Patent Application
20050220723
Disclosed herein is an aerosol device comprising a propellant and a styling cosmetic composition comprising, in a cosmetically acceptable medium predominantly comprising water, at least one pseudo-block polymer and at least one additional fixing polymer.
The cosmetic compositions for shaping and/or holding the hairstyle that are the most widely available on the cosmetics market are spray compositions comprising a solution, usually an alcoholic solution, and at least one component, known as fixing components, which are generally random polymer resins whose function is to form welds between the hairs. These fixing components may often be formulated as a mixture with various cosmetic adjuvants. The cosmetic compositions may generally be packaged either in a suitable aerosol container pressurized using a propellant, or in a pump-dispenser bottle.
Aerosol systems for fixing hair may comprise a liquid phase (or fluid) and a propellant. The liquid phase may comprise the fixing components and a suitable solvent.
Once applied to the hair, the liquid phase dries, allowing the formation of welds required for the fixing of the hair by the fixing components. The welds should be rigid enough to hold the hairs, and should do so with a sufficient persistence of effects, such as moisture resistance. However, the welds should also be fragile enough for the user to be able, by combing or brushing the hair, to destroy them without injuring the scalp or damaging the hair. The cosmetic compositions should also be stable over time. At least one good cosmetic effect on the hair may also be sought, for example, softness and disentangling.
It is moreover sought to reduce the amount of volatile solvents present in these compositions, for environmental reasons. The total or partial replacement of the volatile solvents, such as alcohol, with water may generally be reflected by a reduction in fixing properties, in the persistence of the styling effect over time and in the cosmetic properties.
The present disclosure relates to a combination of at least one pseudo-block polymer and at least one fixing polymer which may make it possible to obtain predominantly aqueous styling compositions which, when introduced into an aerosol device, may make it possible to obtain good fixing and good hold of the hair, i.e. a styling effect that persists throughout the day, or even for several days, with good moisture resistance, and which is easy to remove by shampooing. These compositions may also make it possible to give the hair at least one good cosmetic property, such as softness or disentangling.
Furthermore, the compositions predominantly aqueous base makes it highly ecologically advantageous.
Disclosed herein is thus an aerosol device comprising at least one propellant and at least one styling composition comprising, in a cosmetically acceptable medium predominantly comprising water, at least one pseudo-block polymer and at least one additional fixing polymer.
Further disclosed herein is a cosmetic treatment process for shaping and/or holding the hairstyle, comprising vaporizing onto the hair of the contents of the disclosed aerosol device.
Even further disclosed herein are uses of the aerosol device disclosed herein to obtain, after vaporization of the contents onto a head of hair, fixing of the hair that is persistent over time and/or that has good moisture resistance and/or that has good cosmeticity.
Further disclosed herein is the use of the aerosol device disclosed herein to obtain a styling mousse.
Other subjects, characteristics, aspects and advantages of the embodiments disclosed herein will emerge even more clearly on reading the description and the examples that follow.
As used herein, the term “styling composition” means a composition for shaping and/or holding the hairstyle.
As used herein, the term “medium predominantly comprising water” means a medium comprising more than 50%, for example, more than 70% and, further, for example, more than 85% by weight of water, relative to the total weight of the at least one styling composition. In one embodiment, the medium comprises upwards of 99.9% by weight of water, relative to the total weight of the at least one styling composition.
The cosmetically acceptable medium is a medium comprising water and optionally at least one organic solvent.
As used herein, the term “organic solvent” means an organic compound with a molecular weight of less than 500, which is liquid at a temperature of 25° C. and at atmospheric pressure. In one embodiment, the organic compound is polar.
In one embodiment, the at least one organic solvent is an alcohol. For example, the at least organic solvent may be chosen from C1-C4 lower alcohols, such as ethanol, isopropanol, tert-butanol, and n-butanol; polyols, for example, propylene glycol, and polyol ethers, in one embodiment the alcohol is an ethanol.
The aerosol devices disclosed herein comprise at least one propellant. Any suitable propellant may be used. In some embodiments, the aerosol devices may be one-compartment devices, in which case the at least one propellant may be chosen, for example, from liquefied and compressed gases such as nitrogen, dimethyl ether and hydrocarbons. In some embodiments, the aerosol devices may also be two-compartment devices, for example, an aerosol device comprising a pocket with propulsion by air or with a compressed gas.
The at least one propellant may be present in an amount ranging from 6% to 70%, for example, from 6% to 50% and, further, for example, from 30% to 45% by weight, relative to the total weight of materials comprised in the aerosol device. The at least one styling composition in the aerosol device may be present in an amount ranging from 30% to 94%, for example, from 50% to 94% and, even further, for example, from 55% to 70% by weight, relative to the total weight of materials comprised in the device.
Pseudo-Block Polymer
The at least one pseudo-block polymer used in the at least one styling composition disclosed herein is chosen from block polymers comprising at least one first block and at least one second block that are mutually incompatible and that have different glass transition temperatures (Tg), wherein the at least one first and the at least one second block are linked together via an intermediate segment comprising at least one constituent monomer of the at least one first block and at least one constituent monomer of the at least one second block, and wherein the at least one pseudo-block polymer has a polydispersity index (I) of greater than 2.
As use herein, the term “at least” one block means one or more blocks.
As used herein, the term “mutually incompatible blocks” means that the mixture formed from the polymer corresponding to the at least one first block and the polymer corresponding to the at least one second block is immiscible in the polymerization solvent that is of the majority amount by weight of the at least one pseudo-block polymer, at room temperature (25° C.) and atmospheric pressure (105 Pa), for a polymer mixture content of greater than or equal to 5% by weight, relative to the total weight of the mixture (polymers and solvent), wherein:
In the case wherein the polymerization solvent comprises a mixture of polymerization solvents, and in the event of two or more solvents present in identical mass proportions, the polymer mixture is immiscible in at least one of them.
Needless to say, in the case of a polymerization performed in only one solvent, this solvent is present in the majority amount.
The intermediate segment is a block comprising at least one constituent monomer of the at least one first block and at least one constituent monomer of the at least one second block of the polymer; it allows these blocks to be “compatibilized”.
In one embodiment, the at least one pseudo-block polymer disclosed herein may be chosen from film-forming linear block ethylenic polymers.
As used herein, the term “ethylenic” polymer means a polymer obtained by polymerization of ethylenically unsaturated monomers.
As used herein, the term “block” polymer means a polymer comprising at least two different blocks, such as at least three different blocks.
