Patent Application
20120172457
The invention relates to novel thickeners as well as use thereof in cosmetics and in pharmacy.
The cosmetics industry and the pharmaceutical industry very regularly use synthetic polymer thickeners for increasing the viscosity of creams, emulsions and various topical solutions. The synthetic polymer thickeners currently used in these fields are in two physical forms, the powder form and the liquid form for which the polymer is prepared by inverse emulsion polymerization by means of surfactants, and which is commonly called inverse latex.
The best-known of the polymer thickeners in powder form are polymers based on acrylic acid or copolymers based on acrylic acid and acrylic acid esters. We may mention for example the polymers marketed by the company Noveon under the brand names CARBOPOL™ and PEMULEN™. They are notably described in the American patents U.S. Pat. No. 5,373,044, U.S. Pat. No. 2,798,053 and in European patent EP 0 301 532. In the cosmetics industry, homopolymers or copolymers based on 2-acrylamido-2-methyl-propanesulfonic acid are also used, again in powder form. These polymer thickeners are marketed under the brand name Aristoflex™ and are notably described in European patents EP 816 403, EP 1 116 733 and EP 1 069 142. These thickeners in powder form are obtained by precipitation polymerization; the monomer(s) is (are) dissolved in an organic solvent such as benzene, ethyl acetate, cyclohexane, tert-butanol. Thickeners in the form of inverse latices and notably those marketed by the applicant are also very widely used in the cosmetics industry. We may mention for example the thickeners Sepigel™ 305, Simulgel™ 600, Simulgel™ EG, Simulgel™ EPG, Simulgel™ NS, Simulgel™A, Sepiplus™ 400, Sepiplus™ 250 and Sepiplus™ 265. These thickeners are obtained by inverse emulsion polymerization. They have the advantage of easier handling, and they disperse in water very quickly. Moreover, these products develop remarkably high thickening performance; this performance probably results from their method of preparation, a dispersed-phase polymerization reaction, which leads to polymers with very high molecular weights.
The international application published under number WO 2006/002936 discloses water-soluble copolymers, which are used as water retention agents, stabilizers and rheology modifiers for cements, plasters, mortars, water-based paints and other compositions based on aqueous binders. These copolymers are obtained from monomers with a sulfonic acid function, monomers with an amine function and monomers derived from polyethoxylated alkyl (meth)acrylate. This international application discloses, more particularly, a terpolymer of partially salified or completely salified 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonic acid, of acrylamide and of pentacosa-ethoxylated stearyl methacrylate (monomer marketed under the name PLEX 6877-O™.
However, these thickeners in the form of inverse latex contain an oil and one or more surfactants, which can sometimes induce reactions of cutaneous intolerance in subjects who are particularly sensitive; moreover, said presence of oil makes them unusable for preparing clear gels.
The inventors have therefore developed thickener systems like those described in the French patent application published under number 2 910 899, which discloses a linear, branched or crosslinked terpolymer of at least one monomer possessing a strong acid function, free, partially salified or completely salified, with at least one neutral monomer, and at least one monomer of formula (A):
In (A), R1 represents a hydrogen atom or a methyl radical, R represents a linear or branched alkyl radical having from eight to thirty carbon atoms and n represents a number greater than or equal to one and less than or equal to fifty. These polymers display very pronounced thickening properties, notably in the presence of electrolytes. They function over a wide range of pH and can be used for making transparent gels. However, the low-pH formulations thickened with certain of them do not have satisfactory long-term resistance to salts and some of them, which contain fatty alcohols, have a rather unappealing elastic appearance and produce sensations of stickiness to the touch and/or have the appearance of a cream or an emulsion that is grainy and discontinuous.
The applicant demonstrated that these drawbacks could be avoided by selecting certain of these terpolymers that were not disclosed in the French patent application published under number 2 910 899.
That is why according to a first aspect the invention relates to a branched or crosslinked anionic polyelectrolyte resulting from the polymerization of partially salified or completely salified 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonic acid, with at least one neutral monomer selected from acrylamide, (2-hydroxy-ethyl) acrylate or N,N-dimethyl acrylamide, and at least one monomer of formula (I):
in which R represents a linear or branched alkyl radical having from eight to twenty carbon atoms and n represents a number greater than or equal to one and less than or equal to twenty, selected from tetraethoxylated lauryl methacrylate or eicosaethoxylated stearyl methacrylate in the presence of at one crosslinking agent.
