EP1585777A2 - Cosmetic composition comprising a polymer - Google Patents
Cosmetic composition comprising a polymerInfo
- Publication number
- EP1585777A2 EP1585777A2 EP03813184A EP03813184A EP1585777A2 EP 1585777 A2 EP1585777 A2 EP 1585777A2 EP 03813184 A EP03813184 A EP 03813184A EP 03813184 A EP03813184 A EP 03813184A EP 1585777 A2 EP1585777 A2 EP 1585777A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- weight
- chosen
- silicone
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/91—Graft copolymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/08—Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/04—Preparations for care of the skin for chemically tanning the skin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- Cosmetic composition comprising a polymer
- the subject of the present invention is a cosmetic composition comprising a particular polymer intended to be applied to the skin of human beings.
- composition according to the invention can be a makeup composition or a skin care composition, and preferably a makeup composition.
- the makeup composition can be a foundation, an eyeshadow, a blush, a concealer, an eyeliner, a body makeup product. More specifically, the invention relates to a foundation composition.
- the care composition may be a care product for the skin of the body and the face, in particular a sun care product, a product for coloring the skin (such as a self-tanner).
- Foundation compositions are commonly used to provide an aesthetic color to the skin, in particular to the face.
- These makeup products generally contain oils, pigments and / or fillers and possibly additives such as cosmetic or dermatological active ingredients.
- compositions when applied to the skin, have the drawback of transferring, that is to say of depositing at least in part, leaving traces, on certain supports with which they can be brought into contact. and in particular a glass, a cup, a cigarette, a garment or the skin. This results in poor hold of the applied film, requiring regular renewal of the application of the foundation or lipstick composition. Furthermore, the appearance of these unacceptable traces, in particular on the collars of the hem, may exclude certain women from the use of this type of make-up.
- sebum excreted by the skin over time also changes the properties of makeup.
- sebum does not promote the adhesion of makeup on the skin and the transfer of makeup is even more important, causing a significant loss of the makeup remaining on the skin.
- the present invention therefore aims to provide a new way of formulating a cosmetic product which makes it possible to obtain good transfer resistance properties, in particular in the presence of sebum.
- the inventors have discovered that it is possible to obtain such a composition using a particular polymer.
- the present invention therefore relates to a cosmetic composition for making up or caring for the skin comprising a dispersion of particles, preferably solid, of an ethylenic polymer grafted in a liquid fatty phase as described below. , the composition being in particular as defined below.
- the grafted ethylenic polymer is such that, when it is present in a sufficient amount in the composition, the latter is capable of forming a deposit-having-an indie transfer in the presence of sebum-less than-4. -
- the subject of the invention is also a method for making up the skin, comprising the application to keratin materials, in particular to the skin, of a composition as defined above.
- the invention also relates to the use of a composition as defined above for obtaining a deposit, in particular a make-up on the skin having good resistance to transfer, in particular in the presence of sebum.
- Another subject of the invention is the use, in a cosmetic composition, of a dispersion of (preferably solid) particles of an ethylenic polymer grafted in dispersion in a liquid fatty phase, the composition being in particular capable of forming a deposit having a transfer index in the presence of sebum of less than 4, to obtain a deposit, in particular make-up, on the skin having good resistance to transfer, in particular in the presence of sebum.
- the grafted ethylenic polymer used in the composition according to the invention is such that when it is present in a sufficient amount in the composition, the latter is capable of forming a deposit having a transfer index in the presence of sebum of less than 4, in particular less than or equal to 3.5, preferably less than or equal to 3, in particular less than or equal to 2.5, preferably less than or equal to 2, more preferably less than or equal to 1.5, and in particular less than or equal to 1.
- the transfer index in the presence of sebum of the deposit obtained with the composition according to the invention is determined according to the measurement protocol described below.
- a support is prepared (square 40 mm X 40 mm) consisting of a layer of adhesive neoprene foam on one of its faces (sold under the name RE70X40 212B from the company JOINT TECHNIQUE LYONNAIS IND).
- an adhesive crown is fixed having an internal diameter of -24 mm and the thickness of which is approximately -250 ⁇ m - ⁇ n -applies- inside the crown the composition which is leveled off with a glass slide to obtain a deposit of the composition of approximately 250 ⁇ m thick, then the crown is removed and left to dry for 20 hours in an oven at 37 ° C.
- the support is then bonded by its adhesive side to a tip with a diameter of 27 mm fixed on a press (MANUAL STATIF SV-1 from the company IMADA Co LTD) equipped with a dynanometer (DPS-5R from the company IMADA Co LTD).
- a drop of 10 ⁇ l of artificial sebum having the following composition is placed in the center of the first box:
- the support (comprising the composition sample) is pressed on the first box of the paper strip at a force of approximately 4 kg exerted for 5 seconds. Then the paper is moved in a rectilinear and regular fashion over the entire length of the strip so that the support is in contact with the entire length of the strip.
- the speed of movement of the strip is of the order of 10 cm / s.
- a score ranging from 0 to 5 is assigned in increments of 0.5 depending on the number of boxes, from the first to the fifth, crossed in whole or in part by the possible streak of product.
- a revealing step may be necessary in order to make the product trail visible.
- a compound is used which is capable of producing a colored reaction on contact with the transferred product.
- an active ingredient which emits at least part of the UV radiation (Wood lamp) is incorporated into the product to be tested.
- a score of 5 is awarded when, upon observation, after having made the relative displacement between the paper and the support, substantially no product remains on the support (less than 10%). In the latter case, the transfer can be qualified as total.
- a score of 5 is also awarded when the product trail extends beyond the fifth box, regardless of the amount of product remaining on the support.
