Patent Application
20050176600
Disclosed herein are novel cosmetic compositions with one or more improved properties, intended for cleaning, conditioning, and/or styling keratin materials, such as the hair, and comprising, in a cosmetically acceptable medium, a washing base comprising at least one surfactant with detergent power, at least one nonaminated silicone, and at least one drawing polymer of high molecular weight. Also disclosed herein is the use of the compositions in a cosmetic application.
It is common practice to use detergent hair compositions (or shampoos) based, for example, essentially on standard anionic, nonionic and/or amphoteric surfactants, such as anionic surfactants, to clean and/or wash the hair. These compositions are applied to wet hair and the lather generated by massaging or rubbing with the hands removes, after rinsing with water, the various types of soiling initially present on the hair.
These base compositions may have good washing power, but the intrinsic cosmetic properties associated therewith nevertheless remain fairly poor. Poor cosmetic properties may be attributed to the relatively aggressive nature of such a cleaning treatment which can, in the long run, lead to more or less pronounced damage to the hair fiber, this damage being associated with the gradual removal of the lipids and/or proteins contained in or on the surface of this fiber.
Thus, in order to improve the cosmetic properties of the above detergent compositions, such as those that are intended to be applied to sensitized hair (i.e., hair that has been damaged or made brittle, for example due to the chemical action of atmospheric agents and/or hair treatments such as permanent-waving, dyeing, and/or bleaching), it is now common practice to introduce additional cosmetic agents known as conditioners into these compositions. These conditioners are intended mainly to repair or limit the harmful or undesirable effects induced by the various treatments or aggressions to which the hair fibers may be subjected more or less repeatedly. These conditioners may, of course, also improve the cosmetic behavior of natural hair.
The conditioners most commonly used in shampoos are cationic polymers, which give washed, dry, or wet hair an ease of disentangling, softness, and/or smoothness that may be better than those that may be obtained with corresponding cleaning compositions from which the conditioners are absent.
Moreover, it has for some time been sought to obtain conditioning shampoos that are capable of giving washed hair not only the cosmetic properties mentioned above, but also, to a greater or lesser extent, styling, volume, shaping, and/or hold properties. These washing shampoos with one or more improved general cosmetic properties may be referred to for simplicity as “styling shampoos”, and this term will be adopted in the description hereinbelow.
However, despite the progress made recently in the field of styling shampoos, these shampoos are not really completely satisfactory, and as such there is currently still a strong need to provide novel products that give better performance with respect to one or more of the cosmetic properties mentioned above. For example, it may be necessary to use a styling product after shampooing, to give the hair a shape and to fix the style.
The present disclosure is directed towards satisfying such a need.
Thus, after considerable research conducted in this matter, it has now been found that by combining at least one nonaminated silicone of a particular viscosity, as defined below, with at least one polymer that has a particular drawing power in detergent compositions, it may be possible to substantially and significantly improve the styling and hold properties, while at the same time maintaining good intrinsic washing power and cosmetic properties.
These compositions may make it possible to obtain very good hold and a certain amount of volume for the hair, i.e., a styling effect similar to that obtained with a fixing styling gel used after shampooing. It is moreover found that the keratin fibers are strengthened (hardened).
These discoveries form the basis of the present disclosure.
Thus, according to certain embodiments disclosed herein, novel compositions for washing keratin materials, such as the hair, are now proposed, comprising, in a cosmetically acceptable aqueous medium, at least one nonaminated silicone with a viscosity lower than 100,000 cst (mm2/s), at least one anionic, nonionic, or amphoteric detergent surfactant, and at least one polymer with a drawing power of greater than 5 cm.
One embodiment disclosed herein is also the cosmetic use of the above compositions for cleaning, conditioning, caring for, and styling keratin materials, such as the hair and the eyelashes.
Another embodiment disclosed herein comprises a cosmetic process for treating keratin materials, such as keratin fibers, for example the hair and the eyelashes, using the composition disclosed herein.
A further embodiment is the use of the composition disclosed herein as a shampoo.
However, other characteristics, aspects, and advantages will emerge even more clearly on reading the description that follows, as well as the concrete, but in no way limiting, examples intended to illustrate certain embodiments.
As used herein, the drawing power of a polymer corresponds to the length of the polymer yarn obtained at the breaking point of the yarn according to the procedure defined below.
The drawing power of the polymers that may be used according to the present disclosure may be the power measured for a composition containing (% by weight):
The drawing power may be measured using a TA-TX2 texture analyser (Rheo/stable Micro Systems).
The measurement may be performed after compression of the product:
In the present disclosure, the polymers with a drawing power of greater than 5 cm will also be referred to as drawing polymers.
