EP4412582A1 - Thickening polymeric composition for cosmetic and detergent compositions - Google Patents

Thickening polymeric composition for cosmetic and detergent compositions

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Publication number
EP4412582A1
EP4412582A1 EP22801367.8A EP22801367A EP4412582A1 EP 4412582 A1 EP4412582 A1 EP 4412582A1 EP 22801367 A EP22801367 A EP 22801367A EP 4412582 A1 EP4412582 A1 EP 4412582A1
Authority
EP
European Patent Office
Prior art keywords
polymer
cosmetic
labile crosslinker
polymeric composition
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22801367.8A
Other languages
German (de)
French (fr)
Inventor
Frédéric BLONDEL
Céline BESSET
Benoît Clement
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SNF Group
Original Assignee
SNF Group
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SNF Group filed Critical SNF Group
Publication of EP4412582A1 publication Critical patent/EP4412582A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C09D7/44—Combinations of two or more thickening agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides
    • C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen

Definitions

  • TITLE THICKENING POLYMERIC COMPOSITION FOR COSMETIC AND DETERGENT COMPOSITION
  • the invention relates to a polymeric composition for thickening a cosmetic or detergent composition.
  • Cosmetic and detergent compositions such as fabric softeners, present stability problems during their shelf life and/or storage at the consumer. These instabilities are correlated with an increase in the electrolyte content in the compositions over time. These electrolytes come from secondary reactions of ingredients contained in the composition, such as quaternary amine esters. Time and temperature are the main parameters influencing these secondary reactions.
  • Thickening polymers obtained by inverse emulsion, such as polymers based on quaternized dimethylaminoethyl (meth)acrylate ((M)ADAME) are known for stabilizing cosmetic and detergent compositions.
  • the stabilizing property is provided by a compact stack of hydrated polymers (or hydrogels) thickening the aqueous phase of the cosmetic or detergent composition by a charge repulsion mechanism.
  • the range of viscosity obtained depends on the volume developed by the hydrogel which itself depends on the structure of the polymer and more precisely the density of crosslinking in the network of the polymer constituting it.
  • the viscosity obtained by this mechanism shows an increased sensitivity to the presence of electrolytes in the stabilized medium.
  • the amount of electrolytes generated by the secondary reactions mentioned leads to a drop in viscosity and therefore in the stability of cosmetic and detergent compositions over time.
  • Electrolytes are positively or negatively charged chemicals capable of transporting or conducting electrical charge, usually in solution.
  • the problem that the invention sets out to solve is to provide an effective thickener for cosmetic and detergent compositions, and making it possible to compensate for the loss of viscosity over time of said cosmetic and detergent compositions.
  • the invention relates to a polymeric composition for thickening cosmetic and detergent compositions which makes it possible to significantly reduce the loss of viscosity of said compositions over time, and preferably to maintain their viscosity over time.
  • the better performance provided by the invention makes it possible to reduce the quantity of thickening polymer, which implies a reduction in the release of greenhouse gases such as CO2 associated with the manufacture and use of these polymers.
  • the invention relates to a polymeric composition, for thickening a cosmetic or detergent composition, said polymeric composition comprising:
  • the invention also relates to a cosmetic or detergent composition comprising at least one thickening polymeric composition according to the invention.
  • the invention also relates to a method for viscosifying a cosmetic or detergent composition with at least one thickening polymeric composition according to the invention.
  • the invention relates to a method for maintaining the viscosity of a cosmetic or detergent composition over time with at least one thickening polymeric composition according to the invention.
  • the polymeric composition according to the invention makes it possible to maintain a constant viscosity over time despite an increase in the concentration of electrolyte in the cosmetic or detergent composition. Thus it is no longer necessary to overdose the thickening polymer.
  • the expression “maintaining the viscosity over time” means that the viscosity of the cosmetic or detergent composition thickened with the polymer composition according to the invention is maintained at the same value over a period of at least one year, preferably at least less than three years.
  • This expression also includes the case where the viscosity is slightly reduced (at most 15% of the initial value, preferably at most 10%, more preferably at most 5%), but also the case where the loss of viscosity is significantly reduced ( of at least 50%, preferably of at least 80%) relative to a cosmetic or detergent composition not comprising the polymeric composition according to the invention, and this after a period of one year.
  • the addition of a labile crosslinker in combination with a non-labile crosslinker makes it possible to compensate for the drop in viscosity linked to the increase in the concentration of electrolyte in the medium.
  • a compact stack of hydrated polymers also called hydrogels is formed, as mentioned above.
  • the hydrolysis of the labile crosslinking agent (de-crosslinking) over time, and under the action of temperature makes it possible to increase the volume of the hydrogels in the cosmetic or detergent composition and thus to maintain the volume fraction occupied in said composition cosmetic or detergent. The viscosity of the cosmetic or detergent composition is therefore maintained over time.
  • the viscosity is measured with a Brookfield apparatus, the measurement being carried out at 20°C.
  • a person skilled in the art knows how to adapt not only the module of the Brookfield viscometer but also the speed of the module according to the viscosity of the fluid whose viscosity he wishes to measure. In the rest of the description, this viscosity is called Brookfield viscosity or quite simply viscosity.
  • the polymeric composition according to the invention comprises at least one crosslinked polymer with at least one labile crosslinker and at least one non-labile crosslinker.
  • said polymer is crosslinked with a single labile crosslinker and with a single non-labile crosslinker.
  • it can be crosslinked with several labile crosslinkers and several non-labile crosslinkers.
  • the polymeric composition according to the invention comprises at least one polymer crosslinked with at least one labile crosslinker and at least one polymer crosslinked with at least one non-labile crosslinker.
  • the crosslinked polymer according to the invention is preferably a synthetic polymer. It is preferably obtained from at least one monomer having ethylenic unsaturation. It is preferably a polymer obtained from at least one nonionic monomer and/or at least one anionic monomer and/or at least one cationic monomer and/or one zwitterionic monomer.
  • Labile crosslinker means a crosslinker which can be degraded by certain heat conditions and/or over time, after it has been incorporated into the polymer structure, to reduce the degree of crosslinking in the crosslinked polymer.
  • the storage conditions, the temperature, the appearance of electrolytes lead to the cleavage of the bonds in the labile crosslinker without substantially degrading the rest of the polymer backbone.
  • labile crosslinker is meant a crosslinker of which at least 10 mol% is degraded in 5 to 10 days, at a temperature between 50 and 100°C.
  • Determining the degree of degradation of the labile crosslinker can be done by comparative measurement with standards. The measurement is made in a 1% by weight solution of polymer comprising the labile crosslinker, at pH 2.5.
  • the labile crosslinker can be chosen from diamine diacrylamides and methacrylamides such as piperazine diacrylamide, di, tri, tetra acrylate or methacrylate esters such as ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylopropane trimethacrylate , ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, and vinyl or allylic esters of di or trifunctional acids.
  • diamine diacrylamides and methacrylamides such as piperazine diacrylamide, di, tri, tetra acrylate or methacrylate esters such as ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylopropane trimethacrylate , ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, and vinyl or allylic esters of di or trifunctional acids
  • the labile crosslinker can also be chosen from diamine diacrylamides and methacrylamides such as piperazine diacrylamide, acrylate or methacrylate esters, ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylopropane trimethacrylate, ethoxylated trimethylol, ethoxylated pentaerythritol tetracrylate, and vinyl or allylic esters of di or trifunctional acids.
  • diamine diacrylamides and methacrylamides such as piperazine diacrylamide, acrylate or methacrylate esters, ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylopropane trimethacrylate, ethoxylated trimethylol, ethoxylated pentaerythritol tetracrylate, and vinyl or allylic esters of di or trifunctional acids.
  • the labile crosslinker is preferably chosen from water-soluble diacrylates such as PEG 200 diacrylate, PEG 400 diacrylate, PEG 600 diacrylate, PEG 1000 diacrylate, ethylene glycol diacrylate, diethylene glycol, trethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyfunctional vinyl derivatives of a polyalcohol such as ethoxylated trimethylol (9-20) triacrylate.
  • water-soluble diacrylates such as PEG 200 diacrylate, PEG 400 diacrylate, PEG 600 diacrylate, PEG 1000 diacrylate, ethylene glycol diacrylate, diethylene glycol, trethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyfunctional vinyl derivatives of a polyalcohol such as ethoxylated trimethylol (9-20) triacrylate.
  • the di, tri, tetra acrylate or methacrylate esters are preferably obtained by esterification between a compound comprising at least two OH functions, preferably two, three or four OH functions, and acrylic or methacrylic acid.
  • the amount of labile crosslinker in the crosslinked polymer is preferably between 100 and 200,000 ppm, more preferably between 200 and 100,000 ppm, even more preferably between 300 and 70,000 ppm, even more preferably between 400 and 50,000 ppm even more preferably between 500 and 30,000 ppm on total monomer basis.
  • the ppm are expressed by weight.
  • Non-labile crosslinker means a crosslinker which is not degraded under temperature conditions or over time.
  • a non-labile cross-linker helps control the expanded conformation of the hydrogel.
  • a non-labile crosslinker is different from a labile crosslinker as defined above, i.e. less than 1 mol% is degraded in 5 to 10 days, at a temperature between 50 and 100 °C.
  • the non-labile crosslinker can be selected from methylene bisacrylamide, diallylamine, triallylamine, divinyl sulfone, diallyl ether of diethylene glycol and the like.
  • the non-labile crosslinker is preferably methylene bisacrylamide.
  • the amount of non-labile crosslinker in the crosslinked polymer is preferably between 1 and 2000 ppm, more preferably between 10 and 1500 ppm, and even more preferably between 20 and 1000 ppm, and even more preferably between 100 and 1000 ppm on the total basis. of monomer.
  • the ppm are expressed by weight.
  • the nonionic monomer(s) that can be used in the context of the invention can be chosen, in particular, from the group comprising water-soluble vinyl monomers.
  • Preferred monomers belonging to this class are, for example, acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N-methylolacrylamide.
  • N-vinylformamide, N-vinyl acetamide, N-vinylpyridine and N-vinylpyrrolidone, acryloyl morpholine (ACMO), glycidyl methacrylate, glyceryl methacrylate and diacetone acrylamide can be used.
  • a preferred nonionic monomer is acrylamide.
