Use of a copolymer with acetoacetate functions or a composition comprising it to protect keratin fibers from humidity

Abstract

The present invention relates to the use of a copolymer with acetoacetate functions or a composition comprising it to protect keratin fibers from humidity.

Description

Title of the invention: Use of a copolymer with acetoacetate functions or of a composition comprising it to protect keratin fibers from humidity Technical field of the invention

[0001] The present invention relates to the use of a copolymer with acetoacetate functions or a composition comprising it to protect keratin fibers from humidity. Background to the invention

[0002] Due to their nature, certain types of hair are more sensitive to humidity and can therefore tend to form frizz, which can cause an increase in the volume of the hair. These types of hair are particularly difficult to style in humid environments.

[0003] In order to remedy this, it is usual to use hair compositions based on silicone raw materials which can however give a greasy and heavy appearance to the touch or based on oils whose conditioning effect can tend to fade quickly over time, being in particular not very resistant to external aggressions, in particular to shampoos.

[0004] Thus, there is a real need to find a way of remedying these drawbacks, in particular to facilitate the styling of hair in a humid environment by lastingly limiting the formation of frizz and / or the increase in volume of the hair in a humid environment, the observed effect being particularly persistent after at least one shampoo.

[0005] The applicant has surprisingly discovered that all or part of these objectives can be achieved by the use of a particular acetoacetate functional copolymer or a composition comprising it to protect keratin fibers from humidity. Summary of the invention

[0006] According to a first aspect, the subject of the present invention is the use of one or more CP copolymers or of a composition (C) comprising the CP copolymer(s) to protect keratin fibers from humidity, preferably to limit the formation of frizz and / or the increase in volume of the hair in a humid environment, the CP copolymer(s) being obtained by the polymerization of: - 0% to 99% by weight relative to the total weight of the monomers, of at least one monomer A chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl acrylate, isobutyl methacrylate, and mixtures thereof; - 1% to 20% by weight, relative to the total weight of the monomers, of at least one monomer B of formula (I): in which: • Ra represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group, preferably Ra represents a methyl group, • Rb and Rc, identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group, preferably Rb and Rc represent a hydrogen atom, • Rd represents a (CrC4)alkyl group, linear or branched, preferably Rd represents a methyl group, and • L represents a linear or branched (Ci-C6)alkylene or cycloalkylene group, in particular L represents a (CrC4)alkylene group, preferably L represents ethylene; and - 0% to 99% by weight relative to the total weight of the monomers, of at least one monomer C chosen from Cr-C4 alkyl acrylates, Cr-C4 alkyl methacrylates, silicone macromonomers, and mixtures thereof; it being understood that the copolymer(s) CP are obtained by polymerization of at least one monomer B with at least one monomer A and / or at least one monomer C.

[0007] According to a second aspect, the present invention relates to a CP copolymer obtained by copolymerization: - isobutyl methacrylate, isobutyl acrylate and acetoacetoxyethyl methacrylate, in a mass ratio of isobutyl methacrylate / isobutyl acrylate / acetoacetoxyethyl methacrylate of 70 / 20 / 10; or - isobornyl acrylate and acetoacetoxyethyl methacrylate, in a mass ratio of isobornyl acrylate / acetoacetoxyethyl methacrylate of 95 / 5. Detailed description of the invention

[0008] For the purposes of the present invention, and unless otherwise indicated:

[0009] 'by "keratin fibers" is meant fibers of human or animal origin such as hair, body hair, eyelashes, eyebrows, wool, angora, cashmere or fur. According to the present invention, the keratin fibers are preferably human keratin fibers, more preferably hair.

[0010] The expressions “between ... and ...”, “includes from ... to ...”, “formed from ... to ...”, and “ranging from ... to ...” must be understood inclusively, unless otherwise specified.

[0011] The expressions "at least one" and "one or more" are synonymous and can be used interchangeably. Use

[0012] According to a first aspect, the subject of the present invention is the use of the CP copolymer(s) as defined above or of a composition (C) comprising the CP copolymer(s) as defined above to protect keratin fibers from humidity, preferably to limit the formation of frizz and / or the increase in volume of the hair in a humid environment.

[0013] The applicant has found, surprisingly, that the CP copolymer(s) or the composition (C) comprising it(them) makes it possible to facilitate the styling of keratin fibres in a humid environment and in particular to limit the formation of frizz and / or the increase in volume of the hair in a humid environment, the observed effect being persistent after at least one shampoo. CP copolymers

[0014] The CP copolymer(s) may be random, alternating (block) or gradient copolymers.

[0015] Preferably, the CP copolymer(s) are random copolymers.

