Oil-in-water emulsion comprising a specific polyurethane and filler
An oil-in-water emulsion with polyurethane prepolymers and fillers addresses the issue of immediate wrinkle smoothing and resistance to external aggressions, forming a durable film on keratin materials.
Patent Information
- Application Number
- FR2022007213
- Authority / Receiving Office
- FR · FR
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2022-07-13
- Publication Date
- 2025-10-24
- Estimated Expiration
- 2042-07-13
AI Technical Summary
Existing cosmetic compositions fail to provide immediate and long-lasting smoothing of wrinkles and fine lines, and they are not resistant to external aggressions such as sweat, sebum, and oils, leading to poor adhesion and detachment of the film on keratin materials.
A cosmetic composition in the form of an oil-in-water emulsion containing polyurethane prepolymers derived from polyester polyols and polyisocyanates, combined with cellulose particles or hydrophobic silicas, which forms a durable and elastic film that adheres well to keratin materials, resisting detachment and discoloration.
The composition achieves lasting fixation of the film on keratin materials for at least a day, providing resistance to external aggressions and maintaining adhesion despite exposure to sweat, sebum, and oils.
Abstract
Description
Title of the invention: Oil-in-water emulsion comprising a specific polyurethane and filler
[0001] The present invention relates to a cosmetic composition in the form of an oil-in-water (O / W) emulsion comprising:
[0002] - at least one polyurethane obtainable by reaction of one or more water-insoluble, water-indispersible, isocyanate-functional polyurethane prepolymers A) with one or more amino-functional compounds B), said polyurethane prepolymer A) being obtainable by reaction of one or more polyester polyols having a glass transition temperature Tg of at least -50°C and one or more polyisocyanates; and
[0003] - at least one filler chosen from cellulose particles, silicas hydrophobic and their mixtures.
[0004] During the aging process, various signs appear on the skin, very characteristic of this aging, resulting in particular in a modification of the structure and functions of the skin. The main clinical signs of skin aging include the appearance of fine lines and deep wrinkles, which increase with age.
[0005] It is known to treat these signs of aging by using cosmetic or dermatological compositions containing active ingredients capable of combating aging, such as α-hydroxy acids, β-hydroxy acids and retinoids. These active ingredients act on wrinkles by eliminating dead skin cells and accelerating the cell renewal process. However, these active ingredients have the disadvantage of only being effective for the treatment of wrinkles after a certain period of application. However, there is an increasing desire to obtain an immediate effect from the active ingredients used, leading quickly to a smoothing of wrinkles and fine lines and the disappearance of signs of fatigue.
[0006] Cosmetic products often require the use of a film-forming polymer to obtain a deposit of the product on keratin materials having good cosmetic properties. In particular, it is necessary for the film-forming deposit to have good hold, in particular that the deposit does not transfer when in contact with fingers or clothing, as well as good hold in contact with water, in particular rain or when showering, or that the deposit is insensitive to perspiration or sebum, as well as to food fats, in particular food fats such as oils.
[0007] It is known to use dispersions of polymer particles in organic media such as hydrocarbon oils. Polymers are used in particular as film-forming agents in makeup products such as mascaras, eyeliners, eye shadows or lipsticks.
[0008] Thus, the aim of the present invention is to provide a composition for treating keratin materials, in particular the skin, preferably human skin, and more preferably facial skin, the residual film of which after application to said materials adheres well to the keratin materials, is elastic with the least possible fragmentation, the least possible detachment from the substrate, non-sticky, exhibiting good resistance to external aggressions, and over time, not discoloring, resistant to sweat, sebum, and little sensitive to oils such as food oils, in particular sebum. In particular, an aim of the invention is to provide a cosmetic composition exhibiting improved resistance (i.e. resistance to friction and the action of bodily fluids), in particular with respect to the deposited fillers.
[0009] The present invention addresses this problem.
[0010] The present invention therefore provides a cosmetic composition in the form of an oil-in-water (O / W) emulsion comprising:
[0011] - at least one polyurethane obtainable by reaction of one or more water-insoluble, water-indispersible, isocyanate-functional polyurethane prepolymers A) with one or more amino-functional compounds B), said polyurethane prepolymer A) being obtainable by reaction of one or more polyester polyols having a glass transition temperature Tg of at least -50°C and one or more polyisocyanates; and
[0012] - at least one filler chosen from cellulose particles, silicas hydrophobic and their mixtures.
[0013] The composition according to the invention, in the form of an H / W emulsion, makes it possible to permanently fix the charges in the form of deposits. By lasting fixation, we mean at least one day.
[0014] The composition according to the invention is an oil-in-water emulsion. By "oil-in-water emulsion" or "O / W emulsion" is meant a composition comprising an oily phase dispersed in a continuous aqueous phase.
[0015] The present invention also relates to a cosmetic process for caring for keratin materials, comprising the application of a composition according to one of the preceding claims, to the keratin materials, preferably the skin. Polyurethane
[0016] The composition according to the invention comprises at least one specific polyurethane.
[0017] Preferably, the polyurethane can be obtained according to the description of application WO2021 / 198051. It can be obtained by reacting one or more polyurethane prepolymers with isocyanate function A) comprising essentially neither ionic nor ionogenic groups, with one or more compounds with amino function B).
[0018] In the context of the invention, the expression "water-insoluble, non-water-dispersible polyurethane prepolymer" means in particular that the solubility in water of the prepolymer used according to the invention at 23°C is less than 10 g / liter, more preferably less than 5 g / liter and the prepolymer at 23°C has no dispersion stable to sedimentation in water, in particular demineralized water. In other words, the prepolymer settles when an attempt is made to disperse it in water.
[0019] The polyurethane prepolymer A) used according to the invention preferably has terminal isocyanate groups, i.e. the isocyanate groups are located at the ends of the chains of the prepolymer. All chain ends of a polymer particularly preferably have isocyanate groups.
[0020] Furthermore, the polyurethane prepolymer A) used according to the invention preferably has essentially neither ionic nor ionogenic groups, i.e. groups capable of forming ionic groups, i.e. the content of ionic and ionogenic groups is advantageously less than 15 milliequivalents per 100 g of polyurethane prepolymer A), preferably less than 5 milliequivalents, particularly preferably less than 1 milliequivalent and very particularly preferably less than 0.1 milliequivalents per 100 g of polyurethane prepolymer A). The amino-functional compounds B) are preferably chosen from primary and / or secondary amines and / or diamines. In particular, the amino-functional compounds B) comprise at least one diamine. The amino-functional compounds B) are preferably produced from amino-functional compounds B2).
[0021] In a particularly preferred embodiment of the invention, the amino-functional compounds B) comprise at least one amino-functional compound B2) which has ionic and / or ionogenic groups. The sulfonate or sulfonic acid group, more preferably the sodium sulfonate group, is particularly preferably used as the ionic and / or ionogenic group.
[0022] In another preferred embodiment of the invention, the amino-functional compounds B) comprise both amino-functional compounds B2) which have an ionic and / or ionogenic group and amino-functional compounds B1) which do not have ionic or ionogenic groups.
[0023] According to the invention, polyurethanes are polymer compounds which have at least two, preferably at least three, repeating units containing urethane groups: O
[0024] According to the invention, polyurethanes are also included which, due to the production process, also contain repeating units containing urea groups: O
[0025] The polyurethane may be dispersed, i.e. essentially not present in solution. In addition to other liquid media that may be present, such as solvents, water may be the main component (> 50% by weight) of the dispersing media, relative to the total amount of liquid dispersing media in the cosmetic compositions according to the invention, and it may also be the only liquid dispersing medium.
[0026] The aqueous polyurethane dispersions used to prepare the cosmetic compositions according to the invention preferably have a volatile organic compound (VOC) content of less than 10% by weight, more preferably less than 3% by weight, even more preferably less than 1% by weight relative to the aqueous polyurethane dispersion. In the context of the present invention, the volatile organic compound (VOC) content is determined in particular by gas chromatographic analysis.
[0027] The prepolymers A) used to manufacture the polyurethanes can be obtained by reacting one or more polyester polyols having a glass transition temperature Tg of at least -50°C and one or more polyisocyanates. The polyester polyol(s) used to prepare the prepolymers A) more preferably have a glass transition temperature Tg of -50 to 0°C, particularly preferably of -40 to -10°C, determined in each case by DSC measurement according to DIN 65467, with a heating rate of 20 K / min. The polyurethanes used according to the invention preferably have a glass transition temperature Tg of at least -50°C, particularly preferably from -50 to 0°C, particularly preferably from -30 to 0°C, very particularly preferably from -20 to -10°C, determined in each case by DSC measurement according to DIN 65467 with a heating rate of 20 K / min.
[0028] Preferably, one or more polyurethanes according to the invention are used, with at least 50% by weight of the components used to construct the polyurethane(s), in particular the polyester polyol(s), more preferably the dicarboxylic acids and / or the dicarboxylic acids used to construct the polyester polyol(s). dihydroxylated, from renewable sources. The resulting polymer, which is based on at least 50% by weight of bio-sourced raw materials, can be described as "naturally derived" (ingredients of natural origin) according to ISO 16128-1.
[0029] According to the invention, the term "from renewable sources" means that a source is chosen for the corresponding material which represents at least 90% by weight, preferably at least 95% by weight, particularly preferably at least 99% by weight, of the material, called "from renewable sources", resulting from plant or fermentation processes in which only living organisms and plants participate in the fermentation process.
[0030] The polyurethane(s) used according to the invention are preferably derived from renewable sources, i.e. biosourced, at a level of at least 30 mol%, particularly preferably at least 40 mol%, particularly preferably at least 50 mol%.