The at least one pseudo-block polymer is a polymer of linear structure. In contrast, a polymer of non-linear structure is, for example, a polymer of branched, star or grafted structure, or the like.
As used herein, the term “film-forming” polymer means a polymer that is capable of forming by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to a support, such as to keratin materials.
In some embodiments, the at least one pseudo-block polymer disclosed herein does not comprise any silicon atoms in its skeleton. As used herein, the term “skeleton” means the main chain of the polymer, as opposed to the pendent side chains.
In one embodiment, the at least one pseudo-block polymer disclosed herein is not water-soluble, i.e. the polymer is not soluble in water or mixtures of water and linear or branched lower monoalcohols comprising from 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, without pH modification, at an active material content of at least 1% by weight, at room temperature (25° C.).
In one embodiment, the at least one pseudo-block polymer disclosed herein is not an elastomer.
As used herein, the term “non-elastomeric polymer” means a polymer which, when it is subjected to a constraint intended to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its initial length when the constraint ceases.
More specifically, the term “non-elastomeric polymer” means a polymer with an instantaneous recovery Ri<50% and a delayed recovery R2h<70% after having been subjected to a 30% elongation. For example, Ri is <30% and R2h<50%.
More specifically, the non-elastomeric nature of the at least one pseudo-block polymer used is determined according to the following protocol:
A polymer film is prepared by pouring a solution of the polymer in a Teflon-coated mould, followed by drying for 7 days in an environment conditioned at 23±5° C. and 50±10% relative humidity.
A film on the order of 100 μm thick is thus obtained, from which are cut rectangular specimens (for example using a punch) 15 mm wide and 80 mm long.
This sample is subjected to a tensile stress using a machine sold under the reference Zwick, under the same temperature and humidity conditions as for the drying.
The specimens are pulled at a speed of 50 mm/min and the distance between the jaws is 50 mm, which corresponds to the initial length (l0) of the specimen.
The instantaneous recovery Ri is determined in the following manner:
The percentage instantaneous recovery (Ri) is given by the following formula:
Ri=(εmax−εi)/εmax)×100
To determine the delayed recovery, the percentage residual elongation of the specimen (ε2h) is measured, 2 hours after returning to zero constraint.
The percentage delayed recovery (R2h) is given by the following formula:
R2h=(εmax−ε2h)/εmax)×100
Purely as a guide, a polymer according to one embodiment has an instantaneous recovery Ri of 10% and a delayed recovery R2h of 30%.
For example, the at least one pseudo-block polymer used in the compositions disclosed herein comprises at least one first block and at least one second block that are mutually incompatible and that have different glass transition temperatures (Tg), wherein the at least one first and the at least one second block are linked together via an intermediate segment comprising at least one constituent monomer of the at least one first block and at least one constituent monomer of the at least one second block, wherein the at least one pseudo-block polymer has a polydispersity index (I) of greater than 2.
It is pointed out that, in the text hereinabove and hereinbelow, the terms “first block” and “second block” do not in any way condition the order of the blocks in the structure of the at least one pseudo-block polymer.
The polydispersity index (I) of the at least one pseudo-block polymer is equal to the ratio of the weight-average mass (Mw) to the number-average mass (Mn).
The weight-average molar mass (Mw) and number-average molar mass (Mn) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometrc detector).
The weight-average mass (Mw) of the at least one pseudo-block poly mer used in the composition disclosed herein is, for example, less than or equal to 300,000; it ranges, for example, from 35,000 to 200,000, such as from 45,000 to 150,000.
The number-average mass (Mn) of the at least one pseudo-block polymer used in the composition disclosed herein is, for example, less than or equal to 70,000; it ranges, for example, from 10,000 to 60,000, such as from 12,000 to 50,000.
In one embodiment, the polydispersity index of the at least one pseudo-block polymer used in the at least one styling composition disclosed herein is greater than or equal to 2, for example, ranging from 2 to 9, such as greater than or equal to 2.5, for example, ranging from 2.5 to 8, such as greater than or equal to 2.8, and, for example, ranging from 2.8 to 6.
Each block of the at least one pseudo-block polymer used in the at least one styling composition disclosed herein is derived from one type of monomer or from several different types of monomers.
This means that each block may comprise a homopolymer or a copolymer; this copolymer constituting the block may in turn be random or alternating.
In one embodiment, the intermediate segment comprising at least one constituent monomer of the at least one first block and at least one constituent monomer of the at least one second block of the at least one pseudo-block polymer is a random polymer.
In another embodiment, the intermediate segment is derived essentially from constituent monomers of the at least one first block and of the at least one second block.
As used herein, the term “essentially” means at least 85%, such as at least 90%, for example, at least 95% and, further, for example, 100%.
In another embodiment, the intermediate segment has a glass transition temperature Tg that is between the glass transition temperatures of the at least one first and at least one second blocks.
The at least one first and at least one second blocks have different glass transition temperatures.
The glass transition temperatures indicated for the at least one first and at least one second blocks may be theoretical Tg values determined from the theoretical Tg values of the constituent monomers of each of the blocks, which may be found in a reference manual such as the Polymer Handbook, 3rd Edition, 1989, John Wiley, according to the following relationship, known as Fox's law:
Wherein: {overscore (ω)}i is the mass fraction of the monomer (i) in the block under consideration and Tgi is the glass transition temperature of the homopolymer of the monomer (i).
Unless otherwise indicated, the Tg values indicated for the at least one first and at least one second blocks disclosed herein are theoretical Tg values.
The difference between the glass transition temperatures of the at least one first and at least one second blocks may be greater than 10° C., for example, greater than 20° C. and, further, for example, greater than 30° C.
In some embodiments, the at least one first block may be chosen from:
a) Block with a Tg of Greater than or Equal to 40° C.
The block with a Tg of greater than or equal to 40° C. has, for example, a Tg ranging from 40 to 150° C., such as greater than or equal to 50° C., for example, ranging from 50° C. to 120° C., and, further, such as from 50° C. to 100° C. and, further, such as greater than or equal to 60° C., for example, ranging from 60° C. to 120° C.
The block with a Tg of greater than or equal to 40° C. may be chosen from homopolymers and copolymers.
In the case where this block is a homopolymer, it is derived from at least one monomer, which is such that the homopolymer prepared from the at least one monomer has a glass transition temperature of greater than or equal to 40° C. This first block may be a homopolymer comprising only one type of monomer (for which the Tg of the corresponding homopolymer is greater than or equal to 40° C.).