[0016] For the purposes of the present invention, "random copolymer" means a copolymer formed from macromolecules in which the sequential distribution of the monomer units B, A if present, and C if present, obeys known statistical laws. In other words, in a random copolymer, the different monomers follow one another in any order. Random copolymers are also called random copolymers. For example, the sequence of a random copolymer, formed from monomers A and B, may be the following: AABABBBBAABA.

[0017] The CP copolymer(s) are preferably devoid of a monomeric unit other than a monomer B, A and C. Monomer A

[0018] The copolymer(s) CP may be obtained by the polymerization of at least one monomer A chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl acrylate, isobutyl methacrylate, and mixtures thereof.

[0019] According to a first variant of the invention, the copolymer(s) CP are devoid of monomer(s) A. In other words, the copolymer(s) CP are then made up of monomers B and monomers C as defined above.

[0020] According to a second variant of the invention, the CP copolymer(s) comprise: 50% to 99% by weight, and preferably from 55% to 95% by weight, of at least one monomer A chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl acrylate, isobutyl methacrylate, and mixtures thereof, relative to the total weight of the monomers.

[0021] 2-Ethylhexyl acrylate, also called 2-ethylhexyl prop-2-enoate, is a compound with the empirical formula CnH2o02, and the semi-developed formula: O

[0022] As 2-ethylhexyl acrylate, mention may in particular be made of that marketed under the name 2-Ethylhexyl acrylate by the company Sigma-Aldrich.

[0023] 2-Ethylhexyl methacrylate, also called 2-ethylhexyl 2-methylprop-2-enoate, is a compound with the empirical formula Ci2H22O2, and the structural formula: O * YOY CH S

[0024] As 2-ethylhexyl methacrylate, mention may in particular be made of that marketed under the name 2-Ethylhexyl methacrylate by the company Sigma-Aldrich.

[0025] Isocarboxylic acid acrylate is a compound with the empirical formula Ci3H20O2, and the semi-developed formula:

[0026] As isobomyl acrylate, mention may in particular be made of that marketed under the name Isobomyl acrylate by the company Sigma-Aldrich.

[0027] Isocarboxylic acid methacrylate is a compound with the empirical formula C14H22O2, and the structural formula:

[0028] As isobornyl methacrylate, mention may in particular be made of that marketed under the name Isobornyl methacrylate by the company Sigma-Aldrich.

[0029] Preferably, monomer A is at least 2-ethylhexyl acrylate and / or isobornyl acrylate.

[0030] According to a third variant of the invention, the copolymer(s) CP comprise at least one monomer A chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isocarboxylic acid acrylate, isocarboxylic acid methacrylate, and mixtures thereof, in an amount of less than 50% relative to the total weight of the monomers, preferably between 0.01 and 49.9% relative to the total weight of the monomers. Monomer B

[0031] The CP copolymer(s) are obtained by the polymerization of 1% to 20% by weight, and preferably of 5% to 15% by weight, relative to the total weight of the monomers, of at least one monomer B of formula (I): in which: • Ra represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group, preferably Ra represents a methyl group, • Rb and Rc, identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group, preferably Rb and Rc represent a hydrogen atom, • Rd represents a (CrC4)alkyl group, linear or branched, preferably Rd represents a methyl group, and • L represents a linear or branched (Ci-C6)alkylene group, or cycloalkylene, preferably L represents a (Ci-C4)alkylene group, more preferably L represents ethylene.

[0032] Preferably, the monomer(s) B are chosen from acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof and more preferably, the monomer B is acetoacetoxyethyl methacrylate.

[0033] Acetoacetoxyethyl acrylate is a compound of empirical formula C9H12O5, and of semi-developed formula:

[0034] As acetoacetoxyethyl acrylate, mention may in particular be made of that marketed under the name Butanoic acid, 3-oxo-,2-[(l-oxo-2-propen-l-yl)oxy]ethyl ester by the company Alfa Chemistry.

[0035] Acetoacetoxyethyl methacrylate is a compound of empirical formula C10H14O5, and of semi-developed formula:

[0036] Acetoacetoxyethyl methacrylate may include, in particular, that marketed under the name Eastman™ AAEM by the Eastman Company. Monomer C

[0037] The CP copolymer(s) may be obtained by the polymerization of 0% to 99% by weight of at least one monomer C chosen from C1-C4 alkyl acrylates, C1-C4 alkyl methacrylates, silicone macromonomers, and mixtures thereof, relative to the total weight of the monomers.

[0038] Thus, according to a variant of the invention, the copolymer(s) CP are devoid of monomer(s) C. In other words, the copolymer(s) CP are then made up of monomer(s) B and monomer(s) A as defined above.

[0039] Preferably, the monomer(s) C are chosen from C rC4 alkyl acrylates and / or C rC4 alkyl methacrylates.

[0040] Among the C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates suitable for the invention, mention may be made in particular of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate and mixtures thereof.

