight, better 0.1 to 8% by weight, even better 0.5 to 5% by weight relative to the total weight of the mixture in step (a). The monomers used in this step (a) are preferably present at a concentration of 40 to 70% by weight, better 45 to 65% by weight relative to the total weight of the mixture in step (a).

[0012] The heating of stage (b) can be achieved by any means useful in this regard. Preferably, heating is done by convection. Preferably the mixture from step (a) during this step (b) is brought to a temperature ranging from 50 °C to 70 °C. If not all monomers have been introduced into the mixture in step (a), the addition of the remaining monomers by weight can be done in one or more additional steps (bi). Preferably the number of these additional sub-steps varies from 1 to 5, better from 1 to 3. These additional steps can be taken with or without an intermediate time delay. Preferably at least one addition is made compared to the previous implementation of monomer(s) with a time delay ranging from 30 minutes to 6 hours, better from 1 hour to 4 hours. After each addition, the heating temperature may or may not be readjusted. Preferably, the process of the invention includes at least one temperature increase relative to the initial heating temperature. Even more preferably, the process of the invention includes at least one heating step (b) to a temperature ranging from 71 to 90 °C, preferably from 75 to 85 °C. The heating is maintained after the last addition of monomer(s) for a period preferably ranging from 30 minutes to 2 hours, better from 45 minutes to 1 hour 30 minutes.

[0013] The above process includes a step (c) of cooling and recovery of the copolymer. This step (c) may include a pH adjustment step. This step is preferably a basification step carried out by adding one or more basic mineral or organic agents. Preferably the pH of the reaction mixture after adjustment varies from 3 to 6, better from 3.5 to 5. This step (c) may include a substep for purifying the copolymer, specifically removing traces of unreacted monomers and other impurities. This purification may involve one or more organic solvents. Step (c) may also include a substep for concentrating the copolymer, specifically aimed at reducing or removing water from the final medium.

[0014] The entire process or certain steps can be carried out under an inert atmosphere, in particular nitrogen. In one embodiment, the final copolymer can be recovered in powder form. In another, preferred embodiment, the final copolymer is recovered as a dispersion, and even more preferably as an aqueous dispersion.

[0015] The copolymers of the invention exhibit good film-forming properties. Film formation can be assessed either from the raw material obtained or from the final composition by spreading on an inert substrate such as a glass plate, a plastic sheet or a petri dish or on the final substrate (skin for example) followed by drying either at room temperature or at a higher temperature then macroscopic and / or microscopic observation. The mechanical resistance of the film can possibly be evaluated via stretching the film using a tensile testing machine. Resistance to friction can be assessed by mechanical action of a finger on the deposited film. The water resistance of the resulting film can be assessed by placing a drop of water on the film or by immersing the film in water with macroscopic and / or microscopic observation. A marker (such as a dye or pigment) can also be embedded in the film, and its removal by water observed. This property can also be evaluated in vivo by monitoring the action of water on the treated anatomical area.

[0016] The invention also covers the uses of the claimed copolymers, and in particular those obtained by the process described above. These uses may take advantage of the film-forming properties of the copolymers of the invention, but also of other properties such as their rheological or sensory behavior. The polymers of the invention can be used in particular in the fields of the food industry, agriculture, horticulture, paint, textiles, and paper, electricity, building, photography, pollution control, humidity control, decoration, cosmetics and personal hygiene. Preferably the cross-linked polymers of the invention are intended for use in personal hygiene or cosmetics. Personal hygiene products, as defined in the invention, refer to products intended to come into contact with or cover the internal cavities of the human body. These mainly include toothpaste, feminine hygiene products, baby diapers, tissues, and adult incontinence products. Cosmetic products within the meaning of the invention are those relating to all applications based on the distribution of products on the surface of external body substrates such as skin, hair, lips, eyelashes, eyebrows, nails. Even more preferably, the cross-linked polymers of the invention are intended for cosmetic use. They can therefore be used for skin makeup, particularly for face and eye makeup, eyelash and eyebrow makeup, lip makeup, and nail makeup. They can also be used for skincare, especially for moisturizers, anti-wrinkle products, sunscreens, and self-tanning products. These polymers can also be used for hair cleansing, coloring or bleaching, curling or straightening, or conditioning (improving feel and shine). Finally, these polymers can be used for scalp treatments, particularly in anti-irritation, anti-dandruff, anti-grease, and anti-hair loss products.