- a score of 0 is assigned in the event that no product present on the support is transferred to the paper strip. No visible trace can be observed on the sheet. The transfer can be called null.
- the table below illustrates how the other scores are assigned based on the location in boxes 1 to 5 where the product streak ends. For these notes, there remains a greater or lesser quantity of product on the support. The transfer is partial.
- the cosmetic composition according to the invention comprises a dispersion of particles, preferably solid, of an ethylenic polymer grafted in a liquid fatty phase.
- the cosmetic composition according to the invention is a composition compatible with keratin materials, in particular the skin.
- ethylenic polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.
- the dispersion of grafted ethylenic polymer is in particular free of stabilizing polymer distinct from said grafted polymer, such as those described in EP749747, and the particles of grafted ethylenic polymer are therefore not surface stabilized by such additional stabilizing polymers.
- the graft polymer is dispersed in ⁇ the liquid fatty phase in the absence of additional surface stabilizer particles of the graft polymer
- grafted polymer is meant a polymer having a skeleton comprising at least one side chain hanging or located at the end of the chain, and preferably pending.
- the grafted ethylenic polymer comprises an ethylenic skeleton insoluble in said liquid fatty phase, and side chains covalently linked to said skeleton and soluble in said dispersion medium.
- the grafted ethylenic polymer is in particular a non-crosslinked polymer.
- the polymer is obtained by polymerization of monomers comprising a single polymerizable group.
- the grafted ethylenic polymer is a film-forming polymer.
- film-forming polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.
- the grafted ethylenic polymer is a grafted acrylic polymer.
- the grafted ethylenic polymer is in particular capable of being obtained by radical polymerization in an organic polymerization medium:
- At least one ethylenic monomer in particular at least one acrylic monomer and optionally at least one additional non-acrylic vinyl monomer, to form said insoluble skeleton;
- At least one macromonomer comprising a polymerizable end group to form the side chains, said macromonomer having a weight average molecular weight greater than or equal to 200 and the content of polymerized macromonomer representing from 0.05 to 20% by weight of the polymer .
- the liquid fatty phase may contain the organic polymerization medium.
- the liquid organic dispersion medium corresponding to the medium in which the grafted polymer is supplied, may be identical to the polymerization medium.
- the polymerization medium can be substituted in whole or in part by another liquid organic medium.
- This other liquid organic medium can be added, after polymerization, to the polymerization medium. The latter is then evaporated in whole or in part.
- the liquid fatty phase can contain organic liquid compounds other than those present in the dispersion medium. These other compounds are chosen so that the grafted polymer remains in the state of dispersion in the liquid fatty phase.
- the organic liquid dispersion medium is present in the liquid fatty phase of the composition according to the invention due to the introduction into the composition of the graft polymer dispersion obtained.
- the liquid fatty phase preferably comprises one or more liquid organic compounds (or oils) as defined below.
- the liquid fatty phase is a non-aqueous liquid organic phase which is immiscible with water at room temperature (25 ° C).
- liquid organic compound is understood to mean a non-aqueous compound which is in the liquid state at room temperature (25 ° C.) and which therefore flows from its own weight.
- silicon compound means a compound containing at least one silicon atom.
- liquid organic compounds or oils in particular volatile or non-volatile, which may be present in the liquid organic dispersion medium
- - liquid organic compounds in particular non-silicone or silicone, having a global solubility parameter according to Hansen solubility space less than or equal to 18 (MPa) 1 2 , preferably less than or equal to 17 (MPa) 1/2
- - monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal at 20 (MPa) 1/2 ; and - their mixtures.
- liquid fatty substances in particular oils, which can be chosen from natural or synthetic, carbon, hydrocarbon, fluorinated, silicone oils, optionally branched, alone or as a mixture.
- Oil means any non-aqueous medium which is liquid at room temperature (25 ° C) and atmospheric pressure (760mm Hg), compatible with application to the skin, mucous membranes (lips) and / or integuments (nails, eyelashes, eyebrows, hair).
- oils formed by esters of fatty acids and polyols, in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or long-chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR 'in which R represents the remainder of a fatty acid higher comprising from 7 to 19 carbon atoms and R ′ represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, such as palmitates, adipates and benzoates, in particular diisopropyl adipate.
- esters of fatty acids and polyols in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or long-chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR 'in which R represents the remainder of a fatty acid higher comprising from 7 to 19 carbon atoms and R
- Mention may also be made of linear, branched and / or cyclic alkanes which may be volatile and in particular paraffin oils, of petrolatum, or hydrogenated polyisobutylene, isododecane, or also 'ISOPARS', volatile isoparaffins. Mention may also be made of esters, ethers and ketones. Mention may also be made of silicone oils such as polydimethylsiloxanes and polymethylphenylsiloxanes, optionally substituted by aliphatic and / or aromatic groups, optionally fluorinated, or by functional groups such as hydroxyl, thiol and / or amino groups, and silicone oils volatile, especially cyclical.
- paraffin oils of petrolatum, or hydrogenated polyisobutylene, isododecane, or also 'ISOPARS', volatile isoparaffins. Mention may also be made of esters, ethers and ketones. Mention may also be made of silicone oils such as polydimethylsi
- silicone oils optionally branched, volatile and / or non-volatile.
- volatile oil any non-aqueous medium capable of evaporating from the skin or the lips, in less than an hour, having in particular a vapor pressure, at ambient temperature and atmospheric pressure ranging from 10 "3 to 300 mm of Hg (0.13 Pa to 40,000 Pa).
- volatile silicone oil which can be used in the invention, mention may be made of linear or cyclic silicones having from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms.
- these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms.