According to one embodiment, the polymers with a drawing power of greater than 5 cm may be either (a1) a dispersion of particles of at least one water-soluble cationic polymer with a weight-average molecular mass of greater than 106 in a saline aqueous solution, obtained by heterogeneous free-radical polymerization of water-soluble monomers with precipitation of the polymer formed, or (a2) an aqueous solution of at least one water-soluble cationic polymer with a weight-average molecular mass of greater than 106, obtained by heterogeneous free-radical polymerization of water-soluble monomers with precipitation of the polymer formed.
As used herein, the term “cationic polymer” includes polymers comprising cationic monomers and optionally comprising nonionic monomers.
The high molecular weight water-soluble cationic polymer can be a polyelectrolyte polymerized using at least one cationic monomer of formula (I), as defined below.
As indicated above, the synthesis of the high molecular weight water-soluble polymers used herein may take place by heterogeneous free-radical polymerization of water-soluble monomers comprising at least one ethylenic unsaturation. The polymerization may take place in an aqueous solution of a mineral electrolyte (salt) having an ionic strength that is sufficient to cause precipitation of the polymer formed as soon as it has reached a certain molecular mass. This polymerization technique thus allows, by virtue of the well-known phenomenon of salting out, the preparation of saline aqueous dispersions of water-soluble polymer particles. The polymers thus synthesized are distinguished by a high weight-average molecular mass, which may be greater than 106.
The technique of heterogeneous free-radical polymerization in an aqueous medium with precipitation of the polymer formed is described, for example, in U.S. Pat. No. 4,929,655, in European Patent Application No. EP 0 943 628, and in PCT International Patent Application No. WO 02/34796.
To ensure the stability of the dispersions of polymer particles during the synthesis and during storage, one may perform the polymerization in the presence of a dispersant. This dispersant may be a polyelectrolyte, which, unlike the high molecular weight polymer used herein, is soluble in the aqueous polymerization medium of high ionic strength.
This dispersing polyelectrolyte may have a charge identical to that of the polymer synthesized. In other words, for the synthesis of cationic polyelectrolytes, a cationic dispersing polyelectrolyte may be used.
Dispersants that may be mentioned include the cationic polyelectrolytes obtained by polymerization of 50 to 100 mol % of at least one cationic monomer chosen from salts, such as hydrochlorides and sulphates of dimethylaminoethyl (meth)acrylate, of N-dimethylaminopropyl(meth)-acrylamide, of di(meth)allylamine, and of 50 to 100 mol % of acrylamide; (meth )acryloyloxy-ethyltrimethylammonium chloride; (meth )acrylamido-propyltrimethylammonium chloride; and dimethyldiallyl-ammonium chloride. A polyamine such as a polyalkyleneamine may also be used.
The dispersant may be used in an amount ranging from 1% to 10% by weight relative to the total weight of the monomers to be polymerized.
The saline aqueous solution that may serve as a synthesis and dispersion medium for the high molecular weight water-soluble polymer may be a solution of at least one mineral salt which may be chosen from divalent anionic salts. Examples of anionic salts that may be mentioned include ammonium sulphate, ammonium hydrogen sulphate, ammonium chloride, sodium sulphate, sodium hydrogen sulphate, magnesium sulphate, magnesium hydrogen sulphate, aluminium sulphate, and aluminium hydrogen sulphate. Ammonium sulphate and sodium sulphate, for example, may be mentioned.
The concentration of this at least one salt may be sufficient to induce the precipitation of the water-soluble polymer formed in the polymerization medium, and may be up to the saturation concentration of each salt. To obtain such a precipitation, the salt concentration may be at least equal to 10% by weight, such as greater than 15% by weight and less than 50% by weight relative to the total weight of the polymer solution or dispersion. The saline aqueous solution may also contain monovalent salts such as sodium chloride and ammonium chloride.
The heterogeneous free-radical polymerization in aqueous medium as described above may be accompanied by a large increase in the viscosity of the reaction medium, which may be reflected by difficulties in stirring, a lack of homogeneity of the reaction medium, and an increase in the particle size of the polymer particles formed. To prevent such an increase in viscosity, it has been proposed, for example in European Patent Application No. EP 0 943 628, to add to the polymerization medium at least one agent for preventing the increase in viscosity of the reaction medium during polymerization.
The high molecular weight water-soluble polymers used herein may be prepared in the presence of at least one such agent for preventing an increase in viscosity.
The at least one agent for preventing an increase in viscosity of the reaction medium may be chosen, for example, from:
The addition of at least one agent for preventing an increase in viscosity as described above may make it possible to perform the polymerization of the water-soluble monomers described above with a low-power stirrer while at the same time avoiding the formation of coarse particles. The at least one agent for preventing an increase in viscosity may be soluble in the aqueous reaction medium.