“Crosslinked polymer” denotes a nonlinear polymer that is in the form of a three-dimensional network, insoluble in water, but swellable in water and therefore leading to the production of a chemical gel.
According to another particular embodiment, the anionic polyelectrolyte is crosslinked with a diethylene or polyethylene compound in the molar proportions, expressed relative to the monomers employed, from 0.005% to 1%, more particularly from 0.01% to 0.5% and quite particularly from 0.01% to 0.25%.
The crosslinking agent is more particularly selected from ethylene glycol dimethacrylate, tetraallyloxyethane, ethylene glycol diacrylate, diallyl urea, triallyl amine, trimethylol propanetriacrylate or methylene-bis(acrylamide) or a mixture of its compounds.
In the context of the present invention, the anionic polyelectrolyte as defined above generally comprises between 5 mol. % and 95 mol. % of monomers with a strong acid function, more particularly between 10 mol. % and 90 mol. % and quite particularly between 20 mol. % and 80 mol. %.
In the context of the present invention, the strong acid function is partially or completely salified as alkali metal salt such as for example sodium salt or potassium salt or as ammonium salt.
According to another particular aspect, the invention relates to an anionic polyelectrolyte as defined above, in which the monomer with strong acid function is 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonic acid partially or completely salified in the form of ammonium salt.
In the context of the present invention the anionic polyelectrolyte as defined above more particularly comprises between 4.9 mol. % and 90 mol. % of neutral monomer, more particularly between 9.5 mol. % and 85 mol. % and quite particularly between 15 mol. % and 75 mol. %.
According to a more particular embodiment, the invention relates to an anionic polyelectrolyte as defined above, in which the neutral monomer is N,N-dimethyl acrylamide.
According to another more particular embodiment, the invention relates to an anionic polyelectrolyte as defined above, in which the neutral monomer is acrylamide.
According to another more particular embodiment, the invention relates to an anionic polyelectrolyte as defined above, in which the neutral monomer is (2-hydroxy-ethyl) acrylate.
According to a quite particular embodiment, the invention relates to an anionic polyelectrolyte as defined above, in which the monomer of formula (I) is tetraethoxylated lauryl methacrylate, corresponding to the compound of formula (I) in which the radical R represents the dodecyl radical and n is equal to 4.
According to a quite particular embodiment, the invention relates to an anionic polyelectrolyte as defined above, in which the monomer is eicosaethoxylated stearyl methacrylate, corresponding to the compound of formula (I) in which the radical R represents the octadecyl radical and n is equal to 20.
In the context of the present invention, the anionic polyelectrolyte as defined above comprises between 0.1 mol. % and 10 mol. % of monomers of formula (I) and more particularly between 0.5 mol. % and 5 mol. %.
The polyelectrolyte according to the present invention can also comprise various additives, such as complexing agents, chain transfer agents or chain limiting agents.
The invention relates more particularly to an anionic polyelectrolyte selected from the following polymers:
According to another particular aspect, the invention relates to a crosslinked anionic polyelectrolyte, as defined above, comprising for 100% of monomers used:
According to another more particular aspect, the invention relates to a crosslinked anionic polyelectrolyte, as defined above, comprising for 100% of monomers used:
The invention also relates to a method of preparing the polyelectrolyte as defined above, characterized in that:
According to a preferred implementation of the method as defined above, the polymerization reaction is initiated at a temperature greater than or equal to 50° C. by means of a radical initiator producing radicals by homolysis, such as dilauroyl peroxide, azo-bis-isobutyronitrile or azo derivatives.
According to another implementation of the method as defined above, the polymerization reaction is initiated by a redox pair, at a temperature less than or equal to 20° C.
The invention also relates to the use of the anionic polyelectrolyte as defined above, as thickener and/or as stabilizer and/or as emulsifier, of a cosmetic, dermopharmaceutical or pharmaceutical topical composition.
A topical composition according to the invention, intended to be applied on the skin or the mucosae of humans or animals, can comprise a topical emulsion comprising at least one aqueous phase and at least one oily phase. This topical emulsion can be of the oil-in-water (O/W), water-in-oil (W/O), oil-in-water-in-oil (O/W/O) or water-in-oil-in-water (W/O/W) type. The oily phase of the topical emulsion can comprise a mixture of one or more oils.