[0017] Another object of the invention lies in compositions comprising one or more claimed copolymers and which can in particular be obtained according to the production process also described above. The compositions of the invention preferably contain one or more copolymers of the invention at a concentration ranging from 0.01% to 80% by weight, better from 0.05% to 50% by weight, even better from 0.1% to 25% by weight and particularly from 0.15% to 15% by weight relative to the total weight of the composition. The compositions of the invention can be aqueous or anhydrous. For the purposes of this invention, anhydrous means a composition containing, at room temperature (20 to 25°C) and atmospheric pressure (1.013 x 10⁵ Pa), less than 5% water by weight, or even better, less than 1% water by weight relative to the total weight. of the composition and preferably not containing water, especially added water. For the purposes of this invention, aqueous means a composition containing, at room temperature (20 to 25°C) and atmospheric pressure (1.013 x 105 Pa), from 5% to 99.5% water by weight relative to the total weight of the composition. If the compositions of the invention contain water, they comprise at room temperature (20 to 25°C) and atmospheric pressure (1.013 x 105 Pa) from 5% to 95% by weight, better from 10% to 90% by weight, even better from 30% to 80% by weight relative to the total weight of the composition. In one embodiment of the invention, the compositions are anhydrous. They can then be in the form of powders, thickened or unthickened oils, pastes or compact solids. In another, preferred, embodiment of the invention, the compositions are aqueous. They can then be in the form of solutions, gels, or emulsions. Emulsions can be oil-in-water (O / W), water-in-oil (W / O), or multiple emulsions. They can notably result in creams or lotions. The compositions of the invention can be packaged in bags or sachets, cardboard cartons, bottles, vials with or without a pump, jars, tubes, aerosols. They can also impregnate substrates such as paper, fabrics or non-woven materials. Preferably the compositions of the invention are cosmetic compositions and even more preferably topical cosmetic compositions. Topical refers to a composition intended to be applied to the surface of external bodily substrates. This type of composition is distinct from compositions for oral use, meaning those intended to be ingested.