- octamethylcyclotetrasiloxane decamethylcyclopentasiloxane
- dodecamethylcyclohexasiloxane heptamethylhexyltrisiloxane
- heptamethyloctyltrisiloxane octamethyltrisiloxane
- decamethyltetrasiloxane and their mixtures.
- non-volatile silicone oil of polydialkylsiloxanes which are not -v0.ati.s 7 - such as - polydimethylsiloxanes (-P-DMS) - non-volatile - polydimethylsiloxanes comprising alkyl, alkoxy or phenyl, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyls dimethicones, diphenyl methyldiphenyl trisiloxanes, polymethylphenylsiloxanes; polysiloxanes modified with fatty acids (especially C8-C20), fatty alcohols (especially C8-C20) or polyoxyalkylenes (especially polyoxyethylene and / or polyoxypropylene); amino
- liquid monoalcohols having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 is meant aliphatic fatty liquid monoalcohols having from 6 to 30 carbon atoms, the hydrocarbon chain not comprising no substitution group.
- monoalcohols according to the invention there may be mentioned oleic alcohol, decanol and linoleic alcohol.
- composition according to the invention may comprise a volatile oil in a content ranging from 1% to 90% by weight, relative to the total weight of -the-composition, -and-da.pr-éfé ⁇ ence-ranging.de_5. .% _ to_70% by weight. ___. ....
- the composition may comprise a non-volatile oil in a content ranging from 0.1% to 80% by weight, relative to the total weight of the composition, and preferably ranging from 3% to 50% by weight.
- the liquid fatty phase can be a non-silicone liquid fatty phase.
- non-silicone liquid fatty phase means a fatty phase comprising one or more liquid organic compounds or non-silicone oils, such as those mentioned above, said non-silicone compounds being present mainly in the liquid fatty phase, it that is to say at least 50% by weight, in particular from 50 to 100% by weight, preferably from 60% to 100% by weight (for example from 60 to 99% by weight), or even from 65% to 100% by weight (for example from 65 to 95% by weight), relative to the total weight of the liquid fatty phase.
- the non-silicone-based liquid organic compounds can in particular be chosen from:
- Said non-silicone-based liquid fatty phase may therefore optionally comprise liquid organic compounds or silicone oils, such as those mentioned above, which may be present in an amount of less than 50% by weight, in particular ranging from 0.1 to 40 % by weight, or even ranging from 1 to 35% by weight, or even ranging from 5 to 30% by weight, relative to the total weight of the liquid fatty phase.
- the non-silicone liquid fatty phase does not contain liquid organic compounds or silicone oils.
- the macromonomers present in the grafted polymer are advantageously carbon macromonomers as described below.
- the macromonomers present in the grafted polymer are advantageously carbon macromonomers as described below.
- non-silicone grafted polymer is intended to mean a grafted polymer mainly containing a carbon macromonomer and optionally containing at most 7% by weight of the total weight of the polymer, preferably at most 5% by weight, or even is free, of silicone macromonomer.
- the liquid fatty phase can be a silicone liquid fatty phase.
- silicone liquid fatty phase means a fatty phase comprising one or more silicone liquid organic compounds or silicone oils such as those described above, said silicone compounds being present mainly in the liquid fatty phase, that is to say at least at least 50% by weight, in particular from 50 to 100% by weight, preferably from 60% to 100% by weight (for example from 60 to 99% by weight), or also from 65% to 100% by weight (for example from 65 to 95% by weight), relative to the total weight of the liquid fatty phase.
- liquid organic silicone compounds can be chosen in particular from:
- liquid organic compounds in particular non-silicone or silicone compounds, having an overall solubility parameter according to the Hansen solubility space less than or equal to 18 (MPa) 1/2 .
- Said liquid silicone fatty phase can therefore optionally comprise liquid organic compounds or non-silicone oils, as described
- the silicone liquid fatty phase does not contain non-silicone liquid organic compounds.
- the macromonomers present in the grafted polymer are advantageously macromonomers
- the macromonomers present in the grafted polymer are advantageously silicone macromonomers as described below.
- the grafted polymer present in the composition is advantageously a silicone grafted polymer.
- grafted silicone polymer is intended to mean a grafted polymer mainly containing a silicone macromonomer and optionally containing at most 7% by weight of the total weight of the polymer, preferably at most 5% by weight, or even is free, of carbonaceous macromonomer, silicone such as described below.
- the choice of monomers constituting the backbone of the polymer, of the macromonomers, the molecular weight of the polymer, the proportion of the monomers and of the macromonomers can be made as a function of the liquid organic dispersion medium so as to advantageously obtain a dispersion of polymer particles grafted in particularly a stable dispersion, this choice can be made by a person skilled in the art.
- stable dispersion is meant a dispersion which is not liable to form a solid deposit or a liquid / solid phase shift, in particular after - - centrifugation, for example; - at 4000 rpm for -15 minutes
- the grafted ethylenic polymer forming the particles in dispersion therefore comprises a skeleton insoluble in said dispersion medium and a part soluble in said dispersion medium.
- the grafted ethylenic polymer can be a random polymer.
- grafted ethylenic polymer means a polymer capable of being obtained by radical polymerization:
- grafted acrylic polymer means a polymer capable of being obtained by radical polymerization:
- the acrylic monomers represent from 50 to 100% by weight, preferably from 55 to 100% by weight (in particular from 55 to 95% by weight), preferably from 60 to 100% by weight (in particular from 60 to 90% by weight) of the mixture of acrylic monomers + optional non-acrylic vinyl monomers.
- the acrylic monomers are chosen from monomers whose homopolymer is insoluble in the dispersion medium under consideration, that is to say that the homopolymer is in solid form (or not dissolved) at a greater or equal concentration. at 5% by weight at room temperature (20 ° C) in said dispersion medium.