In the case where the first block is a copolymer, it may be totally or partially derived from at least one monomer, the nature and concentration of which are chosen such that the Tg of the resulting copolymer is greater than or equal to 40° C. The copolymer may comprise, for example:
The at least one monomer whose homopolymer has a glass transition temperature of greater than or equal to 40° C. is chosen, for example, from the following monomers, also known as main monomers:
In some embodiments, the at least one monomer whose homopolymer has a glass transition temperature of greater than or equal to 40° C. may be chosen from methyl methacrylate, isobutyl(meth)acrylate and isobornyl(meth)acrylate.
b) Block with a Tg of Less than or Equal to 20° C.
The block with a Tg of less than or equal to 20° C. has, for example, a Tg ranging from −100 to 20° C., for example, less than or equal to 15° C., such as ranging from −80° C. to 15° C. and, further, for example, less than or equal to 10° C., for example, ranging from −100° C. to 0° C., such as ranging from −50° C. to 0° C.
The block with a Tg of less than or equal to 20° C. may be chosen from homopolymer and copolymers.
In the case where this block is a homopolymer, it is derived from at least one monomer which is such that the homopolymer prepared from the at least one monomer has a glass transition temperature of less than or equal to 20° C. This second block may be a homopolymer comprising only one type of monomer (for which the Tg of the corresponding homopolymer is less than or equal to 20° C.).
In the case where the block with a Tg of less than or equal to 20° C. is a copolymer, it may be totally or partially derived from at least one monomer, the nature and concentration of which are chosen such that the Tg of the resulting copolymer is less than or equal to 20° C.
It may comprise, for example
In some embodiments, the block with a Tg of less than or equal to 20° C. is a homopolymer.
The at least one monomer whose homopolymer has a Tg of less than or equal to 20° C. may, for example, be chosen from the following monomers, or main monomers:
At least one of the monomers that may be used for the block with a Tg of less than or equal to 20° C. may be chosen from alkyl acrylates whose alkyl chain comprises from 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as methyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.
c) Block with a Tg Ranging from 20 to 40° C.
The block with a Tg ranging from 20 to 40° C. may be chosen from homopolymers and copolymers.
In the case where this block is a homopolymer, it is derived from at least one monomer (or main monomer) which is such that the homopolymer prepared from the at least one monomer has a glass transition temperature ranging from 20 to 40° C. This first block may be a homopolymer, comprising only one type of monomer (wherein the Tg of the corresponding homopolymer ranges from 20° C. to 40° C.).
The at least one monomer whose homopolymer has a glass transition temperature ranging from 20 to 40° C. may be chosen from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate and isodecylacrylamide.
In the case where the block with a Tg ranging from 20 to 40° C. is a copolymer, it is totally or partially derived from at least one monomer (or main monomer) whose nature and concentration is chosen such that the Tg of the resulting copolymer ranges from 20 to 40° C.
For example, the block with a Tg ranging from 20 to 40° C. may be chosen from copolymers totally or partially derived from:
The at least one monomer may be chosen, for example, from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate, triflouroethyl methacrylate, and 2-ethylhexyl acrylate.
In some embodiments, the proportion of the second block with a Tg of less than or equal to 20° C. ranges from 10% to 85% by weight, for example, from 20% to 70% and, even further, for example, from 20% to 50% by weight of the at least one pseudo-block polymer.
However, each of the blocks may contain in small proportion at least one constituent monomer of the other block.
Thus, the at least one first block may contain at least one constituent monomer of the at least one second block, and vice versa.
Each of the at least one first and/or at least one second blocks may comprise, in addition to the monomers indicated above, at least one other monomer known as at least one additional monomer, which are different from the main monomers mentioned above.
The nature and amount of the at least one additional monomer is chosen such that the block in which it is present has the desired glass transition temperature.
The at least one additional monomer may be chosen, for example, from:
In some embodiments, the at least one additional monomer may be chosen from acrylic acid, methacrylic acid, and trifluoroethyl methacrylate.
According to one embodiment, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein is a non-silicone polymer, i.e. a polymer free of silicon atoms.
The at least one additional monomer may be present in an amount less than or equal to 30% by weight, for example, from 1% to 30% by weight, further, for example, from 5% to 20% by weight and, even further, for example, from 7% to 15% by weight, relative to the total weight of the at least one first and/or at least one second blocks.
In some embodiments, each of the at least one first and at least one second blocks comprise at least one monomer chosen from (meth)acrylic acid esters and optionally at least one monomer chosen from (meth)acrylic acid.
For example, each of the at least one first and at least one second blocks may be totally derived from at least one monomer chosen from acrylic acid, (meth)acrylic acid esters and optionally from at least one monomer chosen from (meth)acrylic acid.
According to one embodiment, the at least one pseudo-block polymer used in the compositions disclosed herein is free of styrene. The term “polymer free of styrene” means a polymer comprising less than 10%, for example, less than 5%, further, for example, less than 2% and, even further, for example, less than 1% by weight, relative to the total weight of the polymer, of, or even comprises no, styrene monomeric units such as monomeric units of styrene and styrene derivatives, for instance methylstyrene, chlorostyrene, and chloromethylstyrene.
The at least one pseudo-block polymer used in the at least one styling composition disclosed herein may be obtained by free-radical solution polymerization according to the following preparation process:
As used herein, the term “polymerization solvent” means a solvent or a mixture of solvents. The polymerization solvent may be chosen, for example, from at least one of ethyl acetate, butyl acetate, alcohols such as isopropanol and ethanol, and aliphatic alkanes, such as isododecane. According to one embodiment, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.
According to one embodiment, the at least one pseudo-block polymer used in the compositions disclosed herein comprises at least one (such as one) first block with a Tg of greater than or equal to 40° C., as described above in a) and at least one (such as one) second block with a Tg of less than or equal to 20° C., as described above in b).
For example, the at least one first block with a Tg of greater than or equal to 40° C. is a copolymer derived from at least one monomer which is such that the homopolymer prepared from the at least one monomer has a glass transition temperature of greater than or equal to 40° C., such as the monomers described above.
For example, the second block with a Tg of less than or equal to 20° C. is a homopolymer derived from at least one monomer which is such that the homopolymer prepared from the at least one monomer has a glass transition temperature of less than or equal to 20° C., such as the monomers described above.
For example, the proportion of the block with a Tg of greater than or equal to 40° C. ranges from 20% to 90%, further, for example, from 30% to 80% and even, further, for example, from 50% to 70% by weight of the polymer.