  • the anionic monomer(s) are preferably chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamido tert-butyl sulfonic acid (also called ATBS or 2-acrylamido-2-methylpropane sulfonic acid ), vinylsulphonic acid, vinylphosphonic acid, said anionic monomer being non salified, partially or totally salified, and salts of 3-sulfopropyl methacrylate.
  • the salified form advantageously corresponds to the salts of alkali metals (Li, Na, K, etc.), of alkaline-earth metals (Ca, Mg, etc.) or of ammonium, in particular quaternary ammoniums.
  • Preferred anionic monomers are ATBS and acrylic acid and or their salts.
  • cationic monomers and anionic monomers include non-salified, salified, partially or totally salified forms.
  • the cationic monomer(s) that can be used in the context of the invention can be chosen, in particular from monomers of the acrylamide, acrylic, vinyl, allylic or maleic type possessing a quaternary ammonium function by salification or quaternization. Mention may be made, in particular and without limitation, of quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamido propyltrimethyl ammonium chloride (APT AC) , and methacrylamido propyltrimethyl ammonium chloride (MAPTAC).
  • ADAME quaternized dimethylaminoethyl acrylate
  • MADAME quaternized dimethylaminoethyl methacrylate
  • DADMAC dimethyldiallylammonium chloride
  • APT AC acrylamido propyltrimethyl am
  • the preferred cationic monomers are quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), the quaternization being preferably carried out with the chloride ion.
  • ADAME quaternized dimethylaminoethyl acrylate
  • MADAME quaternized dimethylaminoethyl methacrylate
  • the zwitterionic monomer(s) can also be used within the scope of the invention; they combine both anionic and cationic charges on a single monomer. They can be chosen, in particular from monomers of the betaine, sultaine, sulfobetaine, phosphobetaine and carboxybetaine type. As examples of zwitterionic monomers, mention may be made of sulfopropyl dimethylammonium ethyl methacrylate, sulfopropyl dimethylammonium propylmethacrylamide, sulfopropyl 2-vinylpyridinium, and phosphato ethyl trimethylammonium ethyl methacrylate.
  • the crosslinked polymer according to the invention is preferably a cationic or anionic polymer.
  • the crosslinked polymer is cationic, it is preferably either a cationic homopolymer or a copolymer comprising at least one cationic monomer and at least one nonionic monomer.
  • the amount of cationic monomer is preferably between 50 and 100 mol%, more preferably between 70 and 90 mol% and the amount of nonionic monomer is preferably between 0 and 50 mol%, and more preferably between 10 and 30% mol.
  • the crosslinked polymer is anionic, it is preferably either an anionic homopolymer or a copolymer comprising at least one anionic monomer, and at least a nonionic monomer.
  • the amount of anionic monomer is preferably between 50 and 100 mol%, and the amount of nonionic monomer is preferably between 0 and 50 mol%.
  • the two polymers preferably have the same ionicity.
  • the polymer crosslinked with at least one labile crosslinker is cationic, then the polymer crosslinked with a non-labile crosslinker is also cationic.
  • the crosslinked polymer according to the invention does not require the development of a particular polymerization process. Indeed, it can be obtained according to all the polymerization techniques well known to those skilled in the art. It can in particular be a question of polymerization in solution; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous or reverse); suspension polymerization; reactive extrusion polymerization; water-in-water polymerization; or micellar polymerization.
  • the polymer according to the invention is preferably obtained by inverse emulsion polymerization.
  • the inverse emulsion is preferably distilled to thus obtain a polymer concentration preferably between 3 and 65% by weight.
  • the two polymers are preferably prepared separately from each other, then mixed to obtain the thickening polymeric composition of the invention.
  • the proportion by weight of one relative to the other is preferably between 10:90 and 90:10.
  • the polymer composition of the invention is an inverse emulsion
  • the polymer is then in the water droplets of the emulsion.
  • the polymerization is generally a free radical polymerization.
  • free radical polymerization we include free radical polymerization using UV, azo, redox or thermal initiators as well as controlled radical polymerization (CRP) techniques or matrix polymerization techniques.
  • CRP controlled radical polymerization
  • the implementation of the thickening polymeric composition can be done according to the knowledge and practices of the formulators of the cosmetic and detergent compositions.
  • the invention also relates to a cosmetic or detergent composition comprising at least one thickening polymeric composition according to the invention.
  • cosmetic compositions also include dermatological and pharmaceutical compositions. They generally comprise an aqueous phase. They are applied in particular to the skin or the hair and generally come in the form of oil-in-water emulsions, and sometimes water-in-oil emulsions, to form creams or lotions, for example.
  • Such compositions can, for example, correspond to anti-ageing creams or lotions, after-shave care, moisturizing creams, hair coloring lotions, shampoos, conditioner shampoos, shower products, cleansing creams, or ointments or sun creams or lotions. Creams are distinguished from lotions by their higher viscosity.
  • Thickeners or rheology modifiers are widely used in these compositions to adapt their sensory profile (appearance, application) to consumer requirements, but also to suspend or stabilize active principles.
  • detergent compositions means compositions for cleaning various surfaces, in particular textile fibers, hard surfaces of any kind such as dishes, floors, windows, wooden, metal or composite surfaces. Such compositions correspond, for example, to detergents for washing linen manually or in a washing machine, products for cleaning dishes manually or for dishwashers, detergent products for washing home interiors such as kitchen units , toilets, furniture, floors, windows, and other general-purpose cleaning products.
  • the amount of thickening polymeric composition according to the invention added to the cosmetic or detergent composition is preferably between 0.01 and 5% by weight, more preferably between 0.1 and 3% by weight.
  • the amount of crosslinked polymer, with at least one labile crosslinker and at least one non-labile crosslinker, added to the cosmetic or detergent composition is preferably between 0.005 and 3% by weight, more preferably between 0.05 and 2% by weight.
  • the amount of crosslinked polymer with at least one labile crosslinker added in the cosmetic or detergent composition is preferably between 0.0005 and 2.7% by weight, more preferably between 0.005 and 1.8 % by weight, and the amount of crosslinked polymer with at least one non-labile crosslinker added in the cosmetic or detergent composition is preferably between 0.0005 and 2.7% by weight, more preferably between 0.005 and 1.8% by weight.
  • the cosmetic and detergent compositions also contain other ingredients well known to those skilled in the art, such as water, mineral or vegetable oils, organic solvents, surfactants, cosmetic or pharmaceutical active ingredients, vitamins, chelating agents, emollients, moisturizing agents, botanical extracts, sunscreens, detergency or cleaning aids, fluorescent agents, foaming agents or suds suppressing agents, neutralizing agents, adjusting agents pH, preservatives, perfumes, opacifying compounds, dyes without this list being exhaustive.
  • ingredients well known to those skilled in the art, such as water, mineral or vegetable oils, organic solvents, surfactants, cosmetic or pharmaceutical active ingredients, vitamins, chelating agents, emollients, moisturizing agents, botanical extracts, sunscreens, detergency or cleaning aids, fluorescent agents, foaming agents or suds suppressing agents, neutralizing agents, adjusting agents pH, preservatives, perfumes, opacifying compounds, dyes without this list being exhaustive.
  • the person skilled in the art knows how, with which ingredients he can formulate
  • the invention also relates to a method for viscosifying a cosmetic or detergent composition with at least one thickening polymeric composition as explained above.
  • the method comprises the implementation of the polymeric composition according to the invention by the techniques known to those skilled in the art.
  • the method therefore comprises a step of adding the polymeric composition according to the invention to said cosmetic or detergent composition.
  • the amounts of polymeric composition are as described above.
  • the invention also relates to the use of at least one polymeric composition according to the invention for viscosifying a cosmetic or detergent composition.
  • the amounts of polymeric composition are as described above.
  • the invention relates to a method for maintaining the viscosity of a cosmetic or detergent composition over time with at least one thickening polymeric composition as explained above.
  • the method therefore comprises a step of adding the polymeric composition according to the invention to said cosmetic or detergent composition.
  • the amounts of polymeric composition are as described above.
  • the invention relates to the use of at least one polymeric composition according to the invention for maintaining the viscosity of a cosmetic or detergent composition over time.
  • the amounts of polymeric composition are as described above.
  • Figure 1 is a schematic illustration of the phenomena of loss of viscosity over time according to the prior art (upper part), and of the strategy for maintaining viscosity over time thanks to the polymer composition according to the invention.
  • a hydrogel obtained from a non-labile crosslinker initially has a diameter of 30 pm, then over time, the action of electrolytes and temperature, its diameter gradually decreases to 20 pm and then 10 pm resulting in a drop in viscosity of the thickened medium.
  • the increasing presence of electrolytes decreases the ionic repulsions at the origin of the viscosifying effect leading to this loss of viscosity.
  • a hydrogel of the polymer obtained from a non-labile crosslinker and a labile crosslinker initially has a size of 10 ⁇ m, then with the phenomenon of hydrolysis of the labile crosslinker (de-crosslinking) , its size gradually increases at 20 ⁇ m, then at 30 ⁇ m, leading to an increase in the viscosity of the thickened medium over time. This increase in viscosity compensates over time for the loss of viscosity observed in the upper part of FIG.
  • Figure 2 is a graph representing the evolution of the viscosity of the polymer solution A to E at a concentration of 1% at 80° C. in order to simulate the action of the electrolytes which are formed during the storage of a cosmetic composition or detergent.
  • Example 1 Synthesis of the cationic polymer by inverse emulsion with non-labile crosslinker (Composition A)
  • the aqueous phase is prepared in a 1 L beaker by mixing together the following ingredients:
  • the pH is adjusted to 5.2 +/- 0.1 with a citric acid solution.
  • the organic phase is prepared in a 1 L glass reactor with stirring by mixing together the following ingredients:
  • the aqueous phase is gradually transferred into the organic phase with moderate mechanical stirring.
  • the pre-emulsion thus formed is then subjected to high shear for 1 min (Ultra Turax, IKA).
  • the inverse emulsion is then degassed for 30 minutes using nitrogen sparging.
  • the polymerization is carried out by adding a 1% by weight aqueous solution of a redox couple of sodium metabisulphite and tert-butyl hydroperoxide at a rate of 10 ml/h.
  • the temperature of the reaction medium is maintained for 60 minutes before cooling.