Examples of compounds (A) that may be mentioned include oxalic acid, adipic acid, tartaric acid, malic acid, phthalic acid, and the salts thereof.
Examples of compounds (B) that may be mentioned include resorcinol and pyrogallol.
Examples of compounds (C) that may be mentioned include m-hydroxybenzoic acid, p-hydroxybenzoic acid, salicylic acid, gallic acid, tannic acid, and the salts thereof.
Examples of compounds (D) that may be mentioned include sodium gluconate, potassium gluconate, ammonium gluconate, and various amine salts of gluconic acid.
Examples of compounds (E) that may be mentioned include those obtained by reacting a free-radical-generating compound, under a stream of oxygenated gas, in a solution containing methoxyhydroquinone and/or a cationic (meth)acrylic monomer. The free-radical-generating compound may be an initiator commonly used for free-radical polymerization. Examples that may be mentioned include water-soluble azo initiators such as 2,2′-azobis(2-amidinopropane) hydrochloride sold, for example, under the name V-50 by the company Wako Chemical Industries, and 2,2′-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride sold, for example, under the name VA-044 by the company Wako Chemical Industries, and an initiator from the group of water-soluble redox agents, such as the ammonium persulphate/sodium hydrogen sulphite combination.
The at least one agent for preventing an increase in viscosity (F) may be obtained by reacting a free-radical initiator, under a oxygenated atmosphere, with a dispersant as disclosed herein. The polymerization initiator may be a water-soluble azo initiator or a water-soluble redox agent as described above.
The compounds (G) may be obtained in the form of oxidized polymers of low molecular mass by oxidation of at least one cationic dispersant as disclosed herein obtained by polymerization of a cationic (meth)acrylic monomer, using hydrogen peroxide or a halogen as oxidizing agent.
As cationic (meth)acrylic monomers used for the preparation of the at least one agent for preventing an increase in viscosity (E), (F), and (G), examples that may be mentioned include dimethylaminoethyl (meth)acrylate hydrochloride and sulphate, (meth)acryloyloxyethyl-trimethylammonium chloride, (meth )acryloyloxyethyl-dimethylbenzylammonium chloride, the hydrochloride and sulphate derived from N-dimethylaminopropyl(meth)-acrylamide, (meth)acrylamidopropyltrimethylammonium chloride, dimethylaminohydroxypropyl (meth)acrylate chloride and sulphate, (meth )acryloyloxyhydroxypropyl-trimethylammonium chloride, and (meth)acryloyloxyhydroxypropyldimethylbenzylammonium chloride.
The at least one agent for preventing an increase in viscosity (A) to (G) may be used alone or as a mixture, in an amount ranging, for example, from 10 ppm to 10,000 ppm, relative to the total weight of the reaction solution.
The water-soluble monomers polymerized by heterogeneous free-radical polymerization to obtain high molecular weight water-soluble cationic polymers are monomers comprising at least one ethylenic double bond, for example vinyl, acrylic, and allylic double bonds. They may be cationic or nonionic and may be used as a mixture.
Water-soluble nonionic monomers that may be mentioned include acrylamide, methacrylamide, N-vinylformamide, N-vinylacetonamide, hydroxypropyl acrylate, and hydroxypropyl methacrylate.
The water-soluble cationic monomers may be chosen from di(C1-4 alkyl)diallylammonium salts and the compounds of formula (I)
in which
Examples of water-soluble cationic monomers that may be mentioned include dimethylaminoethyl (meth)acrylate hydrochloride and sulphate, (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, N-dimethylaminopropyl(meth)acrylamide hydrochloride and sulphate, (meth)acrylamidopropyltrimethylammonium chloride, (meth)acrylamidopropyldimethylbenzylammonium chloride, dimethylaminohydroxypropyl (meth)acrylate hydrochloride and sulphate, (meth)acryloyloxyhydroxypropyltrimethylammonium chloride, (meth)acryloyloxyhydroxypropyldimethylbenzylammonium chloride, and dimethyldiallylammonium chloride.
In one embodiment disclosed herein, the high molecular weight water-soluble polymer is obtained by heterogeneous free-radical polymerization of a monomer mixture comprising from 0 to 95.5 mol % of acrylamide and from 4.5 to 100 mol % of at least one cationic monomer of formula (I).
According to one embodiment, the water-soluble polymers are obtained by polymerization of a monomer mixture comprising acrylamide and at least one cationic monomer of formula (I), in which the number of moles of the at least one cationic monomer of formula (I) is greater than the number of moles of acrylamide.