[0041] More preferably, the monomer(s) C are chosen from isobutyl acrylate, tert-butyl acrylate, isobutyl methacrylate, and mixtures thereof.

[0042] Isobutyl acrylate is a compound with the empirical formula C7Hi2O2 and the semi-developed formula:

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050] Isobutyl acrylate can be cited in particular as that marketed under the name isobutyl acrylate by the company Sigma Aldrich. Tert-butyl acrylate is a compound with the molecular formula C7Hi2O2 and the semi-developed formula: Tert-butyl acrylate includes, in particular, that marketed under the name tert-butyl acrylate by the Sigma Aldrich Company. Isobutyl methacrylate is a compound with the empirical formula C8Hi4O2 and the semi-developed formula: Isobutyl methacrylate includes, in particular, that marketed under the name isobutyl methacrylate by the Sigma Aldrich Company. According to another preferred embodiment, at least one monomer C is a silicone macromonomer. A "silicone macromonomer" means a silicone macromolecule with a terminal group that allows it to act as a monomer. Silicone macromonomers will contribute a single monomer unit to a completed macromolecule chain. Concerning silicone macromonomers, these may in particular be polydimethylsiloxanes with a monoacryloyloxy or monomethacryloyloxy terminal group, and in particular those of formula (II): in which: - R8 denotes a hydrogen atom or a methyl group, preferably methyl; - R9 denotes a divalent, linear or branched, preferably linear, hydrocarbon group having from 1 to 10 carbon atoms and optionally containing one or two ether bonds -O-; preferably ethylene, propylene or butylene; - Rio denotes a linear or branched alkyl group, having from 1 to 10 carbon atoms, in particular from 2 to 8 carbon atoms; preferably methyl, ethyl, propyl, butyl or pentyl; - n denotes an integer ranging from 1 to 300, preferably ranging from 3 to 200.

[0051] These may in particular be polydimethylsiloxane methacrylates and in particular those marketed under the name MCR-M17 by Gelest Inc. or x-22-2475 and x-22-2426 by Shin Etsu.

[0052] The silicone macromonomers which are particularly suitable for the invention have a weight-average molecular mass (Mw) ranging from 200 g.mol1 to 100,000 g.mol *, and more preferably from 400 g.mol1 to 20,000 g.mol '.

[0053] In particular, at least one monomer (C) is a silicone macromonomer, more particularly chosen from silicone macromonomers having a glass transition temperature Tg less than or equal to 25°C, more particularly between -100°C and 25°C, and preferably between -90°C and 0°C.

[0054] According to a preferred embodiment, at least one monomer (C) is a polydimethylsiloxane with a mono(meth)acryloyloxy terminal group. Preparation of CP copolymer

[0055] The copolymer CP according to the invention can be prepared by radical polymerization of at least one monomer B with at least one monomer A if present and / or at least one monomer C if present and as described previously. The mixture of monomers to be polymerized, generally in an organic medium having a boiling point greater than or equal to 60°C, can be constituted at the very beginning of the polymerization reaction or be constituted as the polymerization progresses by progressively or sequentially adding certain monomers. The polymerization of these monomers is carried out in the presence of an initiator.

[0056] As organic medium suitable for the preparation of the copolymer, mention may in particular be made of solvents such as isododecane, ethanol, ethyl acetate, tetrahydrofuran, methyltetrahydrofuran, or methyl ethyl ketone and their mixtures.

[0057] According to one method of preparation, the synthesis medium is a mixture of several solvents, in particular two solvents with different boiling points. When the synthesis medium contains several solvents with different boiling points, in particular two solvents, it is possible, at the end of the synthesis of the CP copolymer, to eliminate the solvent(s) with the lowest boiling points, possibly after adding a medium higher boiling point identical to or different from the highest boiling point solvent constituting the synthesis medium.

[0058] According to this embodiment, the synthesis medium is chosen such that the monomers B and A and / or C of the copolymer and the initiator are soluble therein.

[0059] Preferably, the monomers are present in the synthesis solvent, before polymerization, in a content ranging from 5% to 45% by weight, relative to the total weight of the synthesis medium.

[0060] The monomers to be polymerized can be introduced into the synthesis medium before the start of the polymerization reaction either gradually or sequentially, as the polymerization progresses.

[0061] This polymerization is carried out in the presence of an initiator, in particular of the peroxide or azo type.

[0062] In particular, the initiator may be chosen from tert-Butyl peroxy-2-ethylhexanoate, such as Trigonox 21S marketed by AkzoNobel, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, such as Trigonox 141 marketed by AkzoNobel, tert-butyl peroxypivalate, such as Trigonox 25C75 marketed by AkzoNobel, Tazobisisobutyronitrile (AIBN), 2,2'-azo-bis(2-amidinopropane) dihydrochloride (V50). Preferably, the initiator is tert-Butyl peroxy-2-ethylhexanoate, such as Trigonox 21S marketed by AkzoNobel.

