WO2019122102A1 - Composition in the form of a direct emulsion comprising a silicone resin and a film-forming polymer, and process using same - Google Patents

Composition in the form of a direct emulsion comprising a silicone resin and a film-forming polymer, and process using same Download PDF

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Publication number
WO2019122102A1
WO2019122102A1 PCT/EP2018/086154 EP2018086154W WO2019122102A1 WO 2019122102 A1 WO2019122102 A1 WO 2019122102A1 EP 2018086154 W EP2018086154 W EP 2018086154W WO 2019122102 A1 WO2019122102 A1 WO 2019122102A1
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weight
alkyl
composition
chosen
acid
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PCT/EP2018/086154
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French (fr)
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Sandrine FERNANDES
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L'oreal
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Priority to EP18826655.5A priority Critical patent/EP3727322A1/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31Hydrocarbons
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Cosmetics (AREA)

Abstract

The present invention relates to a cosmetic composition in the form of a direct emulsion comprising: •at least 10% by weight of water relative to the weight of the composition; •at least 10% by weight, relative to the weight of the composition, of at least one silicone resin; •at least one aqueous dispersion of particles of at least one film-forming polymer chosen from synthetic polymers of radical type or of polycondensate type, and mixtures thereof; •optionally, at least one hydrocarbon-based or silicone volatile oil, in a content such that the silicone resin/volatile oil(s) weight ratio is greater than 1. The invention also relates to a process for making up and/or caring in particular for keratin materials such as the skin or the lips, and preferably the lips, in which the abovementioned composition is applied.

Description

COMPOSITION IN THE FORM OF A DIRECT EMUESION COMPRISING A SIEICONE RESIN AND A FILM-FORMING POLYMER, AND PROCESS USING SAME
The present invention relates to a composition intended in particular for making up and/or caring for the lips and the skin, which is in the form of a direct emulsion comprising at least 10% by weight of water, at least 10% by weight of a silicone resin, at least one aqueous dispersion of particles of at least one particular film-forming polymer and optionally at least one volatile oil, in a content such that the silicone resin/volatile oil(s) weight ratio is greater than 1 , and also to a process for treating and/or making up keratin materials, such as the skin or the lips, in particular the lips, using such a composition.
The development of compositions for making up and/or caring for the lips, in particular fluid compositions such as liquid lipsticks, which are stable and endowed with satisfactory properties in terms of application (glidance on application, ease of spreading and fineness of the deposit), but also in terms of the makeup effect of the deposit on the lips, for instance the absence of migration of the deposit, preferably without becoming tacky, is an ongoing objective.
Generally, formulations corresponding to liquid presentation forms are conventionally anhydrous and comprise oils, which in particular provide gloss, optionally waxes for structuring the compositions, fillers especially for thickening the composition, film-forming polymers, and dyestuffs.
These liquid lipsticks must be sufficiently fluid to be easily applied, but not too fluid, so as not to degrade the stability of the composition (pigment sedimentation) and the ease of application (running).
With conventional liquid lipstick compositions, it is noted that the deposit is relatively thick, thereby giving it a more or less tacky nature, especially induced by the use of these oils and of the polymers present. This nature may be reflected especially by adhesion of the made-up lips to each other, causing the user an unpleasant sensation in terms of comfort.
Liquid lipstick compositions have quite recently appeared on the market, in the form of direct or inverse aqueous emulsions. When they are applied, they provide a fresh effect, and are sparingly tacky or non-tacky, and comfortable, and remain so once deposited. They also make it possible to obtain a homogeneous, sufficiently glossy deposit which has satisfactory persistence and transfer resistance.
It is nevertheless desired to further improve the gloss and the gloss persistence of these compositions, without excessively degrading the comfort and especially without increasing the tacky nature. It is also desired to increase the colour persistence and to improve the transfer-resistance properties. It is furthermore advantageous to have available compositions that can be applied both to the lips and to the skin, in particular to the face and more precisely the cheeks.
Compositions, in particular liquid compositions, ‘are thus sought’ which can produce a deposit whose persistence and transfer resistance are improved without any significant loss of comfort, in particular without excessively increasing the tack. Compositions of which the deposit on the lips or the skin, in particular the cheeks, although very thin, makes it possible to obtain a visible, glossy colour, with improved colour persistence, are also sought.
These aims and others are achieved by the present invention, one subject of which is a cosmetic composition in the form of a direct emulsion (oil in water emulsion), comprising:
• at least 10% by weight of water relative to the weight of the composition;
• at least 10% by weight, relative to the weight of the composition, of at least one silicone resin;
• at least one aqueous dispersion of particles of at least one film-forming polymer chosen from synthetic polymers of radical type or of polycondensate type, alone or as a mixture;
• optionally, at least one hydrocarbon-based or silicone volatile oil, in a content such that the silicone resin/volatile oil(s) weight ratio is greater than 1.
The composition is thus in the form of an emulsion whose continuous phase is the aqueous phase.
The film deposited on the lips has the advantage of being thin and affords a fresh effect on application, without significant migration into the wrinkles and fine lines.
The composition is stable, easy to apply, comfortable on application since the deposit obtained is sparingly tacky, and remains so once in place. Moreover, the deposit does not give an impression of dryness of the lips.
ln addition, the deposit obtained by applying the composition according to the invention has satisfactory gloss and also satisfactory gloss persistence.
The colour persistence of the deposit obtained by applying the composition is improved, as is its transfer resistance. ft should be noted that, in the remainder of the description, unless otherwise indicated, the limits indicated for a range are included in that range.
The expressions "at least one" and "several" are used without distinction.
Unless otherwise indicated, the percentages are expressed on a weight basis relative to the total weight of the composition.
ln addition, the sum of the amounts of the ingredients of the composition represents 100% by weight of the composition.
The composition according to the invention is advantageously in a liquid form.
The term "liquid" means a fluid texture, in particular of which the viscosity at 25°C is more particularly between 0.01 and 10 Pa.s, and more particularly between 0.05 and 8 Pa.s.
Protocol for measuring the viscosity: The viscosity measurement is generally performed at 25°C, using a Rheomat RM 100 viscometer equipped with a no. 1 or 2 spindle, the measurement being performed after 10 minutes of rotation of the spindle in the composition, at a shear rate of 200 revolutions/min (rpm).
SILICONE RESIN
As indicated previously, the composition according to the invention comprises at least one silicone resin.
More generally, the term "resin" means a compound of which the structure is three- dimensional. Thus, for example, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin within the meaning of the present invention.
The nomenclature of silicone resins (also known as siloxane resins) is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units it comprises, each of the letters "MDTQ" characterizing a type of unit.
The letter M represents the monofunctional unit of formula RlR2R3SiOi/2, the silicon atom being bonded to only one oxygen atom in the polymer comprising this unit.
The letter D means a difunctional unit RlR2Si02/2 in which the silicon atom is bonded to two oxygen atoms.
The letter T represents a trifunctional unit of formula Rl SiC>3/2.
Such resins are described, for example, in the Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley and Sons, New York, (1989), pp. 265-270, and US 2 676 182, US
3 627 851, US 3 772 247, US 5 248 739 or else US 5 082 706, US 5 319 040, US 5 302 685 and US
4 935 484.
In the units M, D and T defined previously, Ri, namely Rl, R2 and R3, which may be identical or different, represent a hydrocarbon-based radical (especially alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group.
Finally, the letter Q means a tetrafirnctional unit S1O4/2 in which the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the rest of the polymer.
Various silicone resins with different properties may be obtained from these different units, the properties of these polymers varying as a function of the type of monomer (or unit), the nature and number of the radical(s) Ri, the length of the polymer chain, the degree of branching and the size of the side chains.
As silicone resins that may be used in the compositions according to the invention, use may be made, for example, of silicone resins of MQ type, of T type or of MQT type.
MQ resins:
As examples of silicone resins of MQ type, mention may be made of the alkyl siloxysilicates of formula [(Rl)3Si0i/2]x(Si04/2)y (units MQ) in which x and y are integers ranging from 50 to 80, and such that the group Rl represents a radical as defined previously, and is preferably an alkyl group containing from 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group. As examples of solid silicone resins of MQ type of trimethyl siloxysilicate type, mention may be made of those sold under the reference SR1000 by the company Momentive Performance Materials, under the reference MQ 1600 by Dow Coming or under the reference Belsil TMS 803 by the company Wacker.
As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkyl siloxysilicate resins, such as phenylpropyldimethyl siloxysilicate (Silshine 151 sold by the company Momentive Performance Materials). The preparation of such resins is described especially in patent US 5 817 302.
T resins:
Examples of silicone resins of T type that may be mentioned include the polysilsesquioxanes of formula (RSi03/2)x (units T) in which x is greater than 100 and such that the group R is an alkyl group containing from 1 to 10 carbon atoms, said polysilsesquioxanes also possibly comprising Si- OH end groups.
Mention may also be made of polymethylsilsesquioxanes, which are polysilsesquioxanes in which none of the methyl radicals is substituted with another group. Such polymethylsilsesquioxanes are described, for example, in US 5 246 694.
Polymethylsilsesquioxane resins that may preferably be used are those in which R represents a methyl group, for instance those sold:
- by the company Wacker under the reference Resin MK, such as Belsil PMS MK: polymer comprising CThSiCh repeating units (units T), which may also comprise up to 1% by weight of (CH3)2Si02/2 units (units D) and having an average molecular weight of about 10 000 g/mol, or
- by the company Shin-Etsu under the references KR-220L, which are composed of units T of formula CEhSi03/2 and contain Si-OH (silanol) end groups, under the reference KR-242A, which comprise 98% of units T and 2% of dimethyl units D and contain Si-OH end groups, or else under the reference KR-251, comprising 88% of units T and 12% of dimethyl units D and contain Si-OH end groups.
- by the company Dow Coming under the references Dow Corning 670 Fluid, Dow Coming 680 Fluid, as a mixture in cyclopentasiloxane and in isododecane, respectively.
MQT resins:
Resins comprising MQT units that are especially known are those mentioned in US 5 110
890.
A preferred form of resins of MQT type are MQT-propyl (also known as MQTpr) resins. Such resins that may be used in the compositions according to the invention are especially the resins described and prepared in patent application WO 2005/075 542, the content of which is incorporated herein by reference.
The MQ-T-propyl resin preferably comprises the following units: - (i) (Rl3SiOi/2)a
- (ii) (R22Si02/2)b
- (iii) (R3SiC>3/2)c and
- (iv) (Si04/2)d
with
- Rl, R2 and R3 independently representing a hydrocarbon-based radical (especially alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical containing from 1 to 8 carbon atoms or a phenyl group,
- a, b, c and d being mole fractions,
- a being between 0.05 and 0.5,
- b being between zero and 0.3,
- c being greater than zero,
- d being between 0.05 and 0.6,
- a + b + c + d = l,
- on condition that more than 40 mol% of the groups R3 of the siloxane resin are propyl groups.
Preferably, the siloxane resin comprises the following units:
- (i) (Rl3SiOi/2)a
- (iii) (R3Si03/2)c and
- (iv) (Si04/2)d
with
- Rl and R3 independently representing an alkyl group containing from 1 to 8 carbon atoms, Rl preferably being a methyl group and R3 preferably being a propyl group,
- a being between 0.05 and 0.5 and preferably between 0.15 and 0.4,
- c being greater than zero, preferably between 0.15 and 0.4,
- d being between 0.05 and 0.6, preferably between 0.2 and 0.6 or alternatively between 0.2 and 0.55,
- a + b + c + d = l, and a, b, c and d being mole fractions,
- on condition that more than 40 mol% of the groups R3 of the siloxane resin are propyl groups.
The siloxane resins that may be used according to the invention may be obtained via a process comprising the reaction of:
A) an MQ resin comprising at least 80 mol% of units (Rl3SiOi/2)a and (Si04/2)d,
- Rl representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
- a and d being greater than zero,
- the ratio a/d being between 0.5 and 1.5, and
B) a T-propyl resin comprising at least 80 mol% of units (R3SiC>3/2)c,
- R3 representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
- c being greater than zero,
- on condition that at least 40 mol% of the groups R3 are propyl groups,
- in which the mass ratio A/B is between 95/5 and 15/85 and preferably the mass ratio A/B is
30/70.
Advantageously, the weight ratio A/B is between 95/5 and 15/85. Preferably, the ratio A/B is less than or equal to 70/30. These preferred ratios have proven to afford comfortable deposits.
Preferably, the composition according to the invention comprises, as silicone resin, at least one resin of MQ type as described previously. ln particular, the silicone resin is a siloxysilicate resin, preferably a trimethylsiloxysilicate resin.
Advantageously, the silicone resin is present in a content of at least 10% by weight relative to the weight of the composition. Preferably, the content of silicone resin represents between 10% and 45% by weight, preferably between 12% and 40% by weight, in particular between 15% and 35% by weight, or even from 18% to 35% by weight, relative to the weight of the composition.
The silicone resin may be used in powder form, in a form dissolved in a solvent, in a form conveyed in a liquid or in a form emulsified in water ft should be noted that, in the latter case, the silicone resin is preferably in a conveyed form, advantageously dissolved in a solvent, and then emulsified.
As regards the silicone resins conveyed in a solvent, said solvent is usually chosen from apolar hydrocarbon-based oils and volatile or non-volatile, preferably volatile, silicone oils.
The term "volatile oil" means an oil with a non-zero vapour pressure, at room temperature (25°C), ranging in particular from 2.66 Pa to 40 000 Pa, in particular ranging up to 13 000 Pa and more particularly ranging up to 1300 Pa. By way of example, the vapour pressure may be measured according to the static method or via the effusion method by isothermal gravimetry, depending on the vapour pressure (standard OCDE 104, for instance regulation (EC) No 761/2009 of 23 July 2009).
Volatile hydrocarbon-based oils that may especially be mentioned include alkanes, preferably branched alkanes of 8 to 16 carbon atoms, especially such as Cx-CV isoalkanes (also known as isoparaffins), isododecane, isodecane and isohexadecane.
Volatile silicone oils that may be mentioned include linear or cyclic silicone oils, such as linear or cyclic polydimethylsiloxanes (PDMSs) containing from 3 to 7 silicon atoms. Examples of such oils that may be mentioned include octyl trimethicone, hexyl trimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethyltetrasiloxane, methyl trimethicone, polydimethylsiloxanes such as those sold under the reference DC 200 by Dow Coming or KF 96 A from Shin-Etsu; alone or as mixtures.
Among the silicone resins, especially of MQ type, which are in a form conveyed in a solvent, mention may be made especially of Koboguard® MQ65TMF (mixture of trimethylsiloxysilicate and methyl trimethicone) sold by Kobo; KF-7312J (mixture in cyclopentasiloxane), KF-7312K, KF- 7312L (mixtures in dimethicone), KF-7312T (mixture in trimethicone), X-21-5249 (mixture in cyclopentasiloxane), X-21-5249L (mixture in dimethicone), X-21-5250, X-21-5250L (mixture in cyclopentasiloxane and dimethicone, respectively), X-21-5595, X-21-5616 (mixtures in isododecane), KF-9021, KF-9021L (mixtures in cyclopentasiloxane and in dimethicone, respectively), sold by Shin-Etsu; Silsoft 74, Silshine 151 (mixtures in isododecane) from Momentive Performance Materials; Xiameter RSN-0749 Resin, Dow Coming 749 Fluid (mixtures in cyclopentasiloxane), Dow Coming 593 Fluid (mixture in dimethicone) from Dow Coming.