[0031] Preferably, the polyurethane may be obtained by reacting one or more water-insoluble, non-water-dispersible, isocyanate-functional polyurethane prepolymers with one or more amino-functional compounds B), and the polyurethane prepolymer A) is obtained by reacting one or more polyester polyols with a glass transition temperature Tg of at least -50°C and one or more polyisocyanates.
[0032] The polyurethanes according to the invention contain, via the prepolymer A), one or more of the aforementioned bio-sourced polyester poles with the specific glass transition temperature described. In addition, the prepolymers present according to the invention may contain at least one block chosen from the group consisting of polyether, polycarbonate, polyether-polycarbonate and other polyester blocks. According to the invention, this may mean that the polyurethanes contain repeating units containing ether groups and / or carbonate groups and ester groups. The polyurethanes according to the invention may, for example, be exclusively polyester blocks based on the polyester polyols described above with a glass transition temperature Tg of at least -50°C inclusive.However, they may also additionally have polyether and polycarbonate sequences, such as those formed, for example, during the production of polycarbonate polyols using polyether diols. In addition, they may have polyether-polycarbonate linkages which result from the use of polyether-polycarbonate polyols, as described in more detail below.
[0033] The preferred polyurethanes according to the invention are obtained using polyester polyols having a glass transition temperature Tg of at least -50°C, which have number average molecular weights preferably of about 400 to about 6000 g / mol, determined here and in the following molecular weight data by chromatography by gel permeation relative to the polystyrene standard in tetrahydrofuran at 23°C. Their use in the production of polyurethanes or polyurethane prepolymers leads to the formation of corresponding polyester blocks in the polyurethanes, with a corresponding molecular weight of these blocks, by reaction with polyisocyanates. According to the invention, particular preference is given to polyurethanes which are made from polyester polyols with a glass transition temperature Tg of at least -50°C with a linear structure and optionally in addition polyether diols and / or polycarbonate diols and / or polyether polycarbonate polyols or other polyester polyols.
[0034] The polyurethanes of the present invention are preferably essentially linear molecules, but may also be branched, which is less preferred.
[0035] The number-average molecular mass of the polyurethanes preferably used according to the invention is, for example, approximately 1000 to 200000 g / mol, preferably 5000 to 150000 g / mol.
[0036] The polyurethanes according to the invention can be formulated in the form of aqueous dispersions.
[0037] There are preferred polyurethanes or polyurethane dispersions for which the following characteristics are present:
[0038] A) isocyanate-functional prepolymers,
[0039] Al) organic polyisocyanates,
[0040] A2) polyester polyols with a glass transition temperature Tg of at least -50°C, preferably with number average molecular weights of 400 to 8000 g / mol, determined here and in the following molecular weight data by gel permeation chromatography relative to a polystyrene standard in tetrahydrofuran at 23°C, more preferably 400 to 6000 g / mol and more preferably 600 to 3000 g / mol, and OH functionalities preferably 1.5 to 6, more preferably 1.8 to 3, more preferably 1.9 to 2.1,
[0041] A3) optionally hydroxyfunctional compounds with masses molecular weights preferably from 62 to 399 g / mol, and
[0042] A4) optionally non-ionic hydrophilizing agents, and
[0043] B) some or all of their free NCO groups are then reacted with one or more amino-functional compounds B), such as primary and / or secondary amines and / or diamines.
[0044] The polyurethanes used according to the invention are preferably dispersed in water before, during or after step B).
[0045] In step B), particular preference is given to the reaction with one or more diamines with chain extension. In addition, amines Monofunctional compounds can be added as chain terminators to control molecular weight.
[0046] In particular, amines may be used as component B) which do not have ionic or ionogenic groups, such as anionic hydrophilizing groups, in the following component B1), and amines may be used which have ionic or ionic groups, such as in particular anionic hydrophilizing groups, in the following component B2).
[0047] In step B) of the prepolymer reaction, a mixture of component B1) and component B2) is preferably reacted. By using component B1), a high molar mass can be established without the viscosity of the previously prepared isocyanate-functional prepolymer increasing to an extent that would prevent processing. By using the combination of components B1) and B2), an optimal balance between hydrophilicity and chain length and thus a pleasant skin feel can be established. The polyurethanes used according to the invention preferably have anionic groups, preferably sulfonate groups. These anionic groups are introduced into the polyurethanes used according to the invention via the amine component B2) reacted in step B). The polyurethanes used according to the invention may also contain non-ionic components for hydrophilic purposes.The polyurethanes used according to the invention particularly preferably contain exclusively sulfonate groups for hydrophilization, which are introduced into the polyurethane as component B2) via corresponding diamines.
[0048] In order to obtain good sedimentation stability, the number average particle size of the special polyurethane dispersions is preferably less than 750 nm, particularly preferably less than 500 nm, determined by laser correlation spectroscopy after dilution with demineralized water, Malvern Zetasizer apparatus used 1000, Malvern Institute Limited.
[0049] The solids content of polyurethane dispersions is generally 10 to 70% by weight, preferably 30 to 65% by weight, particularly preferably 30 to 50% by weight. According to the invention, the solids content is determined by heating a weighed sample at 125°C to constant weight. If the weight remains constant, the solids content is calculated by reweighing the sample.
[0050] These polyurethane dispersions preferably contain less than 5% by weight, particularly preferably less than 0.2% by weight, relative to the mass of the dispersions, of unbound organic amines. The content in decorative cosmetic compositions is correspondingly lower.
[0051] Suitable polyisocyanates of component A1) are in particular aliphatic, aromatic or cycloaliphatic polyisocyanates known per se to those skilled in the art and having an NCO functionality greater than or equal to 2.
[0052] Examples of such suitable polyisocyanates are 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, bisisomer bis(4,4'-isocyanatocyclohexyl)methane or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate), 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluylene diisocyanate, 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and / or 1,4-bis-(2-isocyanatoprop-2-yl)benzene (TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI) and alkyl 2,6-diisocyanatohexanoates (lysine diisocyanates) with C1-C8 alkyl groups.
[0053] Preference is given to polyisocyanates or mixtures of polyisocyanates of the above-mentioned type with exclusively aliphatically or cycloaliphatically bound isocyanate groups or mixtures thereof and an average NCO functionality of the mixture of 2 to 4, preferably 2 to 2.6 and particularly preferably 2 to 2.4, preferably 2.
[0054] Particular preference is given to the use of hexamethylene diisocyanate, isophorone diisocyanate or isomeric bis(4,4'-isocyanatocyclohexyl)methanes and mixtures of the diisocyanates mentioned above in A1).
[0055] In A2) polymeric polyester polyols with a glass transition temperature Tg of at least -50°C and a number-average molecular weight Mn of preferably 400 to 8000 g / mol, more preferably 400 to 6000 g / mol and particularly preferably 600 to 3000 g / mol are used. These preferably have an OH functionality of 1.5 to 6, particularly preferably 1.8 to 3, very particularly preferably 1.9 to 2.1.
[0056] The expression “polymeric” polyester polyols means here in particular that the polyols cited have at least two, more preferably at least three repeating units linked together.
[0057] These polyester polyols according to the invention with a glass transition temperature Tg of at least -50°C can be used in A2) alone or in any mixtures thereof. Other polyols which may also be present are polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols and polyester polycarbonate polyols known per se to those skilled in the art.
[0058] The polyester polyols used according to the invention are the known polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or the corresponding polycarboxylic acid esters of lower alcohols can also be used to produce the polyester.Examples of suitable diols are ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, as well as 1,2-propanediol, 1,3-propanediol, butanediol(1,3), butanediol(1,4), hexanediol(1,6) and isomers thereof, neopentyl glycol or hydroxypivalic acid ester of neopentyl glycol, where hexanediol(1,6) and isomers thereof, butanediol(1,4), neopentyl glycol and hydroxypivalic acid neopentyl glycol ester are preferred. Additionally, polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate can also be used.
[0059] Acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, succinic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and / or 2,2-dimethylsuccinic acid may be used. The corresponding anhydrides may also be used as the acid source.
[0060] Polyols that have more than two OH groups are described above. Instead of or in addition to this, it is also possible to use polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate. If the average functionality of the polyol to be esterified is >2, monocarboxylic acids such as benzoic acid and hexanecarboxylic acid can also be used.
[0061] Preferred acids are aliphatic or aromatic acids, particularly preferably aliphatic acids of the type mentioned above, succinic acid, adipic acid, isophthalic acid and phthalic acid are particularly preferred.
[0062] The succinic acid, which is preferably used for the production of the polyester polyols used according to the invention, is preferably obtained from renewable sources. The succinic acid is produced, for example, by fermentation of starch or biomass, as described in DE 10 2008 051727 A1 and DE 10 2007 019184, for example. According to the invention, at least 50% by weight of the succinic acid used preferably comes from renewable sources. Furthermore or in addition, at least a portion of the dihydroxy compounds used in the polyester polyol according to the invention may also come from renewable sources, and thus increase the proportion of polyurethane components from renewable sources. The polyester polyol used according to the invention preferably contains at least one dihydroxy compound selected from 1,4-butanediol, 1,3-propanediol, isopropanediol, 1,6-hexanediol, ethylene glycol, which are preferably derived from renewable sources, and mixtures thereof, before the hydroxycarboxylic acids used as reactants in the preparation of a hydroxyl-terminated polyester polyol may also be used are, for example, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.Suitable lactones are caprolactone, butyrolactone and their homologues. Caprolactone is preferred.
[0063] Particularly preferred according to the invention as component A2) for the production of polyurethanes are polyester polyols with a glass transition temperature Tg of at least -50°C and a number-average molecular weight of 600 to 3000 g / mol, in particular aliphatic polyester polyols based on aliphatic carboxylic acids and aliphatic polyols, in particular based on succinic acid or adipic acid and aliphatic alcohols such as butanediol(1,4), hexanediol(1,6) and / or neopentyl glycol.