For example, the proportion of the block with a Tg of less than or equal to 20° C. ranges from 5% to 75%, for example, from 15% to 50% and, further, for example, from 25% to 45% by weight of the polymer.
Thus, according to a first variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a second variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a third variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a fourth variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a fifth variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a sixth variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a seventh variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to an eighth variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a ninth variant, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a another embodiment, the at least one pseudo-block polymer used in the compositions disclosed herein comprises at least one (such as one) first block with a glass transition temperature (Tg) ranging from 20 to 40° C., in accordance with the blocks described in c) and at least one (such as one) second block with a glass transition temperature of less than or equal to 20° C., as described above in b) or a glass transition temperature of greater than or equal to 40° C., as described in a) above.
For example, the proportion of the at least one first block with a Tg ranging from 20 to 40° C. ranges from 10% to 85%, further, for example, from 30% to 80% and even further, for example, from 50% to 70% by weight of the polymer.
When the at least one second block is a block with a Tg of greater than or equal to 40° C., it may, for example, be present in a proportion ranging from 10% to 85%, further, for example, from 20% to 70% and, even further, for example, from 30% to 70% by weight of the polymer.
When the at least one second block is a block with a Tg of less than or equal to 20° C., it may, for example, be present in a proportion ranging from 10% to 85%, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer.
For example, the at least one first block with a Tg ranging from 20 to 40° C. is a copolymer derived from at least one monomer which is such that the corresponding homopolymer has a Tg of greater than or equal to 40° C., and from at least one monomer which is such that the corresponding homopolymer has a Tg of less than or equal to 20° C.
For example, the at least one second block with a Tg of less than or equal to 20° C. or with a Tg of greater than or equal to 40° C. may be a homopolymer.
Thus, according to a first variant of this embodiment, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a second variant of this embodiment, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
According to a third variant of this embodiment, the at least one pseudo-block polymer used in the at least one styling composition disclosed herein may comprise:
The at least one styling composition disclosed herein, for example, comprises the at least one pseudo-block polymer in an amount ranging from 0.1% to 60% by weight, further, for example, from 0.5% to 50% by weight and, even further, for example, from 1% to 40% by weight, relative to the total weight of the at least one styling composition.
Additional Fixing Polymer
The at least one styling composition for the aerosol device also comprises a second fixing polymer that is different from the pseudo-block polymer used; this second fixing polymer is referred to in the description hereinbelow as the at least one additional fixing polymer.
The at least one additional fixing polymer may be chosen from anionic, cationic, amphoteric, and nonionic fixing polymers used in the art.
The at least one additional fixing polymer may be soluble in the cosmetically acceptable medium or insoluble in this same medium and, in this case, used in the form of dispersions of solid or liquid polymer particles (latices or pseudolatices).
The anionic fixing polymers generally used are polymers comprising groups derived from carboxylic acid, sulfonic acid or phosphoric acid and have a number-average molecular mass ranging from 500 to 5,000,000.
The carboxylic groups are provided by unsaturated monocarboxylic or dicarboxylic acid monomers such as those corresponding to the formula:
In the abovementioned formula, a lower alkyl group may, for example, be chosen from alkyl groups comprising 1 to 4 carbon atoms, such as methyl and ethyl groups.
Examples of the anionic fixing polymers comprising carboxylic groups that may be used include:
Mention may also be made of methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers as an aqueous dispersion, sold under the name AMERHOLD® DR 25 by the company Amerchol.
These polymers are described, for example, in French Patent Nos. 2 350 384 and 2 357 241.
The homopolymers and copolymers comprising sulfonic groups are polymers comprising at least one monomeric unit chosen from vinylsulfonic, styrenesulfonic, naphthalenesulfonic, and acrylamidoalkylsulfonic units.
These polymers can be chosen, for example, from:
As another anionic fixing polymer that can be used in the at least one styling composition disclosed herein mention may be made of the branched block anionic polymer sold under the name FIXATE G-100 by the company Noveon.
In some embodiments, the anionic fixing polymers may be, for example, chosen from acrylic acid copolymers, such as the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold, for example, under the name ULTRAHOLD® STRONG by the company BASF, copolymers derived from crotonic acid, such as vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold, for example, under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives and acrylic acid and esters thereof, such as the methyl vinyl ether/monoesterified maleic anhydride copolymers sold, for example, under the name GANTREZ® ES 425 by the company ISP, the copolymers of methacrylic acid and of methyl methacrylate sold under the name EUDRAGIT® L by the company Rohm Pharma, the copolymers of methacrylic acid and of ethyl acrylate sold under the name LUVIMER® MAEX or MAE by the company BASF, the vinyl acetate/crotonic acid copolymers sold under the name LUVISET CA 66 by the company BASF, the vinyl acetate/crotonic acid copolymers grafted with polyethylene glycol sold under the name ARISTOFLEX® A by the company BASF, and the polymer sold under the name FIXATE G-100 by the company Noveon.
According to one embodiment, the anionic fixing polymers are chosen from methyl vinyl ether/monoesterified maleic anhydride copolymers sold under the name GANTREZ® ES 425 by the company ISP, the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold under the name ULTRAHOLD® STRONG by the company BASF, the copolymers of methacrylic acid and of methyl methacrylate sold under the name EUDRAGIT® L by the company Rohm Pharma, the vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, the copolymers of methacrylic acid and of ethyl acrylate sold under the name LUVIMER® MAEX or MAE by the company BASF, the vinylpyrrolidone/acrylic acid/lauryl methacrylate terpolymers sold under the name ACRYLIDONE® LM by the company ISP, and the polymer sold under the name FIXATE G-100 by the company Noveon.
The cationic fixing polymers that may be used in the at least one styling composition disclosed herein may be chosen from polymers comprising primary, secondary, tertiary and/or quaternary amine groups forming part of the polymer chain or directly attached thereto, and having a molecular weight ranging from 500 to 5,000,000 and, for example, from 1,000 to 3,000,000.
Among these polymers, mention may be made, for example, of the following cationic polymers:
The copolymers of the family (1) also comprise at least one comonomer unit that may be chosen from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with at least one substituent chosen from lower (C1-4) alkyl groups, groups derived from acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.
Thus, among these copolymers of the family (1), mention may be made of:
Among these compounds, mention may be made of chitosan having a degree of deacetylation of 90.5% by weight, sold under the name KYTAN BRUT STANDARD by the company Aber Technologies, and chitosan pyrrolidonecarboxylate sold under the name KYTAMER® PC by the company Amerchol.
