Thickening polymer composition for cosmetic and detergent formulations

Abstract

THICKENING POLYMERIC COMPOSITION FOR COSMETIC AND DETERGENT COMPOSITIONS The invention relates to a polymeric composition for thickening a cosmetic or detergent composition, said polymeric composition comprising either at least one polymer crosslinked with at least one labile crosslinker and at least one non-labile crosslinker, or 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. The polymeric composition according to the invention makes it possible to maintain the viscosity of a cosmetic or detergent composition over time. Figure for the abstract: None

Description

Description Title of the invention: THICKENING POLYMERIC COMPOSITION FOR COSMETIC AND DE- COMPOSITION DETERGENT TECHNICAL FIELD OF THE INVENTION

[0001] = The invention relates to a polymeric composition for thickening a composition cosmetic or detergent.

[0002] = PRIOR STATE OF THE TECHNOLOGY

[0003] — Cosmetic and detergent compositions, such as fabric softeners, exhibit stability problems during their lifespan and / or storage at the consumer. These instabilities are correlated with an increase in the content of electrolytes in the compositions over time. These electrolytes are derived from side effects of ingredients contained in the composition, such as esters of quaternary thinning. Time and temperature are the main influencing parameters. about these secondary reactions.

[0004] — Thickening polymers, obtained by reverse emulsification, such as polymers with quaternized dimethylaminoethyl ((M)ADAME) methacrylate bases are known to stabilize cosmetic and detergent compositions. The stabilizing property is provided by a compact stacking of hydrated polymers (or hydrogels) thickening the aqueous phase of the cosmetic or detergent composition by a charge repulsion mechanism. The resulting viscosity range depends on the volume developed by the hydrogel which itself depends on the structure of the polymer and more pre- precisely the crosslinking density in the network of the constituent polymer.

[0005] The viscosity obtained by this mechanism exhibits increased sensitivity to the presence of of electrolytes in the stabilized medium. The quantity of electrolytes generated by the The aforementioned secondary reactions lead to a drop in viscosity and therefore in stability. cosmetic and detergent compositions over time.

[0006] Electrolytes are positively or negatively charged chemical substances tively and capable of carrying or conducting an electric charge, generally in a solution.

[0007] — Currently, to compensate for this loss of viscosity or stability, manufacturers They overdose on thickening polymers in cosmetic and detergent compositions. The solution is clearly not satisfactory, and the plaintiff has sought an alternative. alternative technique.