As regards the silicone resins that are in the form of emulsions in water, mention may be made, for example, of KM-9717 (emulsion in the presence of an anionic surfactant, comprising a low- viscosity silicone), X-52-8005 (emulsion in the presence of a nonionic surfactant, comprising a low- viscosity silicone), sold by Shin-Etsu.
FILM-FORMING POLYMER DISPERSION
The composition according to the invention comprises at least one aqueous dispersion of film forming polymer particles.
In the present patent application, the term“film-forming polymer” means a polymer that is capable, by itself or in the presence of an auxiliary film- forming agent, of forming a macroscopically continuous deposit, and preferably a cohesive deposit, and even better still a deposit whose cohesion and mechanical properties are such that said deposit can be isolated and manipulated individually, for example when said deposit is prepared by pouring onto a non-stick surface such as a Teflon- coated or silicone-coated surface.
A composition according to the invention preferably includes a total content of film-forming polymer solids of between 0.5% and 15% by weight, preferably from 1% to 12% by weight and even more preferentially from 2% to 10% by weight, relative to the weight of the composition.
In accordance with a particularly advantageous embodiment of the invention, the content of film-forming polymer solids in the composition is such that the silicone resin (expressed as solids)/film-forming polymer (expressed as solids) weight ratio is greater than or equal to 1 , preferably greater than 1 and even more advantageously greater than or equal to 2.
The composition according to the invention preferably comprises more specifically at least one aqueous dispersion of particles formed from one or more film-forming polymers. Film-forming nolvmer(s) in aqueous dispersion
Such a film-forming polymer present in the preparation of the composition in the form of particles in aqueous dispersion is generally known as a (pseudo)latex, i.e. a latex or pseudolatex. Techniques for preparing these dispersions are well known to those skilled in the art.
A dispersion that is suitable for use in the invention may comprise one or more types of particle, these particles possibly varying as regards their size, their structure and/or their chemical nature.
These particles may be of anionic, cationic or neutral nature and may constitute a mixture of particles of different natures.
As indicated previously, the film-forming polymers that may be used in the composition of the present invention are chosen from synthetic polymers, of free-radical type or of polycondensate type, and mixtures thereof. In general, these polymers may be statistical polymers, block copolymers of A-B type, of A-B-A or also ABCD, etc. multiblock type, or even grafted polymers.
Free- radical film-forming polymer
The term“free-radical polymer” means a polymer obtained by radical polymerization of unsaturated and in particular ethylenically unsaturated monomers, each monomer being capable of homopolymerizing (unlike polycondensates).
The film-forming polymers of free-radical type may in particular be acrylic and/or vinyl homopolymers or copolymers.
The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers.
Ethylenically unsaturated monomers containing at least one acid group or monomer bearing an acid group that may be used include a,b-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid and crotonic acid are used in particular, and more particularly (meth)acrylic acid.
The esters of acid monomers are advantageously chosen from (meth)acrylic acid esters (also known as (meth)acrylates), in particular (meth)acrylates of an alkyl, in particular of a C1-C20 and more particularly Ci-Cs alkyl, (meth)acrylates of an aryl, in particular of a C6-C10 aryl, and (meth)acrylates of a hydroxyalkyl, in particular of a C2-C6 hydroxyalkyl.
Among the alkyl (meth)acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate.
Mention may be made, among hydroxyalkyl (meth)acrylates, of hydroxyethyl acrylate, 2- hydroxypropyl acrylate, hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate.
Mention may be made, among aryl (meth)acrylates, of benzyl acrylate and phenyl acrylate.
The (meth)acrylic acid esters are in particular alkyl (meth)acrylates. According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
Examples of amides of the acid monomers that may be mentioned are (meth)acrylamides, and especially N-alkyl(meth)acrylamides, in particular of a C2-C12 alkyl. Among the N- alkyl(meth) acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide and N- t-octylacrylamide.
The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers at least chosen from vinyl esters and styrene monomers. In particular, these monomers may be polymerized with acid monomers and/or esters thereof and/or amides thereof, such as those mentioned above.
Examples of vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.
Styrene monomers that may be mentioned include styrene and a-methylstyrene.
The list of monomers given is not limiting, and it is possible to use any monomer known to those skilled in the art included in the categories of acrylic and vinyl monomers (including monomers modified with a silicone chain).
Mention may also be made of polymers resulting from free-radical polymerization of one or more free-radical monomers inside and/or partially at the surface of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes, polyureas, polyesters, polyesteramides and/or alkyds. These polymers are generally referred to as“hybrid polymers”.
Polycondensate
As film-forming polymer of polycondensate type, mention may be made of polyurethanes, especially anionic, cationic, nonionic or amphoteric polyurethanes, acrylic polyurethanes, polyvinylpyrrolidone-polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyureas and polyurea/polyurethanes, and mixtures thereof.
The film- forming polyurethane may be, for example, an aliphatic, cycloaliphatic or aromatic polyurethane, polyurea/urethane or polyurea copolymer including, alone or as a mixture, at least one block chosen from:
- a block of aliphatic and/or cycloaliphatic and/or aromatic polyester origin, and/or
- a branched or unbranched silicone block, for example polydimethylsiloxane or polymethylphenylsiloxane, and/or
- a block including fluoro groups.
The film-forming polyurethanes as defined in the invention may also be obtained from branched or unbranched polyesters or from alkyds comprising labile hydrogens, which are modified by reaction with a diisocyanate and a difunctional organic compound (for example dihydro, diamino or hydroxyamino), also comprising either a carboxylic acid or carboxylate group, or a sulfonic acid or sulfonate group, or alternatively a neutralizable tertiary amine group or a quaternary ammonium group.
Among the film-forming polycondensates, mention may also be made of polyesters, polyesteramides, fatty-chain polyesters, polyamides and epoxyester resins.
The polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, especially diols.
The dicarboxylic acid may be aliphatic, alicyclic or aromatic. Examples of such acids that may be mentioned include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3- cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or as a combination of at least two dicarboxylic acid monomers. Among these monomers, the ones chosen in particular are phthalic acid, isophthalic acid and terephthalic acid.
The diol may be chosen from aliphatic, alicyclic and aromatic diols. The diol used is chosen in particular from: ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, cyclohexanedimethanol and 4-butanediol. Other polyols that may be used are glycerol, pentaerythritol, sorbitol and trimethylolpropane.
The polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycondensation of diacids with diamines or amino alcohols. Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or /¾//r/-phcnylcncdiaminc. An amino alcohol that may be used is monoethanolamine.
According to a particular embodiment of the invention, said at least one film-forming polymer in the dispersed state is chosen from acrylic polymer dispersions, polyurethane dispersions, sulfopolyester dispersions, vinyl dispersions, polyvinyl acetate dispersions, vinylpyrrolidone, dimethylaminopropylmethacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride terpolymer dispersions, dispersions of polyurethane/polyacrylic hybrid polymers and dispersions of particles of core-shell type, and mixtures thereof.
Various types of aqueous dispersions, in particular commercial aqueous dispersions, which are suited to the preparation of the composition in accordance with the present invention are detailed below.
1/ Thus, according to a preferred embodiment of the invention, the aqueous dispersion of polymer particles is an aqueous dispersion of acrylic polymer.
The acrylic polymer may be chosen from acrylic polymers resulting in particular from the polymerization of ethylenically unsaturated monomers, for instance acrylic acid, methacrylic acid and/or esters thereof, in particular Ci-Cs alkyl esters thereof; styrene/acrylate copolymers, and especially polymers chosen from those derived from the polymerization of at least one styrene monomer and at least one Ci-Cis alkyl (meth)acrylate monomer, optionally in the presence of a (meth)acrylic acid monomer or a salt (especially an ammonium salt) thereof.
As styrene monomers that may be used in the invention, examples that may be mentioned include styrene and a-methylstyrene, and in particular styrene.
The Ci-C is alkyl (meth)acrylate monomer is particular a Ci-Ci2 alkyl (meth)acrylate and more particularly a Ci-Cio alkyl (meth)acrylate. The Ci-Cis alkyl (meth)acrylate monomer may be chosen from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate.
As acrylic polymer in aqueous dispersion, use may be made according to the invention of the styrene/acrylate copolymers sold under the names Joncryl SCX-8211® or Joncryl 77 by the company BASF, Syntran 5760cg by the company Interpolymer, or Rhoplex® P376 by the company Dow Chemical Company; alkyl acrylates with, for example, Daitosol 3000 VP3, Daitosol 3000SLPN- PE1, Daitosol 5000AD from the company Kobo Products; the styrene/acrylate/ammonium methacrylate copolymers sold under the names Syntran 5009 and Syntran PC 5620 by the company Interpolymer; the acrylic polymer sold under the reference Acronal® DS-6250 by the company BASF, Joncryl® 95 by the company BASF, and the acrylic polymer mixture sold under the name Syntran PC 5775 by the company Interpolymer. Use may also be made of the acrylate/ethylhexyl acrylate copolymers sold, for example, under the name Daitosol 5500GM and Daitosol 4000 SJT by the company Kobo Products.
2/ According to one embodiment variant of the invention, the aqueous dispersion of polymer particles is an aqueous dispersion of polyester-polyurethane and/or poly ether-polyurethane particles, in particular in anionic form.
The anionic nature of the polyester-polyurethanes and of the polyether-polyurethanes used according to the invention is due to the presence in their constituent units of groups bearing a carboxylic acid or sulfonic acid function.
The polyester-polyurethane or polyether-polyurethane particles used according to the invention are generally sold in aqueous dispersion form.
The particle content of said dispersions currently available on the market ranges from about 20% to about 60% by weight relative to the total weight of the dispersion.
Among the anionic polyester-polyurethane dispersions that may be used in the compositions according to the invention, mention may be made in particular of the product sold under the name Avalure UR 405® by the company Noveon or Baycusan Cl 004 by the company Bayer Material Science.
Among the anionic polyether-polyurethane particle dispersions that may be used according to the invention, mention may be made in particular of the products sold under the name Avalure UR 450® by the company Noveon and under the name Neorez R 970® by the company DSM. According to a particular embodiment of the invention, use may be made of a mixture of commercial dispersions consisting of anionic polyester-polyurethane particles as defined above and of anionic polyether-polyurethane particles also defined above.
For example, use may be made of a mixture consisting of the dispersion sold under the name Sancure 861® or a mixture of the product sold under the name Avalure UR 405® and of the product sold under the name Avalure UR 450®, these dispersions being sold by the company Noveon.
3/ According to another particular embodiment of the invention, the aqueous dispersion used comprises a mixture of at least two film- forming polymers in the form of particles that differ by their respective glass transition temperatures (Tg). The polymer(s) may or may not be plasticized.
In particular, according to one embodiment of the invention, the composition in accordance with the invention may comprise at least one first film-forming polymer in the dispersed state and at least one second film-forming polymer in the dispersed state, said first and second polymers having different Tg values and, preferably, the Tg of the first polymer (Tgl) is higher than the Tg of the second polymer (Tg2). In particular, the difference between the Tgl and Tg2 values is, as an absolute value, at least l0°C and preferably at least 20°C.
More precisely, it comprises in an acceptable aqueous medium:
a) particles dispersed in the aqueous medium of a first film- forming polymer having at least one glass transition temperature Tgl greater than or equal to 20°C, and
b) particles dispersed in the aqueous medium of a second film-forming polymer having at least one glass transition temperature Tg2 less than or equal to 70°C.
This dispersion generally results from a mixing of two aqueous dispersions of film-forming polymer.
The first film-forming polymer has at least one, especially one, glass transition temperature Tgl greater than or equal to 20°C, especially ranging from 20°C to l50°C and advantageously greater than or equal to 40°C, in particular ranging from 40°C to l50°C and in particular greater than or equal to 50°C, in particular ranging from 50°C to l50°C.
The second film-forming polymer has at least one, especially one, glass transition temperature Tg2 less than or equal to 70°C, especially ranging from -l20°C to 70°C and in particular less than 50°C, especially ranging from -60°C to +50°C and more particularly ranging from -30°C to 30°C.
The measurement of the glass transition temperature (Tg) of a polymer is performed by DMTA (dynamic and mechanical temperature analysis) as described below.
To measure the glass transition temperature (Tg) of a polymer, viscoelasticity tests are performed with a "Polymer Laboratories" DMTA machine, on a sample of film. This film is prepared by pouring the aqueous dispersion of film- forming polymer in a Teflon-coated matrix followed by drying at l20°C for 24 hours. A film is then obtained, from which specimens are cut out (for example using a punch). These specimens are typically about 150 pm thick, from 5 to 10 mm wide and have a useful length of about 10 to 15 mm. A tensile stress is imposed on this sample. The sample undergoes a static force of 0.01 N on which is superimposed a sinusoidal displacement of ± 8 pm at a frequency of 1 Hz. The test is thus performed in the linear range, at low levels of deformation. This tensile stress is performed on the sample at temperatures ranging from -l50°C to +200°C, with a temperature variation of 3°C per minute.
The complex modulus E* = E’ + iE” of the polymer tested is thus measured as a function of the temperature.
From these measurements, the dynamic moduli E’ and E” and the damping power: tgd = E”/E’ are deduced.
The curve of the tgd values is then plotted as a function of the temperature; this curve has at least one peak. The glass transition temperature Tg of the polymer corresponds to the temperature at the top of this peak.
When the curve has at least two peaks (in this case, the polymer has at least two Tg values), the value taken as the Tg of the polymer tested is the temperature for which the curve has a peak of the largest amplitude (i.e. corresponding to the largest tgd value; in this case, only the "major" Tg is considered as the Tg value of the polymer tested).
In the present invention, the transition temperature Tgl corresponds to the“major” Tg (in the predefined sense) of the first film-forming polymer when the latter presents at least two Tg values; the glass transition temperature Tg2 corresponds to the“major” Tg of the second film-forming polymer when the latter presents at least two Tg values.
The first film-forming polymer and the second film-forming polymer may be chosen, independently of each other, from free-radical polymers, polycondensates and polymers of natural origin as defined previously having the glass transition temperature characteristics defined previously.
As first film-forming polymer in aqueous dispersion, use may be made of the aqueous polymer dispersions sold under the names Neorez R-989® by the company DSM, Joncryl 95 and Joncryl® 8211 by the company BASF.
As second film-forming polymer in aqueous dispersion, use may be made, for example, of the aqueous polymer dispersions sold under the names Avalure® UR-405, Avalure® UR-460 by the company Noveon or Acrilem IC89RT® by the company ICAP, and Neocryl A-45 by the company DSM.
The film-forming polymer of the aqueous dispersion Avalure® UR-460 is a polyurethane obtained by polycondensation of polytetramethylene oxide, tetramethylxylylene diisocyanate, isophorone diisocyanate and dimethylolpropionic acid.
According to a most particularly preferred embodiment of the invention, use is made, as first and second film-forming polymers in aqueous dispersion, of the combination of styrene/acrylate polymer dispersion such as the dispersion sold under the reference Joncryl 8211® by BASF and of acrylic polymer dispersion such as the dispersion sold under the reference Neocryl A-45® by DSM.