The products sold corresponding to this definition are, for example, the products sold under the name “CELQUAT L 200” and “CELQUAT H 100” by the company National Starch.
The amphoteric fixing polymers that can be used in the at least one styling composition disclosed herein may be chosen from polymers comprising units B and C distributed randomly in the polymer chain, wherein B is chosen from units derived from a monomer comprising at least one basic nitrogen atom and C is chosen from units derived from an acid monomer comprising at least one group chosen from carboxylic and sulfonic groups, or alternatively B and C may be chosen from groups derived from carboxybetaine and sulfobetaine zwitterionic monomers;
According to one embodiment, the amphoteric fixing polymers corresponding to the definition given above may be chosen from the following polymers:
The N-substituted acrylamides or methacrylamides that may be used in the styling composition disclosed herein may be chosen from compounds wherein the alkyl groups comprise from 2 to 12 carbon atoms and, for example, N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.
The acidic comonomers are chosen, for example, from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid and alkyl monoesters, comprising from 1 to 4 carbon atoms, of maleic and fumaric acids and anhydrides.
For example, the basic comonomers may be chosen from aminoethyl, butylaminoethyl, N,N′-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.
The copolymers whose CTFA (4th edition, 1991) name is octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold under the name AMPHOMER® or LOVOCRYL® 47 by the company National Starch, may, for example, be used.
The saturated carboxylic acids may, for example, be chosen from acids comprising 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid, acids comprising an ethylenic double bond such as acrylic acid, methacrylic acid and itaconic acid.
The alkane sultones used in the acylation may, for example, be chosen from propane sultone or butane sultone; the salts of the acylating agents may, for example, be chosen from sodium and potassium salts.
The polymers comprising such units can also comprise units derived from non-zwitterionic monomers, such as monomers chosen from dimethyl- and diethylaminoethyl acrylate and methacrylate, alkyl acrylates and methacrylates, acrylamides and methacrylamides, and vinyl acetate.
By way of example, mention may be made of the copolymers of methyl methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company Sandoz.
According to one embodiment, the amphoteric fixing polymers are chosen from those of family (3), such as the copolymers whose CTFA name is octylacryl-amide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold under the names AMPHOMER®, AMPHOMER® LV 71 or LOVOCRYL® 47 by the company National Starch and those of family (4) such as the copolymers of methyl methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate, sold, for example, under the name DIAFORMER Z301 by the company Sandoz.
The nonionic fixing polymers that may be used in the styling composition disclosed herein may be chosen, for example, from:
The alkyl groups of the nonionic polymers mentioned above may, for example, comprise from 1 to 6 carbon atoms.
According to one embodiment, it is also possible to use grafted silicone fixing polymers 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-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0 582 152 and WO 93/23009 and U.S. Pat. No. 4,693,935, U.S. Pat. No. 4,728,571 and U.S. Pat. No. 4,972,037.
The grafted silicone polymers may be chosen from amphoteric, anionic, and non-ionic polymers, and, in some embodiments, may be chosen from anionic and non-ionic polymers.
Such polymers are, for example, copolymers that can be obtained by free radical polymerization from the monomer mixture formed from:
Other examples of grafted silicone polymers include polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, mixed polymer units of poly(meth)acrylic acid and of polyalkyl(meth)acrylate and polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene connecting chain, polymer units of polyisobutyl(meth)acrylate.
Another type of silicone fixing polymer that may be mentioned is the product LUVIFLEX® SILK, sold by the company BASF.
The at least one additional fixing polymer may also be chosen from functionalized and non-functionalized, silicone and non-silicone, cationic, nonionic, anionic and amphoteric polyurethanes.
According to one embodiment, the at least one additional fixing polymer is chosen from polyurethanes disclosed in Patent Application Nos. EP 0 751 162, EP 0 637 600, EP 0 648 485 and FR 2 743 297, and Patent Application Nos. EP 0 656 021 and WO 94/03510 from the company BASF and EP 0 619 111 from the company National Starch.
As examples of polyurethanes that may be used, mention may be made of the products sold under the names LUVISET PUR® and LUVISET® SI PUR by the company BASF.
The at least one additional fixing polymer may be present in an amount ranging from 0.1% to 20% by weight and, further, for example, from 0.5% to 10% by weight, relative to the total weight of the at least one styling composition.
The at least one styling composition may also comprise at least one additive chosen from silicones soluble or insoluble, dispersed and microdispersed form, thickening polymers, gelling agents, nonionic, anionic, cationic and amphoteric surfactants, ceramides and pseudoceramides, vitamins and provitamins, including panthenol, plant, animal, mineral and synthetic oils, waxes other than ceramides and pseudoceramides, water-soluble and liposoluble, silicone and non-silicone sunscreens, glycerol, permanent and temporary dyes, nacreous agents and opacifiers, sequestering agents, plasticizers, solubilizers, pH modifiers, mineral thickeners, antioxidants, hydroxy acids, penetrating agents, fragrances, fragrance solubilizers (peptizers), preserving agents, and anticorrosion agents.
The at least one additive may be present in an amount ranging from 0 to 20% by weight, relative to the total weight of the at least one styling composition.
A person skilled in the art will take care to select the optional additives and the amount thereof such that they do not harm the properties of the at least one styling composition disclosed herein.
According to one embodiment, the at least one styling composition comprises at least one additional cosmetic additive chosen from thickening polymers, gelling agents and surfactants.
In one embodiment, the at least one styling composition disclosed herein comprises at least one thickener, also known as a “rheology modifier”.
The rheology modifiers may be chosen from fatty acid amides (coconut monoethanolamide, diethanolamide, and oxyethylenated carboxylic acid alkyl ether monoethanolamide), cellulose-based thickeners (hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose), guar gum and derivatives thereof (hydroxypropyl guar), gums of microbial origin (xanthan gum and scleroglucan gum), acrylic acid and acrylamidopropanesulfonic acid crosslinked homopolymers and copolymers, and associative thickening polymers as described below.
These associative polymers are water-soluble polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.
Their chemical structure comprises hydrophilic zones and hydrophobic zones characterized by at least one fatty chain.
The associative polymers may be chosen from anionic, cationic, amphoteric and nonionic polymers.
The associative thickeners may be present in an amount ranging from 0.01% to 10% by weight and, for example, 0.1% to 5% by weight, relative to the total weight of the styling composition.
Examples of anionic associative polymers include:
Anionic associative polymers of this type are described and prepared, according to an emulsion polymerization process, in Patent No. EP-0 216 479.