[0064] In addition to the polyester polyol described above as component A2), other polyols may be present in the polyurethane used according to the invention, for example polycarbonates containing hydroxyl groups, preferably polycarbonate diols, with number-average molecular weights Mn preferably from 400 to 8000 g / mol, preferably 600 to 3000 g / mol are used. These can be obtained by reacting carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols.
[0065] Examples of such diols are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1,3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A and lactone-modified diols of the type mentioned above.
[0066] The diol component preferably contains 40 to 100% by weight of hexanediol, with preference being given to 1,6-hexanediol and / or hexanediol derivatives. Such hexanediol derivatives are based on hexanediol and have ester or ether groups in addition to the terminal OH groups. Such derivatives can be obtained by reacting hexanediol with excess caprolactone or by etherifying hexanediol with itself to form di- or trihexylene glycol.
[0067] Instead of or in addition to pure polycarbonate diols, polyether polycarbonate diols may also be used.
[0068] Polycarbonates containing hydroxyl groups preferably have a linear structure.
[0069] It is also possible to use polyether polyols in addition to the polyester polyols according to the invention. Particularly suitable are, for example, polytetramethylene glycol polyethers known per se in polyurethane chemistry, such as can be obtained by polymerization of tetrahydrofuran by means of cationic ring opening.
[0070] Likewise, suitable polyether polyols are the known addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxide and / or epichlorohydrin to difunctional or polyfunctional starter molecules. In particular, polyalkylene glycols such as polyethylene, polypropylene and / or polybutylene glycols can be used, especially with the preferred molecular weights mentioned above.
[0071] All compounds known from the prior art can be used as suitable starter molecules, such as for example water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, 1,4-butanediol.
[0072] Particularly preferred polyols which may be present in addition to component A2) are polytetramethylene glycol polyethers and polycarbonate polyols or mixtures thereof, and polytetramethylene glycol polyethers are particularly preferred.
[0073] In a preferred embodiment of the present invention, the following polyol mixtures may be used in addition to the polyester polyol according to the invention (component A2): mixtures containing at least one polyether polyol and at least one polycarbonate polyol, mixtures containing more than one polyether polyol, or a mixture of several polyether polyols of different molecular weights, in particular poly(tetramethylene glycol) polyether polyols (such as (HO-(CH 2 -CH 2 -CH 2 -CH 2 -O) xH), mixtures containing more than one polyether polyol and at least one polycarbonate polyol, and the aforementioned polyester poles, the polyol component by definition comprising essentially neither ionic nor ionogenic groups.
[0074] Optionally, polyols, in particular non-polymeric polyols, in the molecular weight range of 62 to 399 mol / g with up to 20 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis(4-hydroxyphenyl) propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl) propane), trimethylolpropane, trimethylolethane, glycerin, pentaerythritol and all mixtures thereof, especially neopentyl glycol, are used. Also suitable are ester diols in the mentioned molecular weight range, such as α-hydroxybutyl-β-hydroxycaproic acid ester, co-hydroxyhexyl-γ-hydroxybutyric acid ester,
[0075] In addition, monofunctional compounds reactive with isocyanates containing hydroxyl groups can also be used as component A3). Examples of such monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol.
[0076] In a preferred embodiment of the invention, the polyurethane used according to the invention contains less than about 10% by weight of component A3), preferably less than 5% by weight of component A3), in each case relative to the total mass of the polyurethane, even more preferably the component A3) not used to produce the polyurethane.
[0077] Optionally, one or more non-ionic hydrophilizing agents, in particular reactive with isocyanates, are used as component A4) for the production of the polyurethanes used according to the invention. The hydrophilizing agents used as component A4) differ in particular from components A2) and A3).
[0078] Examples of suitable non-ionic hydrophilizing compounds as component A4) are polyoxyalkylene ethers which have isocyanate-reactive groups such as hydroxyl, amino or thiol groups. Preference is given to monohydroxyfunctional polyalkylene oxide polyether alcohols having a statistical average of 5 to 70, preferably 7 to 55, ethylene oxide units per molecule since they are conventionally accessible by alkoxylation of suitable starter molecules (e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, Verlag Chemie, Weinheim, pp. 31-38). These are either pure polyethylene oxide ethers or mixed polyalkylene oxide ethers, containing at least 30 mol%, preferably at least 40 mol%, relative to all alkylene oxide units present, of ethylene oxide units.
[0079] Particularly preferred nonionic compounds are monofunctional mixed poly(alkylene oxide) polyethers which have 40 to 100 mol% ethylene oxide units and 0 to 60 mol% propylene oxide units. Suitable starter molecules for such non-ionic hydrophilizing agents are, in particular, saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, pentanoic, hexanoic isomers, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, methylcyclohexanol or hydroxymethylcyclohexane isomers, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers, such as diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleyl alcohol,aromatic alcohols such as phenol, isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anise alcohol or cinnamyl alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis-(2-ethylhexyl)amine, N-methyl and N-ethylcyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred starter molecules are saturated monoalcohols of the type mentioned above, diethylene glycol monobutyl ether or n-butanol. ,
[0080] Suitable alkylene oxides for the alkoxylation reaction include ethylene oxide and propylene oxide, which may be used in any order or as a mixture in the alkoxylation reaction.
[0081] Component B) is preferably chosen from primary or secondary amines and / or diamines. It includes in particular diamines.
[0082] In particular, amines may be used as component B) which do not have ionic or ionogenic groups such as anionically hydrophilizing groups (hereinafter component B1)), and amines may be used which have ionic or ionogenic groups such as in particular anionically hydrophilizing groups (hereinafter component B2)). In step B) of the prepolymer reaction, a mixture of component B1) and component B2) is preferably reacted.
[0083] For example, organic diamines or polyamines such as 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, mixture of isomers of 2, 2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 4,4-diaminodicyclohexylmethane, hydrazine hydrate and / or dimethylethylenediamine may be used.
[0084] Furthermore, as component B1), it is also possible to use compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also have OH groups. Examples of these are primary / secondary amines such as diethanolamine, 3-amino-l-methylaminopropane, 3-amino-l-ethylaminopropane, 3-amino-l-cyclohexylaminopropane, 3-amino-l-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine.
[0085] Furthermore, monofunctional amine compounds reactive with isocyanates can also be used as component B1), such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethylmethyl aminopropylamine, morpholine, piperidine or their suitable substituted derivatives, amide amines of diprimary amines and monocarboxylic acids, monoketime of diprimary amines, primary / tertiary amines such as N,N-dimethylaminopropylamine.
[0086] Preferably used as component B1) are 1,2-ethylenediamine, bis(4-aminocyclohexyl)methane, 1,4-diaminobutane, isophoronediamine, ethanolamine, diethanolamine and diethylenetriamine.
[0087] Particularly preferably, component B) comprises at least one component B2). Suitable anionic hydrophilizing compounds as component B2) preferably contain a sulfonic acid or sulfonate group, particularly preferably a sodium sulfonate group. Suitable anionic hydrophilizing compounds as component B2) are, in particular, the alkali metal salts of mono- and diaminosulfonic acids. Examples of such anionic hydrophilizing agents are the salts of 2-(2-aminoethylamino)ethanesulfonic acid, ethylenediaminepropyl or butylsulfonic acid, 1,2- or 1,3-propylenediamine-[3-ethylsulfonic acid] or taurine. Furthermore, the cyclohexylaminopropanesulfonic acid salt (CAPS) of WO-A 01 / 88006 can be used as an anionic hydrophilizing agent.
[0088] Particularly preferred anionic hydrophilizing agents B2) are those which contain sulfonate groups as ionic groups and two amino groups, such as the salts of 2-(2-aminoethylamino)ethylsulfonic acid and 1,3-propylenediamine-[3-ethylsulfonic acid.
[0089] The polyurethanes used according to the invention particularly preferably contain at least one sulfonate group.
[0090] Optionally, the anionic group in component B2) may also be a carboxylate or carboxylic acid group. Component B2) is then preferably selected from diaminocarboxylic acids. However, this embodiment is less preferred because the carboxylic acid-based components B2) must be used at higher concentrations. Mixtures of anionic hydrophilic agents B2) and non-ionic hydrophilic agents A4) may also be used for the hydrophilic treatment.
[0091] In a preferred embodiment for the preparation of the special polyurethane dispersions, components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
[0092] 5 to 40% by weight of component Al),
[0093] 55 to 90% by weight A2),
[0094] 0.5 to 20% by weight of the sum of components A3) and / or B1),
[0095] 0.1 to 25% by weight of the sum of components A4) and / or B2), with a particular preference for 0.1 to 5% by weight, relative to the total amounts of components Al) to A4) and Bl) to B2) to be used on anionic or potentially anionic hydrophilizers B2).
[0096] In a particularly preferred embodiment for the production of the special polyurethane dispersions, components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
[0097] 5 to 35% by weight of component Al),
[0098] 60 to 90% by weight A2),
[0099] 0.5 to 15% by weight of the sum of components A3) and / or B1),
[0100] 0.1 to 15% by weight of the sum of the components A4) and / or B2), of particularly preferably 0.2 to 4% by weight, relative to the total amounts of components A1) to A4) and B1) to B2).
[0101] In a particularly preferred embodiment for the preparation of the special polyurethane dispersions, components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
[0102] 10 to 30% by weight of component Al),
[0103] 65 to 85% by weight A2),
[0104] 0.5 to 14% by weight of the sum of components A3) and / or B1),
[0105] 0.1 to 13.5% by weight of anionic or potentially anionic hydrophilizing agents anionic B2).
[0106] According to the invention, it is particularly preferred to use polyurethanes bearing the INCI name Polyurethane-93 and / or Polyurethane-99.