  • the emulsion obtained is then distilled under reduced pressure to remove the water and the volatile organic solvent to give after distillation a product with 58% by weight of active polymer material.
  • Example 2 Synthesis of the cationic polymer by inverse emulsion with labile and non-labile crosslinker (1100 ppm labile crosslinker, Composition B)
  • the protocol of example 1 is reproduced by adding 0.42 g (1100 ppm) of labile crosslinker polyethylene glycol (200) diacrylate (PEG200DA, Sartomer SR 259).
  • Example 3 Synthesis of the cationic polymer by inverse emulsion with labile and non-labile crosslinker (3500 ppm labile crosslinker, Composition C)
  • the protocol of example 2 is reproduced by changing the amount of labile crosslinker to 1.33 g (3500 ppm/active material).
  • Example 4 Synthesis of the cationic polymer by inverse emulsion with labile and non-labile crosslinker (5000 ppm labile crosslinker, Composition D)
  • Example 2 The protocol of Example 2 is reproduced by changing the amount of labile crosslinker to 1.91 g (5000 ppm/active material).
  • Example 4' Synthesis of the cationic polymer by inverse emulsion with labile crosslinker (4000 ppm, Composition D')
  • the protocol of example 2 is reproduced by changing the quantity of labile crosslinker to 1.91 g (5000 ppm) and the quantity of non-labile crosslinker to 0 g.
  • Example 5 Combination of a polymer comprising a non-labile crosslinker and a polymer comprising a labile crosslinker (Composition E)
  • Composition E is obtained by mixing 50/50% by weight of composition A (non-labile crosslinker) with composition D' (labile crosslinker) before their respective distillation step, then distillation of the mixture of the two compositions.
  • the viscosity is measured on a Brookfield RVT type viscometer at a shear rate of 10 RPM.
  • Viscosity profile monitoring The solutions of each composition A to E are placed in an oven at 80° C. to simulate the accelerated aging of the polymer over time and the impact of the electrolytes which are formed during the storage of a detergent or cosmetic composition.
  • Brookfield viscosities are monitored over time at a temperature of 23°C +/- 1°C. The viscosity is measured over several days.
  • composition A a drop in viscosity is observed for the reference polymer (composition A) and that it increases from 8 days to end with a loss of viscosity reaching 37% after 34 days.
  • compositions B to E it is observed that the drop in viscosity observed over time is reduced and compensated with the degradation of the labile crosslinker.

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Abstract

The invention relates to a polymeric composition for thickening a cosmetic or detergent composition, said polymeric composition comprising either at least one crosslinked polymer crosslinked with at least one labile crosslinker and at least one non-labile crosslinker, or at least two crosslinked polymers with at least one being crosslinked with at least one labile crosslinker and at least one being crosslinked with at least one non-labile crosslinker. The polymeric composition according to the invention allows the viscosity of a cosmetic or detergent composition to be maintained over time.

Description

TITRE : COMPOSITION POLYMERIQUE EPAISSISSANTE POUR COMPOSITION COSMETIQUE ET DETERGENTE TITLE: THICKENING POLYMERIC COMPOSITION FOR COSMETIC AND DETERGENT COMPOSITION
DOMAINE TECHNIQUE DE L’INVENTION TECHNICAL FIELD OF THE INVENTION
L’invention concerne une composition polymérique pour épaissir une composition cosmétique ou détergente. The invention relates to a polymeric composition for thickening a cosmetic or detergent composition.
ETAT ANTERIEUR DE LA TECHNIQUE PRIOR STATE OF THE TECHNIQUE
Les compositions cosmétiques et détergentes, comme les adoucissants pour le textile, présentent des problèmes de stabilité pendant leur durée de vie et/ou de stockage chez le consommateur. Ces instabilités sont corrélées à une augmentation de la teneur en électrolytes dans les compositions au fil du temps. Ces électrolytes sont issus de réactions secondaires d’ingrédients contenus dans la composition, comme les esters d’amine quaternaire. Le temps et la température sont les principaux paramètres influant sur ces réactions secondaires. Cosmetic and detergent compositions, such as fabric softeners, present stability problems during their shelf life and/or storage at the consumer. These instabilities are correlated with an increase in the electrolyte content in the compositions over time. These electrolytes come from secondary reactions of ingredients contained in the composition, such as quaternary amine esters. Time and temperature are the main parameters influencing these secondary reactions.
Les polymères épaississants, obtenus par émulsion inverse, tels que les polymères à base de (méth)acrylate de diméthylaminoéthyle ((M)ADAME) quaternisé sont connus pour stabiliser les compositions cosmétiques et détergentes. La propriété stabilisante est apportée par un empilement compact de polymères hydratés (ou hydrogels) épaississant la phase aqueuse de la composition cosmétique ou détergente par un mécanisme de répulsion de charge. La plage de viscosité obtenue dépend du volume développé par l’hydrogel qui lui-même dépend de la structure du polymère et plus précisément la densité de réticulation dans le réseau du polymère le constituant. Thickening polymers, obtained by inverse emulsion, such as polymers based on quaternized dimethylaminoethyl (meth)acrylate ((M)ADAME) are known for stabilizing cosmetic and detergent compositions. The stabilizing property is provided by a compact stack of hydrated polymers (or hydrogels) thickening the aqueous phase of the cosmetic or detergent composition by a charge repulsion mechanism. The range of viscosity obtained depends on the volume developed by the hydrogel which itself depends on the structure of the polymer and more precisely the density of crosslinking in the network of the polymer constituting it.
La viscosité obtenue par ce mécanisme présente une sensibilité accrue à la présence d’électrolytes dans le milieu stabilisé. La quantité d’électrolytes générée par les réactions secondaires citées, entraîne une chute de viscosité et donc de stabilité des compositions cosmétiques et détergentes au cours du temps. The viscosity obtained by this mechanism shows an increased sensitivity to the presence of electrolytes in the stabilized medium. The amount of electrolytes generated by the secondary reactions mentioned leads to a drop in viscosity and therefore in the stability of cosmetic and detergent compositions over time.
Les électrolytes sont des substances chimiques chargées positivement ou négativement et capable de transporter ou conduire une charge électrique, généralement dans une solution. Electrolytes are positively or negatively charged chemicals capable of transporting or conducting electrical charge, usually in solution.
Actuellement, pour compenser cette perte de viscosité ou de stabilité, les industriels surdosent en polymère épaississant les compositions cosmétiques et détergentes. Cette solution n’est bien entendu pas satisfaisante et la demanderesse a recherché une alternative technique. Currently, to compensate for this loss of viscosity or stability, manufacturers overdose cosmetic and detergent compositions with thickening polymer. This solution is of course not satisfactory and the applicant sought a technical alternative.
Le problème que se propose de résoudre l’invention est de fournir un épaississant efficace pour des compositions cosmétiques et détergentes, et permettant de palier à la perte de viscosité dans le temps desdites compositions cosmétiques et détergentes. The problem that the invention sets out to solve is to provide an effective thickener for cosmetic and detergent compositions, and making it possible to compensate for the loss of viscosity over time of said cosmetic and detergent compositions.
L’invention concerne une composition polymérique pour épaissir les compositions cosmétiques et détergentes qui permet de réduire significativement la perte de viscosité dans le temps desdites compositions, et préférentiellement de maintenir leur viscosité dans le temps. The invention relates to a polymeric composition for thickening cosmetic and detergent compositions which makes it possible to significantly reduce the loss of viscosity of said compositions over time, and preferably to maintain their viscosity over time.
Les meilleures performances apportées par l’invention permettent de réduire la quantité de polymère épaississant, ce qui implique une réduction des rejets de gaz à effets de serre tels que le CO2 associés à la fabrication et à l’utilisation de ces polymères. The better performance provided by the invention makes it possible to reduce the quantity of thickening polymer, which implies a reduction in the release of greenhouse gases such as CO2 associated with the manufacture and use of these polymers.
EXPOSE DE L’INVENTION DISCLOSURE OF THE INVENTION
L’invention concerne une composition polymérique, pour épaissir une composition cosmétique ou détergente, ladite composition polymérique comprenant : The invention relates to a polymeric composition, for thickening a cosmetic or detergent composition, said polymeric composition comprising:
- Soit au moins un polymère réticulé avec au moins un réticulant labile et au moins un réticulant non labile, - Either at least one crosslinked polymer with at least one labile crosslinker and at least one non-labile crosslinker,
- Soit au moins deux polymères réticulés, au moins un étant réticulé avec au moins un réticulant labile, et au moins un étant réticulé avec au moins un réticulant non labile. - Either at least two crosslinked polymers, at least one being crosslinked with at least one labile crosslinker, and at least one being crosslinked with at least one non-labile crosslinker.
L’invention concerne également une composition cosmétique ou détergente comprenant au moins une composition polymérique épaississante selon l’invention. The invention also relates to a cosmetic or detergent composition comprising at least one thickening polymeric composition according to the invention.
L’invention concerne aussi une méthode pour viscosifier une composition cosmétique ou détergente avec au moins une composition polymérique épaississante selon l’invention. The invention also relates to a method for viscosifying a cosmetic or detergent composition with at least one thickening polymeric composition according to the invention.
Enfin, l’invention concerne une méthode pour maintenir la viscosité d’une composition cosmétique ou détergente dans le temps avec au moins une composition polymérique épaississante selon l’invention. La composition polymérique selon l’invention permet de maintenir une viscosité constante au cours du temps malgré une augmentation de la concentration en électrolyte dans la composition cosmétique ou détergente. Ainsi il n’est plus nécessaire de surdoser le polymère épaississant. Finally, the invention relates to a method for maintaining the viscosity of a cosmetic or detergent composition over time with at least one thickening polymeric composition according to the invention. The polymeric composition according to the invention makes it possible to maintain a constant viscosity over time despite an increase in the concentration of electrolyte in the cosmetic or detergent composition. Thus it is no longer necessary to overdose the thickening polymer.