According to another embodiment, the anionic associative polymers may be chosen from polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl(meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (XV), and from 0% to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, such as diallyl phthalate, allyl(meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.
Among the latter polymers, those that may, for example, be mentioned include crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), such as those sold by the company Allied Colloids under the names SALCARE SC 80® and SALCARE SC 90®, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10).
For example, these polymers are chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid corresponds to the monomer of formula (XVI) below:
Examples of (C10-C30) alkyl esters of unsaturated carboxylic acids include lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
Anionic polymers of this type are described and prepared, for example, according to U.S. Pat. No. 3,915,921 and U.S. Pat. No. 4,509,949.
Examples of anionic associative polymers of this type include polymers formed from a monomer mixture comprising:
Examples of anionic associative polymers of this type include polymers comprising from 60% to 95% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0% to 6% by weight of crosslinking polymerizable monomer, or alternatively those comprising from 96% to 98% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer such as those described above.
Among the above-polymers, those that may be used include the products sold by the company Goodrich under the trade names PEMULEN TR1®, PEMULEN TR2® and CARBOPOL 1382®, and, further, for example, PEMULEN TR1®, and the product sold by the company SEPPIC under the name COATEX SX®.
For example, these compounds also comprise as a monomer an ester of a carboxylic acid comprising α,β-monoethylenic unsaturation and a C1-C4 alcohol.
An example of a compound of this type that may be mentioned is ACULYN 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/stearyl methacrylate oxyalkylenated terpolymer.
Among the cationic associative polymers of cationic type that may be mentioned:
In one embodiment of these polyurethanes, the only hydrophobic groups are the groups R and R′ at the chain ends.
According to one embodiment, the cationic associative polyurethanes are chosen from those corresponding to formula (XVIII) described above and wherein:
In another embodiment, the cationic associative polyurethanes are chosen from those corresponding to formula (XVIII) above wherein:
The fact that n and p are 0 means that these polymers do not comprise units derived from a monomer comprising an amine functional group, incorporated into the polymer during the polycondensation. The protonated amine functional groups of these polyurethanes result from the hydrolysis of excess isocyanate functional groups, at the chain end, followed by alkylation of the primary amine functional groups formed with alkylating agents comprising a hydrophobic group, i.e. compounds of the type RQ or R′Q, wherein R and R′ are as defined above and Q is chosen from leaving groups, such as a halide, a sulfate, etc.
In yet another embodiment the cationic associative polyurethanes are chosen from those corresponding to formula (Ia) above wherein:
The number-average molecular mass of the cationic associative polyurethanes ranges from 400 to 500,000, for example, from 1,000 to 400,000 and, further, for example, from 1,000 to 300,000.
As used herein, the “hydrophobic group” means a radical or polymer comprising a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may comprise at least one hetero atom, such as P, O, N or S, or a radical comprising a perfluoro or silicone chain. When the hydrophobic group is chosen from hydrocarbon-based radicals, it comprises at least 10 carbon atoms, for example, from 10 to 30 carbon atoms, for example, from 12 to 30 carbon atoms and, further, for example, from 18 to 30 carbon atoms.
In one embodiment, the hydrocarbon-based group is derived from a monofunctional compound.
By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also be chosen from hydrocarbon-based polymers, such as polybutadiene.
When X and/or X′ are chosen from groups comprising at least one group chosen from tertiary and quaternary amines, X and/or X′ may be chosen from one of the following formulae:
The groups L, L′ and L″ are chosen from groups of formula:
The groups P and P′, which may be identical or different, comprising at least one amine functional group may be chosen from at least one of the following formulae:
With regard to the meaning of Y, the term “hydrophilic group” means a polymeric or non-polymeric water-soluble group.
By way of example, when Y is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
When Y is a hydrophilic polymer, it may be chosen, for example, from at least one of polyethers, sulfonated polyesters, and sulfonated polyamides. The hydrophilic compound may, for example, be a polyether and, for example, a poly(ethylene oxide) or poly(propylene oxide).
The cationic associative polyurethanes of formula (XVIII) that may be used are formed from diisocyanates and from various compounds with functional groups comprising labile hydrogen. The functional groups comprising labile hydrogen may be chosen from alcohol, primary and secondary amine and thiol functional groups, forming, after reaction with diisocyanate functional groups, polyurethanes, polyureas and polythioureas, respectively. As used herein, the expression “polyurethanes” encompasses these three types of polymer, for example, polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
A first type of compound involved in the preparation of the polyurethane of formula (XVIII) is a compound comprising at least one unit comprising an amine functional group. This compound may be multifunctional, but the compound may, for example, be difunctional, that is to say that, according to one embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol functional groups. A mixture of multifunctional and difunctional compounds, in which the percentage of multifunctional compounds is low, may also be used.
As mentioned above, this compound may comprise more than one unit comprising an amine functional group. In this case, it is a polymer bearing a repetition of the unit comprising an amine functional group.
Compounds of this type may be chosen from one of the following formulae:
HZ-(P)n-ZH
and
HZ-(P′)p-ZH
Examples of compounds comprising an amine functional group that may be mentioned include N-methyldiethanolamine, N-tert-butyldiethanolamine and N-sulfoethyldiethanolamine.
The second compound involved in the preparation of the polyurethane of formula (XVIII) is a diisocyanate corresponding to the formula:
O═C═N—R4—N═C═O
By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate, and hexane diisocyanate.
A third compound involved in the preparation of the polyurethane of formula (XVIII) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (XVIII).
This compound comprises a hydrophobic group and a functional group comprising labile hydrogen, for example, a hydroxyl, primary or secondary amine, or thiol functional groups.
For example, this compound may be a fatty alcohol chosen from stearyl alcohol, dodecyl alcohol, and decyl alcohol. When this compound comprises a polymeric chain, it may be, for example, α-hydroxylated hydrogenated polybutadiene.
The hydrophobic group of the polyurethane of formula (XVIII) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced via the quaternizing agent. This quaternizing agent is a compound chosen from RQ and R′Q, wherein R and R′ are as defined above and Q is chosen from leaving groups such as a halide, a sulfate, etc.
The cationic associative polyurethane may also comprise a hydrophilic block. This block is provided by a fourth type of compound involved in the preparation of the polymer. This compound may be multifunctional, for example, difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
The functional groups comprising labile hydrogen are chosen from alcohol, primary and secondary amine and thiol functional groups. This compound may be a polymer terminated at the chain ends with one of these functional groups comprising labile hydrogen.