[0107] The preparation of the polyurethane dispersions can be carried out in one or more steps in the homogeneous phase or, in the case of a multi-step reaction, partially in the dispersed phase. After the polyaddition of A1) to A4) has been carried out completely or partially, a dispersion, emulsification or dissolution step is preferably carried out. This is followed, if appropriate, by a further polyaddition or modification in the dispersed phase.
[0108] Any methods known from the prior art, such as a prepolymer mixing process, an acetone process or a melt dispersion process can be used. The acetone process is preferably used.
[0109] For the preparation by the acetone process, components A2) to A4) and the polyisocyanate component A1) for the preparation of an isocyanate-functional polyurethane prepolymer are generally introduced in whole or in part and optionally diluted with a water-miscible but isocyanate-group-inert solvent and at temperatures in the heated range of 50 to 120°C. Catalysts known in polyurethane chemistry can be used to accelerate the isocyanate addition reaction.
[0110] Suitable solvents are the usual keto-functional aliphatic solvents, such as acetone and 2-butanone, which can be added not only at the beginning of the preparation, but also later, if necessary, in parts. Acetone and 2-butanone are preferred, and acetone is particularly preferred. The addition of other solvents without isocyanate-reactive groups is also possible, but not preferred.
[0111] The components of Al) to A4) possibly not added at the start of the reaction are then measured.
[0112] In the production of the polyurethane prepolymer of A1) to A4), the molar ratio of isocyanate groups to isocyanate-reactive groups is generally 1.05 to 3.5, preferably 1.1 to 3.0, particularly preferably 1.1 to 2.5.
[0113] The conversion of components A1) to A4) into a prepolymer takes place partially or completely, but preferably completely. In this way, polyurethane prepolymers containing free isocyanate groups are obtained in bulk or in solution. In the neutralization step for the partial or complete conversion of potentially anionic groups into anionic groups, bases can be used, such as tertiary amines, for example trialkylamines, having 1 to 12, preferably 1 to 6, carbon atoms, particularly preferably 2 to 3 carbon atoms in each alkyl radical.
[0114] The use of organic amines is not preferred.
[0115] Inorganic bases, such as aqueous ammonia solution or sodium or potassium hydroxide, are preferably used as neutralizing agents.
[0116] Sodium hydroxide and potassium hydroxide are preferred,
[0117] The amount of bases is 50 to 125 mol%, preferably between 70 and 100 mol% of the amount of acid groups to be neutralized. Neutralization can also take place at the same time as dispersion, in that the dispersion water already contains the neutralizing agent.
[0118] Then, in another step of the process, if it is not already carried out or is only partially carried out, the prepolymer obtained is dissolved using aliphatic ketones such as acetone or 2-butanone.
[0119] The conversion of components A1) to A4) into a prepolymer takes place partially or completely, but preferably completely. In this way, polyurethane prepolymers containing free isocyanate groups are obtained in bulk or in solution.
[0120] During the chain extension in step B), NH2 and / or NH functional components are reacted with the remaining isocyanate groups of the prepolymer. The chain extension / termination is preferably carried out before dispersion in water.
[0121] Components B) suitable for chain extension are in particular organic di- or polyamines B1) such as ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, the mixture of isomers of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, diaminodicyclohexylmethane and / or dimethylethylenediamine.
[0122] Furthermore, it is also possible to use compounds B1) which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also have OH groups. Examples of these are primary / secondary amines such as diethanolamine, 3-amino-l-methylaminopropane, 3-amino-l-ethylaminopropane, 3-amino-l-cyclohexylaminopropane, 3-amino-l-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine can be used for chain extension or termination.
[0123] Mention may be made of amines B1) with a group reactive with isocyanates such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl(methyl)aminopropylamine, morpholine, piperidine, or their suitable substituted derivatives, amine amides of diprimary amines and monocarboxylic acids, monoketime of diprimary amines, primary / tertiary amines, such as N,N-dimethylaminopropylamine.
[0124] If anionic hydrophilizing agents corresponding to definition B2) with NH2 or NH groups are used for chain extension, the chain extension of the prepolymers preferably takes place before dispersion.
[0125] The degree of chain extension, i.e. the equivalent ratio of the NCO-reactive groups of the compounds used for chain extension and termination to the free NCO groups of the prepolymer, is generally between 40 and 150%, preferably between 50 and 110%, particularly preferably between 60 and 100%.
[0126] The amine components B1) and B2) can optionally be used in the process according to the invention in diluted form in water or in a solvent individually or in mixtures, any order of addition being in principle possible.
[0127] If water or organic solvents are also used as diluents, the diluent content in the chain extender component used in B) is preferably 40 to 95% by weight.
[0128] The dispersion preferably takes place after the chain extension. For this purpose, the solubilized, chain-extended polyurethane polymer is optionally added to the dispersion water under high shear, for example, vigorous stirring, or, conversely, the dispersion water is stirred to give the chain-extended polyurethane polymer solutions. The water is preferably added to the dissolved chain-extended polyurethane polymer.
[0129] The solvent still present in the dispersions after the dispersion step is then generally removed by distillation. Removal already during dispersion is also possible. The residual content of organic solvents in the polyurethane dispersions thus produced is typically less than 10% by weight, preferably less than 3% by weight, relative to the entire dispersion.
[0130] The pH of the aqueous polyurethane dispersions used according to the invention is typically less than 8.0, preferably less than 7.5 and is particularly preferably between 5.5 and 7.5.
[0131] Preferably, an aqueous dispersion of polyurethane is used, containing 30% active material, said polyurethane having the INCI name “polyurethane-93”. This polyurethane is a complex polymer formed by reacting succinic acid, 1,4-butanediol, neopentyl glycol and isophorone diisocyanate to form a prepolymer. The prepolymer then reacts with sodium N-(2-aminoethyl)-2-aminoethanesulfonate and isophoronediamine. This bio-sourced polyurethane contains more than 50% of carbon from plant biomass. It is marketed by Covestro under the name Baycusan® ECO E 1000 (INCI: Polyurethane-93).
[0132] The polyurethane is preferably present in an amount of active material of between 0.1% and 5% by weight, preferably between 0.2% and 3% by weight, preferably 0.5% and 2% by weight relative to the total weight of the composition. Charge
[0133] The composition according to the invention also comprises at least one filler chosen from cellulose particles, hydrophobic silicas and their mixtures.
[0134] Cellulose particles
[0135] The cellulose particles that can be used according to the invention are preferably spherical (cellulose beads).
[0136] By spherical particles for the purposes of the present invention is meant solid or porous particles having a circularity parameter of at least 0.95. The circularity parameter is defined as the ratio of the circumference of a disc having the same area as the particle to the perimeter of the particle. A value of 1 characterizes perfectly spherical particles.
[0137] They preferably have an average size of less than 40 pm, preferably ranging from 1 to 20 pm, more preferably from 2 to 10 pm.
[0138] Among the cellulose particles that can be used according to the invention, mention may be made in particular of those sold by the company Daito under the brand name CELLULOBEADS® such as CELLULOBEADS USF® (D
[50] = 4 pm), CELLULOBEADS D-5® (D
[50] < 10 pm), CELLULOBEADS D-10® (D
[50] < 15 pm), CELLULOBEADS D-30® (D
[50] < 30 pm).
[0139] Preferably, the cellulose particles are present in a content ranging from 0.5% to 10% by weight, more preferably from 1 to 6% by weight relative to the total weight of the composition.
[0140] Hydrophobic silica aerogel particles
[0141] The hydrophobic silica is preferably present in the form of hydrophobic silica aerogel particles.
[0142] Aerogels are ultra-light porous materials, the first of which were made by Kristler in 1932.
[0143] They are generally synthesized by a sol-gel process in a liquid medium and then dried by extraction of a supercritical fluid. The most commonly used supercritical fluid is supercritical CO2. This type of drying prevents contraction of the pores and the material. Other types of drying also make it possible to obtain porous materials from gel, namely for example (i) drying by cryodesiccation, consisting of solidifying the gel at low temperature and then sublimating the solvent and (ii) drying by evaporation. The materials thus obtained are called respectively cryogels and xerogels. The sol-gel process and the different drying processes are described in detail in Brinker CL, and Scherer GW, Sol-Gel Science: New York: Academy Press, 1990.
[0144] By "hydrophobic silica" is meant any silica whose surface is treated with silylating agents, for example with halogenated silanes such as alkylchlorosilanes; siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane; or silazanes, so as to functionalize the OH groups with Si-Rn silyl groups, for example trimethylsilyl groups.
[0145] Preferably, the hydrophobic silica aerogel particles capable of being used in the present invention advantageously have a specific surface area per unit mass (MS) ranging from 500 to 1500 m2 / g, preferably from 600 to 1200 m2 / g and better still from 600 to 800 m2 / g.
[0146] Preferably, the hydrophobic silica aerogel particles capable of being used in the present invention advantageously have an oil absorption capacity measured at the WET POINT ranging from 5 to 18 ml / g of particles, preferably from 6 to 15 ml / g and better still from 8 to 12 ml / g.
[0147] Preferably, the hydrophobic silica aerogel particles capable of being used in the present invention advantageously have a size, expressed as average diameter (D[0.5]), of less than 1500 pm and preferably ranging from 1 to 30 pm, preferably from 5 to 25 pm, better still from 5 to 20 pm and even better still from 5 to 15 pm.
[0148] Preferably, the hydrophobic silica aerogel particles capable of being used in the present invention advantageously have a packed density p ranging from 0.04 g / cm3 to 0.10 g / cm3, preferably from 0.05 g / cm3 to 0.08 g / cm3.
[0149] Preferably, the hydrophobic silica aerogel particles capable of being used in the present invention advantageously have a specific surface area per unit volume (SV) ranging from 5 to 60 m2 / cm3, preferably from 10 to 50 m2 / cm3 and better still from 15 to 40 m2 / cm3.