According to another preferred embodiment of this particular embodiment of point 3/ above, use is made, as first film-forming polymer in aqueous dispersion, of an acrylic polymer dispersion such as the dispersion sold under the reference Joncryl 95® by BASF and, as second film-forming polymer, of a dispersion of anionic polyurethane polymer sold under the reference Avalure UR405® by DSM.
As aqueous dispersions of film- forming polymer, use may be made of:
- the acrylic dispersions sold under the names Acronal DS-6250® by the company BASF, Neocryl A-45®, Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by the company DSM, Joncryl 95® and Joncryl 821 l®by the company BASF, Daitosol 5000 AD® or Daitosol 5000 SJ by the company Daito Kasey Kogyo; Syntran 5760 CG by the company Interpolymer,
- the aqueous polyurethane dispersions sold under the names Neorez R-981® and Neorez R- 974® by the company DSM, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR- 450®, Sancure 875®, Avalure UR 445® and Avalure UR 450® by the company Noveon, Impranil 85® by the company Bayer, and Baycusan Cl 004® by the company Bayer Material Science,
- the sulfopolyesters sold under the brand name Eastman AQ® by the company Eastman Chemical Products,
- vinyl dispersions such as Mexomere PAM, aqueous dispersions of polyvinyl acetate such as Vinybran® from the company Nisshin Chemical or the products sold by the company Union Carbide, aqueous dispersions of vinylpyrrolidone, dimethylaminopropylmethacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride terpolymer such as Styleze W® from ISP,
- aqueous dispersions of polyurethane/polyacrylic hybrid polymer such as the products sold under the references Hybridur® by the company Air Products or Duromer® from National Starch,
- dispersions of particles of core-shell type such as the products sold by the company Arkema under the reference Kynar® (core: fluorinated - shell: acrylic) or alternatively those described in US 5 188 899 (core: silica - shell: silicone) and mixtures thereof.
According to a preferred embodiment, a composition in accordance with the invention comprises an aqueous dispersion of particles chosen from ionic or nonionic acrylic polymers, resulting especially from the polymerization of ethylenically unsaturated monomers, for instance acrylic acid, methacrylic acid and/or esters thereof, in particular Ci-Cs alkyl esters thereof; styrene/acrylate copolymers, and especially polymers chosen from those derived from the polymerization of at least one styrene monomer and at least one Ci-Cis alkyl (meth)acrylate monomer, optionally in the presence of a (meth)acrylic acid monomer; aqueous dispersions of polyurethane polymer(s), in particular of polyester-polyurethane, and derivatives thereof, and mixtures thereof.
Thus, preferably, the film-forming polymer does not comprise silicone units.
Use is preferably made of an aqueous dispersion of plasticized or non-plasticized film forming polymer(s), at least one of which has a glass transition temperature (Tg) ranging from -l5°C to 90°C, more particularly from 0°C to 50°C. NON-VOLATILE SILICONE OILS
As indicated previously, the composition according to the invention may optionally comprise at least one non-volatile silicone oil, not comprising any (poly)oxyalkylene groups in which the oxyalkylene unit is C2-C3, or any (poly)glycerol groups.
In other words, the non-volatile silicone oil(s) are not non-volatile amino silicone oils since they are free of nitrogen atoms.
Preferably, the non-volatile silicone oil is free of -Si-H groups.
It also preferably does not comprise any C8-C22 alkyl groups, when the non-volatile silicone oil does not comprise any phenyl groups.
The term“ non-volatile oil " means an oil whose vapour pressure at 25°C is non-zero and is less than 2.66 Pa and more particularly less than 0.13 Pa.
Preferably, the non-volatile silicone oil is nonionic.
According to the invention, the term“nonionic" means that the compound does not comprise any ionic groups, irrespective of the pH of the composition.
Among the non-volatile silicone oils that may be used in the present invention, examples that may be mentioned include non-volatile non-phenyl silicone oils and non-volatile phenyl silicone oils, optionally bearing a dimethicone fragment, and also mixtures thereof.
The silicone oil may be used in the composition according to the invention in unmodified form, or in a form dissolved in at least one volatile or non-volatile oil, or in the form of an emulsion.
Non-volatile non-phenyl silicone oils
The expression "non-phenyl silicone oil" denotes a silicone oil not comprising phenyl substituents.
Representative examples of these non-volatile non-phenyl silicone oils that may be mentioned include polydimethylsiloxanes; vinyl dimethicones and copolymers with dimethicone.
Moreover, the term "dimethicone" (INCI name) corresponds to a polydimethylsiloxane (chemical name).
In particular, these oils may be chosen from the following non-volatile oils:
- polydimethylsiloxanes (PDMSs),
- polydimethylsiloxanes comprising functional groups such as hydroxyl groups,
- divinylmethicone/dimethicone copolymers,
- mixtures thereof.
The non-volatile non-phenyl silicone oil may be chosen in particular from silicones of formula
(I): R1 R3 R5 F†1
X - Si o - Si o Si - O Si - X R2 R4 R6_ R2
n p
(I)
in which:
- Ri, R2, R5 and R6 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms,
- R3 and R4 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, or a hydroxyl radical,
- X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical,
- n and p are integers chosen so as to have a fluid compound, in particular of which the viscosity at 25°C is between 8 centistokes (cSt) (8 mm2/s) and 800 000 cSt (800 000 mm2/s), advantageously less than 600 000 cSt (600 000 mm2/s).
As non-volatile non-phenyl silicone oils that are suitable for performing the invention, mention may be made of those for which:
- the substituents Ri to R6 and X represent a methyl group, and p and n are such that the viscosity is 500 000 cSt (500 000 mm2/s), for example the product sold under the name Silsoft SE30 by the company Momentive Performance Materials, the product sold under the name AK 500000 by the company Wacker, the product sold under the name Mirasil DM 500 000 by the company Bluestar, and the product sold under the name Dow Coming 200 Fluid 500 000 cSt by the company Dow Coming,
- the substituents Ri to R6 and X represent a methyl group, and p and n are such that the viscosity is 60 000 cSt (60 000 mm2/s), for example the product sold under the name Dow Coming 200 Fluid 60 000 CS by the company Dow Coming, and the product sold under the name Belsil DM 60 000 by the company Wacker,
- the substituents Ri to R6 and X represent a methyl group, and p and n are such that the viscosity is 100 cSt (100 mm2/s) or 350 cSt (350 mm2/s), for example the products sold respectively under the names Belsil DM100 and Dow Coming 200 Fluid 350 CS by the company Dow Coming, and
- the substituents Ri to R6 represent a methyl group, the group X represents a hydroxyl group, and n and p are such that the viscosity is 700 cSt (700 mm2/s), for example the product sold under the name Baysilone Fluid TO.7 by the company Momentive Performance Materials.
Dimethiconols such as the products Xiameter PMX-1503 (as a mixture with a dimethicone) and Xiameter PMX-1502 (mixture with Cl 1-33 isoparaffin, isohexadecane, dimethicone) from Dow Coming may also be suitable for use. The silicone oil may be used in unmodified form, or in a form dissolved in at least one volatile or non-volatile oil, or in the form of an emulsion.
As examples of emulsions of non-volatile silicone oil, mention may be made of the products Xiameter MEM-1352 Emulsion (dimethicone, laureth-23, C12-15 pareth-3), Xiameter MEM 1491 Emulsion (dimethicone, laureth-23, C12-15 pareth-3), Xiameter MEM-1691 Emulsion (dimethicone, Cl 2- 13 pareth-4 and Cl 2- 13 pareth-23 and salicylic acid), Xiameter MEM 1652 Emulsion (dimethicone, Cl 2- 13 pareth-23; C12-C15 pareth 3, salicylic acid), Xiameter MEM 1664 Emulsion (dimethicone, laureth-4, laureth-23), Xiameter MEM-2664 Emulsion (dimethicone, laureth-23, laureth-4), Xiameter MEM- 1784 Emulsion or Dow Coming CE2060 (dimethicone, cocamidopropylbetaine, C12-15 pareth-3, guar hydroxypropyltrimonium chloride), Xiameter MEM-1785 Emulsion, Xiameter MEM— 1784 Emulsion or Xiameter MEM— 1788 Emulsion (dimethiconol, TEA dodecylbenzenesulfonate), Belsil DM 3560 VP (dimethiconol, sodium dodecylbenzenesulfonate, trideceth-lO), Dow Coming HMW 2220 nonionic emulsion (divinyl dimethicone/dimethicone copolymer, C12-13 pareth-3, C12-13 pareth-23), sold by Dow Coming; KM-862T (nonionic) from Shin-Etsu.
Non-volatile phenyl silicone oils
The expression "phenyl silicone oil" denotes a silicone oil bearing at least one phenyl substituent.
These non-volatile phenyl silicone oils may be chosen from those also bearing at least one dimethicone fragment, or from those not bearing any. ft should be noted that the term "dimethicone fragment" denotes a divalent siloxane group in which the silicon atom bears two methyl radicals, this group not being located at the end of the molecule ft may be represented by the following formula: -(Si(CH3)2-0)-.
The non-volatile phenyl silicone oil may thus be chosen from:
- phenyl silicone oils optionally bearing a dimethicone fragment corresponding to formula (1) below:
Figure imgf000018_0001
in which the groups R, which are monovalent or divalent, represent, independently of each other, a methyl, methylene, phenyl or phenylene, with the proviso that at least one group R represents a phenyl.
Preferably, in this formula, the phenyl silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six. - phenyl silicone oils optionally bearing a dimethicone fragment corresponding to formula (II) below:
R R R
R - Si - O - Si - O - Si - R
R R R (II)
in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.
Preferably, in this formula, the compound of formula (II) comprises at least three phenyl groups, for example at least four or at least five.
Mixtures of different compounds of formula (II) described previously may be used.
Examples that may be mentioned include mixtures of triphenyl-, tetraphenyl- or pentaphenylorganopolysiloxanes.
Among the compounds of formula (II), mention may be made more particularly of phenyl silicone oils not bearing any dimethicone fragments, corresponding to formula (II) in which at least 4 or at least 5 radicals R represent a phenyl radical, the remaining radicals representing methyls.
Such non-volatile phenyl silicone oils are preferably trimethylpentaphenyltrisiloxane or tetramethyltetraphenyltrisiloxane. They are in particular sold by Dow Coming under the reference PH-1555 HRI or Dow Coming 555 Cosmetic Fluid (chemical name: l,3,5-trimethyl-l,l,3,5,5- pentaphenyltrisiloxane; INCI name: trimethylpentaphenyltrisiloxane), or the tetramethyltetraphenyltrisiloxane sold under the reference Dow Coming 554 Cosmetic Fluid by Dow Coming may also be used.
They correspond especially to formulae (III) and (IIP) below:
Figure imgf000019_0001
in which Me represents methyl, and Ph represents phenyl.
- phenyl silicone oils bearing at least one dimethicone fragment corresponding to formula (IV) below:
Figure imgf000019_0002
in which Me represents methyl, y is between 1 and 1000 and X represents -CFb- CH(CH3)(Ph).
- phenyl silicone oils optionally bearing a dimethicone fragment, corresponding to formula (V) below, and mixtures thereof:
Figure imgf000020_0001
in which:
- Ri to Rio, independently of each other, are saturated or unsaturated and linear, cyclic or branched C1-C30 hydrocarbon-based radicals,
- m, n, p and q are, independently of each other, integers between 0 and 1000, preferably 900, with the provisos that the sum m+n+q is other than 0 and that the silicone oil is non-volatile.
Preferably, the sum m+n+q is between 1 and 100. Advantageously, the sum m+n+p+q is between 1 and 1000, more particularly between 1 and 900 and preferably between 1 and 800.
Preferably, q is equal to 0.
More particularly, Ri to Rio represent, independently of each other, a saturated or unsaturated, preferably saturated, and linear or branched C1-C30 hydrocarbon-based radical, and in particular a preferably saturated C1-C20, in particular Ci-Cis, hydrocarbon-based radical, or a monocyclic or polycyclic C6-C14 and in particular C10-C13 aryl radical, or an aralkyl radical, the alkyl part of which is preferably a C1-C3 alkyl.
Preferably, Ri to Rio may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or as a variant a phenyl, tolyl, benzyl or phenethyl radical. Ri to Rio may in particular be identical, and in addition may be a methyl radical.
As particular embodiments of formula (V), mention may be made of:
o phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to formula (VI) below, and mixtures thereof:
Figure imgf000020_0002
in which: Ri to R6, independently of each other, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based radicals, a preferably C6-C14 aryl radical or an aralkyl radical, the alkyl part of which is a C1-C3 alkyl,
m, n and p are, independently of each other, integers between 0 and 1000, preferably between 0 and 100, with the proviso that the sum n+m is between 1 and 1000, preferably between 1 and 100.
Preferably, Ri to R6, independently of each other, represent a C1-C20, in particular Ci- Ci8, hydrocarbon-based, preferably alkyl, radical, or a C6-C14 aryl radical which is monocyclic (preferably O,) or polycyclic and in particular C10-C13, or an aralkyl radical (preferably the aryl part is Ce aryl; the alkyl part is C1-C3 alkyl).
Preferably, Ri to R6 may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or as a variant a phenyl, tolyl, benzyl or phenethyl radical.
Ri to R6 may in particular be identical, and in addition may be a methyl radical. Preferably, m = 1 or 2 or 3, and/or n = 0 and/or p = 0 or 1 may be applied, in formula (VI).
According to a particular embodiment, the non-volatile phenyl silicone oil is chosen from phenyl silicone oils bearing at least one dimethicone fragment.
Preferably, such oils correspond to compounds of formula (VI) in which:
m = 0 and n and p are, independently of each other, integers between 1 and 100. Preferably, Ri to R6 are methyl radicals.
According to this embodiment, the silicone oil is preferably chosen from a diphenyl dimethicone, such as KF-54 from Shin-Etsu (400 cSt - 400 mm2/s), KF54HV from Shin-Etsu (5000 cSt - 5000 mm2/s)), KF-50-300CS from Shin-Etsu (300 cSt - 300 mm2/s), KF-53 from Shin- Etsu (175 cSt - 175 mm2/s) or KF-50-100CS from Shin-Etsu (100 cSt-lOO mm2/s).
p is between 1 and 1000, the sum n+m is between 1 and 1000, and n = 0.
These phenyl silicone oils optionally bearing at least one dimethicone fragment correspond more particularly to formula (Vll) below:
Figure imgf000021_0001
in which Me is methyl and Ph is phenyl, OR' represents an -OSiMe3 group and p is 0 or is between 1 and 1000, and m is between 1 and 1000. ln particular, m and p are such that compound (Vll) is a non-volatile oil.
According to a first embodiment of non-volatile phenyl silicone bearing at least one dimethicone fragment, p is between 1 and 1000 and m is more particularly such that compound (Vll) is a non-volatile oil. Use may be made, for example, of trimethylsiloxyphenyl dimethicone, sold in particular under the reference Belsil PDM 1000 or Belsil PDM 20 by the company Wacker. According to a second embodiment of a non-volatile phenyl silicone not bearing any dimethicone fragments, p is equal to 0 and m is between 1 and 1000, and in particular is such that compound (VII) is a non-volatile oil.