[0018] The compositions of the invention may contain one or more surfactants. These surfactants may be selected from anionic, nonionic, cationic, or amphoteric surfactants. Anionic surfactants, used particularly in cleaning compositions, may be selected from fatty acid soaps, alkyl sulfates, alkyl ether sulfates, alkyl ether carboxylates, acyl glutamates, acyl isethionates, and alkyl sulfonates. Amphoteric surfactants may be selected from alkyl betaines, amidoalkyl betaines, and camphodiacetates. Cationic surfactants may be selected from quaternary ammonium salts such as trialkyl ammonium halides and from quaternary diesters. Non-ionic compounds can be chosen in particular from among oxyalkylated or glycerolated alcohols or fatty amides and alkyl polyglucosides. Surfactants may be present in the compositions of the invention at levels ranging from 0.001% to 40% by weight, better from 0.05% to 30% by weight, even better from 0.1% to 20% by weight relative to the total weight of the composition. The compositions of the invention may contain one or more fatty substances. The fatty substance(s) are chosen from oils or waxes. The compositions of the invention may contain one or more oils. For the purposes of this invention, oil means a compound that is immiscible with liquid water at room temperature and atmospheric pressure. Oils can be polar or nonpolar, volatile or non-volatile (an oil is said to be non-volatile when its vapor pressure is less than 0.02 mm of mercury at atmospheric pressure and room temperature). Oils can be hydrocarbon, vegetable, mineral or synthetic. They can also be siliconed or fluorinated. Silicone oils can be linear, branched, or cyclic polydimethylsiloxanes, possibly containing aryl groups, particularly phenyl groups. Nonpolar hydrocarbon oils are preferably chosen from paraffin oil, isoparaffins (isodecane, isodecanes), linear alkanes (n-dodecane), squalane, eicosane, hydrogenated or non-hydrogenated polybutylenes or polyisobutylenes, and hydrogenated or non-hydrogenated polydecenes. Polar oils are preferably hydrocarbon-based. They can be chosen from branched or unsaturated fatty alcohols such as oleyl alcohol and octyldodecanol. They are preferably chosen from triglycerides of vegetable or synthetic origin and esters of fatty acids other than triglycerides. Among the vegetable oils, we can notably mention sweet almond oil, argan oil, avocado oil, peanut oil, camellia oil, safflower oil, calophyllum oil, rapeseed oil, coconut oil, coriander oil, pumpkin seed oil, wheat germ oil, jojoba oil or liquid jojoba wax, linseed oil, macadamia oil, corn germ oil, hazelnut oil, walnut oil, vernonia oil, apricot kernel oil, olive oil, evening primrose oil, palm oil, passionflower oil, grapeseed oil, castor oil, rosehip oil, rye oil, and other oils. sesame, rice bran oil, soybean oil and sunflower oil. These vegetable oils may optionally be hydrogenated. Preferably the oil or oils is or are chosen from among oils of vegetable origin. The compositions according to the invention may contain one or more waxes. For the purposes of this invention, wax is defined as a lipophilic compound that is solid at room temperature and atmospheric pressure, has a reversible solid / liquid phase change, and a melting point above 30°C and preferably below 120°C. The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example, the one offered by METTLER under the reference DSC 30. Waxes can be hydrocarbon, silicone, or fluorinated, and can be of natural mineral, animal, vegetable, or synthetic origin. They can be polar or non-polar. Examples of non-polar waxes include microcrystalline waxes, paraffin waxes, ozokerite, and polyethylene waxes. Polar waxes are preferably hydrocarbon-based and even more preferably chosen from ester waxes comprising at least one ester function and alcohol waxes comprising at least one alcohol function. Ester waxes are preferably chosen from esters of fatty acid(s) and / or fatty alcohols in solid form at room temperature and atmospheric pressure. These ester waxes may be derived from hydrogenated animal or vegetable oils. Alcohol waxes are preferably chosen from fatty alcohols in solid form at room temperature and atmospheric pressure such as cetyl alcohol or cetostearyl (or cetostearyl) alcohol. Natural waxes are ester-based waxes (mono, di or triesters) and are preferably chosen from beeswax, camauba wax, candelilla wax, rice bran wax, ouricury wax, esparto grass wax, cork fiber wax, sugar cane wax, Japanese wax, sumac wax, montan wax, orange wax, laurel wax, apple wax, shea butter, mango butter. Preferably the wax(s) is / are chosen from waxes of vegetable origin. In compositions according to the invention the fat content, if present, can vary from 1 to 98% by weight, better from 10 to 95% by weight, even better from 20 to 95% by weight relative to the total weight of the composition. The compositions of the invention may also include one or more additional polymers different from the copolymers of the invention. These polymers may be cationic, nonionic, anionic, or amphoteric. They may be used as conditioning agents for skin or hair in the cosmetic field, particularly when they are cationic or amphoteric. They may also be They are used as hair styling agents. They can also be used as thickeners or viscosity regulators. These added polymers can be of natural or synthetic origin. Examples include guar gum and derivatives, cellulose and derivatives, xanthan gum, and scleroglucans. In the compositions of the invention, these additional polymers may represent from 0.01% to 20% by weight, or better yet from 0.1% to 10% by weight relative to the total weight of the composition. The compositions of the invention may also include one or more coloring agents. The coloring agents may be pigments insoluble in the composition (solubility less than 0.1% at room temperature (20 to 25°C) and atmospheric pressure (1.013 x 10⁵ Pa)), or dyes or dye precursors soluble in the composition under the same temperature and pressure conditions. The pigments may be of natural mineral or organic origin. Examples of natural mineral pigments include iron oxides and mica-titans. Examples of natural organic pigments include cochineal carmine and pigments of plant origin such as indigo. The pigments may also be of synthetic origin, such as many metallic lakes derived in particular from azo dyes. Soluble dyes can be of natural or synthetic origin. They are like the pigments of the colored species themselves. They are sometimes described as direct dyes. These dyes can be electrically neutral or charged, like anionic or cationic dyes. Many chemical families are involved. Examples of naturally occurring soluble dyes include anthocyanins, carotenoids, and chlorophylls. Examples of synthetically produced soluble dyes include azo, quinone, xanthene, indoamine, and nitrate dyes. The precursors of soluble dyes are generally colorless species that, under the action of specific compounds, usually oxidants, undergo transformation to form colored species. These oxidants can be atmospheric oxygen (in which case they are called auto-oxidizable compounds) or chemical oxidants such as hydrogen peroxide. In the latter case, they are referred to as oxidation dye precursors, such as oxidative bases like paraphenylenediamines, paraaminophenols, and diaminopyrazoles, whose colors can be modified by the addition of compounds called oxidation couplers, including metaaminophenols, metadiphenols, metaphenylenediamines, and naphthalene or heterocyclic couplers. The coloring agents may be present in the compositions of the invention at concentrations ranging from 0.001% to 40% by weight, preferably from 0.01% to 20% by weight, and even better from 0.1% to 10% by weight relative to the total weight of the composition.