[0150] According to a preferred embodiment, the hydrophobic silica aerogel particles according to the invention have a specific surface area per unit mass (MS) ranging from 500 to 1500 m2 / g, preferably from 600 to 1200 m2 / g and better still from 600 to 800 m2 / g, and a size expressed in average diameter (D[0.5]) ranging from 1 to 30 μm and / or an oil absorption capacity measured at the WET POINT ranging from 5 to 18 ml / g of particles, preferably from 6 to 15 ml / g and better still from 8 to 12 ml / g.
[0151] According to another preferred embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit mass (SM) ranging from 600 to 800 m2 / g and a size expressed as volume average diameter (D[0.5]) ranging from 5 to 20 pm, better still from 5 to 15 pm.
[0152] The specific surface area per unit mass can be determined by the nitrogen absorption method called the BET method (BRUNAUER - EMMET - TELLER) described in "The journal of the American Chemical Society", vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794 / 1 (annex D). The BET specific surface area corresponds to the total specific surface area of the particles considered.
[0153] The absorption capacity measured at the WET POINT, and noted Wp, corresponds to the quantity of oil that must be added to 100 g of particles to obtain a homogeneous paste. It is measured according to the so-called Wet Point method or method for determining the uptake of powder oil according to the principle described in standard NF T 30-022. It corresponds to the quantity of oil adsorbed on the available surface of the powder and / or absorbed by the powder by measuring the Wet Point, described below:
[0154] A quantity m = 2 g of powder is placed on a glass plate and then the oil (isononyl isononanoate) is added drop by drop. After adding 4 to 5 drops of oil to the powder, it is mixed with a spatula and the oil is continued to be added until conglomerates of oil and powder form. From this point on, the oil is added one drop at a time and the mixture is then kneaded with the spatula. The addition of oil is stopped when a firm and smooth paste is obtained. This paste should be spread on the glass plate without cracking or lumps forming. The volume Vs (expressed in ml) of oil used is then noted.
[0155] The oil uptake (oil absorption capacity) corresponds to the ratio Vs / m.
[0156] The sizes of the aerogel particles according to the invention can be measured by static light scattering using a commercial granulometer of the MasterSizer 2000 type from Malvem. The data are processed on the basis of the Mie scattering theory. This theory, which is accurate for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is described in particular in the work of Van de Hulst, HC, "Light Scattering by Small Particles" Chapters 9 and 10, Wiley, New York, 1957.
[0157] In the context of the present invention, the packed density can be assessed according to the following protocol, called the packed density protocol: 40 g of powder are poured into a graduated cylinder and then the cylinder is placed on a STAV 2003 device from STAMPF VOLUMETER. The cylinder is then subjected to a series of 2500 compactions (this operation is repeated until the difference in volume between 2 consecutive tests is less than 2%); then the final volume Vf of packed powder is measured directly on the cylinder. The packed density is determined by the mass ratio (m) A / f, in this case 40 / Vf (Vf being expressed in cm3 and m in g).
[0158] The specific surface area per unit volume is given by the relation: SV = SM xp, where p is the packed density expressed in g / cm3 and SM is the specific surface area per unit mass expressed in m2 / g, as defined above.
[0159] The hydrophobic silica aerogel particles used according to the present invention are preferably silylated silica aerogel particles (INCI name silica silylate).
[0160] The preparation of surface-modified hydrophobic silica aerogel particles by silylation is further described in US 7,470,725.
[0161] In particular, hydrophobic silica aerogel particles modified on the surface by trimethylsilyl groups will be used.
[0162] As hydrophobic silica aerogels which can be used in the invention, mention may be made, for example, of the aerogel marketed under the name VM-2260 (INCI name Silica silylate), by the company Dow Corning, the particles of which have an average size of approximately 1000 microns and a specific surface area per unit of mass ranging from 600 to 800 m2 / g.
[0163] Mention may also be made of the aerogels marketed by the company Cabot under the references AEROGEL TLD 201, AEROGEL OGD 201 and AEROGEL TLD 203, ENOVA AEROGEL MT 1100, ENOVA AEROGEL MT 1200.
[0164] More particularly, the aerogel marketed under the name VM-2270 (INCI name Silica silylate), by the company Dow Corning, the particles of which have an average size ranging from 5 to 15 microns and a specific surface area per unit of mass ranging from 600 to 800 m2 / g, will be used.
[0165] It is of course possible to use a mixture of hydrophobic silica aerogel particles.
[0166] The compositions according to the invention may comprise hydrophobic silica, preferably hydrophobic silica aerogel particles, in an amount of between 0.01 and 5% by weight, preferably between 0.1 and 3% by weight, preferentially between 0.2 and 1% by weight relative to the total weight of the composition. Oily phase
[0167] The compositions in accordance with the invention comprise an oily phase dispersed in an aqueous phase.
[0168] For the purposes of the invention, the term “oily phase” means a phase comprising at least one oil and all of the liposoluble and lipophilic ingredients and fatty substances used for the formulation of the compositions of the invention.
[0169] Oil is understood to mean any fatty substance in liquid form at room temperature (20 - 25°C) and atmospheric pressure (760 mm Hg). An oil suitable for the invention may be volatile or non-volatile.
[0170] For the purposes of the present invention, the term “silicone oil” means an oil comprising at least one silicon atom, and in particular at least one Si-O group.
[0171] The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms.
[0172] The term “fluorinated oil” means an oil comprising at least one fluorine atom.
[0173] The composition may comprise at least one oil. The oil may be chosen from hydrocarbon oils, silicone oils, fluorinated oils and mixtures thereof. A hydrocarbon oil suitable for the invention may be an animal hydrocarbon oil, a vegetable hydrocarbon oil, or a synthetic hydrocarbon oil.
[0174] A hydrocarbon oil suitable for the invention may further optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl, amine, amide, ester, ether or acid groups, and in particular in the form of hydroxyl, ester, ether or acid groups.
[0175] The oil may be volatile or non-volatile.
[0176] For the purposes of the invention, the term "volatile oil" means an oil capable of evaporating on contact with the skin or keratin fiber in less than one hour, at room temperature and atmospheric pressure. The volatile oil(s) of the invention are volatile cosmetic oils, liquid at room temperature, having a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40,000 Pa (103 to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg).
[0177] By "non-volatile oil" is meant an oil remaining on the skin or keratin fiber at room temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure of less than 103 mm Hg (0.13 Pa).
[0178] Hydrocarbon oils
[0179] As non-volatile hydrocarbon oils which can be used according to the invention, mention may in particular be made of:
[0180] (i) hydrocarbon oils of vegetable origin such as glyceride triesters which are generally triesters of fatty acids and glycerol whose fatty acids can have chain lengths varying from C4 to C24, the latter being able to be linear or branched, saturated or unsaturated; these oils are in particular wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean oils, almond oil and in particular sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose oil, of millet, barley, quinoa, rye, safflower, candlenut, passionflower, musk rose, coconut; or even the triglycerides of caprylic / capric acids such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel,
[0181] (ii) synthetic ethers having from 10 to 40 carbon atoms;
[0182] (iii) linear or branched hydrocarbons, of mineral or synthetic origin such as vaseline oil, polydecenes, hydrogenated polyisobutene such as parleam, squalane and mixtures thereof (mineral oils);
[0183] (iv) synthetic esters such as oils of formula RCOOR' in which R represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R' represents a hydrocarbon chain, in particular a branched chain, containing from 1 to 40 carbon atoms provided that R + R' is >10, such as, for example, Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alcohol benzoate such as the product sold under the trade name "Finsolv TN" or "Witconol TN" by the company WITCO or "TEGOSOFT TN" by the company EVONIK GOLDSCHMIDT, 2-ethylphenyl benzoate such as the commercial product sold under the name "X-TEND 226" by the company ISP, isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate,diisopropyl sebacate such as the product sold under the name “Dub Dis” by the company Stearinerie Dubois, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxyl esters such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters; citrates or tartrates such as C12-C13 linear dialkyl tartrates such as those sold under the name COSMACOL ETI by the company ENICHEM AUGUSTA INDUSTRIALE as well as C14-C15 linear dialkyl tartrates such as those sold under the name COSMACOL ETL by the same company; acetates; ,
[0184] (y) fatty alcohols which are liquid at room temperature with a branched carbon chain and / or unsaturated having from 12 to 26 carbon atoms such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, 2-undecylpentadecanol;
[0185] (vi) higher fatty acids such as oleic acid, linoleic acid, linolenic acid;
[0186] (vii) carbonates such as dicaprylyl carbonate such as the product sold under the name “Cetiol CC” by the company Cognis;
[0187] (viii) fatty amides such as isopropyl N-lauroyl sarcosinate such as the product sold under the trade name Eldew SL 205 from Ajinomoto and mixtures thereof.
[0188] Preferably, the oily phase comprises at least one non-volatile mineral oil and at least one non-volatile hydrocarbon oil of plant origin.
[0189] Preferably, the non-volatile plant-based hydrocarbon oil is chosen from glyceride triesters, in particular fatty acid and glycerol triesters whose fatty acids have linear or branched, saturated or unsaturated chain lengths ranging from 4 to 24 carbon atoms.
[0190] More preferably, the non-volatile hydrocarbon oil of plant origin is chosen from wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean oils, almond oil and in particular sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passionflower, musk rose, coconut oil; and caprylic / capric acid triglycerides.
[0191] As volatile hydrocarbon oils which can be used according to the invention, mention may in particular be made of hydrocarbon oils having from 8 to 16 carbon atoms, and in particular branched C8-C16 alkanes such as C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, oils sold under the trade names Isopars or Permetyls, branched C8-C16 esters, isohexyl neopentanoate, and mixtures thereof.