By way of example, when the hydrophilic compound is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
When it is a hydrophilic polymer, mention may be made, for example, of at least one of polyethers, sulfonated polyesters and sulfonated polyamides. The hydrophilic compound may, for example, be polyether and, further, for example, poly(ethylene oxide) or poly(propylene oxide).
The hydrophilic group termed Y in formula (XVIII) is optional. For example, the units comprising a quaternary amine or protonated functional group may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes comprising such a group may, for example, be used.
The quaternized cellulose derivatives may, for example, be chosen from:
The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses comprises, for example, from 8 to 30 carbon atoms. The aryl radicals are chosen, for example, from phenyl, benzyl, naphthyl and anthryl groups.
Examples of quaternized alkylhydroxyethylcelluloses comprising C8-C30 fatty chains that may be mentioned include the products QUATRISOFT LM 200®, QUATRISOFT LM-X 529-18-A®, QUATRISOFT LM-X 529-18B® (C12 alkyl) and QUATRISOFT LM-X 529-8® (C18 alkyl) sold by the company Amerchol, and the products CRODACEL QM®, CRODACEL QL® (C12 alkyl) and CRODACEL QS® (C18 alkyl) sold by the company Croda.
The amphoteric associative polymers are, for example, chosen from those comprising at least one non-cyclic cationic unit. In one embodiment, the amphoteric associative polymers that are preferred are those prepared from or comprising 1 to 20 mol %, for example, 1.5 to 15 mol % and, further, for example, from 1.5 to 6 mol % of fatty-chain monomer relative to the total number of moles of monomers.
The amphoteric associative polymers that may be used comprise or are prepared by copolymerizing:
The monomers of formulae (XIX) and (XX) may be chosen from the following:
In one embodiment, the monomer of formula (XIX) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyl-trimethylammonium chloride.
The monomers of formula (XXI) may, for example, be chosen from acrylic acid, methacrylic acid, crotonic acid, and 2-methylcrotonic acid. In one embodiment, the monomer of formula (XXI) is acrylic acid.
The monomers of formula (XXII) may, for example, be chosen from the group comprising C12-C22 and, for example, C16-C18 alkyl acrylates and methacrylates.
The monomers constituting the fatty-chain amphoteric polymers of the invention may, for example, be already neutralized and/or quaternized.
The ratio of the number of cationic charges/anionic charges may, for example, be equal to 1.
The amphoteric associative polymers disclosed herein may comprise from 1 mol % to 10 mol % of the monomer comprising a fatty chain (monomer of formula (XIX), (XX) or (XXII)), and, for example, from 1.5 mol % to 6 mol %.
The weight-average molecular weights of the amphoteric associative polymers disclosed herein may range from 500 to 50,000,000 and, further, for example, from 10 000 to 5,000,000.
The amphoteric associative polymers disclosed herein may also comprise other monomers such as nonionic monomers and, for example, C1-C4 alkyl acrylates and methacrylates.
Amphoteric associative polymers disclosed herein are described and prepared, for example, in Patent Application No. WO 98/44012.
For example, the amphoteric associative polymers may be chosen from acrylic acid/(meth)acrylamidopropyltrimethylammon ium chloride/stearyl methacrylate terpolymers.
The non-ionic associative polymers that may be used may, for example, be chosen from:
For example, the polyurethane polyethers comprise at least two hydrocarbon-based lipophilic chains comprising from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains, or chains at the end of the hydrophilic block. For example, it is possible for at least one pendent chain to be included. In addition, the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
The polyurethane polyethers may be multiblock, such as in triblock form. Hydrophobic blocks may be at each end of the chain (for example: triblock copolymer with a hydrophilic central block) or distributed both at the ends and in the chain (for example: multiblock copolymer). These same polymers may also be graft polymers or starburst polymers.
The nonionic fatty-chain polyurethane polyethers may be triblock copolymers in which the hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1,000 oxyethylene groups. The nonionic polyurethane polyethers comprise a urethane linkage between the hydrophilic blocks, whence arises the name.
By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.
Examples of nonionic fatty-chain polyurethane polyethers that may be used include RHEOLATE 205® comprising a urea functional group, sold by the company Rheox, or RHEOLATE® 208, 204 or 212, and also ACRYSOL RM 184®.
Mention may also be made of the product ELFACOS T210® comprising a C12-14 alkyl chain, and the product ELFACOS T212® comprising a C18 alkyl chain, from Akzo.
The product DW 1206B® from Rohm & Haas comprising a C20 alkyl chain and a urethane linkage, sold at a solids content of 20% in water, may also be used.
It is also possible to use solutions or dispersions of these polymers, for example, in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned are RHEOLATE® 255, RHEOLATE® 278 and RHEOLATE® 244 sold by the company Rheox. The products DW 1206F and DW 1206J sold by the company Rohm & Haas may also be used.
The polyurethane polyethers that may be used include those described in the article by G. Formum, J. Bakke and Fk. Hansen—Colloid Polym. Sci 271, 380.389 (1993).
In one embodiment, it is possible to use a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.
Such polyurethane polyethers are sold, for example, by the company Rohm & Haas under the names ACULYN 44® and ACULYN 46® [ACULYN 46® is a polycondensate of polyethylene glycol comprising 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44® is a polycondensate of polyethylene glycol comprising 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexylisocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
Non-associative gelling agents may also be used as thickeners; included among these are polymers or copolymers of unsaturated carboxylic organic acids or of unsaturated esters, polysaccharide derivatives, gums, colloidal silicates, polyethylene glycols, polyvinyl pyrrolidones and hydrophilic silica gels.
The at least one thickener may be present in the at least one styling composition disclosed herein in an amount ranging from 0.01% to 10% by weight and, further, for example, from 0.1% to 5% by weight, relative to the total weight of the composition.
According to one embodiment, the at least one styling composition disclosed herein also comprises at least one surfactant.