[0063] Preferably, the polymerization is carried out at a temperature ranging from 70°C to 110°C.

[0064] According to a particular form of the invention, the synthesis of the copolymer CP is carried out in a mixture of two solvents with different boiling points, in particular in a mixture of isododecane and ethyl acetate. At the end of the reaction, the solvent with the lower boiling point, in particular ethyl acetate, is removed, in particular by distillation. In this case, at the end of the synthesis, a composition is obtained comprising the copolymer CP in the solvent with the higher boiling point, in particular in isododecane.

[0065] According to a preferred embodiment, the CP copolymer(s) used have weight masses ranging from 5000 g.mol1 to 1000000 g.mol ', more preferably ranging from 10000 g.mol1 to 500000 g.mol ' and even more preferably ranging from 15000 g.mol1 to 350000 g.mol '.

[0066] Preferably, the CP copolymer(s) are obtained by copolymerization of: - 2-ethylhexyl acrylate, isobornyl acrylate and acetoacetoxyethyl methacrylate, preferably in a 2-ethylhexyl acrylate / isobornyl acrylate / acetoacetoxyethyl methacrylate mass ratio of 30 / 60 / 10; or - isobutyl acrylate, tert-butyl acrylate and acetoacetoxyethyl methacrylate, preferably in a mass ratio of isobutyl acrylate / tert-butyl acrylate / acetoacetoxyethyl methacrylate of 25 / 65 / 10; or - isobutyl methacrylate, isobutyl acrylate and acetoacetoxyethyl methacrylate, preferably in a mass ratio of isobutyl methacrylate / isobutyl acrylate / acetoacetoxyethyl methacrylate of 70 / 20 / 10; or - isobornyl acrylate and acetoacetoxyethyl methacrylate, preferably in a mass ratio of isobornyl acrylate / acetoacetoxyethyl methacrylate of 95 / 5. Composition (C)

[0067] According to one embodiment, the CP copolymer(s) are included in a composition (C).

[0068] Composition (C) preferably comprises a total content of CP copolymers ranging from 0.005% to 10% by weight, more preferably ranging from 0.05% to 9% by weight, even more preferably ranging from 0.07% to 6% by weight, relative to the total weight of composition (C).

[0069] Composition (C) is a cosmetic composition, i.e. which comprises a cosmetically acceptable medium, i.e. a medium compatible with human keratin fibers.

[0070] Composition (C) preferably comprises one or more oils, more preferably chosen from hydrocarbon oils.

[0071] By "oil" is meant a non-aqueous compound, immiscible with water, liquid at room temperature (20°C) and atmospheric pressure (760 mm Hg).

[0072] By "hydrocarbon oil" is meant an oil formed essentially, or even consisting of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.

[0073] The hydrocarbon oils can be chosen from: - C8-Ci4 hydrocarbon oils, and in particular: branched C8-C14 alkanes such as C8-C14 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and for example oils sold under the trade names Isopars or Permetyls, linear alkanes, for example such as n-dodecane (Ci2) and n-tetradecane (CM ) sold by Sasol respectively under the references Parafol 12-97 and Parafol 14-97, as well as their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (Cn) and n-tridecane (Cn) obtained in examples 1 and 2 of application WO2008 / 155059 from Cognis, and their mixtures, and short-chain esters (having 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate and n-butyl acetate; - hydrocarbon oils of vegetable origin, such as triglycerides consisting of esters of fatty acids and glycerol, the fatty acids of which may have chain lengths varying from C4 to C24, the latter being able to be linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or even wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passionflower, musk rose oils; shea butter;or even the triglycerides of caprylic / capric acids such as those sold by the company Stéa-rineries Dubois; - synthetic ethers having 10 to 40 carbon atoms; - linear or branched hydrocarbons, of mineral or synthetic origin, in particular petroleum jelly, polydecenes, hydrogenated polyisobutene, in particular Parleam®, squalane, paraffin oils, and their mixtures; - synthetic esters such as oils of formula RiCOOR2 in which Ri represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched chain, containing from 1 to 40 carbon atoms, provided that the sum of the numbers of carbon atoms in Ri and R2 is greater than or equal to 10, such as, for example, Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C[2 to C15] alcohol benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, palmitate 2-octyl-decyl, 2-octyl-dodecyl myristate, heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate;hydroxylated esters such as isostearyl lactate, diisostearyl malate, 2-octyl-dodecyl lactate; polyol esters and pentaerythritol esters; - fatty alcohols which are liquid at room temperature with a branched and / or unsaturated carbon chain having from 12 to 26 carbon atoms such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol; - and their mixtures.