Water-soluble cationic polymers that may be mentioned include, for example, those polymerized using monomer mixtures comprising, respectively:
The water-soluble polymers used herein have a weight-average molecular mass of greater than 1,000,000, such as a mass ranging from 1,000,000 to 50,000,000 or ranging from 1,000,000 to 20,000,000. This weight-average molecular mass may be determined via the RSV (Reduced Specific Viscosity) method as defined in “Principles of Polymer Chemistry”, Cornell University Press, Ithaca, N.Y., 1953, chapter VII entitled “Determination of Molecular Weight”, pages 266-316.
The concentration of the high molecular weight water-soluble polymer dispersion or solution may be chosen such that the concentration of the water-soluble polymer ranges from 0.01% to 20% by weight, such as from 0.05% to 5%, by weight relative to the total weight of the final composition.
The concentration of the at least one drawing polymer disclosed herein may range from 0.01% to 10% by weight, such as from 0.05% to 5% by weight, relative to the total weight of the final composition.
The at least one detergent surfactant is chosen from anionic, amphoteric, nonionic, and zwitterionic surfactants.
Thus, according to the present disclosure, the at least one detergent surfactant may represent from 4% to 50% by weight, such as from 6% to 30% by weight or from 8% to 25% by weight, relative to the total weight of the final composition.
The at least one detergent surfactant that may be suitable for carrying out certain embodiments disclosed herein include the following:
(i) At Least One Anionic Surfactant:
As disclosed herein, the at least one anionic surfactant is optional.
Thus, as examples of the at least one anionic surfactant that may be used, mention may be made (as a non-limiting list) of salts (such as alkaline salts, for example sodium salts, ammonium salts, amine salts, amino alcohol salts, and magnesium salts) of the following compounds: alkyl sulphates, alkyl ether sulphates, alkylamido ether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates, alkyl sulphonates, alkyl phosphates, alkylamide sulphonates, alkylaryl sulphonates, α-olefin sulphonates, paraffin sulphonates, alkyl sulphosuccinates, alkyl ether sulphosuccinates, alkylamide sulphosuccinates, alkyl sulphosuccinamates, alkyl sulphoacetates, alkyl ether phosphates, acyl sarcosinates, acyl isethionates, and N-acyltaurates, wherein the alkyl or acyl radical of all of these various compounds may have from 12 to 20 carbon atoms, and the aryl radical may be chosen from phenyl and benzyl groups. Among the at least one anionic surfactant that may be used, mention may also be made of fatty acid salts such as the salts of oleic, ricinoleic, palmitic, and stearic acids; coconut oil acid; hydrogenated coconut oil acid; and acyl lactylates in which the acyl radical contains 8 to 20 carbon atoms. Use may also be made of at least one weakly anionic surfactant, such as alkyl-D-galactosiduronic acids and their salts, and polyoxyalkylenated carboxylic ether acids and their salts, such as those containing from 2 to 50 ethylene oxide groups. Anionic surfactants of the polyoxyalkylenated carboxylic ether acid or salt type may, for example, correspond to formula (1) below:
R1-(OC2H4)n—OCH2COOA (1)
in which:
Compounds of formula (1) are sold, for example, by the company Chem Y under the name Akypo® (NP40, NP70, OP40, OP80, RLM25, RLM38, RLMQ 38 NV, RLM 45, RLM 45 NV, RLM 100, RLM 100 NV, RO 20, RO 90, RCS 60, RS 60, RS 100, and RO 50) and by the company Sandoz under the name Sandopan® (DTC Acid and DTC).
(ii) At Least One Nonionic Surfactant:
Nonionic surfactants are likewise compounds that are well known per se (see in this respect “Handbook of Surfactants” by M. R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178) and, as used herein, the at least one nonionic surfactant is optional. Thus, it may be chosen from (as a non-limiting list) polyethoxylated, polypropoxylated, and polyglycerolated fatty alcohols; polyethoxylated, polypropoxylated, and polyglycerolated fatty α-diols; polyethoxylated, polypropoxylated, and polyglycerolated fatty alkylphenols; and polyethoxylated, polypropoxylated, and polyglycerolated fatty acids, all having a fatty chain containing, for example, 8 to 18 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range, for example, from 2 to 50 and for the number of glycerol groups to range, for example, from 2 to 30. Mention may also be made of copolymers of ethylene oxide and of propylene oxide; condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides, for example polyoethoxylated fatty amides having from 2 to 30 mol of ethylene oxide; polyglycerolated fatty amides having on average 1 to 5, such as 1.5 to 4, glycerol groups; oxyethylenated fatty acid esters of sorbitan having from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol alkylpolyglycosides; N-alkylglucamine derivatives; amine oxides such as (C10-C14)alkylamine oxides; and N-acylaminopropylmorpholine oxides. The alkylpolyglycosides may be mentioned as nonionic surfactants that are suitable in the context of the present disclosure.