The at least one surfactant may be chosen from:
(i) Anionic Surfactant(s):
By way of example of anionic surfactants that can be used, alone or as mixtures mention may be made, for example, of at least one (non-limiting list) of salts (such as alkali metal salts, for example, sodium salts, ammonium salts, amine salts, amino alcohol salts and magnesium salts) of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates; alkyl sulfonates, alkyl phosphates, alkylamide sulfonates, alkylaryl sulfonates, α-olefin sulfonates, paraffin sulfonates; (C6-C24)alkyl sulfosuccinates, (C6-C24)alkyl ether sulfosuccinates, (C6-C24)alkylamide sulfosuccinates; (C6-C24)alkyl sulfoacetates; (C6-C24)acyl sarcosinates; and (C6-C24)acyl glutamates. It is also possible to use (C6-C24)alkylpolyglycoside carboxylic esters such as alkylglucoside citrates, alkylpolyglycoside tartrates and alkylpolyglycoside sulfosuccinates, alkylsulfosuccinamates; acyl isethionates and N-acyl taurates, wherein the alkyl or acyl radical of all of these different compounds comprises, for example, from 12 to 20 carbon atoms and the aryl radical is chosen, for example, from phenyl and benzyl groups. Among the anionic surfactants which can also be used, mention may also be made of fatty acid salts, such as oleic, ricinoleic, palmitic and stearic acid salts; coconut oil acid and hydrogenated coconut oil acid; and acyl lactylates, wherein the acyl radical comprises 8 to 20 carbon atoms. It is also possible to use alkyl D-galactoside uronic acids and salts thereof, polyoxyalkylenated (C6-C24)alkyl ether carboxylic acids, polyoxyalkylenated (C6-C24)alkylaryl ether carboxylic acids, polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids and salts thereof, such as those comprising from 2 to 50 alkylene oxide groups, for example, ethylene oxide groups.
(ii) Nonionic Surfactant(s):
The nonionic surfactants are, themselves also, compounds that are well known per se (see, for example, “Handbook of Surfactants” by M. R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178) and their nature is not a critical factor in the context of the present disclosure. Thus, the non-ionic surfactants can be chosen, for example, from (non-limiting list) polyethoxylated and polypropoxylated, alkylphenols, alpha-diols and alcohols, comprising at least one fatty chain comprising, 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. 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, comprising from 2 to 30 mol of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5, and, for example, 1.5 to 4, glycerol groups; oxyethylenated fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkylpolyglycosides, N-alkylglucamine derivatives, and amine oxides such as (C10-C14)alkylamine oxides and N-acylaminopropylmorpholine oxides.
(iii) Amphoteric or Zwitterionic Surfactant(s):
The amphoteric or zwitterionic surfactants, the nature of which is not a critical factor in the context of the present disclosure may, for example, be chosen from (non-limiting list), aliphatic secondary and tertiary amine derivatives, wherein the aliphatic radical is chosen from linear and branched chains comprising from 8 to 18 carbon atoms and comprising at least one water-solubilizing anionic group (for example, carboxylate, sulfonate, sulfate, phosphate and phosphonate); mention may also be made of (C8-C20)alkylbetaines, sulfobetaines, (C8-C20)alkylamido(C1-C6)alkylbetaines, and (C8-C20)alkylamido(C1-C6)alkylsulfobetaines.
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:
R2—CONHCH2CH2—N(R3)(R4)(CH2COO−)
These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium Caprylamphodipropionate, Disodium Capryloamphodipropionate, Lauroamphodipropionic acid, and Cocoamphodipropionic acid.
For example, mention may be made of the cocoamphodiacetate sold under the trade name MIRANOL® C2M concentrate by the company Rhodia Chimie.
(iv) Cationic Surfactants:
Among the cationic surfactants, mention may be made, for example, (non-limiting list) of: salts of optionally polyoxyalkylenated primary, secondary and tertiary fatty amines; quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium and alkylpyridinium chlorides and bromides; imidazoline derivatives; and amine oxides of cationic nature.
The at least one surfactant may be present in an amount ranging from 0.01% to 40% and, for example, from 0.1% to 30% by weight, relative to the total weight of the composition.
Further disclosed herein is a cosmetic process for shaping and/or holding the hairstyle, comprising vaporizing onto the hair the contents of the aerosol device disclosed herein.
When the contents of the aerosol device are vaporized onto the hair, the aerosol device disclosed herein may generate a spray or a mousse.
The invention is illustrated in greater detail by the examples described below. 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 herein. 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 in the disclosure above are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in its respective testing measurements.
100 g of butyl acetate were introduced into a 1 liter reactor and the temperature was then increased so as to go from room temperature (25° C.) to 90° C. in 1 hour.
30 g of acrylic acid, 30 g of methyl acrylate, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 from Akzo Nobel) were then added, at 90° C. and over 1 hour.
The mixture was maintained at 90° C. for 1 hour.
90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introduced into the above mixture, still at 90° C. and over 1 hour.
The mixture was maintained at 90° C. for 3 hours, it was then diluted with 105 g of butyl acetate and 45 g of isopropanol, and the mixture was then cooled.
A solution containing 40% polymer active material in a butyl acetate/isopropanol mixture was obtained.
A polymer comprising a first poly(acrylic acid/methyl acrylate) block with a Tg of 80° C., a second polymethyl acrylate block with a Tg of 10° C. and an intermediate segment that was an acrylic acid/methyl acrylate/polymethyl acrylate random polymer was obtained.
This polymer had a weight-average mass of 50,000 g/mol and a number-average mass of 17,000, i.e. a polydispersity index I of 2.95.
It had a glass transition temperature (Tg) of 49° C.
A styling composition propelled with a liquefied gas in a standard aerosol device was prepared.
The proportions of the various ingredients, given as weight percentages relative to the total contents of the aerosol device, are given in the table below.
A styling mousse was prepared:
The proportions of the various ingredients, given as weight percentages relative to the total contents of the aerosol device, are given in the table below.
A styling composition propelled with compressed air was prepared.
The proportions of the various ingredients, given as weight percentages relative to the total contents of the aerosol device, are given in the table below.
Weight percentage data
This styling composition was packaged in a pocket aerosol device. This device is sold under the name EP SPRAY, and comprises an assembly comprising a pocket hermetically welded to a valve and a turbulent-nozzle diffuser. The valve was fixed onto a standard aerosol can.
The pocket was filled with the composition of Example 4 and compressed air was introduced between the pocket and the aerosol can at a sufficient pressure to cause the product to exit in the form of a spray.
The pressure of the compressed gas ranged from 1 to 12 bar and, for example, from 9 to 11 bar.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0403088 | Mar 2004 | FR | national |
This application claims benefit of U.S. Provisional Application No. 60/572,106, filed May 19, 2004, the contents of which are incorporated herein by reference. This application also claims benefit of priority under 35 U.S.C. § 119 to French Patent Application No. FR 0403088, filed Mar. 25, 2004, the contents of which are also incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| 60572106 | May 2004 | US |