[0074] Preferably, the hydrocarbon oils are apolar, i.e. formed solely of carbon and hydrogen atoms.

[0075] According to a preferred embodiment, the oil(s) are chosen from the oils C8-Ci4 hydrocarbons.

[0076] According to a more preferred embodiment, the oil(s) are chosen from isododecane, cetiol UT, vegelight Silk, dodecane, and mixtures thereof.

[0077] According to an even more preferred embodiment, the oil is isododecane.

[0078] Preferably, the oil(s) are present in composition (C) in a total content by weight ranging from 1% to 98% by weight, preferably ranging from 20% to 97%, more preferably from 50% to 96%, even more preferably from 70% to 95% by weight, relative to the total weight of composition (C).

[0079] Composition (C) may further comprise one or more additional oils other than the hydrocarbon oils described above.

[0080] It may be one or more silicone oils, one or more fluorinated or non-fluorinated oils, and mixtures thereof. In particular, it may be an oil chosen from: - partially hydrocarbon and / or silicone fluorinated oils; - silicone oils such as non-volatile, linear or cyclic polymethylsiloxanes (PDMS), liquid or pasty at room temperature such as cyclomethicones, dimethicones, possibly containing a phenyl group, such as phenyl trimethicones, phenyltrimethylsiloxydiphenyl siloxanes, di-phenylmethyldimethyl-trisiloxanes, diphenyl dimethicones, phenyl dimethicones, polymethylphenyl siloxanes; - and their mixtures.

[0081] These additional oils may be present in a total content ranging from 0.01% to 60%, and better still from 0.1% to 50% by weight, relative to the total weight of the composition (C).

[0082] The term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group.

[0083] The term "fluorinated oil" means an oil comprising at least one fluorine atom.

[0084] Composition (C) preferably comprises one or more organic solvents Z chosen from monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols having from 2 to 18 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C3 and C4 ketones, C2-C4 aldehydes, and mixtures thereof, more preferably chosen from monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, even more preferably composition (C) comprises ethanol.

[0085] Preferably, the organic solvent(s) Z are present in the composition (C) in a total content by weight ranging from 0.1% to 90% by weight, preferably ranging from 1% to 50% by weight, more preferably from 5% to 25% by weight, relative to the total weight of the composition (C).

[0086] According to a preferred embodiment, composition (C) comprises: - one or more oils, preferably chosen from hydrocarbon oils, more preferably chosen from C8-C14 hydrocarbon oils, even more preferably isododecane; and - one or more organic solvents Z chosen from monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, preferably ethanol.

[0087] Preferably, composition (C) is an anhydrous composition.

[0088] The term "anhydrous composition" means a composition containing less than 2% by weight of water, or even less than 0.5% of water, and in particular free of water. Where appropriate, such small quantities of water may in particular be provided by ingredients of the composition which may contain residual quantities thereof.

[0089] Composition (C) may be in any of the galenic forms conventionally used for hair application. In a non-limiting manner, composition (C) may be in the form of a lotion, a cream, a mousse, a gel, a spray or a lacquer.

[0090] Preferably, composition (C) is used in a leave-in application.

[0091] Composition (C) may be in the form of a mask, a conditioning composition or a care composition. Composition (C) may also be in the form of a composition to be added or mixed before application to a mask or a conditioning composition.

[0092] Composition (C) may be packaged in a pump bottle or in an aerosol container, in order to ensure application of composition (C) in vaporized form (lacquer) or in foam form.

[0093] According to a preferred embodiment, the composition (C) comprises a total content of coloring agents of less than 0.1% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight relative to the total weight of the composition, even more preferably, the composition is free of coloring agents.

[0094] By "coloring agent" is meant an oxidation dye, a direct dye or a pigment.

[0095] By "oxidation dye" is meant an oxidation dye precursor chosen from oxidation bases and couplers. Oxidation bases and couplers are compounds with little or no color which, by a condensation reaction in the presence of an oxidizing agent, give a colored species.

[0096] By "direct dye" is meant a natural and / or synthetic dye, including in the form of extract(s), different from oxidation dyes. These are colored compounds which will diffuse superficially on the fiber. They can be ionic or non-ionic, i.e. anionic, cationic, neutral or non-ionic.

[0097] According to a preferred embodiment, composition (C) comprises a total content in silicones less than 0.1% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight relative to the total weight of the composition, even more preferably, composition (C) is free of silicones.

[0098] According to a preferred embodiment, the composition (C) comprises a total content of cationic polymers of less than 0.1% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight relative to the total weight of the composition, even more preferably, the composition (C) is free of cationic polymers.