[0192] Mention may also be made of the alkanes described in the patent applications of the company Cognis WO2007 / 068371 or WO2008 / 155059 (mixtures of distinct alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, themselves obtained from coconut or palm oil. Mention may be made of the mixtures of n-undecane (Cl 1) and n-tridecane (Cl3) obtained in examples 1 and 2 of application WO2008 / 155059 of the company Cognis.
[0193] Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures.
[0194] Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell or by the company SNELL, can also be used.
[0195] According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and their mixtures.
[0196] Silicone oils
[0197] The non-volatile silicone oils can be chosen in particular from non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, pendant and / or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.
[0198] As volatile silicone oils, mention may be made, for example, of volatile linear or cyclic silicone oils, in particular those having a viscosity of 8 centistokes (8.106 m2 / s), and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil which can be used in the invention, mention may be made in particular of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.
[0199] Mention may also be made of volatile linear alkyltrisiloxane oils of general formula (I): CH (l) ........Sif)........Si............O.............SiJ CH J R
[0200] where R represents an alkyl group comprising from 2 to 4 carbon atoms and one or more hydrogen atoms of which may be substituted by a fluorine or chlorine atom.
[0201] Among the oils of general formula (I), mention may be made of: 3-butyl 1,1,1,3,5,5,5-heptamethyl trisiloxane, 3-propyl 1,1,1,3,5,5,5-heptamethyl trisiloxane, and 3-ethyl 1,1,1,3,5,5,5-heptamethyl trisiloxane, corresponding to the oils of formula (I) for which R is respectively a butyl group, a propyl group or an ethyl group.
[0202] Preferably, the oily phase comprises at least one silicone oil, preferably a non-volatile PDMS.
[0203] Fluorinated oils
[0204] Fluorinated volatile oils, such as nonafluoromethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane and mixtures thereof, may also be used.
[0205] The oily phase may also comprise other fatty substances. Another fatty substance (or lipophilic compound) which may be present in the oily phase may be chosen from:
[0206] - fatty acids containing from 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid and oleic acid;
[0207] - waxes such as lanolin, beeswax, Camauba or Candellila wax, paraffin waxes, lignite waxes or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as polyethylene waxes and Fischer-Tropsch waxes;
[0208] - pasty compounds, detailed below, such as butters of vegetable origin;
[0209] - fatty alcohols solid at room temperature with a linear carbon chain having 12 to 26 carbon atoms, such as cetyl alcohol or cetylstearyl alcohol;
[0210] - and mixtures thereof.
[0211] More preferably, the oily phase comprises at least one lipophilic compound chosen from fatty alcohols which are solid at room temperature with a linear carbon chain having from 12 to 26 carbon atoms, silicone oils, fatty acids comprising from 8 to 30 carbon atoms, waxes, pasty compounds, in particular defined below, and mixtures thereof.
[0212] Even more preferably, the oily phase comprises a mixture of a fatty alcohol which is solid at room temperature with a linear carbon chain having from 12 to 26 carbon atoms, a fatty acid comprising from 8 to 30 carbon atoms and a pasty compound (notably defined below).
[0213] As indicated previously, the composition according to the invention may comprise at least one pasty compound (or pasty fatty substance) at 23°C, hydrocarbon or silicone.
[0214] For the purposes of the present invention, the term "pasty fatty body" means a lipophilic fatty compound with a reversible solid / liquid state change, having an anisotropic crystalline organization in the solid state, and comprising at a temperature of 23°C a liquid fraction and a solid fraction.
[0215] In other words, the starting melting temperature of the pasty compound may be less than 23°C. The liquid fraction of the pasty compound measured at 23°C may represent 9 to 97% by weight of the compound. This liquid fraction at 23°C preferably represents between 15 and 85%, more preferably between 40 and 85% by weight.
[0216] The melting point of a solid fatty substance can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name “DSC Q100” by the company TA Instruments with the software “TA Universal Analysis”, according to the protocol defined previously.
[0217] The liquid fraction by weight of the pasty compound at 23°C is more particularly equal to the ratio of the enthalpy of fusion consumed at 23°C to the enthalpy of fusion of the pasty compound.
[0218] The enthalpy of fusion of the pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when its entire mass is in crystalline solid form. The pasty compound is said to be in the liquid state when its entire mass is in liquid form.
[0219] The enthalpy of fusion of the pasty compound is in particular equal to the value under the curve of the thermogram obtained using a differential scanning calorimeter. The enthalpy of fusion of the pasty compound is the quantity of energy required to change the compound from the solid state to the liquid state. It is expressed in J / g.
[0220] The enthalpy of fusion consumed at 23°C is the quantity of energy absorbed by the sample to pass from the solid state to the state it presents at 23°C consisting of a liquid fraction and a solid fraction.
[0221] The pasty compound(s) may in particular be chosen from synthetic pasty compounds and fatty substances of plant origin. The pasty compound(s) may be hydrocarbon-based or silicone-based.
[0222] The pasty compound(s) may in particular be chosen from: - lanolin and its derivatives, such as lanolin alcohol, oxyethylenated lanolins, acetylated lanolin, lanolin esters such as isopropyl lanolate, oxypropylenated lanolins; - petroleum jelly (also called petrolatum), - polyol ethers chosen from pentaerythritol and C2-C4 polyalkylene glycol ethers, fatty alcohol and sugar ethers, and mixtures thereof. For example, mention may be made of pentaerythritol and polyethylene glycol ether comprising 5 oxyethylenated units (5 EO) (CTFA name: PEG-5 Pentaerythrityl Ether), pentaerythritol and polypropylene glycol ether comprising 5 oxypropylenated units (5 OP) (CTFA name: PPG-5 Pentaerythrityl Ether), and mixtures thereof and more specifically the mixture of PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soybean oil, marketed under the name “Lanolide” by the company VEVY, a mixture in which the constituents are in a weight ratio of 46 / 46 / 8: 46% PEG-5 Pentaerythrityl Ether, 46% PPG-5 Pentaerythrityl Ether and 8% soybean oil, - esters of a glycerol oligomer, in particular diglycerol esters, with monocarboxylic acids, optionally hydroxylated, linear or branched, saturated or unsaturated, preferably saturated, in C6-C20, and / or dicarboxylic acids, linear or branched, saturated or unsaturated, preferably saturated, in C6-C10, in particular condensates of adipic acid and diglycerol, for which a part of the hydroxylated groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, such as bis-diglyceryl polyacyladipate-2 marketed under the reference SOFTISAN® 649 by the company Sasol, vinyl ester homopolymers having C8-C30 alkyl groups, such as polyvinyl laurate (notably sold under the reference Mexomère PP by the company Chimex), arachidyl propionate marketed under the brand name Waxenol 801 by ALZO, phytosterol esters, fatty acid triglycerides and their derivatives, in particular fatty acid triglycerides, saturated or not, linear or branched, possibly mono or polyhydroxylated, C6-C30, more particularly C8-C18, possibly hydrogenated (totally or partially); for example with Softisan 100® marketed by the company Sasol, pentaerythritol esters, aliphatic esters resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with an aliphatic carboxylic acid. More particularly, the aliphatic carboxylic acid is C4-C30, preferably C8-C30. It is preferably chosen from hexanoic, heptanoic, octanoic, 2-ethylhexanoic, nonanoic, decanoic, undecanoic, dodecanoic, tridecanoic, tetradecanoic, pentadecanoic, hexadecanoic, hexyldecanoic, heptadecanoic, octadecanoic, isostearic, nonadecanoic, eicosanoic, isoarachidic, octyldodecanoic, heneicosanoic and docosanoic acids, and mixtures thereof. The aliphatic carboxylic acid is preferably branched.The hydroxycarboxylic acid ester is advantageously derived from a C2-C40, preferably C10-C34, and even more preferably C12-C28 hydroxylated carboxylic acid; the number of hydroxylated groups being between 1 and 20, more particularly between 1 and 10, preferably between 1 and 6. dimer diol and dimer diacid esters, where appropriate, esterified on their free alcohol or acid function(s) by acid or alcohol radicals, in particular dimer dilinoleate esters; such esters may in particular be chosen from the esters of the following INCI nomenclature: bis-behenyl / isostearyl / phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G), phytosteryl / isosteryl / cetyl / stearyl / behenyl dimer dilinoleate (Plandool H or Plandool S) and mixtures thereof, - hydrogenated rosin esters (Lusplan DD-DHR or DD-DHR from Nippon Fine Chemical), - butters of vegetable origin such as mango butter, such as that marketed under the reference Lipex 203 by the company AARHUSKARLSHAMN, shea butter, in particular that whose INCI name is Butyrospermum Parkii Butter, such as that marketed under the reference Sheasoft® by the company AARHUSKARLSHAMN, cupuacu butter (Rain forest RF3410 from the company Beraca Sabara), murumuru butter (RAIN FOREST RF3710 from the company Beraca Sabara), cocoa butter, babassu butter such as that marketed under the name Cropure Babassu SS-(LK) by Croda, as well as orange wax such as, for example, that marketed under the reference Orange Peel Wax by the company Koster Keunen, - fully or partially hydrogenated vegetable oils, such as hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rapeseed oil, mixtures of hydrogenated vegetable oils such as the mixture of hydrogenated vegetable oil of soybean, coconut, palm and rapeseed, for example the mixture marketed under the reference Akogel® by the company AARHUSKARLSHAMN (INCI name Hydrogenated Vegetable Oil), partially hydrogenated trans isomerized jojoba oil manufactured or marketed by the company Desert Whale under the commercial reference Iso-Jojoba-50®, partially hydrogenated olive oil such as, for example, the compound marketed under the reference Beurrolive by the company Soliance, - hydrogenated castor oil esters, such as hydrogenated castor oil dimer dilinoleate, for example RISOCAST-DA-L sold by KOKYU ALCOHOL KOGYO, hydrogenated castor oil isostearate, for example SALACOS HCIS (VL) sold by NISSHIN OIL, - and their mixtures.