- - we mean - "macr-omonomer having a polymerizable gr ⁇ upe-terminal" any polymer comprising on one of its ends a polymerizable terminal group capable of reacting during the polymerization reaction with acrylic monomers and optionally the additional non-acrylic vinyl monomers constituting the backbone.
- the macromonomer makes it possible to form the side chains of the grafted acrylic polymer.
- the group The polymerizable macromonomer can advantageously be an ethylenically unsaturated group capable of polymerizing by the radical route with the monomers constituting the skeleton.
- carbon macromonomer is meant a non-silicone macromonomer, and in particular an oligomeric macromonomer obtained by polymerization of non-silicone monomer (s) with ethylenic unsaturation, and mainly by polymerization of acrylic and / or non-acrylic vinyl monomers.
- silicone macromonomer is meant an organopolysiloxane macromonomer, and in particular a polydimethylsiloxane macromonomer.
- the macromonomer is chosen from macromonomers whose homopolymer is soluble in the dispersion medium under consideration, that is to say completely dissolved at a concentration greater than or equal to 5% by weight and at room temperature in said medium of dispersion.
- the grafted acrylic polymer comprises a skeleton (or main chain) consisting of a chain of acrylic units resulting from the polymerization in particular of one or more acrylic monomers and side chains (or grafts) resulting from the reaction of the macromonomers, said chains side being covalently linked to said main chain.
- the skeleton (or main chain) is insoluble in the dispersion medium considered while the side chains (or grafts) are soluble in said dispersion medium.
- acrylic monomers is meant in the present application monomers chosen from (meth) acrylic acid, esters of (meth) acrylic acid (also called - (meth) acrylates), amides of l (methacrylic acid) (also called (meth) acrylamides).
- acrylic monomer capable of being used to form the insoluble backbone of the polymer there may be mentioned, alone or as a mixture, the monomers following, as well as their salts:
- - Ri denotes a hydrogen atom or a methyl group
- R 2 represents a group chosen from:
- - a linear or branched alkyl group, comprising from 1 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S; and / or possibly comprising one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and - NR'R "with R 'and R" identical or different chosen from linear or branched alkyls in C1-C4; and / or may be substituted by at least one polyoxyalkylene group, in particular with C2-C4 alkylene, in particular polyoxyethylene and / or polyoxypropylene, said polyoxyalkylene group consisting of the repetition of 5 to 30 oxyalkylene units;
- a cyclic alkyl group comprising from 3 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S, and / or possibly comprising one or more substituents chosen from OH and the atoms of halogen (F, Cl, Br, I);
- R 2 mention may be made of the methyl, ethyl, propyl, butyl, isobutyl, methoxyethyl, ethoxyethyl, methoxy-polyoxyethylene 350 EO, trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl group.
- R 3 denotes a hydrogen atom or a methyl group
- - R and R 5 identical or different, represent a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms, which may comprise one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched C ⁇ -C4 alkyls, or
- R 5 represents a group 1, 1-dimethyl-3-oxobutyl.
- alkyl groups which may constitute R 4 and R 5 , there may be mentioned n-butyl, t-butyl, n-propyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
- (meth) acrylic monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid.
- acrylic monomers mention may very particularly be made of methyl, ethyl, propyl, butyl and isobutyl (meth) acrylates; methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate; dimethylaminopropylmethacrylamide, (meth) acrylic acid; and their salts; and their mixtures.
- the acrylic monomers are chosen from methyl acrylate, methoxyethyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, (meth) acrylic acid, dimethylaminoethyl methacrylate, and their mixtures.
- R 6 -COO-CH CH 2 in which RQ represents a linear or branched alkyl group, comprising from 1 to 6 atoms, or an alkyl group cyclic with 3 to 6 carbon atoms and / or an aromatic group, for example of the benzene, anthracene and naphthalene type;
- non-acrylic vinyl monomers comprising at least one carboxyic, phosphoric or sulfonic acid function, such as crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, and their salts;
- non-acrylic vinyl monomers comprising at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine; - and their mixes.
- the grafted polymer comprises (meth) acrylic acid.
- the acrylic monomers present in the grafted polymer comprise at least (meth) acrylic acid, and in particular at least (meth) acrylic acid and at least one monomer chosen from (meth) acrylates and (meth) acrylamides described above in points (i) and (ii).
- the acrylic monomers comprise at least (meth) acrylic acid and at least one monomer chosen from C-1-C3 alkyl (meth) acrylates.
- the (meth) acrylic acid may be present in a content of at least 5% by weight, relative to the total weight of the polymer (in particular ranging from 5% to 80% by weight), preferably at least 10% by weight (in particular ranging from 10% by weight to 70% by weight), preferably at least 15% by weight (in particular ranging from 15% to 60% by weight).
- salts mention may be made of those obtained by neutralization of acid groups using inorganic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or organic bases of the aleanol type.
- amines such as monoethanolamine, diethanolamine, triethanolamine, 2-methyl-2-amino-1-propanol.
- acids minerals there may be mentioned sulfuric acid or hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, boric acid.
- organic acids mention may be made of acids comprising one or more carboxylic, sulphonic or phosphonic groups. They can be linear, branched or cyclic aliphatic acids or even aromatic acids. These acids may also contain one or more heteroatoms chosen from O and N, for example in the form of hydroxyl groups. Mention may in particular be made of acetic acid or propionic acid, terephthalic acid, as well as citric acid and tartaric acid.
- the grafted ethylenic polymer does not contain additional non-acrylic vinyl monomers as described above.
- the insoluble skeleton of the grafted ethylenic polymer is formed only from acrylic monomers as described above.