[0099] By "cationic polymer" is meant any non-silicone polymer (not comprising a silicon atom) containing cationic groups and / or groups ionizable into cationic groups, and not containing anionic groups and / or groups ionizable into anionic groups. Special CP copolymers

[0100] According to a second aspect, the present invention relates to a CP copolymer obtained by copolymerization: - isobutyl methacrylate, isobutyl acrylate and acetoacetoxyethyl methacrylate, in a mass ratio of isobutyl methacrylate / isobutyl acrylate / acetoacetoxyethyl methacrylate of 70 / 20 / 10; or - isobornyl acrylate and acetoacetoxyethyl methacrylate, in a mass ratio of isobornyl acrylate / acetoacetoxyethyl methacrylate of 95 / 5. Examples

[0101] The following examples allow a better understanding of the invention without, however, being limiting in nature.

[0102] Example A: Process for the preparation of copolymer 1: Isobornyl acrylate / 2-ethylhexyl acrylate / Acetoacetoxyethyl methacrylate (60 / 30 / 10)

[0103] In a 1 L controlled reactor, 90 g of isobornyl acrylate, 45 g of 2-ethylhexyl acrylate, 30 g of acetoacetoxyethyl methacrylate, 100 g of an isododecane / ethyl acetate (70 / 30) solvent, and 100 g of isododecane alone are introduced.

[0104] The medium is degassed with argon then heated to 90°C with stirring (100 rpm).

[0105] Once the reaction medium reaches the temperature of 90°C, 338 g of a mixture composed of 200 g of isododecane, 90 g of isobornyl acrylate, 45 g of 2-ethylhexyl acrylate and 3 g of Trigonox 21 S initiator, are poured in one hour.

[0106] The reaction medium is maintained for 7 hours at 90°C. The next day, the reaction medium is stripped with 2 x 200 mL of cold isododecane to remove the residual monomers.

[0107] At the end of the reaction, a dry extract of polymer at 49.5% is obtained in isododecane.

[0108] This polymer is characterized by GPC. The results are detailed in the table below.

[0109] [Tableauxl] Mw (g / mol) Mn (g / mol) IP 138,800 12,400 11.2

[0110] Example B: Process for the preparation of copolymer 2: Isobutyl acrylate / Tert-butyl acrylate / Acetoacetoxyethyl methacrylate (25 / 65 / 10)

[0111] In a reactor controlled by IL, 62.5 g of isobutyl acrylate, 162.5 g of tert-butyl acrylate, 25 g of acetoacetoxyethyl methacrylate, 2.5 g of the radical initiator Trigonox T21S and 360 g of an isododecane / ethyl acetate mixture (50 / 50) are introduced. The medium is degassed with argon and then heated to 90 °C with stirring. The reaction medium is maintained for 7 hours at 90 °C. Stripping is then carried out with 300 ml of isododecane to remove the residual monomers.

[0112] At the end of the reaction, a dry polymer extract of 60.36% in isododecane is obtained.

[0113] Example C: Process for the preparation of copolymer 3: Isobutyl methacrylate / Isobutyl acrylate / Acetoacetoxyethyl methacrylate (70 / 20 / 10)

[0114] In a 6L controlled reactor, 200 g of acetoacetate methacrylate, 200 g of isobutyl acrylate, 700 g of isobutyl methacrylate and 1800 g of an isododecane / ethyl acetate mixture (50 / 50) are introduced.

[0115] The medium is degassed with argon then heated to 90°C with stirring.

[0116] Once the reaction medium reaches the temperature of 90°C, a mixture composed of 200 g of isobutyl acrylate, 700 g of isobutyl methacrylate, 1100 g of an isododecane / ethyl acetate mixture (50 / 50) and 20 g of Trigonox T21s initiator are cast in two hours.

[0117] The reaction medium is maintained for 7 hours at 90°C. The ethyl acetate is then distilled and then stripped with 2 x 1350 mL of isododecane to remove the residual monomers.

[0118] At the end of the reaction, a dry extract of polymer at 52.03% in isododecane is obtained.

[0119] Example D: Process for the preparation of copolymer 4: Isobornyl acrylate / Acetoacetoxyethyl methacrylate (95 / 5)

[0120] In a controlled IL reactor, 150 g of isobornyl acrylate, 15 g of acetoacetoxyethyl methacrylate, 100 g of an isododecane / ethyl acetate mixture (70 / 30) and 100 g of isododecane alone are introduced.

[0121] The medium is degassed with argon then heated to 90°C with stirring (100 rpm / minutes). Once the reaction medium reaches a temperature of 90°C, 338 g of a mixture composed of 200 g of isododecane, 135 g of isobornyl acrylate, and 3 g of Trigonox T21s initiator are poured in one hour.

[0122] The reaction medium is maintained for 7 hours at 90°C. The next day, the reaction medium is stripped with 2x200ml of cold isododecane to remove the residual monomers.