L’expression « maintenir la viscosité dans le temps » signifie que la viscosité de la composition cosmétique ou détergente épaissie avec la composition polymérique selon l’invention est maintenue à la même valeur dans une période d’au moins un an, préférentiellement d’au moins trois ans. Cette expression comprend également le cas où la viscosité est légèrement réduite (au maximum de 15% de la valeur initiale, préférentiellement au maximum 10%, plus préférentiellement au maximum 5%), mais également le cas où la perte de viscosité est significativement réduite (d’au moins 50%, préférentiellement d’au moins 80%) par rapport à une composition cosmétique ou détergente ne comprenant pas la composition polymérique selon l’invention, et ce après une période d’un an. The expression "maintaining the viscosity over time" means that the viscosity of the cosmetic or detergent composition thickened with the polymer composition according to the invention is maintained at the same value over a period of at least one year, preferably at least less than three years. This expression also includes the case where the viscosity is slightly reduced (at most 15% of the initial value, preferably at most 10%, more preferably at most 5%), but also the case where the loss of viscosity is significantly reduced ( of at least 50%, preferably of at least 80%) relative to a cosmetic or detergent composition not comprising the polymeric composition according to the invention, and this after a period of one year.
Sans vouloir être lié par une quelconque théorie, l’ajout d’un réticulant labile en combinaison avec un réticulant non labile permet de compenser la chute de viscosité liée à l’augmentation de la concentration en électrolyte dans le milieu. Lors de l’ajout de la composition polymérique dans la composition cosmétique ou détergente, il se forme, comme mentionné plus haut un empilement compact de polymères hydratés appelés également hydrogels. L’hydrolyse du réticulant labile (dé-réticulation) au cours du temps, et sous l’action de la température, permet d’augmenter le volume des hydrogels dans la composition cosmétique ou détergente et ainsi de maintenir la fraction volumique occupée dans ladite composition cosmétique ou détergente. La viscosité de la composition cosmétique ou détergente est donc maintenue au cours du temps. Without wishing to be bound by any theory, the addition of a labile crosslinker in combination with a non-labile crosslinker makes it possible to compensate for the drop in viscosity linked to the increase in the concentration of electrolyte in the medium. When the polymeric composition is added to the cosmetic or detergent composition, a compact stack of hydrated polymers also called hydrogels is formed, as mentioned above. The hydrolysis of the labile crosslinking agent (de-crosslinking) over time, and under the action of temperature, makes it possible to increase the volume of the hydrogels in the cosmetic or detergent composition and thus to maintain the volume fraction occupied in said composition cosmetic or detergent. The viscosity of the cosmetic or detergent composition is therefore maintained over time.
La viscosité est mesurée avec un appareil Brookfield, la mesure étant effectuée à 20°C. L’homme du métier sait adapter non seulement le module du viscosimètre Brookfield mais aussi la vitesse du module en fonction de la viscosité du fluide dont il souhaite mesurée la viscosité. Dans la suite de la description, cette viscosité est appelée viscosité Brookfield ou tout simplement viscosité. The viscosity is measured with a Brookfield apparatus, the measurement being carried out at 20°C. A person skilled in the art knows how to adapt not only the module of the Brookfield viscometer but also the speed of the module according to the viscosity of the fluid whose viscosity he wishes to measure. In the rest of the description, this viscosity is called Brookfield viscosity or quite simply viscosity.
Dans une première alternative, la composition polymérique selon l’invention comprend au moins un polymère réticulé avec au moins un réticulant labile et au moins un réticulant non labile. Préférentiellement, ledit polymère est réticulé avec un seul réticulant labile et avec un seul réticulant non labile. Bien entendu il peut être réticulé avec plusieurs réticulants labiles et plusieurs réticulants non labiles. In a first alternative, the polymeric composition according to the invention comprises at least one crosslinked polymer with at least one labile crosslinker and at least one non-labile crosslinker. Preferably, said polymer is crosslinked with a single labile crosslinker and with a single non-labile crosslinker. Of course, it can be crosslinked with several labile crosslinkers and several non-labile crosslinkers.
Dans une seconde alternative, la composition polymérique selon l’invention comprend au moins un polymère réticulé avec au moins un réticulant labile et au moins un polymère réticulé avec au moins un réticulant non labile. In a second alternative, the polymeric composition according to the invention comprises at least one polymer crosslinked with at least one labile crosslinker and at least one polymer crosslinked with at least one non-labile crosslinker.
Le polymère réticulé selon l’invention est préférentiellement un polymère synthétique. Il est préférentiellement obtenu à partir d’au moins un monomère ayant une insaturation éthylénique. Il est préférentiellement un polymère obtenu à partir d’au moins un monomère non ionique et/ou au moins un monomère anionique et/ou au moins un monomère cationique et/ou un monomère zwittérionique. The crosslinked polymer according to the invention is preferably a synthetic polymer. It is preferably obtained from at least one monomer having ethylenic unsaturation. It is preferably a polymer obtained from at least one nonionic monomer and/or at least one anionic monomer and/or at least one cationic monomer and/or one zwitterionic monomer.
Le réticulant labile signifie un réticulant qui peut être dégradé par certaines conditions de chaleur et/ou au fil du temps, après qu'il a été incorporé dans la structure polymère, pour réduire le degré de réticulation dans le polymère réticulé. Les conditions de stockage, la température, l’apparition d’électrolytes entrainent le clivage des liaisons dans le réticulant labile sans dégrader substantiellement le reste du squelette polymère. Labile crosslinker means a crosslinker which can be degraded by certain heat conditions and/or over time, after it has been incorporated into the polymer structure, to reduce the degree of crosslinking in the crosslinked polymer. The storage conditions, the temperature, the appearance of electrolytes lead to the cleavage of the bonds in the labile crosslinker without substantially degrading the rest of the polymer backbone.
Plus précisément, dans l’invention par réticulant labile on entend un réticulant dont au moins 10 mol% est dégradé en 5 à 10 jours, à une température comprise entre 50 et 100°C.More specifically, in the invention, by labile crosslinker is meant a crosslinker of which at least 10 mol% is degraded in 5 to 10 days, at a temperature between 50 and 100°C.
La détermination du degré de dégradation du réticulant labile peut se faire par mesure comparative avec des étalons. La mesure se fait dans une solution à 1% en poids de polymère comprenant le réticulant labile, à pH de 2,5. Determining the degree of degradation of the labile crosslinker can be done by comparative measurement with standards. The measurement is made in a 1% by weight solution of polymer comprising the labile crosslinker, at pH 2.5.
Le réticulant labile peut être choisi parmi les diacrylamides et les méthacrylamides de diamines tels que le diacrylamide de pipérazine, les di, tri, tétra esters d'acrylate ou de méthacrylate comme le diacrylate d'éthylèneglycol, le diacrylate de polyéthylèneglycol, le triméthacrylate de triméthylopropane, le triacrylate de triméthylol éthoxylé, le tétracrylate de pentaérythritol éthoxylé, et les esters vinyliques ou allyliques d'acides di ou trifonctionnels. Le réticulant labile peut également être choisi parmi les diacrylamides et les méthacrylamides de diamines tels que le diacrylamide de pipérazine, les esters d'acrylate ou de méthacrylate, le diacrylate d'éthylèneglycol, le diacrylate de polyéthylèneglycol, le triméthacrylate de triméthylopropane, le triacrylate de triméthylol éthoxylé, le tétracrylate de pentaérythritol éthoxylé, et les esters vinyliques ou allyliques d'acides di ou trifonctionnels. Le réticulant labile est préférentiellement choisi parmi les diacrylates solubles dans l'eau tels que le diacrylate de PEG 200, le diacrylate de PEG 400, le diacrylate de PEG 600, le diacrylate de PEG 1000, le diacrylate d’éthylène glycol, le diacrylate de diéthylène glycol, le diacrylate de tréthylène glycol, le diacrylate de tetraéthylène glycol, et les dérivés vinyliques polyfonctionnels d'un polyalcool tels que le triacrylate de triméthylol (9-20) éthoxylé. The labile crosslinker can be chosen from diamine diacrylamides and methacrylamides such as piperazine diacrylamide, di, tri, tetra acrylate or methacrylate esters such as ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylopropane trimethacrylate , ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, and vinyl or allylic esters of di or trifunctional acids. The labile crosslinker can also be chosen from diamine diacrylamides and methacrylamides such as piperazine diacrylamide, acrylate or methacrylate esters, ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylopropane trimethacrylate, ethoxylated trimethylol, ethoxylated pentaerythritol tetracrylate, and vinyl or allylic esters of di or trifunctional acids. The labile crosslinker is preferably chosen from water-soluble diacrylates such as PEG 200 diacrylate, PEG 400 diacrylate, PEG 600 diacrylate, PEG 1000 diacrylate, ethylene glycol diacrylate, diethylene glycol, trethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyfunctional vinyl derivatives of a polyalcohol such as ethoxylated trimethylol (9-20) triacrylate.
Les di, tri, tétra esters d’acrylate ou de méthacrylate sont de préférence obtenus par estérification entre un composé comprenant au moins deux fonctions OH, de préférence deux, trois ou quatre fonctions OH, et de l’acide acrylique ou méthacrylique. The di, tri, tetra acrylate or methacrylate esters are preferably obtained by esterification between a compound comprising at least two OH functions, preferably two, three or four OH functions, and acrylic or methacrylic acid.
La quantité de réticulant labile dans le polymère réticulé est préférentiellement comprise entre 100 et 200 000 ppm, plus préférentiellement entre 200 et 100 000 ppm, encore plus préférentiellement entre 300 et 70 000 ppm, encore plus préférentiellement entre 400 et 50 000 ppm encore plus préférentiellement entre 500 et 30 000 ppm sur la base totale de monomère. Les ppm sont exprimés en poids. The amount of labile crosslinker in the crosslinked polymer is preferably between 100 and 200,000 ppm, more preferably between 200 and 100,000 ppm, even more preferably between 300 and 70,000 ppm, even more preferably between 400 and 50,000 ppm even more preferably between 500 and 30,000 ppm on total monomer basis. The ppm are expressed by weight.
Le réticulant non labile signifie un réticulant qui n'est pas dégradé dans les conditions de température ou au fil du temps. Un réticulant non labile permet de contrôler la conformation expansée de l’hydrogel. En particulier, un réticulant non labile est différent d’un réticulant labile tel que défini ci-dessus, c’est-à-dire que moins de 1 mol% est dégradé en 5 à 10 jours, à une température comprise entre 50 et 100°C. Non-labile crosslinker means a crosslinker which is not degraded under temperature conditions or over time. A non-labile cross-linker helps control the expanded conformation of the hydrogel. In particular, a non-labile crosslinker is different from a labile crosslinker as defined above, i.e. less than 1 mol% is degraded in 5 to 10 days, at a temperature between 50 and 100 °C.