A topical composition according to the invention can be intended for cosmetic use or to be used for preparing a medicinal product intended for treating diseases of the skin, scalp and mucosae. In the last-mentioned case, the topical composition then comprises an active principle which can for example comprise an anti-inflammatory agent, a muscle relaxant, an antifungal, an antibacterial or an antidandruff agent.
When the topical composition is used as a cosmetic composition intended to be applied on the skin, scalp or mucosae, it may or may not comprise an active principle, for example a hydrating agent, a tanning agent, a sun filter, an antiwrinkle, an agent for the purpose of slimming, an antiradical agent, an antiacne agent, an antifungal or antidandruff agent.
The invention finally relates to a topical composition according to the invention usually comprises between 0.1% and 10 wt. % and more particularly from 1 to 5 wt. % of the anionic polyelectrolyte as defined above. The pH of the topical composition is preferably greater than or equal to 3.
The topical composition can further comprise compounds conventionally included in compositions of this type, for example perfumes, preservatives, dyes, pigments, sunscreens, active ingredients, emollients or surfactants.
According to another particular aspect, the invention relates to the use of the anionic polyelectrolyte as defined above, for thickening and emulsifying and stabilizing a topical composition comprising at least one aqueous phase.
The anionic polyelectrolyte according to the invention is an interesting substitute for the inverse latices sold under the names SEPIGEL™ 305, SEPIGEL™ 501, SIMULGEL™ EG, SIMULGEL™ EPG, SIMULGEL™ NS, SIMULGEL™ 600, SIMULGEL™ A, SEPIPLUS™ 265, SEPIPLUS™ 250, SEPIPLUS™ 400 or SEPINOV™ EMT 10 by the applicant, as it also displays good compatibility with the other excipients used for preparing formulations such as milks, lotions, creams, soaps, baths, balsams, shampoos or conditioners. It can also be used with said SEPIGEL™ or SIMULGEL™, SEPIPLUS™ and/or SEPINOV™ EMT 10.
Notably it is compatible with the concentrates described and claimed in international publications WO 92/06778, WO 95/04592, WO 95/13863, WO 96/37285, WO 98/22207, WO 98/47610 or in FR 2 734 496, with the surfactants described in WO 93/08204. It is particularly compatible with MONTANOV™ 68, MONTANOV™ 82, MONTANOV™ 202, MONTANOV™ L, MONTANOV™ S, FLUIDANOV™ 20X or EASYNOV™. It can also be used in emulsions of the type such as those described and claimed in EP 0 629 396 and in cosmetically or physiologically acceptable aqueous dispersions with an organopolysiloxane compound selected for example from those described in WO 93/05762 or in WO 93/21316.
It can also be used to form cosmetically or physiologically acceptable aqueous gels with acid pH, such as those described in WO 93/07856; it can also be used together with nonionic celluloses, for example to form styling gels such as those described in EP 0 684 024, or together with esters of fatty acids and of sugar, to form compositions for treating the hair or the skin such as those described in EP 0 603 019, or in shampoos or conditioners as described and claimed in WO 92/21316 or finally together with an anionic homopolymer such as CARBOPOL™ to form hair treatment products such as those described in DE 19523596.
It is also compatible with the N-acylated derivatives of amino acids, which means it can be used in soothing compositions notably for sensitive skin, such as those described or claimed in WO 92/21318, WO 94/27561 or WO 98/09611. It is also compatible with thickening and/or gelling polymers such as hydrocolloids of vegetable origin or biosynthetic, for example xanthan gum, karaya gum, carrageenates, alginates, galactomannans; such as silicates; such as cellulose and derivatives thereof; such as starch and hydrophilic derivatives thereof; such as polyurethanes.
A) Preparation of Polyelectrolytes:
A reactor maintained at 25° C. with stirring is loaded with 592 g of a 15 wt. % aqueous solution of ammonium 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonate in a tert-butanol/water mixture (97.5/2.5 by volume), 10.1 g of N,N-dimethyl acrylamide, 4.2 g of tetraethoxylated lauryl methacrylate and 0.75 g of trimethylol propanetriacrylate. After a sufficient time to achieve good homogenization of the solution, the latter is deoxygenated by bubbling with nitrogen heated to 70° C. Then 0.42 g of dilauroyl peroxide is added and the reaction mixture is then held at 70° C. for about 60 minutes and then at 80° C. for 2 hours. After cooling, the powder that formed during polymerization is filtered and dried, obtaining the desired product, called hereinafter: Polyelectrolyte 1.