[0008] — The problem that the invention aims to solve is to provide a thickener effective for cosmetic and detergent compositions, and making it possible to overcome 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 over time of said compositions, and preferably to maintain their viscosity over time. The improved performance provided by the invention makes it possible to reduce the amount of thickening polymer, which implies a reduction in greenhouse gas emissions such as CO2 associated with the manufacture and use of these polymers. Description of the invention The invention relates to a polymeric composition for thickening a cosmetic or detergent composition, said polymeric composition comprising: Either at least one polymer crosslinked with at least one labile crosslinking agent and at minus a non-labile crosslinking agent, Either at least two crosslinked polymers, at least one being crosslinked with au at least one labile crosslinker, and at least one being crosslinked with at least one re- non-labile ticulant. 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 thickening a cosmetic or detergent composition with at least one thickening polymeric composition according to the invention. 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 electrolyte concentration in the cosmetic or detergent composition. Thus, it is no longer necessary to overdose on the thickening polymer. The expression "maintain viscosity over time" means that the viscosity of the cosmetic or detergent composition thickened with the polymeric composition according to the invention is maintained at the same value for a period of at least one year, preferably at least three years. This expression also includes the case where the viscosity is slightly reduced (by a maximum of 10% of the initial value, preferably by a maximum of 5%), but also the case where the loss of viscosity is significantly reduced (by at least 50%, preferably by at least 80%) compared to a cosmetic or detergent composition not comprising the polymeric composition. lymeric according to the invention, and this after a period of one year. Without being bound by any particular theory, the addition of a labile crosslinking agent in combination with a non-labile one compensates for the drop in viscosity associated with an increase in electrolyte concentration in the medium. When the polymer composition is added to the cosmetic or detergent formulation, a compact stack of hydrated polymers, also called hydrogels, forms, as mentioned above. The hydrolysis of the labile crosslinking agent (decrosslinking) over time, and under the influence of temperature, increases the volume of the hydrogels in the cosmetic or detergent formulation, thus maintaining the volume fraction occupied in said formulation. The viscosity of the cosmetic or detergent formulation is therefore maintained over time. Viscosity is measured using a Brookfield viscometer at 20°C. A skilled technician can adjust not only the Brookfield viscometer's modulus but also its speed according to the viscosity of the fluid being measured. In the following description, this viscosity is referred to as Brookfield viscosity or simply viscosity. In a first alternative, the polymeric composition according to the invention comprises at least one polymer crosslinked 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. 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. The crosslinked polymer according to the invention is preferably a synthetic polymer. It is preferably obtained from at least one monomer having an 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 a zwitterionic monomer. A labile crosslinker is a crosslinker that can degrade under certain heat conditions and / or over time, after being incorporated into the polymer structure, thus reducing the degree of crosslinking in the crosslinked polymer. Storage conditions, temperature, and the presence of electrolytes cause the bonds in the labile crosslinker to break without substantially degrading the rest of the polymer backbone. The labile crosslinking agent can be chosen from among the diacrylamides and diamine methacrylamides such as piperazine diacrylamide, acrylate esters or me- thacrylate, 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 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 diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyfunctional vinyl derivatives of a polyalcohol such as ethoxylated (9-20) trimethylol triacrylate. The amount of labile crosslinking agent 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, and even more preferably between 500 and 30,000 ppm, based on the total moles of monomer. The ppm are expressed by weight. A non-labile crosslinker is one that does not degrade under temperature conditions or over time. A non-labile crosslinker allows for control of the expanded conformation of the hydrogel. The non-labile crosslinking agent can be chosen from methylene bisacrylamide, diallylamine, triallylamine, divinyl sulfone, diethylene glycol diallyl ether, and similar compounds. Methylene bisacrylamide is the preferred non-labile crosslinking agent. 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, based on the total moles of monomer. The ppm are expressed by weight. The nonionic monomer(s) that may be used in the context of the invention may 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, N-vinylpyrrolidone, acryloyl morpholine (ACMO), glycidyl methacrylate, glyceryl methacrylate, and acrylamide diacetone may also 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-butylsulfonic acid (also called ATBS or acid 2-acrylamido-2-methylpropane sulfonic acid), vinylsulfonic acid, vinyl- Phosphonic acid, the anionic monomer being unsalted, partially or totally salified, and the salts of 3-sulfopropyl methacrylate. The salified form advantageously corresponds to the salts of alkali metals (Li, Na, K…), alkaline earth metals (Ca, Mg…) or ammonium, particularly quaternary ammoniums. The preferred anionic monomers are ATBS and acrylic acid and / or their salts. Above and below, cationic monomers and anionic monomers, such as MADAME and ATBS, include unsalified, salified, partially or totally salified forms. The cationic monomer(s) that may be used in the context of the invention may be chosen, in particular, from monomers of the acrylamide, acrylic, vinyl, allylic, or maleic type possessing a quaternary ammonium function by salification or quaternization. Examples include, in particular and without limitation, quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC), and methacrylamidopropyltrimethylammonium chloride (MAPTAC). Preferred cationic monomers are quaternized dimethylaminoethyl acrylate (ADAME) and quaternized dimethylaminoethyl methacrylate (MADAME), with quaternization preferably being carried out with the chloride ion. Zwitterionic monomer(s) can also be used in the context of the invention; they combine both anionic and cationic charges on a single monomer. They can be selected, in particular, from monomers of the betaine, sultaine, sulfobetaine, phosphobetaine, and carboxybetaine types. Examples of zwitterionic monomers include sulfopropyl dimethylammonium ethyl methacrylate, sulfopropyl dimethylammonium propylmethacrylamide, sulfopropyl 2-vinylpyridinium, and phosphatoethyl trimethylammonium ethyl methacrylate. The crosslinked polymer according to the invention is preferably a cationic or anionic polymer. 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 non-ionic 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 non-ionic monomer is preferably between 0 and 50 mol%, and more preferably between 10 and 30 mol%. When the crosslinked polymer is anionic, it is preferably either an anionic homopolymer or a copolymer comprising at least one monomer. anionic, and at least one non-ionic monomer. In this case, the amount of anionic monomer is preferably between 50 and 100 mol%, and the amount of non-ionic monomer is preferably between 0 and 50 mol%. In the second alternative, the two polymers preferentially 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. In general, the crosslinked polymer according to the invention does not require the development of a specific polymerization process. Indeed, it can be obtained using all polymerization techniques well known to those skilled in the art. These may include, in particular, solution polymerization; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous or inverse); suspension polymerization; reactive extrusion polymerization; water-in-water polymerization; or micellar polymerization. The polymer according to the invention is preferably obtained by reverse emulsion polymerization. The reverse emulsion is preferably distilled to obtain a polymer concentration preferably between 3 and 65% by weight. In the second alternative, the two polymers are preferably prepared separately from each other and then mixed to obtain the thickening polymer composition of the invention. The weight proportion of one 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 distill the resulting mixture to obtain a polymer concentration preferably between 3 and 65% by weight. Thus, preferably, the polymeric 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. 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 polymer composition can be done according to the knowledge and practices of formulators of 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. 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 hair and are generally in the form of oil-in-water emulsions, and sometimes water-in-oil emulsions, to form, for example, creams or lotions. Such compositions may, for example, correspond to anti-aging creams or lotions, aftershaves, moisturizing creams, hair coloring lotions, shampoos, conditioners, shampoo-conditioners, shower products, cleansing creams, or even ointments or sunscreens. 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 ingredients. Detergent compositions are defined as compositions for cleaning various surfaces, including textile fibers, hard surfaces of all kinds such as dishes, floors, windows, and surfaces made of wood, metal, or composite materials. Examples of such compositions include laundry detergents for washing clothes by hand or in a washing machine, products for cleaning dishes by hand or in dishwashers, cleaning products for household interiors such as kitchen units, toilets, furniture, floors, windows, and other general-purpose cleaning products. The quantity of the 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. In the first alternative according to the invention, the quantity 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. In the second alternative according to the invention, the quantity of polymer crosslinked with at least one labile crosslinker added to 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 quantity of polymer crosslinked with at least one non-labile crosslinker added to 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. 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, and cosmetic active ingredients. Cosmetic or pharmaceutical ingredients, vitamins, chelating agents, emollients, moisturizing agents, botanical extracts, sunscreens, detergent or cleaning aids, fluorescent agents, foaming or foam-suppressing agents, neutralizing agents, pH-adjusting agents, preservatives, perfumes, opacifying compounds, and colorants are all permitted, without this list being exhaustive. A person skilled in the art knows how and with which ingredients to 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, and EP 0 759 966. The invention also relates to a method for thickening a cosmetic or detergent composition with at least one polymeric thickening composition as previously described. The method comprises the preparation of the polymeric composition according to the invention using techniques known to those skilled in the art. The method therefore includes a step of adding the polymeric composition according to the invention to said cosmetic or detergent composition. The quantities 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 thickening a cosmetic or detergent composition. The quantities 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 polymer composition as previously described. The method therefore includes a step of adding the polymer composition according to the invention to said cosmetic or detergent composition. The quantities of polymer composition are as described above. Finally, the invention relates to the use of at least one polymeric composition according to the invention to maintain the viscosity of a cosmetic or detergent composition over time. The quantities of polymeric composition are as described above. [Fig.1] The [Fig.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 of maintaining viscosity over time thanks to the polymeric composition according to the invention. In the upper part of [Fig. 1], a hydrogel obtained from a non-labile crosslinking agent initially has a diameter of 30 µm. Over time, due to the action of electrolytes and temperature, its diameter gradually decreases to 20 µm and then 10 µm, resulting in a decrease in the viscosity of the thickened medium. The increasing presence of electrolytes reduces the ionic repulsions responsible for the viscosifying effect, leading to this loss of viscosity. In the lower part of [Fig. 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 hydrolysis of the labile crosslinker (de-crosslinking), its size progressively increases to 20 µm, then to 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. 1].