[0223] According to one embodiment, the composition comprises from 0.1 to 5% by weight, preferably from 0.2 to 3%, and even better from 0.3 to 1.5% by weight of pasty fatty substance, relative to the total weight of the composition.
[0224] Preferably, the oily phase content is between 1% and 40% by weight, and preferably from 2 to 35% by weight relative to the total weight of the composition. Aqueous phase
[0225] The compositions according to the invention comprise at least one continuous aqueous phase.
[0226] The aqueous phase contains water, and optionally at least one organic solvent soluble or miscible in water.
[0227] An aqueous phase suitable for the invention may comprise, for example, a water chosen from a natural spring water, such as La Roche-Posay water, Vittel water, or Vichy water, or a floral water.
[0228] Preferably, the water content is between 5% and 80% by weight relative to the total weight of the composition, preferably between 6% and 70% by weight.
[0229] Water-soluble or miscible solvents suitable for the invention include short-chain monoalcohols, for example C1-C4, such as ethanol or isopropanol; diols or polyols, such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol, sorbitol, and mixtures thereof.
[0230] According to a preferred embodiment, it is possible to use more particularly ethanol, butylene glycol, glycerin or one of their mixtures.
[0231] Preferably, the content of water-soluble or miscible solvent is between 4% and 20% by weight relative to the total weight of the composition, preferably between 5% and 15% by weight.
[0232] According to a particular form of the invention, the aqueous phase content is between 30% and 80% by weight relative to the total weight of composition, preferably between 40% and 70% by weight.
[0233] The compositions in accordance with the present invention may also comprise conventional cosmetic adjuvants, in particular chosen from thickeners, perfumes, preservatives, surfactants, active ingredients, in particular moisturizers, coloring materials, alkalizing or acidifying agents or any other ingredient usually used in the cosmetic and / or dermatological field.
[0234] As thickeners, mention may be made of carboxyvinyl polymers such as Carbopols® (Carbomers) and Pemulen such as Pemulen TRI® and Pemulen TR2® (acrylate / C10-C30 alkylacrylate crosspolymer); polyacrylamides such as, for example, crosslinked copolymers sold under the names Sepigel 305® (CTFA name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic; polymers and copolymers of 2-acrylamido 2-methylpropane sulfonic acid, optionally crosslinked and / or neutralized, such as poly(2-acrylamido 2-methylpropane sulfonic acid) marketed by the company Hoechst under the trade name “Hostacerin AMPS®” (CTFA name: ammonium polyacryloyldimethyl taurate) or SIMULGEL 800® marketed by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido 2-methylpropane sulfonic acid and hydroxyethyl acrylate such as SIMULGEL NS® and SEPINOV EMT 10® marketed by SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and in particular gums such as xanthan gum; water-soluble or water-dispersible silicone derivatives such as acrylic silicones, polyether silicones and cationic silicones and their mixtures.
[0235] The thickeners are preferably present in an amount of between 0.1% and 5% by weight, preferably between 0.2% and 3% by weight relative to the total weight of the composition.
[0236] The surfactants are preferably chosen from anionic, cationic, non-ionic, zwitterionic and amphoteric surfactants. Preferably, they are chosen from:
[0237] a) non-ionic surfactants, in particular with an HLB greater than or equal to 8 at 25°C, used alone or as a mixture. Examples include:
[0238] esters and ethers of oses such as the mixture of cetylstearyl glucoside and cetyl and stearyl alcohols such as Montanov 68 from Seppic;
[0239] oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of glycerol;
[0240] oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of fatty alcohols (in particular of C8-C24 alcohol, and preferably of C12-C18 alcohol) such as the oxyethylenated ether of cetearyl alcohol with 30 oxyethylenated groups (CTFA name “Ceteareth-30”), the oxyethylenated ether of stearyl alcohol with 20 oxyethylenated groups (CTFA name “Steareth-20”), the oxyethylenated ether of the mixture of C12-C15 fatty alcohols containing 7 oxyethylenated groups (CTFA name “C12-15 Pareth-7”) sold in particular under the name NEODOL 25-7® by SHELL CHEMICALS;
[0241] polyoxyalkylenated fatty acid esters (in particular polyoxyethylenated and / or polyoxypropylenated) optionally in association with a fatty acid and glycerol ester such as the PEG-100 Stearate / Glyceryl Stearate mixture marketed for example by the company Croda under the name Arlacel 165;
[0242] fatty acid esters (in particular of C8-C24 acid, and preferably C16-C22) and oxyethylenated and / or oxypropylenated glycerol ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups), such as PEG-200 glyceryl monostearate, in particular sold under the name Simulsol 220 TM® by the company SEPPIC; PEG-50 stearate and PEG-40 monostearate, in particular, sold under the name MYRJ 52P® by the company ICI UNIQUEMA; polyethoxylated glyceryl stearate with 30 ethylene oxide groups, such as the product TAGAT S® sold by the company Evonik GOLDSCHMIDT, polyethoxylated glyceryl oleate with 30 ethylene oxide groups such as the product TAGAT O® sold by the company Evonik GOLDSCHMIDT, polyethoxylated glyceryl cocoate with 30 ethylene oxide groups such as the product VARIONIC LI 13® sold by the company SHEREX, polyethoxylated glyceryl isostearate with 30 ethylene oxide groups such as the product TAGAT L® sold by the company Evonik GOLDSCHMIDT and polyethoxylated glyceryl laurate with 30 ethylene oxide groups such as the product TAGAT I® from the company Evonik GOLDSCHMIDT,
[0243] fatty acid esters (in particular C8-C24 acid, and preferably C16-C22) and oxyethylenated and / or oxypropylenated sorbitol ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups), such as polysorbate 20 sold in particular under the name Tween 20® by the company CRODA, polysorbate 60 sold in particular under the name Tween 60® by the company CRODA,
[0244] dimethicone copolyol, such as that sold under the name Q2-5220® by the company DOW CORNING,
[0245] dimethicone copolyol benzoate (FINSOLV SLB 101® and 201® from FINTEX),
[0246] copolymers of propylene oxide and ethylene oxide, also called EO / OP polycondensates,
[0247] and mixtures thereof.
[0248] b) anionic surfactants such as:
[0249] polyoxyethylenated fatty acid salts, in particular those derived from amines or alkali salts, and mixtures thereof;
[0250] phosphoric esters and their salts such as “DEA oleth-10 phosphate” (Crodafos N 10N from the company CRODA) or monocetyl monopotassium phosphate or potassium cetyl phosphate (Amphisol K from Givaudan);
[0251] sulfosuccinates such as “Disodium PEG-5 citrate lauryl sul / osuccinate” and “Disodium ricinoleamido MEA sul / osuccinate”;
[0252] alkyl ether sulfates such as sodium lauryl ether sulfate;
[0253] isethionates;
[0254] acylglutamates such as “Disodium hydrogenated tallow glutamate » (AMISOFT HS-21 R® marketed by AJINOMOTO) and sodium stearoyl glutamate (AMISOFT HS-11 PF® marketed by AJINOMOTO) and their mixtures;
[0255] soy derivatives such as potassium soyate;
[0256] citrates, such as Glyceryl stearate citrate (Axol C 62 Pellets from Degussa);
[0257] proline derivatives, such as Sodium palmitoyl proline (Sepicalm VG from Seppic), or the Mixture of Sodium palmitoyl sarcosinate, Magnesium palmitoyl glutamate, palmitic acid and Palmitoyl proline (Sepifeel One from Seppic);
[0258] lactylates, such as Sodium stearoyl lactylate (Akoline SL from Karlshamns AB);
[0259] sarcosinates, such as sodium palmitoyl sarcosinate (Nikkol sarcosinate PN) or the mixture of Stearoyl sarcosine and Myristoyl sarcosine 75 / 25 (Crodasin SM from Croda);
[0260] sulfonates, such as Sodium C14-17 alkyl sec sulfonate (Hostapur SAS 60 from Clariant);
[0261] glycinates, such as sodium cocoyl glycinate (Ajinomoto's Amilite GCS-12).
[0262] Preferably, the surfactant used is a non-ionic surfactant with an HLB greater than or equal to 8 at 25°C.
[0263] The surfactant is preferably present in an amount of between 0.1% and 10% by weight, preferably between 0.5% and 8% by weight, preferably 1% and 5% by weight relative to the total weight of the composition.
[0264] As coloring matter, mention may be made of water-soluble dyes, organic pigments, composite pigments, lakes, pigments with special effects or with interference effects, mineral pigments, nacres or their mixtures.
[0265] Preferably, the coloring matter is chosen from nacres. Preferably, the nacres are chosen from mica particles coated with titanium dioxide, mica particles coated with titanium dioxide and / or tin oxide and synthetic mica particles (fluorophlogopite) coated with titanium dioxide and / or tin oxide. Such nacres may be marketed by Merck under the name 141465 Spectraval Blue, 141466 Spectraval White, 141469 Spectraval Red or 141470 Spectraval Green.
[0266] The present invention also relates to a cosmetic process for caring for keratin materials, comprising the application of a composition according to one of the preceding claims, to the keratin materials, preferably the skin.
[0267] The invention is illustrated in more detail in the following non-limiting examples.
[0268] EXAMPLES
[0269] Example 1: Preparation of comparative reference compositions CCI* and CC2*
[0270] The comparative reference compositions CCI* and CC2* are prepared with the ingredients mentioned in the table below, according to the following protocol:
[0271] - the fatty phase is prepared by heating the corresponding ingredients to approximately 60°C,
[0272] - the aqueous phase is prepared by heating the corresponding ingredients until boiling,
[0273] - the two phases are mixed at 60°C using an emulsifier until a compact white solution,
[0274] - addition of additional ingredients to the emulsion obtained.