Le réticulant non labile peut être choisi parmi le méthylène bisacrylamide, la diallylamine, la triallylamine, la divinylsulfone, l'éther diallylique de diéthylèneglycol et similaires. Le réticulant non labile est préférentiellement le méthylène bisacrylamide. The non-labile crosslinker can be selected from methylene bisacrylamide, diallylamine, triallylamine, divinyl sulfone, diallyl ether of diethylene glycol and the like. The non-labile crosslinker is preferably methylene bisacrylamide.
La quantité de réticulant non labile dans le polymère réticulé est préférentiellement comprise entre 1 et 2000 ppm, plus préférentiellement entre 10 et 1500 ppm, et encore plus préférentiellement entre 20 et 1000 ppm, et encore plus préférentiellement entre 100 et 1000 ppm sur la base totale de monomère. Les ppm sont exprimés en poids. The amount of non-labile crosslinker in the crosslinked polymer is preferably between 1 and 2000 ppm, more preferably between 10 and 1500 ppm, and even more preferably between 20 and 1000 ppm, and even more preferably between 100 and 1000 ppm on the total basis. of monomer. The ppm are expressed by weight.
Le ou les monomères non ioniques pouvant être utilisés dans le cadre de l’invention peuvent être choisis, notamment, dans le groupe comprenant les monomères vinyliques solubles dans l’eau. Des monomères préférés appartenant à cette classe sont, par exemple, l’acrylamide, le méthacrylamide, le N-isopropylacrylamide, le N,N- diméthylacrylamide et le N-méthylolacrylamide. Egalement, peuvent être utilisés la N- vinylformamide, le N-vinyl acétamide, la N-vinylpyridine et la N-vinylpyrrolidone, l’acryloyl morpholine (ACMO), le méthacrylate de glycidyle, le méthacrylate de glycéryle et la diacétone acrylamide. Un monomère non ionique préféré est l’acrylamide. The nonionic monomer(s) that can be used in the context of the invention can be chosen, in particular, from the group comprising water-soluble vinyl monomers. Preferred monomers belonging to this class are, for example, acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N-methylolacrylamide. Also, N-vinylformamide, N-vinyl acetamide, N-vinylpyridine and N-vinylpyrrolidone, acryloyl morpholine (ACMO), glycidyl methacrylate, glyceryl methacrylate and diacetone acrylamide can be used. A preferred nonionic monomer is acrylamide.
Le ou les monomères anioniques sont préférentiellement choisis parmi l’acide acrylique, l’acide méthacrylique, l’acide itaconique, l’acide maléique, l’acide acrylamido tertio butyl sulfonique (également appelé ATBS ou acide 2-acrylamido-2-méthylpropane sulfonique), l’acide vinylsulphonique, l’acide vinylphosphonique, ledit monomère anionique étant non salifié, partiellement ou totalement salifié, et les sels du méthacrylate de 3-sulfopropyle. La forme salifiée correspond avantageusement aux sels de métaux alcalins (Li, Na, K...), de métaux alcalino-terreux (Ca, Mg...) ou d’ammonium, notamment les ammoniums quaternaires. Les monomères anioniques préférés sont l’ATBS et l’acide acrylique et ou leurs sels. The anionic monomer(s) are preferably chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamido tert-butyl sulfonic acid (also called ATBS or 2-acrylamido-2-methylpropane sulfonic acid ), vinylsulphonic acid, vinylphosphonic acid, said anionic monomer being non salified, partially or totally salified, and salts of 3-sulfopropyl methacrylate. The salified form advantageously corresponds to the salts of alkali metals (Li, Na, K, etc.), of alkaline-earth metals (Ca, Mg, etc.) or of ammonium, in particular quaternary ammoniums. Preferred anionic monomers are ATBS and acrylic acid and or their salts.
Ci-avant et ci-après, les monomères cationiques et les monomères anioniques, comme le MADAME et l’ATBS, incluent les formes non salifiées, salifiées, partiellement ou totalement salifiées. Above and below, cationic monomers and anionic monomers, such as MADAME and ATBS, include non-salified, salified, partially or totally salified forms.
Le ou les monomères cationiques pouvant être utilisés dans le cadre de l’invention peuvent être choisis, notamment parmi les monomères du type acrylamide, acrylique, vinylique, allylique ou maléique possédant une fonction ammonium quaternaire par salification ou quaternisation. On peut citer, en particulier et de façon non limitative, l’acrylate de diméthylaminoéthyle (ADAME) quaternisé, le méthacrylate de diméthylaminoéthyle (MADAME) quaternisé, le chlorure de diméthyldiallylammonium (DADMAC), le chlorure d’acrylamido propyltriméthyl ammonium (APT AC), et le chlorure de methacrylamido propyltrimethyl ammonium (MAPTAC). Les monomères cationiques préférés sont l’acrylate de diméthylaminoéthyle (ADAME) quaternisé, le méthacrylate de diméthylaminoéthyle (MADAME) quaternisé, la quaternisation étant préférentiellement faite avec l’ion chlorure.The cationic monomer(s) that can be used in the context of the invention can be chosen, in particular from monomers of the acrylamide, acrylic, vinyl, allylic or maleic type possessing a quaternary ammonium function by salification or quaternization. Mention may be made, in particular and without limitation, of quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamido propyltrimethyl ammonium chloride (APT AC) , and methacrylamido propyltrimethyl ammonium chloride (MAPTAC). The preferred cationic monomers are quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), the quaternization being preferably carried out with the chloride ion.
Le ou les monomères zwitterioniques peuvent également être utilisés dans le cadre de l’invention ; ils associent à la fois les charges anioniques et cationiques sur un seul et même monomère. Ils peuvent être choisis, notamment parmi les monomères du type bétaïne, sultaïne, sulfobétaïne, phosphobétaïne, et carboxybétaïne. A titre d'exemples de monomères zwitterioniques, on peut mentionner le sulfopropyl diméthylammonium éthyl méthacrylate, le sulfopropyl diméthylammonium propylméthacrylamide, le sulfopropyl 2- vinylpyridinium, et le phosphato éthyl triméthylammonium éthyl méthacrylate. The zwitterionic monomer(s) can also be used within the scope of the invention; they combine both anionic and cationic charges on a single monomer. They can be chosen, in particular from monomers of the betaine, sultaine, sulfobetaine, phosphobetaine and carboxybetaine type. As examples of zwitterionic monomers, mention may be made of sulfopropyl dimethylammonium ethyl methacrylate, sulfopropyl dimethylammonium propylmethacrylamide, sulfopropyl 2-vinylpyridinium, and phosphato ethyl trimethylammonium ethyl methacrylate.
Le polymère réticulé selon l’invention est préférentiellement un polymère cationique ou anionique. The crosslinked polymer according to the invention is preferably a cationic or anionic polymer.
Lorsque le polymère réticulé est cationique, il est préférentiellement soit un homopolymère cationique, soit un copolymère comprenant au moins un monomère cationique, et au moins un monomère non ionique. Dans ce cas, la quantité de monomère cationique est préférentiellement comprise entre 50 et 100 % mol, plus préférentiellement comprise entre 70 et 90 % mol et la quantité de monomère non ionique est préférentiellement comprise entre 0 et 50 % mol, et plus préférentiellement entre 10 et 30 % mol. When the crosslinked polymer is cationic, it is preferably either a cationic homopolymer or a copolymer comprising at least one cationic monomer and at least one nonionic monomer. In this case, the amount of cationic monomer is preferably between 50 and 100 mol%, more preferably between 70 and 90 mol% and the amount of nonionic monomer is preferably between 0 and 50 mol%, and more preferably between 10 and 30% mol.
Lorsque le polymère réticulé est anionique, il est préférentiellement soit un homopolymère anionique, soit un copolymère comprenant au moins un monomère anionique, et au moins un monomère non ionique. Dans ce cas, la quantité de monomère anionique est préférentiellement comprise entre 50 et 100 % mol, et la quantité de monomère non ionique est préférentiellement comprise entre 0 et 50 % mol. When the crosslinked polymer is anionic, it is preferably either an anionic homopolymer or a copolymer comprising at least one anionic monomer, and at least a nonionic monomer. In this case, the amount of anionic monomer is preferably between 50 and 100 mol%, and the amount of nonionic monomer is preferably between 0 and 50 mol%.
Dans la seconde alternative, les deux polymères ont préférentiellement la même ionicité. Autrement dit si le polymère réticulé avec au moins un réticulant labile est cationique, alors, le polymère réticulé avec un réticulant non labile est également cationique. In the second alternative, the two polymers preferably have the same ionicity. In other words, if the polymer crosslinked with at least one labile crosslinker is cationic, then the polymer crosslinked with a non-labile crosslinker is also cationic.
De manière générale, le polymère réticulé selon l’invention ne nécessite pas de développement de procédé de polymérisation particulier. En effet, il peut être obtenu selon toutes les techniques de polymérisation bien connues par l’homme de métier. Il peut notamment s’agir de polymérisation en solution ; polymérisation en gel ; polymérisation par précipitation ; polymérisation en émulsion (aqueuse ou inverse) ; polymérisation en suspension ; polymérisation par extrusion réactive ; polymérisation eau dans eau ; ou de polymérisation micellaire. In general, the crosslinked polymer according to the invention does not require the development of a particular polymerization process. Indeed, it can be obtained according to all the polymerization techniques well known to those skilled in the art. It can in particular be a question of polymerization in solution; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous or reverse); suspension polymerization; reactive extrusion polymerization; water-in-water polymerization; or micellar polymerization.
Le polymère selon l’invention est préférentiellement obtenu par polymérisation en émulsion inverse. L’émulsion inverse est préférentiellement distillée pour ainsi obtenir une concentration en polymère comprise préférentiellement entre 3 et 65% en poids. The polymer according to the invention is preferably obtained by inverse emulsion polymerization. The inverse emulsion is preferably distilled to thus obtain a polymer concentration preferably between 3 and 65% by weight.