Use may be made, for example, of phenyl trimethicone, sold in particular under the reference Dow Coming 556 Cosmetic Grade Fluid (DC556).
o non-volatile phenyl silicone oils not bearing any dimethicone fragments corresponding to formula (VIII) below, and mixtures thereof:
Figure imgf000022_0001
in which:
- R, independently of each other, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based radicals, preferably R is a C1-C30 alkyl radical, a preferably C6-C14 aryl radical, or an aralkyl radical, the alkyl part of which is C1-C3 alkyl,
- m and n are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100.
Preferably, R, independently of each other, represent a saturated or unsaturated, preferably saturated, linear or branched C1-C30 hydrocarbon-based radical, and in particular a preferably saturated, C1-C20, in particular Ci-Cis and more particularly C4-C10, hydrocarbon-based radical, a monocyclic or polycyclic C6-C 14, and in particular C 10-C 13, aryl radical, or an aralkyl radical of which preferably the aryl part is O, aryl and the alkyl part is C1-C3 alkyl.
Preferably, the groups R may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or as a variant a phenyl, tolyl, benzyl or phenethyl radical.
The groups R may in particular be identical, and in addition may be a methyl radical.
According to a preferred embodiment, n is an integer between 0 and 100 and m is an integer between 1 and 100, with the proviso that the sum n+m is between 1 and 100, in formula (VIII). Preferably, R is a methyl radical.
According to one embodiment, a phenyl silicone oil of formula (VIII) with a viscosity at 25°C of between 5 and 1500 mm2/s (i.e. 5 to 1500 cSt), and preferably with a viscosity of between 5 and 1000 mm2/s (i.e. 5 to 1000 cSt), may be used.
According to this embodiment, the non-volatile phenyl silicone oil is preferably chosen from phenyl trimethicones (when n = 0, m more particularly between 1 and 3) such as Dow Coming 556 Cosmetic Grade Fluid from Dow Coming (20 cSt -20 mm2/s), or else from diphenylsiloxyphenyl trimethicone oil (when m and n are between 1 and 100) such as KF56 A from Shin-Etsu, or the oil Silbione 70663V30 from Rhone-Poulenc (28 cSt - 28 mm2/s). The values in parentheses represent the viscosities at 25°C.
- phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to the following formula, and mixtures thereof:
Figure imgf000023_0001
in which:
Ri, R2, R5 and R6, which may be identical or different, are an alkyl radical containing 1 to 6 carbon atoms,
R3 and R4, which may be identical or different, are an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical (preferably Ce-Cw), with the proviso that at least one of R3 and R4 is a phenyl radical,
X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical,
n and p being an integer greater than or equal to 1 , chosen so as to give the oil a weight- average molecular mass preferably less than l50 000 g/mol and more preferably less than 100 000 g/mol.
- and a mixture thereof.
More particularly, the composition comprises at least one non-volatile silicone oil chosen from polydimethylsiloxanes; non-volatile phenyl silicone oils preferably bearing a dimethicone fragment, and also mixtures thereof.
Preferably, the composition comprises as non-volatile silicone oil(s), polydimethylsiloxanes and phenyl silicones of formula (V), and also mixtures thereof.
Preferably, the non-volatile phenyl silicone oil(s) bearing a dimethicone fragment are chosen from trimethylsiloxyphenyl dimethicones and diphenyl dimethicones, and also mixtures thereof.
Needless to say, the composition according to the invention may also comprise, in addition to the abovementioned non-volatile phenyl silicone oils, non-volatile phenyl silicone oils not bearing any dimethicone fragments, for instance phenyl trimethicones, trimethylpentaphenyltrisiloxanes and tetramethyltetraphenyltrisiloxanes, alone or as mixtures.
Advantageously, if the composition contains any, the content of non-volatile silicone oil(s) is more particularly between 2% and 35% by weight and preferably between 4% and 30% by weight, relative to the weight of the composition. Preferably, the composition according to the invention comprises at least one non-volatile silicone oil.
NON-VOLATILE HYDROCARBON-BASED OILS
The composition according to the invention may optionally comprise at least one non-volatile, polar or apolar hydrocarbon-based oil.
The term“oil” denotes a compound that is liquid at 25°C and atmospheric pressure (1.013x 105
Pa).
The term“ hydrocarbon-based oil” denotes a non-aqueous, water-immiscible compound that is liquid at 25°C and atmospheric pressure (T0l3x l05 Pa), formed essentially of, indeed even consisting of, carbon and hydrogen atoms, and optionally of oxygen or nitrogen atoms, and not comprising any silicon or fluorine atoms. The hydrocarbon-based oil is thus distinct from a silicone oil or a fluoro oil.
The hydrocarbon-based oil may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
The term "immiscible” more particularly means that the mixing of the same amount of water and oil, after stirring, does not result in a stable solution comprising only a single phase, under the abovementioned temperature and pressure conditions. Observation is performed by eye or using a phase-contrast microscope, if necessary, on 100 g of mixture obtained after sufficient stirring with a Rayneri blender to produce a vortex within the mixture (as a guide, 200 to 1000 rpm), the resulting mixture being left to stand, in a closed flask, for 24 hours at room temperature before observation.
Polar non-volatile hydrocarbon-based oils
In particular, the non-volatile polar hydrocarbon-based oil(s) are chosen from C10-C26 alcohols; optionally hydroxylated monoesters, diesters and triesters of a C2-C8 monocarboxylic or polycarboxylic acid and of a C2-C8 alcohol; esters of a C2-C8 polyol and of one or more C2-C8 carboxylic acids; ester oils containing at least 17 carbon atoms, in particular containing between 17 and 70 carbon atoms; hydrogenated plant oils; sucrose esters; vinylpyrrolidone/l -hexadecene copolymers; oils comprising at least one carbonate function; mixtures thereof.
As regards the ester oils containing at least 17 carbon atoms, mention may be made of monoesters, diesters or triesters.
The ester oils may be hydroxylated or non-hydroxylated.
More particularly, these oils are chosen from:
- C10-C26 alcohols, preferably monoalcohols;
More particularly, the C10-C26 alcohols are saturated or unsaturated, and branched or unbranched, and comprise from 10 to 26 carbon atoms.
Advantageously, the C10-C26 alcohols are fatty alcohols, which are preferably branched when they comprise at least 16 carbon atoms. As examples of fatty alcohols that may be used according to the invention, mention may be made of linear or branched fatty alcohols, of synthetic origin or alternatively of natural origin, for instance alcohols derived from plant materials (coconut kernel, palm kernel, palm, etc.) or animal materials (tallow, etc.).
Use may also be made of other long-chain alcohols, for instance ether alcohols or "Guerbet" alcohols.
Finally, use may also be made of certain more or less long fractions of alcohols of natural origin, for instance coconut (C12 to Cie) or tallow (Cie to Cis).
Preferably, the fatty alcohol comprises from 10 to 24 carbon atoms and more preferentially from 12 to 22 carbon atoms.
As particular examples of fatty alcohols that may preferably be used, mention may be made especially of lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecylpentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol and octyldodecanol, and mixtures thereof.
According to an advantageous embodiment of the invention, the alcohol is chosen from octyldodecanol.
- optionally hydroxylated monoesters, diesters or triesters of a C?-Cs monocarboxylic or polycarboxylic acid and of a C?-Cs alcohol.
In particular:
* optionally hydroxylated monoesters of a C2-C8 carboxylic acid and of a C2-C8 alcohol,
* optionally hydroxylated diesters of a C2-C8 dicarboxylic acid and of a C2-C8 alcohol, such as diisopropyl adipate, bis(2-ethylhexyl) adipate, dibutyl adipate, diisostearyl adipate or bis(2- ethylhexyl) succinate,
* optionally hydroxylated triesters of a C2-C8 tricarboxylic acid and of a C2-C8 alcohol, such as citric acid esters, such as trioctyl citrate, triethyl citrate, acetyl tributyl citrate or tributyl citrate.
- esters of a C2-C8 polyol and of one or more C2-C8 carboxylic acids, such as glycol diesters of monoacids, such as neopentyl glycol diheptanoate, or glycol triesters of monoacids, such as triacetin.
As non-volatile hydrocarbon-based polar oil that is suitable for use, mention may also be made of:
* monoesters comprising at least 17 carbon atoms, in particular comprising between 18 and 40 carbon atoms in total, in particular the monoesters of formula R1COOR2 in which Ri represents a saturated or unsaturated, linear or branched or aromatic fatty acid residue comprising from 4 to 40 carbon atoms and R2 represents a hydrocarbon-based chain, which is in particular branched, containing from 4 to 40 carbon atoms, on condition that Ri + R2 > 18, for instance Purcellin oil (cetostearyl octanoate), isononyl isononanoate, C 12 to C 15 alcohol benzoate, 2-ethylhexyl palmitate, octyldodecyl neopentanoate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, 2-octyldodecyl benzoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate or 2-octyldodecyl myristate.
Preferably, they are esters of formula R1COOR2 in which Ri represents a linear or branched fatty acid residue containing from 4 to 40 carbon atoms and R2 represents a hydrocarbon-based chain that is in particular branched, containing from 4 to 40 carbon atoms, Ri and R2 being such that Ri + R2 > 17.
Even more particularly, the ester comprises between 17 and 40 carbon atoms in total.
Preferred monoesters that may be mentioned include isononyl isononanoate, oleyl erucate and/or 2-octyldodecyl neopentanoate;
* monoesters of a fatty acid comprising at least 17 carbon atoms, and in particular containing from 18 to 22 carbon atoms, and of diols. They may in particular be esters of lanolic acid, oleic acid, lauric acid or stearic acid, and of diols, for instance propylene glycol monoisostearate.
* diesters comprising at least 17 carbon atoms, which diesters are optionally hydroxylated, linear or branched, saturated, unsaturated or aromatic diesters especially comprising between 17 and 60 carbon atoms in total, in particular between 17 and 50 carbon atoms in total. Use may thus be made more particularly of optionally hydroxylated diesters of dicarboxylic acid and of saturated or unsaturated monoalcohols, preferably such as diisostearyl malate. Use may also be made of diesters of glycol especially of C2-C5, of glycerol or of diglycerol and of linear or branched, saturated, unsaturated or aromatic monocarboxylic acids, such as neopentyl glycol dicaprate, propylene glycol dioctanoate, propylene glycol dibenzoate, diethylene glycol diisononanoate, or poly(2-glyceryl) diisostearate (especially such as the compound sold under the commercial reference Dermol DGDIS by the company Alzo).
* hydroxylated monoesters and diesters comprising at least 18 carbon atoms, preferably with a total carbon number ranging from 18 to 70, for instance poly(3 -glyceryl) diisostearate, isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate or glyceryl stearate;
* triesters comprising at least 35 carbon atoms, especially comprising between 35 and 70 carbon atoms in total, in particular such as triesters of a tricarboxylic acid, such as triisostearyl citrate, or tridecyl trimellitate, or glycol triesters of monocarboxylic acids such as polyglyceryl-2 triisostearate;
* tetraesters comprising at least 35 carbon atoms, especially with a total carbon number ranging from 35 to 70, such as pentaerythritol or polyglycerol tetraesters of a monocarboxylic acid, for instance pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetraisononanoate, glyceryl tris(2-decyl)tetradecanoate, poly(2-glyceryl) tetraisostearate or pentaerythrityl tetrakis(2-decyl)tetradecanoate;
* polyesters obtained by condensation of dimer and/or trimer of unsaturated faty acid and of diol. such as those described in patent application FR 0 853 634, in particular such as dilinoleic acid and 1 ,4-butanediol. Mention may especially be made in this respect of the polymer sold by Biosynthis under the name Viscoplast 14436H (INCI name: dilinoleic acid/butanediol copolymer), or else copolymers of polyols and of dimer diacids, and esters thereof, such as Hailucent ISDA.
* esters and polyesters of diol dimer and of monocarboxylic or dicarboxylic acid, such as esters of diol dimer and of fatty acid and esters of diol dimer and of dicarboxylic acid dimer, in particular which may be obtained from a dicarboxylic acid dimer derived in particular from the dimerization of an unsaturated fatty acid especially of Cx to C34, especially of C12 to C22, in particular of Ci6 to C20 and more particularly of Cis, such as esters of dilinoleic diacids and of dilinoleic diol dimers, for instance those sold by the company Nippon Fine Chemical under the trade names Lusplan DD-DA5® and DD-DA7®.
* Polyesters resulting from the esterification of at least one hydroxylated carboxylic acid triglyceride by an aliphatic monocarboxylic acid and by an aliphatic dicarboxylic acid, which is optionally unsaturated, such as the succinic acid and isostearic acid castor oil sold under the reference Zenigloss by Zenitech.
* hydrocarbon-based plant oils such as fatty acid triglycerides (which are liquid at room temperature), especially of fatty acids containing from 7 to 40 carbon atoms, such as heptanoic or octanoic acid triglycerides or jojoba oil; mention may be made in particular of saturated triglycerides such as caprylic/capric triglyceride and mixtures thereof, for instance the product sold under the reference Myritol 318 from Cognis, glyceryl triheptanoate, glyceryl trioctanoate, and C18-36 acid triglycerides such as those sold under the reference Dub TGI 24 by Stearinerie Dubois, and unsaturated triglycerides such as castor oil, olive oil, ximenia oil or pracaxi oil.
* sucrose esters, preferably chosen from hydrocarbon-based esters of sucrose and of a C2-C6 carboxylic acid, in particular those chosen from mixtures of esters of acetic acid and of isobutyric acid with sucrose, preferably sucrose diacetate hexakis(2-methylpropanoate), especially the compound whose INCI name is Sucrose acetate isobutyrate (sold especially under the reference Sustane SAIB Food Grade Kosher by the company Eastman Chemicals) and the compounds of INCI name Sucrose polysoyate sold under the reference Crodaderm S by the company Croda, sucrose polybehenate sold under the reference Crodaderm B by the company Croda, sucrose polycottonseedate sold under the reference Crodaderm C by the company Croda; and mixtures thereof.
- vinylpyrrolidone/l -hexadecene copolymers, for instance the product sold under the name Antaron V-216 (also known as Ganex V216) by the company ISP.
- dialkyl carbonates, the two alkyl chains possibly being identical or different, such as the dicaprylyl carbonate sold under the name Cetiol CC® by Cognis.
- and mixtures thereof. In accordance with a particular embodiment of the invention, if the composition comprises at least one polar hydrocarbon-based oil chosen from C10-C26 alcohols, preferably monoalcohols; optionally hydroxylated monoesters, diesters and triesters of a C2-C8 monocarboxylic or polycarboxylic acid and of a C2-C8 alcohol; esters of a C2-C8 polyol and of one or more C2-C8 carboxylic acids; alone or as mixtures, then their content is preferably less than 10% by weight, relative to the weight of the composition. More particularly, their content is less than 5% by weight and even more preferentially less than 2% by weight relative to the weight of the composition.
In accordance with an even more preferred embodiment of the invention, the composition according to the invention does not comprise any polar hydrocarbon-based oil of this type.
Non-volatile apolar hydrocarbon-based oils
The non-volatile apolar hydrocarbon-based oil(s) are more particularly chosen from compounds comprising only carbon and hydrogen atoms (hydrocarbons).