A reactor maintained at 25° C. with stirring is loaded with 592g of a 15 wt. % aqueous solution of ammonium 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonate in a tert-butanol/water mixture (97.5/2.5 by volume), 10.1 g of N,N-dimethyl acrylamide, 6.2 g of eicosaethoxylated stearyl methacrylate and 0.75 g of trimethylol propanetriacrylate. After a sufficient time to achieve good homogenization of the solution, the latter is deoxygenated by bubbling with nitrogen heated to 70° C. Then 0.42 g of dilauroyl peroxide is added and the reaction mixture is then held at 70° C. for about 60 minutes and then at 80° C. for 2 hours. After cooling, the powder that formed during polymerization is filtered and dried, obtaining the desired product, called hereinafter: Polyelectrolyte 2.
A reactor maintained at 25° C., with stirring, is loaded with 592 g of a 14% solution of the ammonium salt of 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonic acid in a tert-butanol/water mixture (97.5/2.5 by volume), 18.5 g of hydroxy-ethyl acrylate, 4.2 g of tetraethoxylated lauryl methacrylate and 0.75 g of trimethylol propanetriacrylate. After a sufficient time to achieve good homogenization of the solution, the latter is deoxygenated by bubbling with nitrogen heated to 70° C. Then 0.42 g of dilauroyl peroxide is added and the reaction mixture is then held at 70° C. for about 60 minutes and then at 80° C. for 2 hours. After cooling, the powder that formed during polymerization is filtered and dried, obtaining the desired product, called hereinafter: Polyelectrolyte 3.
A reactor maintained at 25° C. with stirring is loaded with 592g of a 14% solution of the ammonium salt of 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonic acid in a tert-butanol/water mixture (97.5/2.5 by volume), 16 g of acrylamide crystal, 4.2 g of tetraethoxylated lauryl methacrylate and 0.75 g of trimethylol propanetriacrylate. After a sufficient time to achieve good homogenization of the solution, the latter is deoxygenated by bubbling with nitrogen heated to 70° C. Then 0.42 g of dilauroyl peroxide is added and the reaction mixture is then held at 70° C. for about 60 minutes and then at 80° C. for 2 hours. After cooling, the powder that formed during polymerization is filtered and dried, obtaining the desired product, called hereinafter: Polyelectrolyte 4
A reactor maintained at 25° C., with stirring, is loaded with 592 g of a 15.5% solution of the ammonium salt of 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonic acid in a tert-butanol/water mixture (97.5/2.5 by volume), 10.1 g of N,N-dimethyl acrylamide, 4.1 g of tetraethoxylated lauryl acrylate and 0.75 g of trimethylol propanetriacrylate.
After a sufficient time to achieve good homogenization of the solution, it is deoxygenated by bubbling with nitrogen and then the temperature of the reaction mixture is raised to 70° C. When the desired temperature has been reached, 0.42 g of dilauroyl peroxide is added and the reaction mixture is then held at 70° C. for about 60 minutes and then at 80° C. for 2 hours. After cooling, the powder that formed during polymerization is filtered and dried, obtaining the desired product, called hereinafter: Polyelectrolyte T1.