- non-polymerized acrylic monomers may be soluble in the dispersion medium under consideration, but the polymer formed with these monomers is insoluble in the dispersion medium.
- the grafted ethylenic polymer is capable of being obtained by radical polymerization in an organic polymerization medium: - of a main acrylic monomer chosen from C1 (meth) acrylates -C3, alone or as a mixture, and optionally of one or more additional acrylic monomers chosen from acrylic acid, methacrylic acid and the alkyl (meth) acrylates of formula (I) defined below, and their salts, to form said insoluble skeleton; and
- methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl acrylate can be used.
- the additional acrylic monomers can be chosen from:
- R'i denotes a hydrogen atom or a methyl group
- a linear or branched alkyl group comprising from 1 to 6 carbon atoms, said group comprising in its chain one or more oxygen atoms and / or comprising one or more substituents chosen from
- a cyclic alkyl group comprising from 3 to 6 carbon atoms, said group possibly comprising in its chain one or more oxygen atoms and / or possibly comprising one or more substituents chosen from OH and the halogen atoms (F, Cl , Br, I);
- R 2 there may be mentioned the methoxyethyl, _ethoxyethyl, _ trifluoroethyl group; 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
- acrylic acid methoxyethyl or ethoxyethyl (meth) acrylates; the trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, their salts, and mixtures thereof.
- acrylic acid methylacrylic acid.
- the macromonomers comprise at one end of the chain a polymerizable end group capable of reacting during the polymerization with the acrylic monomers and optionally the additional vinyl monomers, to form the side chains of the grafted ethylenic polymer.
- Said polymerizable end group may in particular be a vinyl or (meth) acrylate (or (meth) acryl) group, and preferably a (meth) acrylate group.
- the macromonomers are preferably chosen from macromonomers whose homopolymer has a glass transition temperature (Tg) less than or equal to 25 ° C, in particular ranging from - 100 ° C to 25 ° C, preferably ranging from - 80 ° C to 0 ° C.
- Tg glass transition temperature
- the macromonomers have a weight average molecular weight greater than or equal to 200, preferably greater than or equal to 300, preferably greater than or equal to 500, and more preferably greater than 600.
- the macromonomers have a weight average molecular mass ( Mw) ranging from 200 to 100,000, preferably ranging from 500 to 50,000, preferably ranging from 800 to 20,000, more preferably ranging from 800 to 10,000, and even more preferably ranging from 800 to 6,000.
- the average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (solvent - THF, - - curve - of established calibration - with polystyrene standards - linear , refractometric detector).
- carbon macromonomers mention may in particular be made of: (i) linear or branched C8-C22 homopolymers and copolymers (meth) acrylate of alkyl, having a polymerizable end group chosen from vinyl or (meth) acrylate groups among which mention may be made in particular of: macromonomers of poly (2-ethylhexyl acrylate) with mono (meth) acrylate end; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers with mono (meth) acrylate end; poly (stearyl acrylate) or poly (stearyl methacrylate) macromonomers with mono (meth) acrylate end.
- polyolefins having an ethylenically unsaturated end group, in particular having a (meth) acrylate end group.
- polyolefins mention may be made in particular of the following macromonomers, it being understood that they have a terminal (meth) acrylate group: polyethylene macromonomers, polypropylene macromonomers, polyethylene / polypropylene copolymer macromonomers, macromonomers of polyethylene / polybutylene copolymer, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; polybutadiene macromonomers; poly (ethylene / butylene) -polyisoprene macromonomers;
- Such macromonomers are in particular described in US5625005 which mentions ethylene / butylene and ethylene / propylene macromonomers with reactive (meth) acrylate end group.
- poly (ethylene / butylene) methacrylate such as that marketed under the name Kraton Liquid L-1253 by Kraton Polymers.
- silicone macromonomers mention may in particular be made of polydimethylsiloxanes with a mono (meth) acrylate end group, and in particular those of formula (II) below:
- R ⁇ denotes a hydrogen atom or a methyl group
- Rg denotes a divalent hydrocarbon group having from 1 to 10 carbon atoms and optionally contains one or two ether bonds -O-
- R10 denotes an alkyl group having from 1 to 10 carbon atoms, in particular from 2 to 8 carbon atoms
- n denotes an integer ranging from 1 to 300, preferably ranging from 3 to 200, and preferably ranging from 5 to 100.
- silicone macromonomers use may be made of monomethacryloxypropyl polydimethylsiloxanes such as those sold under the name PS560-K6 by the company United Chemical Technologies Inc. (UCT) or under the name MCR-M17 by the company Gelest Inc.
- the polymerized macromonomer (constituting the side chains of the grafted polymer) represents from 0.1 to 15% by weight of the total weight of the polymer, preferably from 0.2 to 10% by weight, and more preferably from 0.3 to 8% by weight.
- grafted ethylenic polymer dispersed in a non-silicone liquid fatty phase those obtained by polymerization can be used:
- grafted acrylic polymer dispersed in a silicone liquid fatty phase those obtained by polymerization can be used: methyl acrylate and the monomethacryloxypropylpolydimethylsiloxane macromonomer having a weight average molecular weight ranging from 800 to 6000, in particular in decamethylcyclopentasiloxane or phenyltrimethicone;
- Methyl acrylate acrylic acid and monomethacryloxypropylpolydimethylsiloxane monomonomer having a weight average molecular weight ranging from 800 to 6000, in particular in decamethylcyclopentasiloxane or phenyltrimethicone.
- the grafted polymer has a weight-average molecular mass (Mw) -comprises -between 10-000 -and-300 000, in particular between 20 000- and 2-00- 000, better still between 25 000 and 150 000
- the polymers in a given organic dispersion medium, have the capacity to fold in on themselves, thus forming particles of substantially spherical shape, with around the periphery of these particles the deployed side chains, which ensure the stability of these particles.