Said linear or branched oils may be of mineral or synthetic origin, for instance:
- liquid paraffin or derivatives thereof,
- squalane,
- isoeicosane,
- naphthalene oil,
- hydrogenated or non-hydrogenated polybutenes, for instance Indopol H-100, Indopol H-300 or Indopol H-1500 sold or manufactured by the company Amoco,
- polyisobutenes and hydrogenated polyisobutenes, for instance the Parleam® products sold by the company Nippon Oil Fats, Panalane H-300 E sold by the company Amoco, Viseal 20000 sold by the company Synteal, Rewopal PIB 1000 sold by the company Witco or Parleam Lite sold by NOF Corporation,
- decene/butene copolymers and polybutene/polyisobutene copolymers, especially Indopol L- 14,
- polydecenes and hydrogenated polydecenes, for instance Puresyn 10, Puresyn 150 or Puresyn 6 sold by ExxonMobil Chemical,
- and mixtures thereof.
If the composition comprises at least one polar or apolar non-volatile hydrocarbon-based oil, the content of such oils is advantageously between 2% and 35% by weight, preferably from 8% to 30% by weight, relative to the weight of the composition.
In accordance with a more particular embodiment of the invention, if the composition contains any, the content of non-volatile hydrocarbon-based oil(s) is such that the non-volatile silicone oil(s)/second non-volatile hydrocarbon-based oil(s) weight ratio is greater than 1, preferably greater than 2.
VOLATILE OILS The composition according to the invention may optionally comprise at least one volatile oil, more particularly chosen from hydrocarbon-based or silicone volatile oils.
The term "volatile oil" means an oil with a non-zero vapour pressure, at room temperature (25°C), ranging in particular from 2.66 Pa to 40 000 Pa, in particular ranging up to 13 000 Pa and preferably up to 1300 Pa.
The volatile hydrocarbon-based oils are preferably chosen from apolar hydrocarbon-based oils and may in particular be chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms and mixtures thereof, and especially:
-branched C8-Ci6alkanes such as Cx-Cirisoalkancs (also known as isoparaffins), isododecane, isodecane and isohexadecane, and, for example, the oils sold under the trade name lsopar or Permethyl,
- linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane- tridecane mixture (Cetiol UT), the mixtures of n-undecane (Cl 1) and of n-tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis, and
- mixtures thereof.
The volatile silicone oil may be chosen from linear, branched or cyclic silicone oils, such as polydimethylsiloxanes (PDMSs) containing from 3 to 7 silicon atoms.
Examples of such oils that may be mentioned include octyl trimethicone, hexyl trimethicone, methyl trimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethyltetrasiloxane, polydimethylsiloxanes such as those sold under the reference DC 200 (1.5 cSt - 1.5 mm2/s), DC 200 (5 cSt - 5 mm2/s) or DC 200 (3 cSt - 3 mm2/s) by Dow Coming or KF 96 A from Shin-Etsu; alone or as mixtures. lf the composition comprises any, the content of volatile oil(s) is more particularly such that the silicone resin/volatile oil(s) weight ratio is greater than 1.
More particularly, if the composition comprises any, the content of volatile oil(s) is less than 30% by weight relative to the weight of the composition.
Preferably, if the composition comprises any, the content of volatile hydrocarbon-based or silicone oil(s) ranges from 0.1% to less than 30% by weight, more particularly from 0.5% to 20% by weight and preferably from 2% to 20% by weight, relative to the weight of the composition.
SURFACTANTS
The composition according to the invention advantageously comprises at least one surfactant chosen from ionic, in particular anionic, hydrocarbons, or nonionic hydrocarbons, from silicone surfactants, preferably nonionic silicone surfactants, and also mixtures thereof. Preferably, the composition comprises at least one nonionic hydrocarbon-based surfactant. More particularly, it comprises at least one nonionic hydrocarbon-based surfactant with an HLB of greater than or equal to 8.
According to this variant, the composition may comprise at least one additional surfactant chosen from nonionic hydrocarbon-based surfactants with an HLB of less than 8, or from anionic hydrocarbon-based surfactants, and also mixtures thereof.
The composition may optionally comprise at least one nonionic hydrocarbon-based surfactant with an HLB of greater than or equal to 8 and at least one silicone surfactant, preferably a nonionic silicone surfactant. Such emulsions may optionally comprise at least one additional surfactant chosen from nonionic hydrocarbon-based surfactants with an HLB of less than 8 and/or anionic hydrocarbon-based surfactants.
More particularly, the surfactant content ranges from 0.1% to 15% by weight and preferably from 0.5% to 10% by weight relative to the weight of the composition.
It should be noted that the contents and the nature of the surfactants is such that the composition is preferably in the form of an oil- in- water emulsion.
Nonionic hydrocarbon-based surfactants
Nonionic hydrocarbon-based surfactant with a high HLB
According to the invention, the composition may comprise at least one nonionic hydrocarbon- based surfactant with an HLB value of greater than or equal to 8 (HLB: hydrophilic- lipophilic balance; within the Griffin meaning as defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249- 256), and preferably greater than 8.
The nonionic surfactant(s) may be chosen especially from alkyl and polyalkyl esters of polyethylene oxide), alkyl and polyalkyl ethers of poly(ethylene oxide), optionally polyoxyethylenated alkyl and polyalkyl esters of sorbitan, optionally polyoxyethylenated alkyl and polyalkyl ethers of sorbitan, alkyl and polyalkyl glycosides or polyglycosides, in particular alkyl and polyalkyl glucosides or polyglucosides, alkyl and polyalkyl esters of sucrose, optionally polyoxyethylenated alkyl and polyalkyl esters of glycerol, and optionally polyoxyethylenated alkyl and polyalkyl ethers of glycerol, and mixtures thereof.
1) Alkyl and polyalkyl esters of poly(ethylene oxide) that are preferably used are those containing at least one C8-C30 alkyl radical, with a number of ethylene oxide (EO) units ranging from
2 to 200. Mention may be made, for example, of (INCI name) PEG-20 stearate, PEG-40 stearate, PEG- 100 stearate, PEG-20 laurate, PEG-8 laurate, PEG-40 laurate, PEG- 150 distearate, PEG-7 cocoate, PEG-9 cococate, PEG-8 oleate, PEG- 10 oleate and PEG-40 hydrogenated castor oil.
2) Alkyl and polyalkyl ethers of poly(ethylene oxide) that are preferably used are those containing at least one C8-C30 alkyl radical, with a number of ethylene oxide (EO) units ranging from
3 to 200 (i.e. polyethylene oxide) alcohols - or polyoxyethylenated alcohols, and the poly(ethylene oxide) ethers - or polyoxyethylenated ethers). Mention may be made, for example, of laureth-3, laureth-4, laureth-7, laureth-23, ceteth-5, ceteth-7, ceteth-l5, ceteth-23, oleth-5, oleth-7, oleth-lO, oleth-l2, oleth-20, oleth-50, phytosterol 30 EO, steareth-6, steareth-20, steareth-2l, steareth-40, steareth-lOO, beheneth 100, ceteareth-7, ceteareth-lO, ceteareth-l5, ceteareth-25, pareth-3, pareth- 23, C12-15 pareth-3, C12-13 pareth-4, C12-13 pareth-23, trideceth-4, trideceth-5, trideceth-6, trideceth-7 and trideceth-lO, and mixtures thereof.
3) Optionally polyoxyethylenated alkyl and polyalkyl esters of sorbitan that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100. Mention may be made, for example, of sorbitan laurate, sorbitan laurate 4 EO, sorbitan laurate 20 EO (polysorbate 20), sorbitan palmitate 20 EO (polysorbate 40), sorbitan stearate 20 EO (polysorbate 60), sorbitan oleate 20 EO (polysorbate 80) and sorbitan trioleate 20 EO (polysorbate 85).
4) Optionally polyoxyethylenated alkyl and polyalkyl ethers of sorbitan that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100.
5) Alkyl and polyalkyl glucosides or polyglucosides that are preferably used are those containing an alkyl group comprising from 6 to 30 carbon atoms and preferably from 6 to 18 or even from 8 to 16 carbon atoms, and containing a glucoside group preferably comprising from 1 to 5 and especially 1, 2 or 3 glucoside units. The alkylpolyglucosides may be chosen, for example, from decylglucoside (alkyl-GVC -polyglucosidc (1.4)), for instance the product sold under the name Mydol 10® by the company Kao Chemicals or the product sold under the name Plantacare 2000 UP® by the company Henkel and the product sold under the name Oramix NS 10® by the company SEPPIC; caprylyl/capryl glucoside, for instance the product sold under the name Plantacare KE 3711® by the company Cognis or Oramix CG 110® by the company SEPPIC; laurylglucoside, for instance the product sold under the name Plantacare 1200 UP® by the company Henkel or Plantaren 1200 N® by the company Henkel; cocoglucoside, for instance the product sold under the name Plantacare 818 UP® by the company Henkel; caprylylglucoside, for instance the product sold under the name Plantacare 810 UP® by the company Cognis; and mixtures thereof.
6) Examples of alkyl and polyalkyl esters of sucrose that may be mentioned are Crodesta Fl50, sucrose monolaurate sold under the name Crodesta SL 40, and the products sold by Ryoto Sugar Ester, for instance sucrose palmitate sold under the reference Ryoto Sugar Ester P1670, Ryoto Sugar Ester LWA 1695 or Ryoto Sugar Ester 01570. Sucrose monooleate, monomyristate and monostearate are also suitable for use.
7) Optionally polyoxyethylenated alkyl and polyalkyl esters of glycerol that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100 and a number of glycerol units ranging from 1 to 30. Mention may be made, for example, of hexaglyceryl monolaurate, PEG-30 glyceryl stearate, polyglyceryl-2 laurate, polyglyceryl- 10 laurate, polyglyceryl- 10 stearate, polyglyceryl- 10 oleate, PEG-7 glyceryl cocoate and PEG-20 glyceryl isostearate.
8) Optionally polyoxyethylenated alkyl and polyalkyl ethers of glycerol that are preferably used are those with a number of ethylene oxide (EO) units ranging from 0 to 100 and a number of glycerol units ranging from 1 to 30. Examples that may be mentioned include Nikkol Batyl Alcohol 100 and Nikkol Chimyl Alcohol 100.
Nonionic hydrocarbon-based surfactants of low HLB
The composition according to the invention may comprise at least one additional nonionic hydrocarbon-based surfactant chosen in particular from surfactants with an HLB value of less than
8.
Examples of such surfactants that may especially be mentioned, alone or as mixtures, include:
1) (C8-C3o)alkyl ethers of polyethylene oxide) preferably such as those with a number of ethylene oxide (EO) units ranging from 2 to 4. Examples that may especially be mentioned include laureth- 2; steareth-2; oleth-2; deth-3; ceteth-2; ceteareth-3; trideceth-3;
2) (C8-C3o)alkyl and (C8-C3o)polyalkyl esters of ethylene oxide, of propylene oxide, of polyethylene oxide) or of polypropylene oxide), preferably such as those with a number of ethylene oxide (EO) units ranging from 1 to 5, with for example glycol distearate, glycol stearate, PEG-2 oleate; PEG-3 oleate; PEG-4 dilaurate, propylene glycol isostearate; PEG-2.5 castor oil; PEG-3 castor oil;
3) polyoxyalkylenated C12-C20 fatty acid polyesters, which are preferably polyhydroxylated, containing from 4 to 50 mol of ethylene oxide, having water-in-oil emulsifying properties ln particular, these polymers are block polymers, preferably of ABA structure, comprising poly(hydroxylated ester) blocks and polyethylene glycol blocks. The fatty acid of said emulsifying polymer as defined above preferably contains from 14 to 18 carbon atoms. The esters may be chosen in particular from oleates, palmitates or stearates. The polyethylene glycol blocks of said emulsifying polymer as defined above preferably comprise from 20 to 40 mol of ethylene oxide. A polymeric surfactant that is particularly suitable for preparing the compositions of the invention is polyethylene glycol dipolyhydroxystearate containing 30 EO, sold under the trade name Arlacel P 135 by the company Croda.
4) (C8-C3o)alkyl and (C8-C3o)polyalkyl esters of sorbitan, for instance sorbitan trioleate, sorbitan sesquioleate, sorbitan oleate, sorbitan palmitate, sorbitan stearate, sorbitan isostearate, mixtures of sorbitan stearate and sucrose cocoate (Arlacel 2121 sold by the company Croda), or sorbitan glyceryl isostearate; sorbitan isostearate mixed with hydrogenated castor oil, stearic acid and white wax (Arlacel 986 sold by the company Croda), and mixtures thereof.
5) (C8-C3o)alkyl and poly(C8-C3o)alkyl esters of (poly)glycerol that are preferably used are those with a number of glycerol units ranging from 1 to 4. Mention may be made, for example, of polyglyceryl-4 isostearate (lsolan Gl 34 sold by the company Evonik Goldschmidt); polyglyceryl-2 sesquiisostearate, polyglyceryl-3 diisostearate (Lameform TG1 sold by the company Cognis), glyceryl isostearate, glyceryl stearate, glyceryl laurate, alone or as mixtures.
Ionic hydrocarbon-based surfactants
The composition may optionally comprise one or more ionic, in particular anionic, surfactants, which are preferably hydrocarbon-based. These surfactants may be chosen from salts of alkali metals especially such as sodium or potassium, or alternatively of primary or secondary amine or alkanolamine, which is in particular of C2-C4, of the following compounds:
These compounds generally comprise from 8 to 30 carbon atoms, in particular from 8 to 20 carbon atoms, in their longest hydrocarbon-based chain, and are saturated or unsaturated, and linear, branched or cyclic. They may also comprise up to 20 oxyalkylene units, preferably up to 15 units (in particular oxy ethylene units):
alkyl ether sulfates,
salts of fatty acids especially of C8-C20, in particular monocarboxylic salts;
carboxylates such as salts of N-acylamino acids, alkyl glycol carboxylates, ether carboxylates, amido ether carboxylates;
amino acid salts, in particular sarcosinates, alaninates, glutamates, aspartates and glycinates, sulfonates, such as alpha-olefin sulfonates, in particular alkanolamine or alkali metal (especially such as sodium) salts of dodecylbenzene sulfonate,
isethionates, such as acyl isethionates,
taurates, such as N-acyl methyl taurates, in particular N-acyl methyl taurates,
sulfosuccinates, such as alkyl sulfosuccinates, especially dioctyl sulfosuccinate salts, alkylsulfoacetates,
phosphates and alkyl phosphates,
polypeptides obtained, for example, by condensation of a fatty chain onto amino acids from cereals and especially from wheat and oat.
Preferably, when it comprises any, the composition comprises not more than 2.5% by weight, more particularly not more than 1.5% by weight, preferably not more than 1% by weight, or even not more than 0.8% by weight, relative to the weight of the composition, of salts of alkali metals, of amine or alkanolamine, or of fatty acids, especially of Cx-C'20.
Silicone surfactants
The composition according to the invention may optionally comprise at least one silicone surfactant, which is preferably nonionic.
The silicone surfactant(s) may be chosen from compounds with an HLB value of greater than or equal to 8, or less than 8.