(iii) At Least One Amphoteric or Zwitterionic Surfactant:
The at least one amphoteric or zwitterionic surfactant, which is optional according to embodiments disclosed herein, can be, for example (as a non-limiting list), aliphatic secondary and tertiary amine derivatives in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulphonate, sulphate, phosphate and phosphonate groups); mention may also be made of (C8-C20)alkylbetaines, sulphobetaines, (C8-C20)alkylamido (C1-C6)alkylbetaines, and (C8-C20)alkylamido(C1-C6)alkylsulphobetaines.
Among the amine derivatives, mention may be made of the products sold under the name Miranol®, as described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates, with the respective structures (2) and (3):
R2-CONHCH2CH2—N+(R3)(R4)(CH2COO−) (2)
For example, mention may be made of the cocoamphocarboxyglycinate sold under the trade name Miranol® C2M concentrate by the company Miranol.
Mixtures of surfactants, for example mixtures of anionic surfactants, mixtures of anionic surfactants and of amphoteric, cationic or nonionic surfactants, and mixtures of cationic surfactants with nonionic or amphoteric surfactants, may be used in the compositions as disclosed herein. A mixture that may be mentioned is a mixture comprising at least one anionic surfactant and at least one amphoteric surfactant.
The amount of the at least one anionic surfactant ranges from 4% to 50% by weight relative to the total weight of the cosmetic composition. It may, for example, range from 5% to 35% by weight or from 8% to 25% by weight, relative to the total weight of the cosmetic composition.
The amount of the at least one amphoteric and/or nonionic surfactant, when it is present, may range from 0.5% to 20% by weight, such as from 1% to 15% by weight, relative to the total weight of the composition.
In general, as used herein, the term “nonaminated silicone” denotes any silicone not containing at least one primary, secondary, or tertiary amine or one quaternary ammonium group.
Nonaminated silicones having a viscosity of less than 100,000 mm2/s which can be used in accordance with certain embodiments may include polyorganosiloxanes that are insoluble in the composition and may be in the form of oils, waxes, and resins. The silicones may have a viscosity ranging from 1,000 to 100,000 cst, such as from 10,000 to 80,000 cst.
The organopolysiloxanes are defined in greater detail in Walter NOLL “Chemistry and Technology of Silicones” (1968) Academie Press.
Non-volatile silicones may be used according to certain embodiments, including for example at least one of polydialkylsiloxanes, polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums, silicone resins, and polyorganosiloxanes modified with organofunctional groups.
These silicones, may, for example, be chosen from polyalkylsiloxanes, among which mention may be made of polydimethylsiloxanes containing trimethylsilyl end groups and having a viscosity ranging from 100 to 100,000 mm2/s (cSt) at 25° C., such as from 1,000 to 100,000 mm2/s (cSt) or from 10,000 to 80,000 mm2/s (cSt). The viscosity of the silicones may be measured, for example, at 25° C. according to ASTM standard 445 Appendix C.
Among these polyalkylsiloxanes, mention may be made, in a non-limiting manner, of the following commercial products:
Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhône Poulenc.
In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil® Wax 9800 and 9801 by the company Goldschmidt, which are poly(C1-C20)dialkylsiloxanes.
The polyalkylarylsiloxanes may be chosen from polydimethyl/methylphenylsiloxanes, linear and/or branched polydimethyldiphenylsiloxanes with a viscosity ranging from 10 mm2/s to 5,000 mm2/s at 25° C., such as a viscosity ranging from 100 mm2/s to 5,000 mm2/s.
Among these polyalkylarylsiloxanes, examples that may be mentioned include the products sold under the following names:
The organomodified silicones that can be used in accordance with certain embodiments are silicones as defined above and containing in their structure one or more organofunctional groups attached via a hydrocarbon-based radical.
Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising:
According to certain embodiments, it is also possible to use silicones comprising a polysiloxane portion and a portion comprising a non-silicone organic chain, one of the two portions constituting the main chain of the polymer and the other being grafted onto the main chain. These polymers are described for example in Patent Application Nos. EP A 412 704, EP A 412 707, EP A 640 105, WO 95/00578, EP A 582 152, and WO 93/23009 and U.S. Pat. Nos. 4,693,935, 4,728,571, and 4,972,037. These polymers may be anionic or non-ionic.