- Such particles resulting from the characteristics of the grafted polymer have the particularity of not agglomerating in said medium and therefore of self-stabilizing and of forming a dispersion of particularly stable polymer particles.
- the grafted ethylenic polymers of the dispersion can form nanometric particles, of average size ranging from 10 to 400 nm, preferably from 20 to 200 nm. Because of this very small size, the particles of polymer grafted in dispersion are particularly stable and therefore unlikely to form agglomerates.
- the dispersion of grafted polymer can therefore be a stable dispersion and does not form sediments, when it is placed for a prolonged period (for example 24 hours) at room temperature (25 ° C).
- the dispersion of particles of grafted polymer has a content of dry matter (or dry extract) in polymer which can range from 40% to 70% by weight of dry matter, in particular ranging from 45% to 65% by weight.
- the dispersion of grafted polymer particles can be prepared by a process comprising a step of radical copolymerization, in an organic polymerization medium, of one or more acrylic monomers as defined above with one or more macromonomers as defined above.
- liquid organic dispersion medium can be identical to or different from the polymerization medium.
- the copolymerization can be carried out in the presence of a polymerization initiator.
- the polymerization initiators can be radical initiators.
- such a polymerization initiator can be chosen from organic peroxide compounds such as dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2- ethylhexanoate; diazotized compounds such as azobisisobutyronitrile, azobisdimethylvalero-nitrile.
- the reaction can also be initiated using photoinitiators or by radiation such as UV, neutrons or plasma.
- the organic polymerization medium is introduced into a reactor of a size appropriate to the quantity of polymer that is to be produced, and / or additional vinyls, which will constitute, after polymerization, the insoluble skeleton, all of the macromonomer (which will constitute the side chains of the polymer) and part of the polymerization initiator.
- the reaction medium forms a relatively homogeneous medium.
- the reaction medium is then stirred and heated to a temperature to obtain a polymerization of the monomers and macromonomers. After a certain time, the initially homogeneous and clear medium leads to a dispersion of milky appearance. A mixture consisting of the remaining part of the monomers and of the polymerization initiator is then added. After an adequate time during which the mixture is heated with stirring, the medium stabilizes in the form of a milky dispersion, the dispersion comprising particles of polymers stabilized in the medium in which they were created, said stabilization being due to the presence , in the polymer, of side chains soluble in said dispersion medium.
- the graft polymer described above can be present in the composition according to the invention in a content ranging from 0.5% to 45% by weight, relative to the total weight of the composition, preferably ranging from 1% to 30% by weight , and preferably ranging from 2% to 25% by weight.
- composition - according to the invention - may comprise one or more coloring matters. chosen from water-soluble dyes, and pulverulent dyestuffs such as pigments, nacres and flakes well known to those skilled in the art.
- Dyestuffs may be present in the composition, in a content ranging from 0.01% to 50% by weight, relative to the weight of the composition, preferably from 0.01% to 30% by weight.
- pigments should be understood to mean particles of any shape, white or colored, mineral - or organic, insoluble in the physiological medium, intended to color the composition.
- the pigments can be white or colored, mineral and / or organic.
- mineral pigments mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red) or chromium, violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metallic powders such as aluminum powder, copper powder.
- organic pigments mention may be made of carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.
- effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being or not covered with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metallic oxides such as titanium dioxide, iron oxide, chromium and their mixtures.
- the pearlescent pigments can be chosen from white pearlescent pigments such as
- the grafted polymer present in the composition according to the invention makes it possible to obtain a good homogeneous dispersion of the pulverulent dyestuffs such as pigments or nacres.
- the invention therefore also relates to a foundation composition
- a foundation composition comprising a dispersion of particles of ethylenic polymer grafted in a liquid fatty phase, as described above, and at least one coloring matter, in particular pigments, nacres, or any other charge with optical effect.
- the water-soluble dyes are, for example, beet juice, methylene blue.
- composition according to the invention may also further comprise one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% at 30% by weight.
- fillers it is necessary to understand particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is produced. These charges are used in particular to modify the rheology or the texture of the composition.
- the fillers can be mineral or organic of any shape, platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorombic, etc.). Mention may be made of talc, mica, silica, kaolin, powders of polyamide (Nylon®) (Orgasol® from Atochem), -of poly- ⁇ -alanine and -of polyethylene, powders of -polymers -of - tetrafluoroethylene (Teflon®), lauroyl-lysine, starch, boron nitride, hollow polymeric microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), of acrylic acid copolymers (Polytrap® from Dow Corning) and microbeads silicone resin (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate,
- composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, moisturizers, emollients, anti-free radical agents, thickeners, trace elements, softeners, sequestrants, perfumes , basifying or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, gums, waxes, propellants, or mixtures thereof.
- ingredients commonly used in cosmetics such as vitamins, moisturizers, emollients, anti-free radical agents, thickeners, trace elements, softeners, sequestrants, perfumes , basifying or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, gums, waxes, propellants, or mixtures thereof.
- the composition according to the invention can be in particular in the form of a suspension, dispersion, solution, gel, emulsion, in particular oil-in-water (O / W) or water-in-oil (W / O) emulsion ), or multiple (W / O / W or polyol / O / W or O / W / O), in the form of a cream, paste, foam, vesicle dispersion, in particular of ionic lipids or not, of two-phase lotion or multiphase, spray, powder, paste.
- the composition can be anhydrous, for example it can be a stick or an anhydrous paste.