A reactor maintained at 25° C., with stirring, is loaded with 592 g of a 15.5% solution of the ammonium salt of 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonic acid in a tert-butanol/water mixture (97.5/2.5 by volume), 10.1 g of N,N-dimethyl acrylamide, 6.1 g of eicosaethoxylated stearyl methacrylate and 0.5 g of trimethylol propanetriacrylate. After a sufficient time to achieve good homogenization of the solution, the latter is deoxygenated by bubbling with nitrogen heated to 70° C. Then 0.42 g of dilauroyl peroxide is added and the reaction mixture is then held at 70° C. for about 60 minutes and then at 80° C. for 2 hours. After cooling, the powder that formed during polymerization is filtered and dried, obtaining the desired product, called hereinafter: Polyelectrolyte T2
A reactor maintained at 25° C., with stirring, is loaded with 592 g of a 15.5% solution of the ammonium salt of 2-methyl 2-[(1-oxo 2-propenyl) amino] 1-propanesulfonic acid in a tert-butanol/water mixture (97.5/2.5 by volume), 10.1 g of N,N-dimethyl acrylamide, 7.7 g of pentacosaethoxylated behenyl methacrylate, (1500=MW) and 0.75 g of trimethylol propanetriacrylate. After a sufficient time to achieve good homogenization of the solution, the latter is deoxygenated by bubbling with nitrogen heated to 70° C. Then 0.42 g of dilauroyl peroxide is added and the reaction mixture is then held at 70° C. for about 60 minutes and then at 80° C. for 2 hours. After cooling, the powder that formed during polymerization is filtered and dried, obtaining the desired product, called hereinafter: Polyelectrolyte T3.
B) Comparative Investigations:
The thickeners according to the invention and those according to the prior art were evaluated as follows:
a) Measurement of viscosities (η):
These measurements of viscosity, expressed in mPas, were carried out at 25° C. using a type RVT Brookfield rheometer equipped with spindle number 6 and set to a rotary speed of 5 revolutions per minute (rpm). The pH was adjusted to 3.5 by adding glycolic acid and soda if necessary. The measurements were performed just after preparation T=0 at T=1 month (M1) then at T=3 months (M3).
b) Application formulas for assessment were prepared, thickened with each of the polyelectrolytes 1, 2, 3, 4, T1, T2 and T3 of the following composition:
These formulas are assessed in terms of visual appearance, sensory properties and stability of the formula after 24 hours. The properties found for the polyelectrolytes and the compositions according to the invention are presented in the following table, where they are compared with polyelectrolytes and compositions according to the prior art.
These results demonstrate that the polyelectrolytes according to the present invention give compositions that are more resistant to salts, owing to the presence of the monomer of formula (I) within them.
C) Examples of Formulations Prepared with Polyelectrolytes 1, 2, 3 or 4 According to the Invention
Formula
Procedure
Add B to A.
Formula
Procedure
Add C to B, emulsify B in A at 70° C., then add D at 60° C. then E at 30° C.
Formula
SEPICIDE™ HB: 0.30%
Procedure
Add B to A at about 75° C.; add C at about 60° C., then D at about 45° C.
Formula
Procedure
Add B to A; add C, then D, then E.
Formula
Procedure
Emulsify B in A at 75° C. then add C at about 60° C., then D at about 30° C. and adjust the pH if necessary.
Formula
Procedure
Add B to A, then add to the mixture, C then D
Formula
Procedure
Prepare mixtures B+D and A+C at 80° C., then mix and emulsify together.
Formula
Procedure
Prepare A; add B, then C, then D.
Formula
Procedure
Prepare mixture B+C then add A then D.
Formula
Procedure
Emulsify B in A at about 75° C.; add C at about 60° C., then D at about 30° C.
Formula
Procedure
Prepare A; add B, then C, then D.
Formula
Procedure
Melt A at about 75° C. Emulsify B in A at 75° C. then add C at about 60° C., then D.
The definitions of the commercial products used in the examples are as follows:
SIMULSOL™ 1293 is hydrogenated and ethoxylated castor oil, with an ethoxylation index equal to 40, marketed by the company SEPPIC.
CAPIGEL™ 98 is a liquid thickener based on acrylate copolymer marketed by the company SEPPIC.
KETROL™ T is xanthan gum marketed by the company KELCO.
LANOL™ 99 is isononyl isononanoate marketed by the company SEPPIC.
DC1501 is a mixture of cyclopentasiloxane and dimethiconol marketed by the company DOW CHEMICAL.
MONTANOV™ 82 is an emulsifier based on cetearyl alcohol and cocoylglucoside.
MONTANOV™ 68 (cetearyl glucoside), is a self-emulsifiable composition as described in WO 92/06778, marketed by the company SEPPIC.
MICROPEARL™ M 100 is an ultrafine powder with a very soft feel and a matting effect, marketed by the company MATSUMO.
SEPICIDE™ CI, imidazolidine urea, is a preservative marketed by the company SEPPIC.
PEMULEN™ TR1 is an acrylic polymer marketed by GOODRICH.