Dans la seconde alternative, les deux polymères sont préférentiellement préparés séparément l’un de l’autre, puis mélangés pour obtenir la composition polymérique épaississante de l’invention. La proportion en poids de l’un par rapport à l’autre est préférentiellement comprise entre 10 :90 et 90 :10. Lorsque les polymères sont préparés séparément par émulsion inverse, il est préférable de mélanger les deux émulsions inverse dans les proportions adéquates, et d’effectuer ensuite une distillation sur le mélange obtenu pour ainsi obtenir une concentration en polymère comprise préférentiellement entre 3 et 65% en poids. In the second alternative, the two polymers are preferably prepared separately from each other, then mixed to obtain the thickening polymeric composition of the invention. The proportion by weight of one relative to the other is preferably between 10:90 and 90:10. When the polymers are prepared separately by inverse emulsion, it is preferable to mix the two inverse emulsions in the appropriate proportions, and then to carry out a distillation on the mixture obtained to thus obtain a polymer concentration preferably between 3 and 65% by weight. weight.
Ainsi, de préférence, la composition polymérique de l’invention est une émulsion inverse, le polymère est alors dans les gouttelettes d’eau de l’émulsion. Thus, preferably, the polymer composition of the invention is an inverse emulsion, the polymer is then in the water droplets of the emulsion.
La polymérisation est généralement une polymérisation à radicaux libres. Par polymérisation par radicaux libres, nous incluons la polymérisation par radicaux libres au moyen d’initiateurs UV, azoïques, redox ou thermiques ainsi que les techniques de polymérisation radicalaire contrôlée (CRP) ou les techniques de polymérisation sur matrice. La mise en œuvre de la composition polymérique épaississante pourra être faite selon les connaissances et les pratiques des formulateurs des compositions cosmétiques et détergentes. L’invention concerne également une composition cosmétique ou détergente comprenant au moins une composition polymérique épaississante selon l’invention. The polymerization is generally a free radical polymerization. By free radical polymerization we include free radical polymerization using UV, azo, redox or thermal initiators as well as controlled radical polymerization (CRP) techniques or matrix polymerization techniques. The implementation of the thickening polymeric composition can be done according to the knowledge and practices of the formulators of the cosmetic and detergent compositions. The invention also relates to a cosmetic or detergent composition comprising at least one thickening polymeric composition according to the invention.
Dans la présente invention, les compositions cosmétiques incluent également les compositions dermatologiques et pharmaceutiques. Elles comportent en général une phase aqueuse. Elles sont appliquées notamment sur la peau ou les cheveux et se présentent généralement sous la forme d’émulsions huile dans eau, et parfois eau dans huile, pour former par exemple des crèmes ou des lotions. De telles compositions peuvent, par exemple, correspondre à des crèmes ou lotions anti-âge, des soins après-rasage, des crèmes hydratantes, des lotions colorantes pour cheveux, des shampoings, des après shampoings des shampoings conditionneur, des produits de douche, des crèmes nettoyantes, ou encore des pommades ou des crèmes ou lotions solaires. Les crèmes se distinguent des lotions par leur plus forte viscosité. In the present invention, cosmetic compositions also include dermatological and pharmaceutical compositions. They generally comprise an aqueous phase. They are applied in particular to the skin or the hair and generally come in the form of oil-in-water emulsions, and sometimes water-in-oil emulsions, to form creams or lotions, for example. Such compositions can, for example, correspond to anti-ageing creams or lotions, after-shave care, moisturizing creams, hair coloring lotions, shampoos, conditioner shampoos, shower products, cleansing creams, or ointments or sun creams or lotions. Creams are distinguished from lotions by their higher viscosity.
Les épaississants ou modificateur de rhéologie sont largement utilisés dans ces compositions pour adapter leur profil sensoriel (aspect, application) aux exigences du consommateur, mais aussi pour suspendre ou stabiliser des principes actifs. Thickeners or rheology modifiers are widely used in these compositions to adapt their sensory profile (appearance, application) to consumer requirements, but also to suspend or stabilize active principles.
Par compositions détergentes, on entend des compositions pour le nettoyage de diverses surfaces, notamment de fibres textiles, de surfaces dures de toute nature comme la vaisselle, les sols, les vitres, les surfaces en bois, en métal ou en composite. De telles compositions correspondent, par exemple, à des lessives pour laver le linge manuellement ou dans une machine à laver, des produits pour nettoyer la vaisselle manuellement ou pour lave-vaisselle, des produits détergents pour laver les intérieurs de maison comme les éléments de cuisine, les toilettes, l’ameublement, les sols, les vitres, et les autres produits nettoyants à usage universel. The term “detergent compositions” means compositions for cleaning various surfaces, in particular textile fibers, hard surfaces of any kind such as dishes, floors, windows, wooden, metal or composite surfaces. Such compositions correspond, for example, to detergents for washing linen manually or in a washing machine, products for cleaning dishes manually or for dishwashers, detergent products for washing home interiors such as kitchen units , toilets, furniture, floors, windows, and other general-purpose cleaning products.
La quantité de la composition polymérique épaississante selon l’invention ajoutée dans la composition cosmétique ou détergente est préférentiellement comprise entre 0,01 et 5 % en poids, plus préférentiellement entre 0,1 et 3% en poids. The amount of thickening polymeric composition according to the invention added to the cosmetic or detergent composition is preferably between 0.01 and 5% by weight, more preferably between 0.1 and 3% by weight.
Dans la première alternative selon l’invention, la quantité de polymère réticulé, avec au moins un réticulant labile et au moins un réticulant non labile, ajoutée dans la composition cosmétique ou détergente est préférentiellement comprise entre 0,005 et 3 % en poids, plus préférentiellement entre 0,05 et 2% en poids. In the first alternative according to the invention, the amount of crosslinked polymer, with at least one labile crosslinker and at least one non-labile crosslinker, added to the cosmetic or detergent composition is preferably between 0.005 and 3% by weight, more preferably between 0.05 and 2% by weight.
Dans la seconde alternative selon l’invention, la quantité de polymère réticulé avec au moins un réticulant labile ajoutée dans la composition cosmétique ou détergente est préférentiellement comprise entre 0,0005 et 2,7 % en poids, plus préférentiellement entre 0,005 et 1 ,8% en poids, et la quantité de polymère réticulé avec au moins un réticulant non labile ajoutée dans la composition cosmétique ou détergente est préférentiellement comprise entre 0,0005 et 2,7 % en poids, plus préférentiellement entre 0,005 et 1 ,8% en poids. In the second alternative according to the invention, the amount of crosslinked polymer with at least one labile crosslinker added in the cosmetic or detergent composition is preferably between 0.0005 and 2.7% by weight, more preferably between 0.005 and 1.8 % by weight, and the amount of crosslinked polymer with at least one non-labile crosslinker added in the cosmetic or detergent composition is preferably between 0.0005 and 2.7% by weight, more preferably between 0.005 and 1.8% by weight.
Les compositions cosmétique et détergentes contiennent également d’autres ingrédients bien connus de l’homme de métier comme de l’eau, des huiles minérales ou végétales, des solvants organiques, des agents tensioactifs, des principes actifs cosmétiques ou pharmaceutiques, des vitamines, des agents chélatants, des émollients, des agents hydratants, des extraits botaniques, des filtres solaires, des adjuvants de détergence ou de nettoyage, des agents de fluorescence, des agents moussants ou des agents suppresseurs de mousse, des agents neutralisants, des agents d’ajustement du pH, des conservateurs, des parfums, des composés opacifiants, des colorants sans que cette liste soit limitative. L’homme de métier sait comment, avec quels ingrédients il peut formuler une composition cosmétique ou détergente. Pour les compositions cosmétiques on pourra se référer à la demande FR 2 979 821 , et pour les compositions détergentes on pourra se référer aux documents FR 2 766 838, FR 2 744 131 , EP 0 759 966. The cosmetic and detergent compositions also contain other ingredients well known to those skilled in the art, such as water, mineral or vegetable oils, organic solvents, surfactants, cosmetic or pharmaceutical active ingredients, vitamins, chelating agents, emollients, moisturizing agents, botanical extracts, sunscreens, detergency or cleaning aids, fluorescent agents, foaming agents or suds suppressing agents, neutralizing agents, adjusting agents pH, preservatives, perfumes, opacifying compounds, dyes without this list being exhaustive. The person skilled in the art knows how, with which ingredients he can formulate a cosmetic or detergent composition. For cosmetic compositions, reference may be made to application FR 2,979,821, and for detergent compositions, reference may be made to documents FR 2,766,838, FR 2,744,131, EP 0,759,966.
L’invention concerne aussi une méthode pour viscosifier une composition cosmétique ou détergente avec au moins une composition polymérique épaississante comme précédemment exposée. La méthode comprend la mise en œuvre de la composition polymérique selon l’invention par les techniques connues de l’homme de métier. La méthode comprend donc une étape d’addition de la composition polymérique selon l’invention dans ladite composition cosmétique ou détergente. Les quantités de composition polymérique sont telles que décrites ci-dessus. The invention also relates to a method for viscosifying a cosmetic or detergent composition with at least one thickening polymeric composition as explained above. The method comprises the implementation of the polymeric composition according to the invention by the techniques known to those skilled in the art. The method therefore comprises a step of adding the polymeric composition according to the invention to said cosmetic or detergent composition. The amounts of polymeric composition are as described above.
L’invention concerne également l’utilisation d’au moins une composition polymérique selon l’invention pour viscosifier une composition cosmétique ou détergente. Les quantités de composition polymérique sont telles que décrites ci-dessus. The invention also relates to the use of at least one polymeric composition according to the invention for viscosifying a cosmetic or detergent composition. The amounts of polymeric composition are as described above.
L’invention concerne une méthode pour maintenir la viscosité d’une composition cosmétique ou détergente dans le temps avec au moins une composition polymérique épaississante comme précédemment exposée. La méthode comprend donc une étape d’addition de la composition polymérique selon l’invention dans ladite composition cosmétique ou détergente. Les quantités de composition polymérique sont telles que décrites ci-dessus. Enfin, l’invention concerne l’utilisation d’au moins une composition polymérique selon l’invention pour maintenir la viscosité d’une composition cosmétique ou détergente dans le temps. Les quantités de composition polymérique sont telles que décrites ci-dessus. The invention relates to a method for maintaining the viscosity of a cosmetic or detergent composition over time with at least one thickening polymeric composition as explained above. The method therefore comprises a step of adding the polymeric composition according to the invention to said cosmetic or detergent composition. The amounts of polymeric composition are as described above. Finally, the invention relates to the use of at least one polymeric composition according to the invention for maintaining the viscosity of a cosmetic or detergent composition over time. The amounts of polymeric composition are as described above.