Such polymers are for example the copolymers which can be obtained by free-radical polymerization from the mixture of monomers comprising:
Other examples of graft silicone polymers include polydimethylsiloxanes (PDMS) onto which mixed polymer units of the poly(meth)acrylic acid type and of the polyalkyl (meth)acrylate type are grafted via a connecting member of the thiopropylene type and polydimethylsiloxanes (PDMS) onto which polymer units of the polyisobutyl (meth)acrylate type are grafted via a connecting member of the thiopropylene type.
According to certain embodiments, the silicones may also be used in the form of emulsions, nanoemulsions, and microemulsions.
The polyorganosiloxanes that may be mentioned include:
According to certain embodiments, the at least one nonaminated silicone may represent in an amount ranging from 0.001% to 20% by weight, such as from 0.01% to 10% by weight or from 0.1% to 3% by weight, relative to the total weight of the final composition.
According to one embodiment, the compositions may also comprise at least one cationic polymer other than the at least one drawing polymer disclosed herein.
The at least one cationic polymer that may be used may be chosen from those already known per se as improving the cosmetic properties of the hair, i.e., those described in European Patent Application No. EP A 0 337 354 and in French Patent Application Nos. FR A 2 270 846, 2 383 660, 2 598 611, 2 470 596, and 2 519 863, and having a suitable cationic charge density.
As used herein, the term “cationic polymer” denotes any polymer comprising cationic groups and/or groups that may be ionized into cationic groups.
Mention may be made of the cationic polymers that are chosen from those containing units comprising primary, secondary, tertiary, and/or quaternary amine groups that either may form part of the main polymer chain or may be borne by a side substituent directly attached thereto.
The at least one cationic polymer used may have a number-average or weight-average molar mass ranging from 500 to5×106, such as from 103 to 3×106.
Among the cationic polymers that may be mentioned are polymers of the polyamine, polyamino amide, and polyquaternary ammonium type. These are known products.
The polymers of the polyamine, polyamido amide, and polyquaternary ammonium type that may be used in accordance with certain embodiments include those described, for example, in French Patent Nos. 2 505 348 and 2 542 997. Among these polymers, mention may be made of:
The copolymers of this group (1) may also comprise one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides, and methacrylamides substituted on the nitrogen with at least one of lower (C1-C4) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.
Thus, among these copolymers of group (1), mention may be made of:
(2) cationic polysaccharides, such as cationic celluloses and cationic galactomannan gums. Among the cationic polysaccharides that may be mentioned are cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers, cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and cationic galactomannan gums.
The cellulose ether derivatives comprising quaternary ammonium groups are described, for example, in French Patent No.1 492 597. These polymers are also defined in the CTFA dictionary as hydroxyethylcellulose quaternary ammoniums that have reacted with an epoxide substituted with a trimethylammonium group.
The cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described for example in U.S. Pat, No. 4,131,576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl-, or hydroxypropylcelluloses grafted, for example, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
The cationic galactomannan gums are described for example in U.S. Pat. Nos. 3,589,578 and 4,031,307, for example guar gums containing trialkylammonium cationic groups. Use is made, for example, of guar gums modified with a salt (e.g., chloride) of 2,3-epoxypropyltrimethylammonium.
(3) polymers comprising piperazinyl units and divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted by at least one of oxygen, sulphur, nitrogen, and aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers. Such polymers are described, for example, in French Patent Nos. 2 162 025 and 2 280 361.
(4) water-soluble polyamino amides prepared, for instance, by polycondensation of an acidic compound with a polyamine. These polyamino amides can be crosslinked with at least one group chosen from epihalohydrins, diepoxides, dianhydrides, unsaturated dianhydrides, bis-unsaturated derivatives, bis-halohydrins, bis-azetidiniums, bis-haloacyidiamines, bis-alkyl halides, and oligomers resulting from the reaction of a difunctional compound that is reactive with respect to at least one group chosen from bis-halohydrins, bis-azetidiniums, bis-haloacyldiamines, bis-alkyl halides, epihalohydrins, diepoxides, and bis-unsaturated derivatives; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyamino amide. These polyamino amides can be alkylated or, if they contain one or more tertiary amine functions, they can be quaternized. Such polymers are described, for example, in French Patent Nos. 2 252 840 and 2 368 508.
(5) polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms, such as methyl, ethyl, and propyl radicals. Such polymers are described for example in French Patent No.1 583 363.
Among these derivatives, mention may be made of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.
(6) polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid may range from 0.8:1 to 1.4:1. The polyamino amide resulting therefrom may be reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyamino amide ranging from 0.5:1 to 1.8:1. Such polymers are described for example in U.S. Pat. Nos. 3,227,615 and 2,961,347.