[0123] At the end of the reaction, a dry extract of polymer at 51.76% in isododecane is obtained.

[0124] Examples 1 to 8: Examples of application on wicks

[0125] The following compositions were prepared from the contents indicated in the tables below. The contents are expressed as a percentage by weight, relative to the total weight of the composition considered. Composition C1 to C7 according to the invention

[0126] [Tables2] Ingredients Cl C2 C3 C4 Copolymer 1 5 - - - Copolymer 2 - 5 - - Copolymer 3 - - 5 - Copolymer 4 - - - 5 Isododecane / ethanol mixture (85 / 15 by weight) Qsp 100 Qsp 100 Qsp 100 Qsp 100

[0127] [Tables3] Ingredients C5 C6 C7 Copolymer 1 0.5 - - Copolymer 2 - 0.5 - Copolymer 4 - - 0.5 Isododecane / ethanol mixture (85 / 15 by weight) Qsp 100 Qsp 100 Qsp 100 Reference composition RI

[0128] [Tables4] Ingredients RI Isododecane / ethanol mixture (85 / 15 by weight) Qsp 100 Application and evaluation protocol

[0129] 2.7 g of each of the compositions according to the invention C1 to C7 and of the composition of Reference RI were applied to strands of damp type IV hair placed flat on aluminum foil, the strands of hair having been previously shampooed. After application of the compositions, the strands were wrung out with fingers, dried on KIMTECH absorbent paper and then hung in the open air until completely dry.

[0130] The wicks were then placed suspended in an oven at 25°C and 80% humidity for 24 hours.

[0131] Monitoring of the evolution of frizz and volume was carried out using a device designed by the company Bossa Nova, called BOLERO LITE with a measurement at T0 before placing in the oven, a measurement after 24 hours of placing in the oven, a measurement after 24 hours of placing in the oven followed by shampooing applied according to the shampooing protocol described below and then again 24 hours of placing in the oven.

[0132] The BOLERO LITE is a 2D image capture and analysis system dedicated to quickly and efficiently discriminating on a strand of hair, the fibers corresponding to the frizz from those forming part of the body of the strand. By using uniform backlighting, it is possible to measure the variations in light transmission through the hair sample with a standard black and white image and therefore evaluate the hair density. For each pixel of the image, we measure the transmitted light.

[0133] If the transmission: ■ is less than a defined threshold, this corresponds to a high density area and we can define the pixel as part of the body / volume of the strand; ■ is greater than the defined threshold, it is a low density area and we can define the pixel as part of the fly-away / frizz; ■ is above the sensitivity threshold, the perceived signal is considered to be noise. It is therefore not taken into account.

[0134] In the context of our study, the defined threshold is set at 50% and the sensitivity threshold is set at 95%.

[0135] The BOLERO LITE image analysis software makes it possible to obtain the value of the body surface area and the frizz surface area (in cm2) of each of the strands tested. Shampoo protocol

[0136] Apply 0.5 ml of DOP shampoo to the wet hair strand and then rub the strand for 20 seconds with your fingers, starting from the roots and ending at the tips. Then let the strand rest for 1 minute and then rinse with water, making 20 finger strokes from the roots to the tips under water. Then wring out between your fingers and dry on KIMTECH absorbent paper by patting. Then hang the strand in the open air until completely dry. Evaluation results

[0137] The results of the frizz surface measurements (in cm2) are summarized in the table below:

[0138] [Tables5] Examples Composition tested Frizz surface at T0 (in cm2) Frizz surface at T0 + 24H 80% RH (in cm2) Frizz surface at T0 + 24H 80% RH + 1 shampoo + 24H 80% RH (in cm2) 1 (Invention) Cl 9.0 12.1 7.3 2 (Invention) C2 12.4 11.7 17.9 3 (Invention) C3 18.1 17.3 26.9 4 (Invention) C4 10.9 9.6 Not measured 5 (Invention) C5 13.1 39.1 29.0 6 (Invention) C6 15.0 20.8 40.9 7 (Invention) C7 12.4 20.9 Not measured 8 (Control) RI 52.9 67.7 49.6

[0139] The use of the compounds according to the invention makes it possible to limit the formation of frizz and the increase in hair volume in a humid environment. The anti-frizz effect is also maintained after shampooing.