[0019] The compositions according to the invention may further comprise one or more conventional additives well known in the art, different from the compounds defined above. Examples of usable additives include UVA and / or UVB filters, softening agents, solvents, humectants, mattifying or pearlescent agents such as titanium dioxide, vitamins, provitamins, amino acids, perfumes, peptiders, preservatives, including antibacterial and antifungal agents, antioxidants, alkalizing or acidifying agents (especially to regulate the pH of aqueous compositions or to salt the ingredients), and chelating agents. Cosmetic compositions may also contain anti-wrinkle agents, agents for sensitive skin, anti-acne agents, anti-dandruff agents, anti-hair loss agents, anti-seborrheic agents, and moisturizing agents. The compositions of the invention may also include one or more plant extracts. Plant-based extracts can come from all types of plants belonging to the plant kingdom. They can thus come from cryptogams, but more preferentially from phanerogams. In particular, they can come from trees, shrubs, green plants, flowering plants, cacti, and grasses. They can come from all parts of the plant and in particular from the roots, stems or trunks, leaves, flowers and fruits. These extracts may be soluble or insoluble in water at room temperature (20 to 25°C) and atmospheric pressure (1.013 x 105 Pa). They can be used, in particular, as assets for one of the properties mentioned above. Preferably the compositions of the invention include one or more additional ingredients chosen from surfactants and / or fats and / or coloring agents. The following examples illustrate the invention without being limiting in nature.

[0020] [Examples]

[0021] Example 1 Synthesis of a copolymer 1.

[0022] Table 1 lists the monomers used

[0023] [Tables 1] Monomer M (g / mol) CAS Density (g.mL-1) V (ml) m(g) Lauryl methacrylate (LMA) 254.41 142-90-5 0.871 9.10(2.76 + 6.34) 7.92 (2.40 + 5.52) Itaconic acid (IA) 130.1 97-65-4 9.6 Dibutyl itaconate (DBI) 242.31 2155-60-4 0.980 2.45 2.4 2-Octyl methacrylate (20MA) 198.3 63616-15-9 0.879 4.64 4.08