Polymers of this type are sold for example under the name Hercosett® 57 by the company Hercules Inc., in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer.
(7) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (I′) or (I″):
In one embodiment, R10 and R11, independently of each other, may denote an alkyl group containing from 1 to 4 carbon atoms.
Among the polymers defined above, mention may be made of the dimethyldiallylammonium chloride homopolymer sold under the name Merquat® 100 by the company Nalco (and its homologues of low weight-average molar mass) and copolymers of diallyldimethylammonium chloride and of acrylamide.
(8) diquaternary ammonium polymers containing repeating units corresponding to the formula:
in which formula (II):
In certain embodiments, X− is an anion such as chloride and bromide.
These polymers may have a number-average molar mass ranging from 1,000 to 100,000.
Polymers of this type are described for example in French Patent Nos. 2 320 330, 2 270 846, 2 316 271, 2 336 434, and 2 413 907 and U.S. Pat. Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; 2,261,002; 2,271,378; 3,874,870; 4,001,432; 3,929,990; 3,966,904; 4,005,193; 4,025,617; 4,025,627; 4,025,653; 4,026,945; and 4,027,020.
It may also be possible to use polymers that comprise repeating units corresponding to the formula:
One compound of formula (a) which may be mentioned is the one for which R1, R2, R3, and R4 represent a methyl radical, n is equal to 3, p is equal to 6, and X is equal to Cl, which compound is known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.
(9) polyquaternary ammonium polymers comprising units of formula (III):
in which formula:
Such compounds are described for example in European Patent Application No. EP A 122 324.
Among these products, mention may be made, for example, of the products Mirapol® A 15, Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175 sold by the company Miranol.
(10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the company BASF; and
(11) crosslinked polymers of methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with a compound containing olefinic unsaturation, such as methylenebisacrylamide.
Other cationic polymers that may be used in accordance with certain embodiments disclosed herein are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, such as polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, polyquaternary ureylenes and chitin derivatives, such as chitosans, and salts thereof;
The salts that may be used include, for example, chitosan acetate, lactate, glutamate, gluconate, and pyrrolidonecarboxylate.
Among these compounds, mention may be made of chitosan with a degree of deacetylation of 90% by weight, and the chitosan pyrrolidonecarboxylate sold under the name Kytamer® PC by the company Amerchol.
Among all the cationic polymers that may be used in the context of embodiments disclosed herein, mention may be made of the use of cationic cyclopolymers, such as the dimethyldiallylammonium chloride homopolymers and copolymers sold under the names Merquat 100®, Merquat® 550, and Merquat® S by the company Nalco, quaternary polymers of vinylpyrrolidone and of vinylimidazole, crosslinked homopolymers and copolymers of methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium salts, and the chitosan pyrrolidonecarboxylate, and mixtures thereof.
The amphoteric polymers that may be used in accordance with certain embodiments may be chosen from polymers comprising units K and M randomly distributed in the polymer chain, in which K denotes a unit derived from a monomer comprising at least one basic nitrogen atom and M denotes a unit derived from an acidic monomer comprising one or more groups chosen from carboxylic groups and sulphonic groups, or alternatively K and M may denote groups derived from zwitterionic carboxybetaine or sulphobetaine monomers;
K and M may also denote a cationic polymer chain comprising primary, secondary, tertiary, or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulphonic group linked via a hydrocarbon-based radical, or alternatively K and M may form part of a chain of a polymer containing an α,β-dicarboxylic ethylene unit in which one of the carboxylic groups has been made to react with a polyamine comprising one or more primary or secondary amine groups.
The amphoteric polymers corresponding to the above definition that may be mentioned are chosen from the following polymers:
The polymers comprising such units may also comprise units derived from non-zwitterionic monomers such as dimethyl and diethylaminoethyl acrylate, dimethyl and diethylaminoethyl methacrylate, alkyl acrylates, alkyl methacrylates, acrylamides, methacrylamides, and vinyl acetate.
By way of example, mention may be made of the copolymer of butyl methacrylate/dimethylcarboxymethylammonioethyl methacrylate.
The amphoteric polymers that may be mentioned are those of group (1), above.
The composition disclosed herein may contain at least one of the cationic or amphoteric polymers as described above.
According to certain embodiments disclosed herein, the at least one cationic or amphoteric polymer may be present in an amount ranging from 0.001% to 20% by weight, such as from 0.01% to 10% by weight or from 0.02% to 5% by weight, relative to the total weight of the final composition.
According to one embodiment, the compositions may also comprise at least one aminated silicone.