- the composition can be a leave-in composition - - 0
- the invention also relates to a cosmetic assembly comprising: i) a container delimiting at least one compartment, said container being closed by a closing element; and ii) a composition placed inside said compartment, the composition being in accordance with the invention.
- the container can be in any suitable form. It can in particular be in the form of a bottle, a tube, a pot, a case, a box, a sachet or a case.
- the closure element may be in the form of a removable stopper, a cover, a cover, a tearable strip, or a capsule, in particular of the type comprising a body fixed to the container and an articulated cap. on the body. It can also be in the form of an element ensuring the selective closure of the container, in particular a pump, a valve, or a valve.
- the container can be associated with an applicator, in particular in the form of a block of foam or of elastomer, of a felt, or of a spatula.
- the applicator can be free (puff or sponge) or integral with a rod carried by the closure element, as described for example in US patent 5,492,426.
- the applicator can be integral with the container, as described for example the patent FR 2 761 959.
- the product can be contained directly in the container, or indirectly.
- the product can be placed on an impregnated support, in particular in the form of a wipe-or pad, -and-arranged (individually or several) -in- a box or in A sachet.
- an impregnated support in particular in the form of a wipe-or pad, -and-arranged (individually or several) -in- a box or in A sachet.
- Such a support incorporating the product is described for example in application WO 01/03538.
- the closure element can be coupled to the container by screwing.
- the coupling between the closure element and the container is done other than by screwing, in particular via a bayonet mechanism, by snap-fastening, tightening, welding, bonding, or by magnetic attraction.
- snap-fastening is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the closure element, then by return to the non-elastically constrained position of said portion after crossing the bead or cord.
- the container can be at least partly made of thermoplastic material.
- thermoplastic materials mention may be made of polypropylene or polyethylene.
- the container is made of non-thermoplastic material, in particular glass or metal (or alloy).
- the container may have rigid walls or deformable walls, in particular in the form of a tube or a tube bottle.
- the container may include means for causing or facilitating the distribution of the composition.
- the container may have deformable walls so as to cause the exit of the composition in response to an overpressure inside the container, which overpressure is caused by elastic (or inelastic) crushing of the walls of the container. .
- the latter can be driven by a piston mechanism.
- the container may include a mechanism, in particular rack and pinion, or with a threaded rod, or with a helical ramp, and able to move a stick in the direction of said opening.
- the container may consist of a housing with a bottom delimiting at least one housing containing the composition, and a cover, in particular articulated on the bottom, and capable of covering said bottom at least in part.
- a case is described, for example, in application WO 03/018423 or in patent FR 2,791,042.
- the container can be equipped with a wringer disposed near the opening of the container.
- a wringer makes it possible to wipe the applicator and possibly, the rod of which it may be integral.
- Such a wringer is described for example in patent FR 2 792 618.
- the composition can be at atmospheric pressure inside the container (at room temperature) or pressurized, in particular by means of a propellant gas (aerosol).
- a propellant gas as an aerosol
- the container is fitted with a valve (of the type used for aerosols).
- the present examples illustrate the preparation of polymers in accordance with the invention, capable of forming a dispersion of particles in a considered organic medium.
- the average molar masses by weight (Mw) and by number (Mn) of the polymer are determined, the glass transition temperature of the polymer, the dry matter (or dry extract) content of the dispersion and size of the polymer particles.
- the average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).
- THF solvent gel permeation
- the measurement of the glass transition temperature (Tg) is carried out according to standard ASTM D3418-97, by differential enthalpy analysis (DSC "Differential Scanning Calorimetry") on a calorimeter, over a temperature range between -100 ° C and +150 ° C at a heating rate of 10 ° C / min in 150 ⁇ l aluminum crucibles.
- the crucibles are prepared as follows: 100 ⁇ l of the dispersion obtained is introduced into an aluminum crucible of 150 ⁇ l and the solvent is allowed to evaporate for 24 hours at room temperature and at 50% relative humidity. The operation is repeated and then the crucible is introduced into the Mettler DSC30 calorimeter.
- the rate of dry matter (or dry extract), that is to say the content of non-volatile matter, can be measured in different ways: there may be mentioned, for example, methods by drying in an oven or methods by drying by exposure. to infrared radiation.
- the dry matter content is measured by heating the sample by infrared rays from 2 ⁇ m to 3.5 ⁇ m in wavelength.
- the substances contained in the composition which have a high vapor pressure evaporate under the effect of this radiation. Measuring the weight loss of the sample makes it possible to determine the dry extract of the composition.
- These measurements are carried out using a commercial infrared dryer LP16 from Mettler. This technique is fully described in the device documentation provided by Mettler.
- the measurement protocol is as follows: approximately 1 g of the composition is spread over a metal dish. This, after introduction into the desiccator, is subjected to a temperature set point of 120 ° C for one hour. The wet mass of the sample, corresponding to the initial mass and the dry mass of the sample. - corresponding to the mass after exposure to radiation, - are measured using a precision balance.
- Dry extract 100 x (dry mass / wet mass).
- Particle sizes can be measured by different techniques: we can cite in particular light scattering techniques (dynamic and static), Coulter counter methods, measurements by sedimentation speed (related to size via the law of Stokes) and microscopy. These techniques make it possible to measure a particle diameter and for some of them a particle size distribution.
- the sizes and size distributions of the particles of the compositions according to the invention are measured by static light scattering using a commercial granuiometer of the MasterSizer 2000 type from Malvern.
- the data is processed on the basis of Mie diffusion theory.
- This theory exact for isotropic particles, makes it possible to determine in the case of non-spherical particles, an "effective" diameter of particles.
- This theory is notably described in the work of Van de Hulst, HC, "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.