Description des figures Description of figures
La Figure 1 est une illustration schématique des phénomènes de perte de viscosité dans le temps selon l’art antérieur (partie haute), et de stratégie de maintien de viscosité dans le temps grâce à la composition polymérique selon l’invention. Figure 1 is a schematic illustration of the phenomena of loss of viscosity over time according to the prior art (upper part), and of the strategy for maintaining viscosity over time thanks to the polymer composition according to the invention.
Dans la partie haute de la figure 1 , un hydrogel obtenu à partir d’un réticulant non labile a initialement un diamètre de 30pm, puis avec le temps, l’action des électrolytes et de la température, son diamètre diminue progressivement à 20pm puis 10pm entraînant une baisse de viscosité du milieu épaissit. La présence croissante d’électrolytes diminue les répulsions ioniques à l’origine de l’effet viscosifiant conduisant à cette perte de viscosité.In the upper part of Figure 1, a hydrogel obtained from a non-labile crosslinker initially has a diameter of 30 pm, then over time, the action of electrolytes and temperature, its diameter gradually decreases to 20 pm and then 10 pm resulting in a drop in viscosity of the thickened medium. The increasing presence of electrolytes decreases the ionic repulsions at the origin of the viscosifying effect leading to this loss of viscosity.
Dans la partie basse de la figure 1 , un hydrogel du polymère obtenu à partir d’un réticulant non labile et d’un réticulant labile a initialement une taille de 10pm, puis avec le phénomène d’hydrolyse du réticulant labile (dé-réticulation), sa taille augmente progressivement à 20pm, puis à 30pm conduisant à une augmentation de la viscosité du milieu épaissit dans le temps. Cette augmentation de viscosité vient compenser dans le temps la perte de viscosité observée dans la partie haute de la figure 1 . In the lower part of figure 1, a hydrogel of the polymer obtained from a non-labile crosslinker and a labile crosslinker initially has a size of 10 μm, then with the phenomenon of hydrolysis of the labile crosslinker (de-crosslinking) , its size gradually increases at 20 μm, then at 30 μm, leading to an increase in the viscosity of the thickened medium over time. This increase in viscosity compensates over time for the loss of viscosity observed in the upper part of FIG.
La Figure 2 est un graphique représentant l’évolution de la viscosité de la solution de polymère A à E à une concentration de 1% à 80°C afin de simuler l’action des électrolytes qui se forment durant le stockage d’une composition cosmétique ou détergente. Figure 2 is a graph representing the evolution of the viscosity of the polymer solution A to E at a concentration of 1% at 80° C. in order to simulate the action of the electrolytes which are formed during the storage of a cosmetic composition or detergent.
Exemples Examples
L’ensemble des quantités exprimé en ppm sont par rapport à la quantité total de monomère en poids. All the quantities expressed in ppm are relative to the total quantity of monomer by weight.
Exemple 1 (comparatif) : Synthèse du polymère cationique par émulsion inverse avec réticulant non labile (Composition A) Example 1 (comparative): Synthesis of the cationic polymer by inverse emulsion with non-labile crosslinker (Composition A)
La phase aqueuse est préparée dans un bêcher de 1 L en mixant ensemble les ingrédients suivants : The aqueous phase is prepared in a 1 L beaker by mixing together the following ingredients:
470,0 g d’une solution d’acrylate de diméthylaminoéthyl, méthyl chloré (75% en poids dans l’eau), 470.0 g of a solution of dimethylaminoethyl acrylate, chlorinated methyl (75% by weight in water),
60,0 g d’une solution d’acrylamide (50% en poids dans l’eau), - 0,19 g de méthylènebisacrylamide (541 ppm), 60.0 g of an acrylamide solution (50% by weight in water), - 0.19 g of methylenebisacrylamide (541 ppm),
Le pH est ajusté à 5.2 +/- 0.1 avec une solution d’acide citrique. The pH is adjusted to 5.2 +/- 0.1 with a citric acid solution.
La phase organique est préparée dans un réacteur en verre de 1 L sous agitation en mixant ensemble les ingrédients suivants : The organic phase is prepared in a 1 L glass reactor with stirring by mixing together the following ingredients:
- 20,0 g de monooléate de sorbitan, - 20.0 g of sorbitan monooleate,
- 25,0 g de stabilisant polymérique (Hypermer 6212) - 25.0 g of polymeric stabilizer (Hypermer 6212)
210,0 g d’huile minérale blanche, 210.0 g of white mineral oil,
63,0 g d’hydrocarbure aliphatique (Isopar L) 63.0 g aliphatic hydrocarbon (Isopar L)
La phase aqueuse est transférée progressivement dans la phase organique sous agitation mécanique modérée. La pré-émulsion ainsi formée est alors soumise à un fort cisaillement pendant 1 min (Ultra Turax, IKA). The aqueous phase is gradually transferred into the organic phase with moderate mechanical stirring. The pre-emulsion thus formed is then subjected to high shear for 1 min (Ultra Turax, IKA).
L’émulsion inverse est alors dégazée pendant 30 minutes grâce à un barbotage d’azote.The inverse emulsion is then degassed for 30 minutes using nitrogen sparging.
La polymérisation est réalisée par addition de solution aqueuse à 1 % en poids d’un couple redox de métabisulfite de sodium et de tert-butyl hydropéroxide à un débit de 10 ml/h. The polymerization is carried out by adding a 1% by weight aqueous solution of a redox couple of sodium metabisulphite and tert-butyl hydroperoxide at a rate of 10 ml/h.
Une fois la température maximum atteinte (polymérisation adiabatique), on maintient la température du milieu réactionnel pendant 60 minutes avant refroidissement. Once the maximum temperature has been reached (adiabatic polymerization), the temperature of the reaction medium is maintained for 60 minutes before cooling.
L’émulsion obtenue est ensuite distillée sous pression réduite pour éliminer l’eau et le solvant organique volatile pour donner après distillation un produit à 58% en poids de matière active polymère. The emulsion obtained is then distilled under reduced pressure to remove the water and the volatile organic solvent to give after distillation a product with 58% by weight of active polymer material.
Enfin, en dernière étape, on ajoute 50,0 g d’un émulsionnant huile-dans-eau de type d’alcool Tridecylique 6 moles éthoxylés pour obtenir la dispersion liquide de polymère prêt à l’emploi. Finally, in the last step, 50.0 g of an oil-in-water emulsifier of the ethoxylated 6 mol tridecyl alcohol type are added to obtain the liquid dispersion of ready-to-use polymer.
Exemple 2 : Synthèse du polymère cationique par émulsion inverse avec réticulant labile et non labile (1100 ppm réticulant labile, Composition B) Example 2: Synthesis of the cationic polymer by inverse emulsion with labile and non-labile crosslinker (1100 ppm labile crosslinker, Composition B)
Le protocole de l’exemple 1 est reproduit en ajoutant 0,42 g (1 100 ppm) de réticulant labile polyéthylène glycol (200) diacrylate (PEG200DA, Sartomer SR 259). The protocol of example 1 is reproduced by adding 0.42 g (1100 ppm) of labile crosslinker polyethylene glycol (200) diacrylate (PEG200DA, Sartomer SR 259).
Exemple 3 : Synthèse du polymère cationique par émulsion inverse avec réticulant labile et non labile (3500 ppm réticulant labile, Composition C) Le protocole de l’exemple 2 est reproduit en changeant la quantité de réticulant labile à 1 ,33 g (3500 ppm/matière active). Example 3: Synthesis of the cationic polymer by inverse emulsion with labile and non-labile crosslinker (3500 ppm labile crosslinker, Composition C) The protocol of example 2 is reproduced by changing the amount of labile crosslinker to 1.33 g (3500 ppm/active material).
Exemple 4 : Synthèse du polymère cationique par émulsion inverse avec réticulant labile et non labile (5000 ppm réticulant labile, Composition D) Example 4: Synthesis of the cationic polymer by inverse emulsion with labile and non-labile crosslinker (5000 ppm labile crosslinker, Composition D)
Le protocole de l’exemple 2 est reproduit en changeant la quantité de réticulant labile à 1 ,91 g (5000 ppm/matière active). The protocol of Example 2 is reproduced by changing the amount of labile crosslinker to 1.91 g (5000 ppm/active material).
Exemple 4’ : Synthèse du polymère cationique par émulsion inverse avec réticulant labile (4000 ppm, Composition D’) Example 4': Synthesis of the cationic polymer by inverse emulsion with labile crosslinker (4000 ppm, Composition D')
Le protocole de l’exemple 2 est reproduit en changeant la quantité de réticulant labile à 1 ,91 g (5000 ppm) et la quantité de réticulant non labile à 0g. The protocol of example 2 is reproduced by changing the quantity of labile crosslinker to 1.91 g (5000 ppm) and the quantity of non-labile crosslinker to 0 g.
Exemple 5 : Combinaison d’un polymère comprenant un réticulant non labile et d’un polymère comprenant un réticulant labile (Composition E) Example 5: Combination of a polymer comprising a non-labile crosslinker and a polymer comprising a labile crosslinker (Composition E)
La composition E est obtenue par mélange 50/50 % en poids de la composition A (réticulant non labile) avec le la composition D’ (réticulant labile) avant leur étape respective de distillation, puis distillation du mélange des deux compositions. Composition E is obtained by mixing 50/50% by weight of composition A (non-labile crosslinker) with composition D' (labile crosslinker) before their respective distillation step, then distillation of the mixture of the two compositions.
Exemple 6 : Etude des compositions A à E Example 6: Study of compositions A to E
Préparation des solutions de polymère et mesure de la viscosité Preparation of polymer solutions and measurement of viscosity
Une solution de chaque composition A à E est préparée à 1 ,0% d’émulsion commerciale en ajoutant 5,0 g de la dispersion liquide correspondante obtenue selon les exemples 1 à 5 dans 495,0 g d’eau déionisée acidifié à pH = 2.8 +/- 0.1 (acide citrique) sous agitation mécanique demi-lune à 600 RPM pendant 15 min. A solution of each composition A to E is prepared at 1.0% commercial emulsion by adding 5.0 g of the corresponding liquid dispersion obtained according to Examples 1 to 5 in 495.0 g of deionized water acidified to pH = 2.8 +/- 0.1 (citric acid) under half-moon mechanical stirring at 600 RPM for 15 min.