Among the nonionic silicone surfactants that are suitable for use, mention may be made of alkyl or alkoxy dimethicone copolyols bearing an alkyl or alkoxy chain on the side or at the end of the silicone backbone, containing, for example, from 6 to 22 carbon atoms; dimethicone copolyols, which are more particularly oxypropylenated and/or oxyethylenated poly dimethyl methyl siloxanes, branched (poly)glycerolated polysiloxanes, and also crosslinked elastomeric solid organopolysiloxanes comprising at least one oxyalkylene group, and mixtures thereof. Examples of alkyl or alkoxy dimethicone copolyols that may be mentioned include the compounds of formula (I) below:
Figure imgf000034_0001
in which:
- PE represents (-C2H40)x-(C3H60)y-R, R being chosen from a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms, x ranging from 0 to 100 and y ranging from 0 to 80, x and y not simultaneously being 0; preferably, R represents a hydrogen atom;
- m ranging from 1 to 40, preferably from 1 to 10;
- n ranging from 10 to 200, preferably from 10 to 100;
- 0 ranging from 1 to 100, preferably from 1 to 30;
- p ranging from 5 to 21, more particularly from 7 to 21 ;
- q ranging from 0 to 4, preferably from 1 to 3.
As examples of dimethicone copolyols, use may be made of those corresponding more particularly to formula (II) below:
Figure imgf000034_0002
in which:
- Ri, R2 and R3, independently of each other, represent a Ci-Ce alkyl radical or a radical -(CEb (OCH2CH2)y-(OCH2CH2CH2)z-OR4, at least one radical Ri, R2 or R3 not being an alkyl radical; R4 being a hydrogen, a C 1-C3 alkyl radical or a C2-C4 acyl radical;
- A is an integer ranging from 0 to 200;
- B is an integer ranging from 0 to 50; on condition that A and B are not simultaneously equal to zero;
- x is an integer ranging from 1 to 6;
- y is an integer ranging from 1 to 30; and
- z is an integer ranging from 0 to 30, preferably ranging from 0 to 20.
Among the silicone surfactants that are particularly preferred, mention may be made of:
- dimethicone copolyols, for instance those sold under the names KF-6015 (PEG-3 dimethicone), KF-6016 (PEG-9 methyl ether dimethicone), KF-6017 (PEG-10 dimethicone), KF- 6028 (PEG-9 polydimethylsiloxyethyl dimethicone), KF-6050 L (PEG/PPG 18/18 dimethicone in cyclopentasiloxane), X-22-6711D (PEG/PPG 18/18 dimethicone in dimethicone), sold by the company Shin-Etsu; the dimethicone copolyols sold under the names Xiameter OFX-0193 Fluid (PEG- 12 dimethicone); Dow Coming 3225C® (PEG/PPG- 18/18 dimethicone in a mixture of cyclotetrasiloxane and cyclopentasiloxane), DC 5225 C Formulation Aid (PEG/PPG- 18/18 dimethicone in cyclopentasiloxane); or the product sold under the name SF 1528 GE (mixture of PEG/PPG-20/15 dimethicone and of cyclopentasiloxane) by Momentive Performance Materials.
Use may be made of the product Abil Care 85 (bis-PEG/PPG-l6/l6 PEG/PPG- 16/16 dimethicone as a mixture with capric/caprylic acid triglyceride).
Use may also be made of alkyl dimethicone copolyols such as lauryl PEG/PPG- 18/18 methicone (which is more particularly an alkoxylated derivative of lauryl methicone containing on average 18 mol of ethylene oxide and 18 mol of propylene oxide, sold under the name Dow Coming 5200 Formulation Aid by the company Dow Coming; cetyl PEG/PPG-10/1 dimethicone (which is more particularly a copolymer of cetyl dimethicone and of an alkoxylated derivative of dimethicone containing on average 10 mol of ethylene oxide and 1 mol of propylene oxide) such as the product sold under the name Abil EM 90 by the company Evonik Goldschmidt and also the mixture of cetyl PEG/PPG- 10/1 dimethicone, of polyglyceryl isostearate (4 mol) and of hexyl laurate sold under the name Abil WE 09 by the company Evonik Goldschmidt.
Use may also be made of polyglyceryl-3 disiloxane dimethicone (KF 6100 from Shin-Etsu).
Emulsion surfactants that may also be mentioned include, in particular for water-in-oil emulsions, crosslinked elastomeric solid organopolysiloxanes comprising at least one oxyalkylene group, such as the products obtained according to the procedure of Examples 3, 4 and 8 of US-A-5 412 004 and the examples of US-A-5 811 487, especially the product of Example 3 (synthetic example) of patent US-A-5 412 004, and such as the product sold under the references KSG 21 and KSG-210 by the company Shin-Etsu.
Preferably, the C8-C22 alkyl dimethicone copolyol that is used is cetyl dimethicone copolyol, especially the product whose INCI name is Cetyl PEG/PPG- 10/1 Dimethicone, for instance the product sold under the name Abil EM-90 by the company Evonik Goldschmidt. Use may also be made of a mixture of cetyl dimethicone copolyol with polyglyceryl-4 isostearate and hexyl laurate, for instance the product sold under the name Abil WE-09 by the company Evonik Goldschmidt (the INCI name is polyglyceryl-4 isostearate (and) hexyl laurate (and) cetyl PEG/PPG-10/1 dimethicone).
Advantageously, if they are present, the silicone surfactant(s) are chosen from dimethicone copolyols, the alkyl dimethicone copolyols described previously, alone or as mixtures.
More particularly, the silicone surfactant(s) are chosen from C8-C22 alkyl dimethicone copolyols such as cetyl dimethicone copolyol (INCI name: Cetyl PEG/PPG-10/1 Dimethicone), dimethicone copolyols, for instance PEG dimethicone, PEG/PPG 18/18 dimethicones (INCI name), and also mixtures thereof. Use may also be made of a mixture of cetyl dimethicone copolyol with polyglyceryl-4 isostearate and hexyl laurate, for instance the product sold under the name Abil WE- 09 by the company Evonik Goldschmidt (the INCI name is polyglyceryl-4 isostearate (and) hexyl laurate (and) cetyl PEG/PPG-10/1 dimethicone).
AQUEOUS PHASE
As indicated previously, the composition according to the invention is in the form of an emulsion in which the aqueous phase constitutes the continuous phase of the emulsion.
The term "composition with an aqueous continuous phase" more particularly means that a pH value can be measured for the composition with a suitable electrode (for example an MPC227 conductimeter from Mettler Toledo).
Preferably, the composition according to the invention comprises at least 10% by weight of water, relative to the weight of the composition.
Advantageously, the water content is between 10% and 70% by weight, preferably between 15% and 65% by weight, in particular between 20% and 60% by weight, relative to the weight of the composition.
The composition in accordance with the invention may comprise, besides water, at least one water-soluble solvent.
In the present invention, the term“water-soluble solvent” denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50% by weight at 25°C and atmospheric pressure).
The water-soluble solvents that may be used in the compositions according to the invention may also be volatile.
Among the water-soluble solvents that may be used in the compositions in accordance with the invention, mention may be made especially of lower monoalcohols containing from 1 to 5 carbon atoms, such as ethanol and isopropanol, C3 and C4 ketones and C2-C4 aldehydes.
Preferably, the composition according to the invention comprises a total content of monoalcohols comprising between 2 and 8 carbon atoms of between 0 and 15% by weight (limits inclusive) relative to the weight of the composition.
Preferably, the composition according to the invention comprises a total content of monoalcohols comprising between 2 and 8 carbon atoms of between 0 and 10% by weight (limits inclusive), advantageously between 0 and 5% by weight (limits inclusive) relative to the weight of the composition.
Preferably, the composition according to the invention is free of monoalcohols comprising between 2 and 8 carbon atoms.
Preferably, said monoalcohol(s) comprising between 2 and 8 carbon atoms are chosen from ethanol, butanol, methanol and isopropanol.
C2-Cs POLYOL The composition may optionally comprise at least one polyol chosen more particularly from saturated or unsaturated, linear or branched C2-C8 and preferably C3-C6 polyol, comprising from 2 to 6 hydroxyl groups.
Preferably, the polyol is chosen from glycerol, propylene glycol, 1, 3-butylene glycol, dipropylene glycol, dibutylene glycol and diglycerol, and mixtures thereof.
Preferably, if the composition comprises any, the polyol content represents less than 10% by weight, more particularly from 0.05% to less than 10% by weight and preferably from 0.1% to less than 10% by weight relative to the weight of the composition. According to an even more advantageous mode, the content of polyol ranges from 1% to 6% by weight relative to the weight of the composition.
HYDROPHTT JC THICKENERS
The composition according to the invention may comprise at least one hydrophilic thickening polymer (also known as an aqueous-phase-thickening polymer).
More particularly, this thickening polymer may be chosen from:
- homopolymers or copolymers of acrylic or methacrylic acid or salts thereof and esters thereof. Examples that may be mentioned in particular include the products sold under the names Versicol F or Versicol K by the company Allied Colloid, Ultrahold 8 by the company Ciba-Geigy, Cosmedia SP by the company BASF, Lecigel (mixture of sodium acrylate copolymer/lecithin) by the company Lucas Meyer Cosmetics; polyacrylic acids of Synthalen K type, and salts, especially sodium salts, of polyacrylic acid (corresponding to the INCI name sodium acrylate copolymer) and more particularly a crosslinked sodium polyacrylate (corresponding to the INCI name sodium acrylate copolymer (and) caprylic/capric triglyceride) sold under the name Luvigel EM.
Mention may also be made of polyacrylic acid/alkyl acrylate copolymers, preferably modified or unmodified carboxyvinyl polymers, most particularly acrylate/C 10-C30-alkyl acrylate copolymers (INCI name: Acrylate/Cl 0-30 Alkyl Acrylate Crosspolymer) such as the products sold by the company Lubrizol under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382, Carbopol EDT 2020 and even more preferentially Pemulen TR-2; copolymers of methacrylic acid, of methyl methacrylate, of methylstyrene isocyanate and of PEG-40 behenate (INCI name: polyacrylate-3) (Viscophobe DB 1000 sold by the company Dow),
- copolymers of acrylic acid and of acrylamide sold in the form of the sodium salt thereof under the Reten names by the company Hercules, the sodium polymethacrylate sold under the name Darvan No. 7 by the company Vanderbilt, and the sodium salts of polyhydroxycarboxylic acids sold under the name Hydagen F by the company Henkel,
- homopolymers and copolymers based on acrylamidopropanesulfonic acid, for instance:
- polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked, for example the product Hostacerin AMPS sold in particular by the company Clariant, - copolymers of acrylamidomethylpropanesulfonic acid/acrylamide for example of Sepigel or Simulgel type sold especially by the company SEPPIC,
- polyoxyethylenated acrylamidomethylpropanesulfonic acid/alkyl methacrylate copolymers (crosslinked or non-crosslinked) of the type such as, inter alia, Aristoflex HMS and Aristoflex TAC, sold by the company Clariant,
- copolymers of acrylamidomethylpropanesulfonic acid and of hydroxy ethyl acrylate, for instance the acrylamidomethylpropanesulfonic acid/hydroxyethyl acrylate copolymer especially such as the product used in the commercial product sold under the name Simulgel NS by the company SEPPIC, or the acrylamidomethylpropanesulfonic acid/hydroxyethyl acrylate copolymer especially such as the product used in the commercial product sold under the name Sepinov EMT 10 sold by the company SEPPIC (INCI name: Hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer);
- copolymers of acrylamidomethylpropanesulfonic acid and of vinylpyrrolidone, such as the product Aristoflex AVC (ammonium acryloyldimethyl taurate/VP copolymer in water) sold by the company Clariant;
- and mixtures thereof.
Other examples of hydrophilic gelling polymers that may be mentioned include:
- anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;
- cellulose polymers, in particular (Ci-C3)hydroxyalkylcelluloses, chosen from hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose; carboxymethylcellulose, and also quatemized celluloses derivatives;
- vinyl polymers, for instance polyvinylpyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, the copolymer of vinyl acetate and of crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and of caprolactam; polyvinyl alcohol;
- optionally modified polymers of natural origin, such as galactomannans and derivatives thereof, for instance konjac gum, gellan gum, locust bean gum, fenugreek gum, karaya gum, gum tragacanth, gum arabic, acacia gum, guar gum, hydroxypropyl guar, hydroxypropyl guar modified with sodium methylcarboxylate groups (Jaguar XC97-1, Rhodia), xanthan gum and derivatives thereof;
- alginates and carrageenans;
- muccopolysaccharides such as hyaluronic acid;
- and mixtures thereof.
According to a preferred embodiment, the thickening polymer is chosen from copolymers of acrylamidomethylpropanesulfonic acid and in particular from copolymers of acrylamidomethylpropanesulfonic acid and of hydroxyethyl acrylate, or mixtures thereof. Preferably, when the composition contains any, the content of hydrophilic thickening polymer is between 0.01% and 1.5% by weight, preferably between 0.05% and 1% by weight and advantageously 0.1% to 0.8%, relative to the weight of the composition.
DYESTUFFS
A composition according to the invention preferably comprises at least one dyestuff. Preferably, it is chosen from water-soluble or water-insoluble, liposoluble or non-liposoluble, organic or mineral dyestuffs, and materials with an optical effect, and mixtures thereof.
For the purposes of the present invention, the term "dyestuff means a compound that is capable of producing a coloured optical effect when it is formulated in sufficient amount in a suitable cosmetic medium.
Water-soluble dyestuffs
The water-soluble dyestuffs used according to the invention are more particularly water- soluble dyes.
For the purposes of the invention, the term "water-soluble dye" means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water-miscible solvents and which is capable of imparting colour. In particular, the term "water-soluble" is intended to characterize the capacity of a compound to be dissolved in water, measured at 25°C, to a concentration at least equal to 0.1 g/1 (production of a macroscopically isotropic, transparent, coloured or colourless solution). This solubility is in particular greater than or equal to 1 g/1.
As water-soluble dyes that are suitable for use in the invention, mention may be made in particular of synthetic or natural water-soluble dyes, for instance DC Red 6 (Lithol Rubine Na; Cl: 15850), DC Red 22 (Cl: 45380), DC Red 28 (Cl: 45410 Na salt), DC Red 30 (Cl: 73360), DC Red 33 (Cl: 17200), FDC Red 40 (Cl 16035), DC Orange 4 (Cl: 15510 Na salt), FDC Yellow 5 (Cl: 19140), FDC Yellow 6 (Cl: 15985), DC Yellow 8 (Cl: 45350 Na salt), FDC Green 3 (Cl: 42053), DC Green 5
(Cl: 61570), FDC Blue 1 (Cl: 42090).
As non-limiting illustrations of sources of water-soluble dyestuff(s) that may be used in the context of the present invention, mention may be made in particular of those of natural origin, such as extracts of cochineal carmine, of beetroot, of grape, of carrot, of tomato, of annatto, of paprika, of henna, of caramel and of curcumin.
Thus, the water-soluble dyestuffs that are suitable for use in the invention are especially carminic acid, betanin, anthocyans, enocyanins, lycopene, bixin, norbixin, capxanthin, capsorubin, flavoxanthin, lutein, cryptoxanthin, rubixanthin, violaxanthin, riboflavin, rhodoxanthin, cantaxanthin and chlorophyll, and mixtures thereof.
They may also be copper sulfate, iron sulfate, water-soluble sulfopolyesters, rhodamine, betaine, methylene blue, the disodium salt of tartrazine and the disodium salt of fuchsin. Some of these water-soluble dyestuffs are especially permitted for food use. Representatives of these dyes that may be mentioned more particularly include dyes of the carotenoid family, referenced under the food codes E120, E162, E163, El60a-g, El50a, E101, E100, E140 and E141.