As used herein, the term “cosmetically acceptable medium” means a medium that is compatible with keratin materials, such as the skin, the eyelashes, and the hair.
The cosmetically acceptable medium may comprise only water or a mixture of water and at least one cosmetically acceptable solvent, such as C1-C4 lower alcohols, for instance ethanol, isopropanol, tert-butanol, n-butanol; alkylene glycols, for instance propylene glycol; and polyol ethers.
The composition may comprise from 50% to 95% by weight of water relative to the total weight of the composition.
The washing compositions disclosed herein may have a final pH ranging from 3 to 10. This pH may, for example, range from 5 to 8. The pH may be adjusted to the desired value conventionally, by adding a base (organic or mineral base) to the composition, for example aqueous ammonia or primary, secondary, or tertiary (poly)amines, for instance monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and 1,3-propanediamine, or alternatively by adding an acid, such as a carboxylic acid, for instance citric acid.
The compositions disclosed herein may contain, in addition to the combination defined above, viscosity regulators such as electrolytes and thickeners (associative and non-associative thickeners). Mention may be made of sodium chloride, sodium xylenesulphonate, scleroglucans, xanthan gums, fatty acid alkanolamides, alkyl ether carboxylic acid alkanolamides optionally oxyethylenated with up to 5 mol of ethylene oxide, such as the product sold under the name Aminol® A15 by the company Chem Y, crosslinked polyacrylic acids and acrylic acid copolymers such as crosslinked acrylic acid/C10-C30 alkyl acrylate copolymers. These viscosity regulators may be used in the compositions disclosed herein in an amount that may be up to 10% by weight relative to the total weight of the composition.
The compositions disclosed herein may also contain up to 5% of nacreous agents or opacifiers that are known in the art, such as, for example, fatty alcohols higher than C16, fatty-chain acyl derivatives such as ethylene glycol polyethylene glycol monostearates, and polyethylene glycol distearates, and fatty-chain (C10-C30) ethers such as, for example, distearyl ether and 1-(hexadecyloxy)-2-octadecanol.
The compositions disclosed herein may optionally also comprise at least one additive chosen from foam synergists such as C10-C18 1,2-alkanediols; fatty alkanolamides derived from monoethanolamine or diethanolamine; silicone or non-silicone sunscreens; anionic or nonionic polymers; cationic surfactants; proteins; protein hydrolysates; ceramides; pseudoceramides; linear or branched C12-C40 fatty acids such as 18-methyleicosanoic acid; hydroxy acids; vitamins; provitamins such as panthenol; animal, mineral, or synthetic oils; and any other additive conventionally used in cosmetics that does not affect the properties of the compositions disclosed herein.
The washing compositions disclosed herein may also comprise any adjuvant usually encountered in the field of shampoos, for instance fragrances, preserving agents, sequestering agents, softeners, dyes, moisturizers, anti-dandruff agents, anti-seborrhoeic agents, and the like.
A person skilled in the art will take care to select this or any optional additional compound(s) and/or the amounts thereof such that the advantageous properties intrinsically associated with the combination in accordance with the present disclosure are not, or are not substantially, adversely affected by the envisioned addition(s).
These compositions may be in the form of optionally thickened liquids, creams, or gels, and they may be suitable for washing, caring for, and/or styling the hair.
Further disclosed herein is a cosmetic process for treating keratin materials, comprising applying an effective amount of a composition as described above to the keratin materials, and rinsing after an optional leave-in time.
According to one embodiment, the composition may be used as a shampoo.
When the compositions disclosed herein are used as standard shampoos, they are simply applied to wet hair and the lather generated by massaging or friction with the hands, after which the composition is removed, after an optional action time, by rinsing with water, the operation possibly being repeated one or more times.
Concrete, but in no way limiting, examples illustrating certain embodiments disclosed herein follow.
Other than in the examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, unless otherwise indicated the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements. The following examples are intended to illustrate the invention without limiting the scope as a result.
The following shampoo composition was prepared:
Hair treated with this shampoo had good styling and volumizing properties.
Hair treated with these compositions had the same properties as hair treated with the composition of Example 1.
| Number | Date | Country | Kind |
|---|---|---|---|
| 04 50031 | Jan 2004 | FR | national |
| 04 50039 | Jan 2004 | FR | national |
This application claims benefit of U.S. Provisional Application No. 60/537,898, filed Jan. 22, 2004, and U.S. Provisional Application No. 60/538,248, filed Jan. 23, 2004.
| Number | Date | Country | |
|---|---|---|---|
| 60537898 | Jan 2004 | US | |
| 60538248 | Jan 2004 | US |