Claims

Demands

1. Polymeric composition for thickening a cosmetic composition or detergent, said polymeric composition comprising: - Either at least one polymer crosslinked with at least one labile crosslinking agent and at least one non-labile crosslinking agent. - Either at least two cross-linked polymers, at least one of which is cross-linked with at least one labile crosslinking agent, and at least one being crosslinked with at minus a non-labile crosslinking agent.

2. Polymeric composition according to claim 1, characterized in that that the cross-linked polymer is a synthetic polymer obtained from of at least one monomer having an ethylenic unsaturation.

3. Polymeric composition according to claim 1 or 2, ca- characterized in that the labile crosslinking agent is chosen from among the diacrylamides and diamine methacrylamides such as pi- diacrylamide perazine, acrylate or methacrylate esters, diacrylate ethylene glycol, polyethylene glycol diacrylate, trimethacrylate trimethylopropane, ethoxylated trimethylol triacrylate, the te- ethoxylated pentaerythritol tacrylate, and vinyl or al- esters 1ylics of di or trifunctional acids.

4. Polymeric composition according to any one of claims 1 to 3, ca- characterized in that the amount of labile crosslinking agent in the polymer The crosslinked concentration is between 100 and 200,000 ppm based on moles. total monomer.

5. Polymeric composition according to any one of claims 1 to 4, ca- characterized in that the non-labile crosslinking agent is chosen from methylene bisacrylamide, diallylamine, triallylamine, divinylsulfone, ether diallylic diethylene glycol.

6. Polymeric composition according to any one of claims 1 to 5, ca- characterized in that the amount of non-labile crosslinker in the polymer The cross-linked concentration is between 1 and 2000 ppm based on total moles. of monomer.

7. Polymeric composition according to any one of claims 1 to 6, ca- characterized in that the crosslinked polymer is a cationic polymer or anionic.

8. Polymeric composition according to any one of claims 1 to 7, ca- characterized in that it is in the form of a reverse emulsion.

9. Cosmetic or detergent composition comprising at least one com- polymeric position as described in any one of claims 1 to 8.

10. Cosmetic or detergent composition according to claim 9 ca- characterized by its containing a quantity of polymeric composition between 0.01 and 5% by weight.

11. | Use of at least one polymeric composition according to one of the re- recommendations 1 to 8 for thickening a cosmetic composition or de- tergent.

12. Use of at least one polymeric composition according to one of the re- Recommendations 1 to 8 for maintaining the viscosity of a composition cosmetic or detergent over time.