Liposoluble dyestuffs
Among the liposoluble dyes, mention may be made particularly of dyes of fluoran type, for instance Sudan Red, FDC Red 4, DC Red 17, Red 21, Red 27, DC Green 6, b-carotene, Sudan Brown, Yellow 10, DC Yellow 11, DC Violet 2, DC Orange 4, DC Orange 5 and quinoline yellow, or mixtures thereof.
Pigments
The term“pigments” should be understood as meaning white or coloured, inorganic (mineral) or organic particles, which are insoluble in the medium, and which are intended to colour and/or opacify the composition and/or deposit produced with the composition.
The pigments may be chosen from mineral pigments, organic pigments and composite pigments (i.e. pigments based on mineral and/or organic materials).
The pigments may be chosen from monochromic pigments, lakes, nacres, and pigments with an optical effect, for instance reflective pigments and goniochromatic pigments.
The mineral pigments may be chosen from metal oxide pigments, chromium oxides, iron oxides, titanium dioxide, zinc oxides, cerium oxides, zirconium oxides, manganese violet, Prussian blue, ultramarine blue and ferric blue, and mixtures thereof.
The organic pigments may be, for example:
- cochineal carmine,
- organic pigments of azo dyes, anthraquinone dyes, indigoid dyes, xanthene dyes, pyrene dyes, quinoline dyes, triphenylmethane dyes or fluoran dyes,
- organic lakes or insoluble sodium, potassium, calcium, barium, aluminium, zirconium, strontium or titanium salts of acidic dyes such as azo, anthraquinone, indigoid, xanthene, pyrene, quinoline, triphenylmethane or fluoran dyes. These dyes generally comprise at least one carboxylic or sulfonic acid group,
- melanin-based pigments.
Among the organic pigments, mention may be made of D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11 , D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. l l, FD&C Blue No. 1, FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No. 5 and FD&C Yellow No. 6. The pigments may have undergone a hydrophobic treatment. The hydrophobic treatment agent may be chosen, for example, from silicones such as methicones, dimethicones and perfluoroalkylsilanes; fatty acids such as stearic acid; metal soaps such as aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate, perfluoroalkyl phosphates, perfluoroalkylsilanes, perfluoroalkylsilazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups, amino acids; N- acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, and mixtures thereof.
The N-acylamino acids may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid may be, for example, lysine, glutamic acid or alanine.
The term“alkyl” mentioned in the compounds cited previously especially denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.
Hydrophobic-treated pigments are described especially in patent application EP-A-l 086 683.
The pigments may also have undergone a hydrophilic treatment, for example with polyalkoxylated silicones.
It may also be envisaged to use pigments that are in a form dispersed in water, sorbitol, glycerol or glycols, alone or as mixtures, for instance the products of the Covarine, Covasorb and Covasop ranges from Sensient, the pigments of the WD series from Daito, and Worlee Base AQ from Worlee.
Nacres
For the purposes of the present patent application, the term "nacre" means coloured particles of any form, which may or may not be iridescent, in particular produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference.
Examples of nacres that may be mentioned include nacreous pigments such as titanium mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye in particular of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. They may also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.
The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.
As illustrations of nacres that may be introduced as interference pigments into the first composition, mention may be made of the gold-coloured nacres sold in particular by the company Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold in particular by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); the orange nacres sold in particular by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold in particular by the company Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold in particular by the company Engelhard under the name Copper 340A (Timica); the nacres with a red tint sold in particular by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold in particular by the company Engelhard under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold in particular by the company Engelhard under the name Sunstone GO 12 (Gemtone); the pink nacres sold in particular by the company Engelhard under the name Tan opale G005 (Gemtone); the black nacres with a gold tint sold in particular by the company Engelhard under the name Nu antique bronze 240 AB (Timica), the blue nacres sold in particular by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery tint sold in particular by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold in particular by the company Merck under the name Indian summer (Xirona), and mixtures thereof.
The content of dyestuffs is advantageously between 0.05% and 10% by weight and preferably between 0.05% and 5% by weight relative to the weight of the composition.
FILLERS
The composition according to the invention may comprise at least one filler, of organic or mineral nature.
The term“filler” should be understood as meaning colourless or white solid particles of any form, which are in an insoluble form dispersed in the medium of the composition. These particles, of mineral or organic nature, give body or rigidity to the composition and/or softness and uniformity to the makeup. They are different from dyestuffs.
Among the fillers that may be used in the compositions according to the invention, mention may be made of silica, kaolin, starch, lauroyllysine, fumed silica particles, which are optionally hydrophilic -treated, mica, talc, sericite, polyamide (Nylon®) powder, roΐn-b-alaninc powder and polyethylene powder, powders of tetrafluoroethylene polymers (Teflon®), hollow polymer microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industries), acrylic acid copolymer microspheres, silicone resin microbeads (for example Tospearls® from Toshiba), polyorganosiloxane elastomer particles, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, barium sulfate, aluminium oxides, polyurethane powders, composite fillers, hollow silica microspheres, glass or ceramic microcapsules, and metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate and magnesium myristate, and mixtures thereof. A composition used according to the invention may comprise one or more fillers in a content ranging from 0.1% to 10% by weight and in particular from 0.2% to 8% by weight relative to the weight of the composition.
T JPOPHTT JC THICKENER
The hydrophobic thickener may be chosen from mineral thickeners especially such as organophilic clays; hydrophobic fumed silicas; hydrophobic silica aerogels; from organic thickeners such as oil-gelling polymers of the block polymer type, especially triblock or star polymers, resulting from the copolymerization of at least one styrene monomer and of at least one hydrocarbon monomer bearing one or two C2-C5 ethylenic unsaturations, such as ethylene, propylene, butadiene, isoprene and/or pentadiene, such as the polymers sold under the name Kraton; polyamide resins comprising alkyl groups containing from 12 to 22 carbon atoms, such as those described in US-A-5 783 657; polysaccharide alkyl ethers, especially in which the alkyl group is of C1-C24, preferably C1-C10 and better still Ci-Ce, described especially in EP 898 958, and in particular alkyl guar gums (with a Ci- Ce alkyl group), such as those described in EP 708 114; esters of dextrin and of a fatty acid, preferably of C12-C24, in particular CM-CIS, for example dextrin palmitate and dextrin myristate; N- acylglutamides in which the acyl group is a linear or branched C8-C22 alkyl chain; preferably dialkyl N-acylglutamides, for instance lauroylglutamic acid dibutylamide or N-2-ethylhexanoyl glutamic acid dibutylamide; hydroxystearic acid; ethylenediamine stearyl dimer dilinoleate copolymer (sold, for example, under the name Oleocraft by Croda); and also mixtures thereof.
Preferably, when the composition comprises at least one hydrophobic thickener, this thickener is preferably chosen from mineral thickeners.
Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereof. Examples of such products that may be mentioned include clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also of the family of vermiculites, stevensite and chlorites. These clays may be of natural or synthetic origin. Organophilic clays are clays modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkyl aryl sulfonates and amine oxides, and mixtures thereof.
Mention may thus be made of hectorites modified with a quaternary amine, more specifically with a C 10 to C22 fatty acid ammonium halide, such as a chloride, such as hectorite modified with distearyldimethylammonium chloride (CTFA name: Disteardimonium hectorite), for instance the product sold under the name Bentone 38 V®, Bentone 38V CG or Bentone EW CE by the company Elementis, or stearalkonium hectorites, such as Bentone 27 V.
Mention may also be made of quatemium-l 8 bentonites, such as those sold under the names Bentone 34 by the company Elementis, Tixogel VP by the company United Catalyst and Claytone 40 by the company Southern Clay; stearalkonium bentonites, such as those sold under the names Tixogel LG by the company United Catalyst and Claytone AF and Claytone APA by the company Southern Clay; or quatemium-l 8/benzalkonium bentonites, such as those sold under the name Claytone HT by the company Southern Clay.
According to a preferred embodiment, the thickener is chosen from organophilic modified clays, in particular organophilic modified hectorites, in particular modified with stearylbenzyldimethylammonium halides, preferably chlorides, or with distearyldimethylammonium chloride .
The hydrophobic fumed silicas may be obtained by modification of the surface of the silica via a chemical reaction that generates a reduction in the number of silanol groups, these groups possibly being substituted especially with hydrophobic groups. The hydrophobic groups may be:
- trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as Silica silylate according to the CTFA (6th Edition, 1995) They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS-530® by the company Cabot;
- dimethylsilyloxyl or polydimethylsiloxane groups, which are especially obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as Silica dimethyl silylate according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.
Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air. They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical CO2. This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York: Academic Press, 1990.
Use will preferably be made of hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups.
Hydrophobic silica aerogels that may be mentioned, for example, include the aerogel sold under the name VM-2260 (1NC1 name: Silica silylate), by the company Dow Coming, the particles of which have a mean size of about 1000 microns and a specific surface area per unit mass ranging from 600 to 800 m2/g. Mention may also be made of the aerogels sold by the company Cabot under the references Aerogel TLD 201, Aerogel OGD 201, Aerogel TLD 203, Enova® Aerogel MT 1100 and Enova Aerogel MT 1200.
The elastomeric polyorganosiloxanes are generally partially or totally crosslinked and possibly of three-dimensional structure. The elastomeric polyorganosiloxanes combined with a fatty phase are generally in the form of a gel constituted of an elastomeric organopolysiloxane combined with a fatty phase, included in at least one hydrocarbon-based oil and/or one silicone oil. They may be chosen especially from the crosslinked polymers described in patent application EP-A-0 295 886. According to said patent application, the elastomeric organopolysiloxanes are obtained by addition reaction and crosslinking of at least: (a) one organopolysiloxane bearing at least two lower alkenyl groups per molecule;
(b) one organopolysiloxane bearing at least two hydrogen atoms linked to a silicon atom per molecule; and
(c) a platinum-type catalyst.
The hydrophobic thickener may be present in a content ranging from 0.05% to 10% by weight and preferably ranging from 0.1% to 8% by weight relative to the weight of the composition.
COMMON ADDITIVES
The composition according to the invention may also comprise any common cosmetic ingredient that may be chosen especially from waxes, pasty compounds, additional moisturizers (also known as humectants) other than the abovementioned polyols, antioxidants, fragrances, menthol or menthol derivatives, preserving agents, neutralizers, sunscreens, sweeteners, vitamins, free-radical scavengers, sequestrants, salts (magnesium sulfate, sodium chloride), pH regulators, and mixtures thereof.
ln addition, the composition according to the invention advantageously does not comprise any alkylcellulose whose alkyl residue comprises from 1 to 6 carbon atoms, more particularly from 2 to 3 carbon atoms, and more particularly does not comprise any ethylcellulose.
Needless to say, a person skilled in the art will take care to select the optional additional ingredients and/or the amount thereof such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.
The composition according to the invention can be prepared in a conventional manner, by mixing the various ingredients that compose it in the required quantities, in particular the silicone resin, preferably a silicone resin of MQ type and particularly a trimethylsiloxysilicate resin, an aqueous dispersion of film-forming polymer particles (latex or pseudolatex), preferably ionic or nonionic acrylic polymers, polyurethane polymer(s), and if appropriate, a hydrocarbon-based or silicone volatile oil.
The silicone resin may be used in powder form, in a form dissolved in a solvent, in a form conveyed in a liquid or in a form emulsified in water.
Everything previously stated about the ingredients and their contents will not be repeated here again.
Another subject of the invention is a process for making up and/or caring for keratin materials, in particular the skin and/or the lips, and more particularly the lips, which consists in applying the composition according to the invention. The composition according to the invention may be packaged in any type of device that is common in the field of fluid cosmetic compositions intended especially to be applied to the lips or the face (for instance the cheeks).
It may thus be envisaged to use devices containing a container comprising an applicator equipped with a ball (roll-on), a container of dispensing pen type, terminated with an end provided with at least one orifice through which the composition may be expelled, or alternatively terminated with a felt or with a flocked tip, or with a brush; a container comprising a dip applicator, for instance a brush.
Such devices may or may not be provided with a mechanism for dispensing the composition making it possible to expel said composition from the container to the application member, or to the support. It should be noted that this mechanism may advantageously comprise a means for metering out the composition.
The examples which follow serve to illustrate the invention without, however, limiting the scope thereof.
EXAMPLE 1
The composition whose ingredients are listed in the table below is prepared (the percentages are expressed as weight of starting material, unless otherwise indicated):
Figure imgf000046_0001
Procedure
The sodium dehydroacetate is dissolved in water with stirring using a Rayneri blender.
At 50°C, the polysorbate 60 is added to the preceding mixture, with stirring using a Rayneri blender, and the resulting mixture is allowed to cool with stirring once dissolution has taken place. At 30°C, the Red 33 is added to the preceding phase.
The styrene/acrylates/ammonium methacrylate copolymer latex is then added with stirring using a Rayneri blender.
The thickening polymer (Hostacerin AMPS) is then added with stirring until the mixture thickens and a homogeneous mixture is obtained.
The mixture of silicone resin and isododecane is then poured slowly onto the mixture obtained previously while increasing the stirring speed, and stirring is continued for 10 minutes.
Evaluation of the compositions
Composition according to the invention
A liquid direct emulsion which does not flow and which is homogeneous and stable is obtained. The composition is easy to apply to the lips.
A thin film which does not migrate into the fine lines and which does not stain the teeth is obtained.
The deposit obtained is fresh, sparingly tacky and glossy, with an intense colour.
ft has very good colour persistence on the lips and good gloss persistence and does not transfer.
Comparative composition
A liquid direct emulsion with an oily release on the surface is obtained.
The composition is difficult to apply because it is too liquid. Moreover, it is not applied homogeneously, and leaves uncolored areas on the lips.
The resulting deposit is very thin, fresh, slightly sticky. It stains the teeth but does not migrate into the fine lines ft quickly loses its initial shine to become satin.
Evaluation of the stability:
No phase separation is observed after storing in a closed bottle for one week, at 20°C.
Protocol for measuring the tack:
The composition is deposited in several stainless steel dishes 100 pm deep and is levelled off as quickly as possible. The dishes are left to dry at room temperature for one hour.
The apparatus used is a TACT2Ϊ texturometer. The clip mounted on the apparatus grips an AU4G cylinder 6 mm in diameter at the end of which is attached a smooth beige-coloured end piece made of synthetic skin, which has the same diameter and is 2 mm thick.
The end piece is cleaned with ethanol between each measurement.
Several measurements are never taken at the same place of the deposit.
The parameters of the compression tests with maintenance over time are indicated below:
Figure imgf000047_0001
The tackiness is characterized by the separation force measured during the pressure reduction (pull phase), corresponding to the integral of the curve under the time axis. This force is expressed positively in joules per square metre. EXAMPLE 2
The composition whose ingredients are listed in the table below is prepared (the percentages are expressed as weight of starting material, unless otherwise indicated):
Figure imgf000048_0001
Procedure
The sodium dehydroacetate is dissolved in water with stirring using a Rayneri blender. At 50°C, the polysorbate 60 is added to the preceding mixture, with stirring using a Rayneri blender, and the resulting mixture is allowed to cool with stirring once dissolution has taken place.