[0024] The synthesis process is as follows. In a two-necked flask fitted with a condenser, add 2.40 g (2.76 mL) of Lauryl methacrylate + 9.6 g of itaconic acid + 20 g of water + 0.4508 g of SDS + 1.4262 g of sodium persulfate. Stir thoroughly with a magnetic stir bar (large and flat) and heat to 64°C. The following products are placed in the same syringe and injected: 2.4 g (2.45 mL) of dibutyl itaconate + 5.52 g (6.34 mL) of Lauryl methacrylate for 3 h (flow rate = 2.943 mL / h), while stirring at 64°C. Increase the temperature to 80°C, then let it stir for 1 hour. Add, using a syringe pump, 4.08 g (4.64 mL) of 2-octyl methacrylate for 2 hours, while stirring at 80°C (flow rate = 2.32 mL / h). Allow to polymerize under stirring at 80°C. Stop heating and stirring, transfer into a tared bottle and homogenize using a Turax stirrer. Measure the pH using a pH probe after cooling. Basify by adding a saturated NaHCO3 solution drop by drop, while stirring, until a pH of 4 is obtained. The final product can be used as is after pH adjustment in the form of an aqueous dispersion of approximately 30% copolymer 1. It may also possibly undergo a purification stage. The monomers of copolymer 1 are preferably bio-based. This copolymer, spread evenly on a glass plate, results in a regular film after drying. This film is water and abrasion resistant.

[0025] Example 2 of a cosmetic composition We prepare the aqueous formula whose composition is indicated in table 2. This composition A can be used as eyeliner.

[0026] [Tables2] Ingredient Supplier Quantity per 100g Aqueous dispersion of copolymer 1 described in Example 1 20.0 g Makilene GC Butylene glycol DAITO KASEI 1.00 g Xanthan gum AROMA-ZONE 1.00 g Makicolor WD Blue PE CI74160, Water, Glycerin, Sodium Laureth Sulfate, Phenoxyethanol, Caprylyl glycol, Caprylic / Capric triglyceride DAITO KASEI 20.00 g Preservative 0.30 g Deionized water q.s. 100 g

[0027] This composition is stable over time. It applies easily to the eyelids without leaving a greasy or sticky residue. The resistance of the effects obtained to water or rubbing is very good.

[0028] Example 3 Comparisons The copolymer in aqueous dispersion form of Example 1 is compared to the raw material marketed under the name DAITOSOL 5000AD by the company DAITO KASEI. This raw material is an aqueous dispersion of approximately 50% of a film-forming copolymer resulting from the copolymerization of acrylic acid, methyl methacrylate, and ethyl acrylate. First, it is observed that the film obtained directly from the deposition at room temperature of the copolymer dispersion of the invention onto a plastic sheet is significantly less sticky than that obtained under identical conditions from the deposition of DAITOSOL 5000AD, whether for the ingredients as such or brought back at equal copolymer concentrations (water dilution of DAITOSOL 5000AD to obtain a final dispersion of 30% copolymer). DAITOSOL 5000AD is then introduced to replace the dispersion of copolymer 1 with an equal quantity of copolymer (i.e. 12% of DAITOSOL 5000AD) in the composition of example 2. We obtain a composition B. Compositions A and B are then applied to the skin under identical conditions. After drying, the films obtained on the skin are subjected either to a dry rubbing treatment under identical conditions or to a water treatment under identical conditions, with evaluation of the film's resistance by mechanical action. It is then observed that the resistance to dry rubbing is excellent. It is slightly better for composition A (rating 5 / 5) than for composition B (rating 4.5 / 5). We also note, and above all, that the resistance to the action of water is much better in the case of the composition of invention A than for that of the composition outside the invention B (rating 4 / 5 for composition A against 1 / 5 for composition B).