Claims

Claims

1. Use of one or more CP copolymers or of a composition (C) comprising the CP copolymer(s) to protect keratin fibres from humidity, preferably to limit the formation of frizz and / or the increase in volume of the hair in a humid environment, the CP copolymer(s) being obtained by the polymerisation of: - 0% to 99% by weight relative to the total weight of the monomers, of at least one monomer A chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof; - 1% to 20% by weight, relative to the total weight of the monomers, of at least one monomer B of formula (I): in which: • Ra represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group, preferably Ra represents a methyl group, • Rb and Rc, identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group, preferably Rb and Rc represent a hydrogen atom, • Rd represents a linear or branched (Ci-C4)alkyl group, preferably Rd represents a methyl group, and • L represents a linear or branched (Ci-C6)alkylene group, or cycloalkylene, in particular L represents a (CrC4)alkylene group, preferably L represents ethylene; and - 0% to 99% by weight relative to the total weight of the monomers, of at least one monomer C chosen from Cr-C4 alkyl acrylates, Cr-C4 alkyl methacrylates, silicone macromonomers, and mixtures thereof; it being understood that the copolymer(s) CP are obtained by polymerization of at least one monomer B with at least one monomer A and / or at least one monomer C.

2. Use according to claim 1, wherein the CP copolymer(s) are random copolymers.

3. Use according to any one of the preceding claims, in which the copolymer(s) CP are free of monomer(s) A.

4. Use according to claim 1 or 2, wherein the CP copolymer(s) comprise as monomer A at least 2-ethylhexyl acrylate and / or isocarboxylic acid acrylate.

5. Use according to any one of claims 1, 2 or 4 in which the CP copolymer(s) are free of C monomer(s).

6. Use according to any one of claims 1 to 4, in which the copolymer(s) CP comprise as monomer C at least one monomer chosen from C1-C4 alkyl acrylates and / or C1-C4 alkyl methacrylates, preferably at least one monomer chosen from isobutyl acrylate, tert-butyl acrylate, isobutyl methacrylate, and mixtures thereof.

7. Use according to any one of the preceding claims, in which the copolymer(s) CP comprise as monomer B at least one monomer chosen from acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof, preferably acetoacetoxyethyl methacrylate.

8. Use according to any one of the preceding claims, in which the CP copolymer(s) are devoid of a monomeric unit other than a monomer B, A and C.

9. Use according to any one of the preceding claims, in which the CP copolymer(s) are obtained by copolymerization of: - 2-ethylhexyl acrylate, isobornyl acrylate and acetoacetoxyethyl methacrylate, preferably in a 2-ethylhexyl acrylate / isobornyl acrylate / acetoacetoxyethyl methacrylate mass ratio of 30 / 60 / 10; or - isobutyl acrylate, tert-butyl acrylate and acetoacetoxyethyl methacrylate, preferably in a isobutyl acrylate / tert-butyl acrylate / acetoacetoxyethyl methacrylate mass ratio of 25 / 65 / 10; or - isobutyl methacrylate, isobutyl acrylate and acetoacetoxyethyl methacrylate, preferably in a mass ratio of isobutyl methacrylate / isobutyl acrylate / acetoacetoxyethyl methacrylate of 70 / 20 / 10; or - isobornyl acrylate and acetoacetoxyethyl methacrylate, preferably in a mass ratio of isobornyl acrylate / acetoacetoxyethyl methacrylate of 95 / 5.

10. Use according to any one of the preceding claims in which the composition (C) comprises a total content of CP copolymers ranging from 0.005% to 10% by weight, preferably ranging from 0.05% to 9% by weight, more preferably ranging from 0.07% to 6% by weight, relative to the total weight of the composition (C).

11. Use according to any one of the preceding claims, in which the composition (C) comprises one or more oils, preferably chosen from hydrocarbon oils, more preferably chosen from C8-Ci4 hydrocarbon oils, even more preferably isododecane.

12. Use according to the preceding claim, in which the composition (C) comprises a total oil content ranging from 1% to 98% by weight, preferably ranging from 20% to 97% by weight, more preferably ranging from 50% to 96% by weight, even more preferably ranging from 70% to 95% by weight, relative to the total weight of the composition (C).

13. Use according to any one of the preceding claims, in which the composition (C) comprises one or more organic solvents Z chosen from monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols having from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C3 and C4 ketones and C2-C4 aldehydes, and mixtures thereof, preferably chosen from monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, more preferably ethanol.

14. Use according to the preceding claim, in which the composition (C) comprises a total content of organic solvents Z ranging from 0.1% to 90% by weight, preferably ranging from 1% to 50% by weight, more preferably ranging from 5% to 25% by weight, relative to the total weight of the composition (C).

15. Use according to any one of the preceding claims, wherein composition (C) is an anhydrous composition.

16. CP copolymer obtained by copolymerization of: - isobutyl methacrylate, isobutyl acrylate and acetoacetoxyethyl methacrylate, in a mass ratio of isobutyl methacrylate / isobutyl acrylate / acetoacetoxyethyl methacrylate of 70 / 20 / 10; or - isobornyl acrylate and acetoacetoxyethyl methacrylate, in an isobornyl acrylate / acetoacetoxyethyl methacrylate mass ratio of 95 / 5.