At 30°C, the Red 33 is added to the preceding phase, followed by the latex with continued stirring using a Rayneri blender.
The thickening polymer (Hostacerin AMPS) is then added with stirring until the mixture thickens without gel lumps.
The silicone resin and the isododecane are then poured slowly onto the mixture obtained previously while increasing the stirring speed, and stirring is continued for 10 minutes.
The mixture of phenyl silicone and remaining surfactants (PEG-8 isostearate and PEG- 10 dimethicone) is then poured into the preceding mixture and stirring is continued for 10 minutes.
Evaluation of the composition
A liquid homogeneous stable direct emulsion is obtained.
A thin film which does not migrate into the fine lines and which does not stain the teeth is obtained. The deposit obtained is fresh and glossy, with an intense colour. The deposit is slightly tacky.
It has very good colour persistence on the lips and good gloss persistence and does not transfer.
EXAMPLE 3
The composition whose ingredients are listed in the table below is prepared (the percentages are expressed as weight of starting material, unless otherwise indicated):
Figure imgf000049_0001
Procedure
The sodium dehydroacetate is dissolved in water with stirring using a Rayneri blender. At 50°C, the polysorbate 60 is added to the preceding mixture, with stirring using a Rayneri blender, and the resulting mixture is allowed to cool with stirring once dissolution has taken place.
At 30°C, the Red 33 is added to the preceding phase, followed by the latex (Polyurethane-6) with continued stirring using a Rayneri blender.
The thickening polymer (Hostacerin AMPS) is then added with stirring until the mixture thickens without gel lumps.
The silicone resin and the isododecane are then poured slowly onto the mixture obtained previously while increasing the stirring speed, and stirring is continued for 10 minutes.
Evaluation of the composition
A liquid homogeneous stable direct emulsion is obtained.
A thin film which does not migrate into the fine lines and which does not stain the teeth is obtained. The deposit obtained is fresh and glossy, with an intense colour.
The deposit is slightly tacky.
ft has very good colour persistence on the lips and good gloss persistence and does not transfer.

Claims

1. Cosmetic composition in the form of a direct emulsion, comprising:
• at least 10% by weight of water relative to the weight of the composition;
• at least 10% by weight, relative to the weight of the composition, of at least one silicone resin;
• at least one aqueous dispersion of particles of at least one film-forming polymer chosen from synthetic polymers of radical type or of polycondensate type, and mixtures thereof;
• optionally, at least one hydrocarbon-based or silicone volatile oil, in a content such that the silicone resin/volatile oil(s) weight ratio is greater than 1.
2. Composition according to the preceding claim, characterized in that the composition comprises a water content of between 10% and 70% by weight, preferably between 15% and 65% by weight, in particular between 20% and 60% by weight, relative to the weight of the composition.
3. Composition according to either of the preceding claims, characterized in that the silicone resin is chosen from:
- silicone resins of MQ type, such as the alkyl siloxysilicates especially of formula [(Rl)3Si0i/2]x(Si04/2)y (units MQ) in which x and y are integers ranging from 50 to 80, and such that the group Rl represents a hydrocarbon-based radical (especially alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group, and is preferably an alkyl group containing from 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group,
- silicone resins of T type, such as the polysilsesquioxanes in particular of formula (RSi03/2)x (units T) in which x is greater than 100 and such that the group R is an alkyl group containing from 1 to 10 carbon atoms, said polysilsesquioxanes also possibly comprising Si-OH end groups,
- resins of MQT type, in particular MQT-propyl resins, preferably comprising the following units:
- (i) (Rl3SiOi/2)a
- (ii) (R22Si02/2)b
- (iii) (R3Si03/2)c and
- (iv) (Si04/2)d
with
- Rl, R2 and R3 independently representing a hydrocarbon-based radical, especially alkyl, containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical containing from 1 to 8 carbon atoms or a phenyl group, - a, b, c and d being mole fractions,
- a being between 0.05 and 0.5,
- b being between zero and 0.3,
- c being greater than zero,
- d being between 0.05 and 0.6,
- a + b + c + d = l,
- on condition that more than 40 mol% of the groups R3 of the siloxane resin are propyl groups.
4. Composition according to the preceding claim, characterized in that the silicone resin is a resin of MQ type, more particularly an alkyl siloxysilicate resin, such as trimethylsiloxysilicate resin.
5. Composition according to any one of the preceding claims, characterized in that said silicone resin is present in a content of between 10% and 45% by weight, preferably between 12% and 40% by weight, in particular between 15% and 35% by weight, relative to the weight of the composition.
6. Composition according to any one of the preceding claims, in which the film-forming polymer particles in aqueous dispersion form, are chosen from polymer dispersions of radical type chosen from vinyl polymers resulting from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers, the acids being chosen especially from acrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid; vinyl polymers resulting from the homopolymerization or copolymerization of monomers at least chosen from vinyl esters and styrene monomers; hybrid polymer dispersions; dispersions of polymers of polycondensates type chosen from polyurethanes; polyurethane-acrylics; polyurethane-polyvinylpyrrolidones; polyester-polyurethanes; polyether-polyurethanes; polyureas; polyurea/polyurethanes; polyesters; polyester amides; fatty-chain polyesters; polyamides; and epoxyester resins, dispersions of particles of core-shell type, and mixtures thereof; and preferably from dispersions of acrylic polymers, styrene-acrylic polymer dispersions, and polyurethane dispersions, in particular polyester-polyurethane, and derivatives thereof, and mixtures thereof.
7. Composition according to any one of the preceding claims, characterized in that the composition comprises at least one aqueous dispersion of particles chosen from ionic or nonionic acrylic polymers, resulting especially from the polymerization of ethylenically unsaturated monomers, for instance acrylic acid, methacrylic acid and/or esters thereof, in particular Ci-Cs alkyl esters thereof; styrene/acrylate copolymers, and especially polymers chosen from those derived from the polymerization of at least one styrene monomer and at least one Ci-Cis alkyl (meth)acrylate monomer, optionally in the presence of a (meth)acrylic acid monomer; ionic or nonionic aqueous dispersions of polyurethane polymer(s), in particular of polyester-polyurethane, and derivatives thereof, and mixtures thereof.
8. Composition according to any one of the preceding claims, characterized in that the film forming polymer solids content is between 0.5% and 15% by weight, preferably from 1% to 12% by weight, and even more preferentially 2% to 10% by weight, relative to the weight of the composition.
9. Composition according to any one of the preceding claims, characterized in that the film forming polymer solids content is such that the silicone resin (expressed as solids)/film- forming polymer (expressed as solids) weight ratio is greater than or equal to 1.
10. Composition according to any one of the preceding claims, characterized in that it comprises at least one non-volatile silicone oil, free of (poly)glycerol and (poly)oxyalkylene groups, the oxyalkylene units being C2-C3; preferably chosen from non-volatile non-phenyl silicone oils and non-volatile phenyl silicone oils, optionally bearing a dimethicone fragment, and also mixtures thereof.
11. Composition according to the preceding claim, characterized in that the non-volatile silicone oil(s) are chosen from polydimethylsiloxanes; non-volatile phenyl silicone oils bearing at least one dimethicone fragment, and also mixtures thereof; and in particular chosen from poly dimethylsiloxane, trimethylsiloxyphenyl dimethicone and diphenyl dimethicone, and also mixtures thereof.
12. Composition according to either of Claims 10 and 11, characterized in that the content of non-volatile silicone oil(s) represents from 2% to 35% by weight and preferably from 4% to 30% by weight, relative to the weight of the composition.
13. Composition according to any one of the preceding claims, characterized in that the content of volatile hydrocarbon-based or silicone oil(s) is less than 30% by weight relative to the weight of the composition, preferably ranging from 0.1% to less than 30% by weight and more particularly from 2% to 20% by weight relative to the weight of the composition.
14. Composition according to any one of the preceding claims, characterized in that it comprises at least one non-volatile hydrocarbon-based polar oil, preferably chosen from C10-C26 alcohols; optionally hydroxylated monoesters, diesters and triesters of a C2-C8 monocarboxylic or polycarboxylic acid and of a C2-C8 alcohol; esters of a C2-C8 polyol and of one or more C2-C8 carboxylic acids; ester oils containing at least 17 carbon atoms, in particular containing between 17 and 70 carbon atoms; hydrogenated plant oils; sucrose esters; vinylpyrrolidone/l-hexadecene copolymers; oils comprising at least one carbonate function; mixtures thereof.
15. Composition according to any one of the preceding claims, characterized in that it comprises at least one non-volatile apolar hydrocarbon-based oil, preferably chosen from liquid paraffin, squalene, isoeicosane, naphthalene oil, hydrogenated or non-hydrogenated polybutenes, polyisobutenes, hydrogenated polyisobutenes, decene/butene copolymers, polybutene/polyisobutene copolymers, polydecenes and hydrogenated polydecenes, and mixtures thereof.
16. Composition according to either of Claims 14 and 15, characterized in that the content of non-volatile polar or apolar hydrocarbon-based oil(s) is between 2% and 35% by weight, preferably from 8% to 30% by weight, relative to the weight of the composition.
17. Composition according to any one of the preceding claims, characterized in that the composition comprises at least one nonionic or anionic surfactant, preferably a hydrocarbon-based surfactant, or mixtures thereof, and preferably at least one nonionic hydrocarbon-based surfactant.
18. Composition according to the preceding claim, characterized in that the nonionic hydrocarbon-based surfactant(s) are chosen from alkyl and polyalkyl esters of poly(ethylene oxide), alkyl and polyalkyl ethers of polyethylene oxide), polyoxyethylenated or non- polyoxyethylenated alkyl and polyalkyl esters of sorbitan, polyoxyethylenated or non- polyoxyethylenated alkyl and polyalkyl ethers of sorbitan, alkyl and polyalkyl glycosides or polyglycosides, in particular alkyl and polyalkyl glucosides or polyglucosides, alkyl and polyalkyl esters of sucrose, polyoxyethylenated or non-polyoxyethylenated alkyl and polyalkyl esters of glycerol, polyoxyethylenated or non-polyoxyethylenated alkyl and polyalkyl ethers of glycerol, and mixtures thereof; preferably chosen from alkyl and polyalkyl esters of polyethylene oxide), alkyl and polyalkyl ethers of poly(ethylene oxide), polyoxyethylenated or non-polyoxyethylenated alkyl and polyalkyl esters of sorbitan, polyoxyethylenated or non-polyoxyethylenated alkyl and polyalkyl ethers of sorbitan, polyoxyethylenated or non-polyoxyethylenated alkyl and polyalkyl esters of glycerol, polyoxyethylenated or non-polyoxyethylenated alkyl and polyalkyl ethers of glycerol, and mixtures thereof; advantageously, the nonionic hydrocarbon-based surfactant(s) have an HLB (hydrophilic/lipophilic balance) of greater than or equal to 8.
19. Composition according to Claim 17, characterized in that the anionic hydrocarbon-based surfactant(s) are chosen from salts of alkali metals especially such as sodium or potassium, or alternatively of primary or secondary amine or alkanolamine, which is in particular of C2-C4, of the following compounds:
• alkyl ether sulfates,
• salts of fatty acids especially of C8-C20, in particular monocarboxylic salts,
• carboxylates such as N-acylamino acids, alkyl glycol carboxylates, ether carboxylates, amido ether carboxylates,
• amino acid salts, in particular sarcosinates, alaninates, glutamates, aspartates and glycinates,
• sulfonates, such as alpha-olefin sulfonates, in particular alkanolamine or alkali metal salts of dodecylbenzene sulfonate,
• isethionates, such as acyl isethionates,
• taurates, such as N-acyl methyl taurates, in particular N-acyl methyl taurates,
• sulfosuccinates, such as alkyl sulfosuccinates, especially dioctyl sulfosuccinate salts,
• alkylsulfoacetates,
• phosphates and alkyl phosphates,
• polypeptides obtained, for example, by condensation of a fatty chain onto amino acids from cereals and especially from wheat and oat,
• and also mixtures thereof,
• these compounds comprising at least one group comprising from 8 to 30 carbon atoms in their longest saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain, optionally comprising up to 20 C2-C3, (preferably C2), oxyalkylene units.
20. Composition according to any one of the preceding claims, characterized in that the surfactant content represents from 0.1% to 15% by weight and preferably from 0.5% to 10% by weight relative to the weight of the composition.
21. Composition according to any one of the preceding claims, characterized in that it comprises at least one hydrophilic thickening polymer, preferably chosen from homopolymers or copolymers of acrylic or methacrylic acid or salts thereof and esters thereof; copolymers of acrylic acid and of acrylamide; homopolymers and copolymers based on acrylamidopropanesulfonic acid; anionic, cationic, amphoteric or nonionic chitin or chitosan polymers; cellulose polymers; vinyl polymers; optionally modified polymers of natural origin; alginates and carrageenans; mucopolysaccharides, and mixtures thereof.
22. Composition according to the preceding claim, characterized in that the content of hydrophilic thickener is between 0.01% and 1.5% by weight and preferably from 0.05% to 1% by weight relative to the weight of the composition.
23. Composition according to any one of the preceding claims, characterized in that it comprises at least one dyestuff, preferably chosen from pigments, nacres, water-soluble dyes and liposoluble dyes, and also mixtures thereof.
24. Process for making up and/or caring for keratin materials such as the skin or the lips, and preferably the lips, which consists in applying the composition claimed according to any one of the preceding claims.
PCT/EP2018/086154 2017-12-22 2018-12-20 Composition in the form of a direct emulsion comprising a silicone resin and a film-forming polymer, and process using same WO2019122102A1 (en)

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WO2021222764A1 (en) 2020-04-30 2021-11-04 L'oreal Water-in-oil emulsions containing surfactant, silicone gum and/or latex, and siloxysilicate resin
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FR3113588A1 (en) 2020-08-28 2022-03-04 L'oreal WATER-IN-OIL EMULSIONS CONTAINING LOW HLB SURFACTANT, SILICONE GUM AND SILOXYSILICATE RESIN
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FR3130134A1 (en) 2021-12-14 2023-06-16 L'oreal Water-in-oil emulsions comprising a surfactant, an acrylic polymer and an organosiloxane

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FR3097746A1 (en) * 2019-06-27 2021-01-01 L'oreal EMULSION COMPRISING A FILM-GENERATING POLYMER LATEX, A HIGH VISCOSITY SILICONE OIL AND PROCESS USING IT
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FR3112949A1 (en) 2020-07-29 2022-02-04 L'oreal WATER-IN-OIL EMULSIONS CONTAINING LATEX AND SILOXYSILICATE RESIN
FR3113588A1 (en) 2020-08-28 2022-03-04 L'oreal WATER-IN-OIL EMULSIONS CONTAINING LOW HLB SURFACTANT, SILICONE GUM AND SILOXYSILICATE RESIN
CN113520916A (en) * 2021-07-02 2021-10-22 上海永熙信息科技有限公司 Cosmetic makeup fixing composition with high film forming property
WO2023273381A1 (en) * 2021-07-02 2023-01-05 上海永熙信息科技有限公司 Makeup finishing composition having high film-forming performance
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FR3130134A1 (en) 2021-12-14 2023-06-16 L'oreal Water-in-oil emulsions comprising a surfactant, an acrylic polymer and an organosiloxane

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