[0275] The quantities of each ingredient are expressed in mass ratio relative to the total weight of the composition (% w / w).
[0276] [Tables 1] Phase Ingredient (INCI) CCI* (% w / w) (comparative) CC2* (% w / w) (comparative) Fatty phase GLYCERYL STEARATE (and) PEG-100 STEAR ATE 2.5 2.5 Stearic acid 1.80 1.80 CETYL ALCOHOL 1.5 1.5 POLY C10-30 ALKYL ACRYLATE 1.13 1.15 Hydrogenated jojoba oil 0.61 0.6 OCTYLDODECANOL 2 2 PENTAERYTHRITYL TETRA-DLT-BUTYL HYD ROXYHYDROCINNAMATE 0.07 0.07 Aqueous phase Water QSP 100 QSP 100 GLYCERIN 7 7 TRISODIUM ETHYLENEDIAMINE DISUCCINATE 0.1 0.1 BUTYLENE GLYCOL 2 2 Preservatives Qs Qs POLOXAMER 338 0.3 0.3 Additional ingredients Xanthan gum 0.15 0.15 ACRYLATES / C10-30 ALKYL ACRYLATE CRO SSPOLYMER 0.2 0.2 Potassium hydroxide Qs Qs Water 25 25 POLYACRYLAMIDE (and) C13-14ISOPARAFFIN (and) LAURETH-7 (Sepigel 305® from Seppic) 1.5 1.5 BIOSACCHARIDE GUM-1 2 2 CELLULOSE 1.39 1.4 SILICA SILYLATE 0.27 0.27 Pearlescent pigments (Spectraval from Merck) - 3
[0277] Example 2: Preparation of compositions C3 and C4 according to the invention
[0278] The compositions of the invention C3 and C4 are prepared with the ingredients mentioned in the table below, according to the protocol described in example 1.
[0279] [Tables2] Phase Ingredient (INCI) C3 (% w / w) (inventio n) C4 (% w / w) (inventio n) Fatty phase GLYCERYL STEARATE (and) PEG-100 STEAR ATE 2.5 2.5 Stearic acid 1.80 1.80 CETYL ALCOHOL 1.5 1.5 POLY C10-30 ALKYL ACRYLATE 1.15 1.15 Hydrogenated jojoba oil 0.6 0.6 OCTYLDODECANOL 2 2 PENTAERYTHRITYL TETRA-DLT-BUTYL HYDROXYHYDROCINNAMATE 0.07 0.07 Aqueous phase Water QSP 100 QSP 100 GLYCERIN 7 7 TRISODIUM ETHYLENEDIAMINE DISUCCI NATE 0.1 0.1 BUTYLENE GLYCOL 2 2 Preservatives Qs Qs POLOXAMER 338 0.3 0.3 Additional ingredients Xanthan gum 0.15 0.15 ACRYLATES / C10-30 ALKYL ACRYLATE CRO SSPOLYMER 0.2 0.2 Potassium hydroxide Qs Qs Water 25 25 POLYACRYLAMIDE (and) C13-14 ISOPARAFF IN (and) LAURETH-7 (Sepigel 305® from Seppic) 1.5 1.5 BIOSACCHARIDE GUM-1 2 2 CELLULOSE 1.4 1.4 SILICA SILYLATE 0.27 0.27 PEARL - 3 (Spectraval from Merck) Aqueous dispersion of polyurethane-93 (Baycusan ECO E1000 from Covestro, aqueous dispersion at 30% active matter or ma) 6 (1.8% ma) 6 (1.8% ma)
[0280] Example 3: Evaluation of compositions CCI*, CC2*, C3 and C4
[0281] The resistance to different chemical and physical actions of the compositions CCI*, CC2*, C3 and C4 was evaluated in vitro according to the following protocol:
[0282] - the compositions CCI* and C3 are deposited on a transparent BYK substrate using to a film puller, forming a wet film 12.5 µm thick. The film is left to dry for approximately 3 hours. The CC2* and C4 compositions are deposited on ERICHSEN contrast cards using a film puller, forming a wet film 100 µm thick. The film is left to dry for approximately 24 hours.
[0283] After the drying step, 2 types of stress are applied to the deposit: - mechanical stress using cotton wool, rubbing the dry deposit 10 times by hand; - a spray of 0.3g of fluid evenly on the deposit. Then, after 5 min of drying at room temperature, mechanical stress is carried out using a cotton pad, rubbing 10 times by hand.
[0284] Solutions (fluids)
[0285] The fluids are as follows:
[0286] - 79% Vichy water (mineral water), 20% oleic acid and 1% oleic alcohol oxyethylenated (simulates sweat);
[0287] - 28.70% glyceryl triisostearate, 28% oleic acid, 22.90% oleyl erucate stabilized, 13.70% hydrogenated isoparaffin and 6.70% octyldodecanol (simulates 100% sebum secretion); or
[0288] - micellar cleansing water.
[0289] The appearance of the deposits is then evaluated by direct observation or by optical microscopy (xlO).
[0290] The fragmentation ability of the compositions CCI*, CC2*, C3 and C4 was evaluated in vitro according to the following protocol: a deposit of a few μm thick of each composition is formed on FP40 (representative of oily skin) and the substrate is stretched to 50% of its length. The behavior of the deposit is evaluated by direct observation. If there is cracking of the deposit, this indicates a problem of cohesion, therefore of flexibility and elasticity of the composition. If there is detachment of the deposit, this indicates a problem of adhesion of the deposit, therefore of wettability.
[0291] The results of the deposit aspects are summarized below (score from 1 to 3, 3 = a lot of deposit; 1 = little deposit):
[0292]
[0293]
[0294]
[0295]
[0296] [Tables 3] Composition before friction Sweat+friction Sebum+friction Micellar water +friction CCI* 3 1 1.5 1 1.5 C3 3 2 2 1 2 Composition C3 resists better than composition CCI*. [Tables 4] Composition before friction Sweat + friction Sebum + friction Micellar water + friction CC2* RAS Cracking in the middle Large non-homogeneous deposit Agglomerated deposit Detachment C4 RAS RAS Homogeneous deposit Homogeneous deposit Less detachment The results show that the friction phenomenon on the two dry deposits does not cause significant or even almost no tearing. This indicates that the presence of nacre improves the adhesion of the deposit to the substrate. In addition, the C4 composition is more resistant than the CC2* composition.
Claims
Claims
1. Cosmetic composition in the form of an oil-in-water (O / W) emulsion comprising: - at least one polyurethane obtainable by reaction of one or more polyurethane prepolymers A) with isocyanate function, insoluble in water, non-dispersible in water, with one or more compounds with amino function B), said polyurethane prepolymer A) obtainable by reaction of one or more polyester polyols having a glass transition temperature Tg of at least -50°C and one or more polyisocyanates; and - at least one filler chosen from cellulose particles, hydrophobic silicas and mixtures thereof, the cellulose particles being present in a content ranging from 0.5% to 10% by weight relative to the total weight of the composition and / or the hydrophobic silica being present in a content of between 0.01 and 5% by weight relative to the total weight of the composition.
2. A composition according to claim 1, characterized in that the polyurethane is a complex polymer formed by reacting succinic acid, 1,4-butanediol, neopentyl glycol and isophorone diisocyanate to form a prepolymer, then by reacting the prepolymer obtained with sodium N-(2-aminoethyl)-2-aminoethanesulfonate and isophoronediamine.
3. Composition according to claim 1 or 2, characterized in that the polyurethane is present in an amount of active material of between 0.1% and 5% by weight, preferably between 0.2% and 3% by weight, preferably 0.5% and 2% by weight relative to the total weight of the composition.
4. Composition according to one of the preceding claims, characterized in that the cellulose particles are spherical, preferably with an average size of less than 40 pm, preferably ranging from 1 to 20 pm, more preferably from 2 to 10 pm.
5. Composition according to one of the preceding claims, characterized in that the cellulose particles are present in a content ranging from 1 to 6% by weight relative to the total weight of the composition.
6. Composition according to one of the preceding claims, characterized in that the hydrophobic silica is preferably present in the form of hydrophobic silica aerogel particles.
7. Composition according to claim 6, characterized in that the hydrophobic silica aerogel particles are silylated silica aerogel particles (INCI name silica silylate).
8. Composition according to one of the preceding claims, characterized in that the hydrophobic silica is present in an amount of between 0.1 and 3% by weight, preferably between 0.2 and 1% by weight relative to the total weight of the composition.
9. Composition according to one of the preceding claims, characterized in that it comprises an oily phase dispersed in an aqueous phase, said oily phase comprising at least one oil chosen from hydrocarbon oils, silicone oils, fluorinated oils and mixtures thereof.
10. Composition according to one of the preceding claims, characterized in that it comprises an oily phase comprising a mixture of a fatty alcohol solid at room temperature with a linear carbon chain having from 12 to 26 carbon atoms, a fatty acid comprising from 8 to 30 carbon atoms and a pasty compound.
11. Composition according to one of the preceding claims, characterized in that it comprises at least one continuous aqueous phase, said aqueous phase comprising water, and optionally at least one organic solvent soluble or miscible in water.
12. Composition according to one of the preceding claims, characterized in that it further comprises at least one adjuvant chosen from thickeners, perfumes, preservatives, surfactants, active ingredients, in particular moisturizers, coloring materials and alkalizing or acidifying agents.
13. Composition according to claim 12, characterized in that the coloring materials are chosen from water-soluble dyes, organic pigments, composite pigments, lakes, pigments with special effects or with interference effect, mineral pigments, nacres and their mixtures.
14. Cosmetic process for caring for keratin materials, comprising the application of a composition according to one of the preceding claims, to the keratin materials, preferably the skin.