SIMULSOL™ 165 is self-emulsifiable glycerol stearate marketed by the company SEPPIC.
LANOL™ 1688 is a non-greasy emollient ester marketed by the company SEPPIC.
LANOL™ 14M and LANOL™ S are consistency factors marketed by the company SEPPIC.
SEPICIDE™ HB, which is a mixture of phenoxyethanol, methylparaben, ethylparaben, propylparaben and butylparaben, is a preservative marketed by the company SEPPIC.
AQUAXYL™ is a moisturizing agent marketed by the company SEPPIC.
SCHERCEMOL™ OP is a non-greasy emollient ester.
LANOL™ P is an additive with stabilizing effect marketed by the company SEPPIC.
PARSOL™ MCX is octyl para-methoxy cinnamate; marketed by the company GIVAUDAN.
MONTANOV™ S is a luster agent, marketed by the company SEPPIC, based on a mixture of alkyl polyglucosides such as those described in WO 95/13863.
MICROPEARL™ SQL is a mixture of microparticles containing squalane, which is released under the action of massaging; it is marketed by the company MATSUMO.
LANOL™ 37T is glycerol triheptanoate, marketed by the company SEPPIC.
SOLAGUM™ L is a carrageenan marketed by the company SEPPIC.
MARCOL™ 82 is a paraffin oil marketed by the company EXXON.
LANOL™ 84D is dioctyl malate marketed by the company SEPPIC.
PARSOL™ NOX is a sun filter marketed by the company GIVAUDAN.
EUSOLEX™ 4360 is a sun filter marketed by the company MERCK.
DOW CORNING™ 245 Fluid is cyclomethicone, marketed by the company DOW CORNING.
LIPACIDE™ PVB is an acylated hydrolyzate of wheat proteins marketed by the company SEPPIC.
MICROPEARL™ LM is a mixture of squalane, polymethylmethacrylate and menthol, marketed by the company SEPPIC.
SEPICONTROL™ AS is a mixture of capryloy glycine, sarcosine, cinnamon extract zylanicum, marketed by the company SEPPIC, such as those described in international patent application PCT/FR98/01313 filed on 23 Jun. 1998.
LANOL™ 2681 is a mixture of copra caprylate and caprate, marketed by the company SEPPIC.
MONTANOV™ 202 is an APG/fatty alcohols composition as described in WO9 98/47610, marketed by the company SEPPIC.
PROTEOL™ APL is a foaming surfactant, marketed by the company SEPPIC.
SCHERCEMOL™ TISC is an ester (tri-isostearyl citrate) marketed by the company SCHER.
VISTANOL™ NPGC is an ester (neopentyl glycol dicaprate) marketed by the company SEWA KASEI.
ANTARON™ V216 is a synthetic polymer (PVP/hexadecene copolymer) distributed by the company UNIVAR.
C MALTIDEX™ H16322 is a polyol (maltitol syrup) marketed by the company CERESTAR.
SEPIWHITE™MSH is a depigmenting agent (N-undecylenoyl phenylalanine) marketed by the company SEPPIC.
DC 345 is a cyclomethicone marketed by the company Dow Corning.
DC 5225C is a mixture of cyclopentasiloxane and dimethicone copolyol marketed by the company DOW CORNING.
SEPICALM™ VG is a soothing agent (sodium palmitoylproline) marketed by the company SEPPIC.
MT100VT is a micronized titanium dioxide that has undergone a surface treatment (aluminum hydroxide/stearic acid) distributed by the company UNIPEX.
Z COTE HP1 is a micronized zinc oxide that has undergone a surface treatment, distributed by GATTEFOSSE.
CANDURIN PAPRIKA is a mixture of potassium and aluminum silicate and iron oxide.
MICROPEARL™ M 310 is an ultrafine powder that has a very soft feel and a matting effect, marketed by the company MATSUMO.
PRIMOL™ 352 is a mineral oil marketed by the company EXXON.
PECOSIL™DCT is Sodium Dimethicone PEG-7 Acetyl Methyltaurate marketed by the company PHOENIX.
PECOSIL™PS 100 is Dimethicone PEG-7 marketed by the company PHOENIX.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0956224 | Sep 2009 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/FR2010/051819 | 9/1/2010 | WO | 00 | 3/12/2012 |