Claims

Demands

1. Copolymer obtained from at least one monomer of formula (I), at least one ester monomer of formula (II) and at least one ester monomer of formula (III). CO2 M O i ::::::::::: f' U ——— KI one__, U R2 — CO2 M' Formula (I) CO2 R / "' Ld Ta. J* U / T* U / R'2— CO2 R' Formula (II) Formula (III) formulas in which: R, R', R1, R'1, R"1 and R"2 independently denote a hydrogen atom or a linear or branched C1-C4 alkyl group. R2 denotes a linear or branched C1-C4 alkylene group. R'2 denotes a methylene group. R3 denotes a linear, branched or cyclic C4-C20 alkyl group, a tetrahydrofurfuryl group. M and M' independently denote a hydrogen atom or a residue of an alkali agent and at least one of the radicals R and R' being other than hydrogen, knowing that the monomer(s) of formula (I) represent at least 5% by weight of all the monomers used to obtain the said copolymer.

2. Copolymer according to claim 1 wherein R3 denotes a linear, branched or cyclic C8-C20 alkyl group.

3. Copolymer according to claims 1 or 2 wherein RI, R'1 and R"2 denote a hydrogen atom, and / or R"1 denotes a hydrogen atom or a methyl group, and / or R2 denotes a methylene or ethylene group, preferably methylene, and / or M and M' independently denote a hydrogen atom or an ionized metallic residue.

4. Copolymer according to any one of the preceding claims wherein at least one of the radicals R or R' designates an n-butyl group or an isobutyl group.

5. Copolymer according to any one of the preceding claims wherein the monomer of formula (I) is itaconic acid or one of its salts, preferably itaconic acid or one of its alkali metal salts.

6. Copolymer according to any one of the preceding claims wherein the monomer of formula (II) is an ester of itaconic acid, preferably an itaconic acid diester, more preferably dibutylitaconate.

7. Copolymer according to any one of the preceding claims wherein R"1 designates a methyl group, preferably the monomer of formula (III) being lauryl methacrylate or 2-octyl methacrylate.

8. Copolymer according to any one of the preceding claims obtained from at least two monomers of formula (III).

9. Copolymer according to any one of the preceding claims in which the monomer(s) of formula (I) represent 10 at 60%, or better, 20 to 50% by weight of all monomers of formulas (I), (II) and (III) used for the preparation of said copolymer.

10. Copolymer according to any one of the preceding claims wherein the monomer(s) of formulas (I), (II) and (III) are the only monomers.

11. Copolymer according to any one of the preceding claims characterized because it is a block copolymer.

12. A process for obtaining a copolymer according to any one of the preceding claims by means of a process incorporating at least the following steps: (a) preparing a mixture comprising at least some of the monomers with at least one polymerization initiator; (b) heating and then optionally (b') adding the remaining monomers and / or the remaining monomers by weight already introduced into the mixture, in one or more steps (b'i) with (b"i) continued heating after each further addition of monomers; (c) cooling and recovering the copolymer.

13. A process for obtaining according to claim 12 wherein the polymerization initiator is a thermal initiator and preferably a persulfate.

14. A process for obtaining according to claims 12 or 13 wherein the mixture in step (a) comprises more than 20% by weight of water and at least one surfactant.

15. Use of a copolymer as defined in any one of claims 1 to 11 or obtained according to any one of claims 12 to 14 in the fields of food industry, agriculture, horticulture, paint, textiles, paper, electricity, building, photography, pollution control, humidity control, decoration, cosmetics and personal hygiene.

16. Use according to claim 15 in the field of cosmetics and preferably for skin makeup and in particular for face and eyelid makeup, for eyelash and eyebrow makeup, for lip makeup and for nail makeup or for skin care, sunscreens, self-tanning products, hair cleansing, coloring or bleaching, curling or straightening, their conditioning, and for scalps anti-irritation, anti-dandruff, anti-grease, anti-hair loss products.

17. Composition comprising one or more copolymers as defined according to any one of claims 1 to 11 or obtained according to any one of claims 12 to 14 in a concentration from 0.01% to 80% by weight, better from 0.05% to 50% by weight, even better from 0.1% to 25% by weight and particularly from 0.15% to 15% by weight relative to the total weight of the composition.

18. Composition according to claim 17, preferably cosmetic, comprising one or more additional ingredients selected from surfactants and / or fats and / or coloring agents.

Images