La viscosité est mesurée sur un viscosimètre Brookfield de type RVT à une vitesse de cisaillement de 10 RPM. The viscosity is measured on a Brookfield RVT type viscometer at a shear rate of 10 RPM.
Suivi du profil de viscosité Les solutions de chaque composition A à E sont placées dans une étuve à 80°C pour simuler le vieillissement accéléré du polymère dans le temps et l’impact des électrolytes qui se forment lors du stockage d’une composition détergente ou cosmétique. Viscosity profile monitoring The solutions of each composition A to E are placed in an oven at 80° C. to simulate the accelerated aging of the polymer over time and the impact of the electrolytes which are formed during the storage of a detergent or cosmetic composition.
Les viscosités Brookfield sont contrôlées au cours du temps à une température de 23°C +/- 1 °C. La viscosité est mesurée sur plusieurs jours. Brookfield viscosities are monitored over time at a temperature of 23°C +/- 1°C. The viscosity is measured over several days.
Les résultats du suivi du profil de viscosité sont résumés dans le tableau 1 . The results of monitoring the viscosity profile are summarized in Table 1.
Tableau 1 Table 1
On voit de ce tableau qu’une chute de viscosité est observée pour le polymère de référence (composition A) et qu’elle s’accentue à partir de 8 jours pour terminer avec une perte de viscosité atteignant 37% après 34 jours. Pour les compositions B à E (selon l’invention), on observe que la chute de viscosité observée dans le temps est réduite et compensée avec la dégradation du réticulant labile. It can be seen from this table that a drop in viscosity is observed for the reference polymer (composition A) and that it increases from 8 days to end with a loss of viscosity reaching 37% after 34 days. For compositions B to E (according to the invention), it is observed that the drop in viscosity observed over time is reduced and compensated with the degradation of the labile crosslinker.

Claims

REVENDICATIONS
1. Composition polymérique pour épaissir une composition cosmétique ou détergente, ladite composition polymérique comprenant : 1. Polymeric composition for thickening a cosmetic or detergent composition, said polymeric composition comprising:
- Soit au moins un polymère réticulé avec au moins un réticulant labile et au moins un réticulant non labile, - Either at least one crosslinked polymer with at least one labile crosslinker and at least one non-labile crosslinker,
- Soit au moins deux polymères réticulés, au moins un étant réticulé avec au moins un réticulant labile, et au moins un étant réticulé avec au moins un réticulant non labile. - Either at least two crosslinked polymers, at least one being crosslinked with at least one labile crosslinker, and at least one being crosslinked with at least one non-labile crosslinker.
2. Composition polymérique selon la revendication 1 , caractérisée en ce que le polymère réticulé est un polymère synthétique obtenu à partir d’au moins un monomère ayant une insaturation éthylénique. 2. Polymer composition according to claim 1, characterized in that the crosslinked polymer is a synthetic polymer obtained from at least one monomer having ethylenic unsaturation.
3. Composition polymérique selon l’une des revendications 1 ou 2, caractérisée en ce que le réticulant labile est choisi parmi les diacrylamides et les méthacrylamides de diamines tels que le diacrylamide de pipérazine, les di, tri, tétra esters d'acrylate ou de méthacrylate, comme le diacrylate d'éthylèneglycol, le diacrylate de polyéthylèneglycol, le triméthacrylate de triméthylopropane, le triacrylate de triméthylol éthoxylé, le tétracrylate de pentaérythritol éthoxylé, et les esters vinyliques ou allyliques d'acides di ou trifonctionnels. 3. Polymeric composition according to one of claims 1 or 2, characterized in that the labile crosslinker is chosen from diacrylamides and methacrylamides of diamines such as piperazine diacrylamide, di, tri, tetra esters of acrylate or methacrylate, such as ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylopropane trimethacrylate, ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, and vinyl or allylic esters of di or trifunctional acids.
4. Composition polymérique selon l’une des revendications 1 à 3, caractérisée en ce que la quantité de réticulant labile dans le polymère réticulé est comprise entre 100 et 200 000 ppm sur la base des moles totales de monomère. 4. Polymer composition according to one of claims 1 to 3, characterized in that the amount of labile crosslinker in the crosslinked polymer is between 100 and 200,000 ppm based on the total moles of monomer.
5. Composition polymérique selon l’une des revendications 1 à 4, caractérisée en ce que le réticulant non labile est choisi parmi le méthylène bisacrylamide, la diallylamine, la triallylamine, la divinylsulfone, l'éther diallylique de diéthylèneglycol. 5. Polymeric composition according to one of claims 1 to 4, characterized in that the non-labile crosslinker is chosen from methylene bisacrylamide, diallylamine, triallylamine, divinylsulfone, diethylene glycol diallyl ether.
6. Composition polymérique selon l’une des revendications 1 à 5, caractérisée en ce que la quantité de réticulant non labile dans le polymère réticulé est comprise entre 1 et 2000 ppm sur la base des moles totales de monomère. 6. Polymer composition according to one of claims 1 to 5, characterized in that the amount of non-labile crosslinker in the crosslinked polymer is between 1 and 2000 ppm based on the total moles of monomer.
7. Composition polymérique selon l’une des revendications 1 à 6, caractérisée en ce que le polymère réticulé est un polymère cationique ou anionique. 7. Polymer composition according to one of claims 1 to 6, characterized in that the crosslinked polymer is a cationic or anionic polymer.
8. Composition polymérique selon l’une des revendications 1 à 7, caractérisée en ce qu’elle est sous forme d’émulsion inverse. 8. Polymeric composition according to one of claims 1 to 7, characterized in that it is in the form of an inverse emulsion.
9. Composition cosmétique ou détergente comprenant au moins une composition polymérique telle que décrite dans l’une des revendications 1 à 8. 9. Cosmetic or detergent composition comprising at least one polymeric composition as described in one of claims 1 to 8.
10. Composition cosmétique ou détergente selon la revendication 9 caractérisé en ce qu’elle contient une quantité de composition polymérique comprise entre 0,01 et 5 % en poids. 10. Cosmetic or detergent composition according to claim 9, characterized in that it contains an amount of polymeric composition of between 0.01 and 5% by weight.
11. Utilisation d’au moins une composition polymérique selon l’une des revendications 1 à 8 pour viscosifier une composition cosmétique ou détergente. 11. Use of at least one polymeric composition according to one of claims 1 to 8 to viscosify a cosmetic or detergent composition.
12. Utilisation d’au moins une composition polymérique selon l’une des revendications 1 à 8 pour maintenir la viscosité d’une composition cosmétique ou détergente dans le temps. 12. Use of at least one polymeric composition according to one of claims 1 to 8 to maintain the viscosity of a cosmetic or detergent composition over time.
EP22801367.8A 2021-10-05 2022-10-05 Thickening polymeric composition for cosmetic and detergent compositions Pending EP4412582A1 (en)

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FR2110531A FR3127758A1 (en) 2021-10-05 2021-10-05 THICKENING POLYMERIC COMPOSITION FOR COSMETIC AND DETERGENT COMPOSITION
PCT/EP2022/077691 WO2023057509A1 (en) 2021-10-05 2022-10-05 Thickening polymeric composition for cosmetic and detergent compositions

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Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3026293A (en) * 1959-08-06 1962-03-20 Eastman Kodak Co Acrylamidic graft copolymers and their preparation
SE424631B (en) * 1975-02-18 1982-08-02 Rohm & Haas PARTICLES OF MAKROPOROS SYNTHETIC POLYMER AND PROCEDURES FOR ITS PREPARATION
JP3042546B2 (en) * 1991-04-23 2000-05-15 昭和電工株式会社 Fine-particle crosslinked N-vinylamide resin and microgel, production method and use thereof
WO1995031523A1 (en) * 1994-05-17 1995-11-23 S.C. Johnson & Son, Inc. Laundry pre-spotter with associative polymeric thickener
US5760100B1 (en) * 1994-09-06 2000-11-14 Ciba Vision Corp Extended wear ophthalmic lens
US6107429A (en) * 1994-10-24 2000-08-22 Amcol International Corporation Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof
FR2744131B1 (en) 1996-01-31 1998-02-27 Rhone Poulenc Chimie SYSTEM BASED ON A NON-IONIC SURFACTANT AND AN ALKALI METAL SILICATE, IN THE FORM OF A DISPERSION OR GRANULES AND THEIR USE IN DETERGENCE
FR2766838B1 (en) 1997-07-29 2003-06-13 Rhodia Chimie Sa PROCESS FOR THE PREPARATION OF A SOLID DIVIDED SYSTEM BASED ON A NON-IONIC SURFACTANT AND AN ALKALI METAL SILICATE AND USE OF THE SAME AS A DETERGENCE SYSTEM
WO2001018065A1 (en) * 1999-09-08 2001-03-15 Nippon Shokubai Co., Ltd. Process for producing porous crosslinked polymer
FR2907677B1 (en) * 2006-10-25 2013-10-11 Oreal USE OF A POLYSILOXANE / POLYUREE BLOCK COPOLYMER FOR THE TREATMENT OF HAIR
WO2009019148A2 (en) * 2007-08-03 2009-02-12 Basf Se Aqueous dispersions, the production thereof, and use thereof
FR2920982B1 (en) * 2007-09-14 2009-12-04 Oreal COSMETIC COMPOSITION COMPRISING AT LEAST ONE PARTICULAR CATIONIC POLYMER, AT LEAST ONE SURFACTANT, AT LEAST ONE CATIONIC OR AMPHOTERIC POLYMER AND AT LEAST ONE ORGANIC PARTICLE, AND COSMETIC TREATMENT PROCESS
FR2979821B1 (en) 2011-09-13 2013-10-25 Oreal COSMETIC TREATMENT PROCESS EMPLOYING ETHYLENE POLYMER
FR2999423B1 (en) * 2012-12-14 2015-03-13 Oreal COSMETIC POWDER COMPOSITION COMPRISING A (METH) ACRYLIC THICKENING POLYMER, A FIXING POLYMER, WATER-INSOLUBLE PARTICLES

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