- the composition is characterized by its "effective" average diameter in volume D [4.3], defined as follows:
- Vj represents the volume of particles of effective diameter dj.
- This parameter is described in particular in the technical documentation of the granuiometer.
- the measurements are carried out at 25 ° C., on a dispersion of dilute particles, obtained from the composition as follows: 1) dilution by a factor of 100 with water, 2) homogenization of the solution, 3) rest of the solution for 18 hours, 4) recovery of the whitish homogeneous supernatant.
- the "effective" diameter is obtained by taking a refractive index of 1.33 for water and an average refractive index of 1.42 for particles.
- Example 1 This example illustrates the preparation of a polymer forming a dispersion of particles in a carbon solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the macromonomer corresponding to a polyethylene / polybutylene copolymer (Kraton L-1253 ).
- Theoretical dry extract 54.9% in isododecane
- the grafted polymer comprises 8% by weight of macromonomer relative to the weight of the polymer.
- the stability of the dispersion obtained is demonstrated by the implementation of the following stability protocol: in a hemolysis tube, 8 ml of the dispersion carried out and centrifuged at 4000 rpm for 15 minutes using a Jouan C100-S5 centrifuge. After 15 minutes, we see that there is no phase shift, which shows that the dispersion is stable.
- This example illustrates the preparation of a polymer forming a dispersion of particles in a silicone solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and of monomethacryloxypropyl polydimethylsiloxane macromonomer having a weight average molecular weight of 5000 sold under the name MCR-M17 by the company Gelest Inc.
- the characteristics of the polymer and of the particles formed by said polymer are as follows: - Dry extract: 50% in decamethylcyclopentasiloxane produced by thermobalance
- This example illustrates the preparation of a polymer forming a dispersion of particles in a carbon solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the macromonomer corresponding to a polyethylene / polybutylene copolymer (Kraton L-1253 ).
- the grafted polymer comprises 8% by weight of macromonomer relative to the weight of the polymer.
- This example illustrates the preparation of a polymer forming a dispersion of particles in a carbonaceous solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the macromonomer corresponding to a polyethylene / polybutylene copolymer with methacrylate end group ( Kraton L-1253).
- the grafted polymer comprises 6% by weight of macromonomer relative to the weight of the polymer.
- This example illustrates the preparation of a polymer forming a dispersion of particles in a silicone oil, said polymer being obtained by polymerization of methyl acrylate and of the macromonomer monométhacryloxypropylpolydiméthylsiloxane having a weight average molecular weight of 5000 sold under the name MCR-M17 by Gelest Inc.
- the heating is maintained with stirring for an additional 15 minutes, then a mixture consisting of 160 g of methyl acrylate and 2 g of Trigonox 21 S. The heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium.
- the grafted polymer comprises 5% by weight of macromonomer (therefore of side chain soluble in D5) relative to the weight of the polymer.
- the polymers of Examples 1 to 5 include the following monomers, their levels being indicated as a percentage by weight of the polymer:
- composition contains 2.1% by weight of graft polymer active material.
- Inwitor 780 K Mono-diglycerides of isosteroic acid esterified with succinic acid, sold by the company Sasol
- Silicone gum mixture of polydiphenyl dimethylsiloxane and cyclopentasiloxane (15/85) sold under the name Mirasil C (DPDM by the company RHODIA
- the 10% of pigments include:
- compositions have a transfer index in the presence of sebum of less than 4.
- compositions of Examples 6 to 8 have better resistance to transfer in the presence of sebum than the compositions of Examples 9 and 10. It is therefore found that the presence of acrylic acid in the grafted polymer promotes the non-transfer property of the deposit obtained with the composition.
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Abstract
Description
Composition cosmétique comprenant un polymère Cosmetic composition comprising a polymer
La présente invention a pour objet une composition cosmétique comprenant un polymère particulier destinée à être appliquée sur la peau d'êtres humains.The subject of the present invention is a cosmetic composition comprising a particular polymer intended to be applied to the skin of human beings.
La composition selon l'invention peut être une composition de maquillage ou une composition de soin de la peau, et de préférence une composition de maquillage.The composition according to the invention can be a makeup composition or a skin care composition, and preferably a makeup composition.
La composition de maquillage peut être un fond de teint, un fard à paupières, un fard à joue, un produit anticernes, un eye-liner, un produit de maquillage du corps. Plus spécialement, l'invention porte sur une composition de fond de teint.The makeup composition can be a foundation, an eyeshadow, a blush, a concealer, an eyeliner, a body makeup product. More specifically, the invention relates to a foundation composition.
La composition de soin peut être un produit de soin de la peau du corps et du visage, notamment un produit solaire, un produit de coloration de la peau (tel qu'un autobronzant).The care composition may be a care product for the skin of the body and the face, in particular a sun care product, a product for coloring the skin (such as a self-tanner).
Les compositions de fond de teint sont couramment employées pour apporter une couleur esthétique à la peau, notamment au visage. Ces produits de maquillage contiennent généralement des huiles, des pigments et/ou charges et éventuellement des additifs comme des actifs cosmétiques ou dermatologiques.Foundation compositions are commonly used to provide an aesthetic color to the skin, in particular to the face. These makeup products generally contain oils, pigments and / or fillers and possibly additives such as cosmetic or dermatological active ingredients.
Ces compositions, lorsqu'elles sont appliquées sur la peau, présentent l'inconvénient de transférer, c'est-à-dire de se déposer au moins en partie, en laissant des traces, sur certains supports avec lesquels elles peuvent être mises en contact et notamment un verre, une tasse, une cigarette, un vêtement ou la peau. Il s'ensuit une tenue médiocre du film appliqué, nécessitant de renouveler régulièrement l'application de la composition de fond de teint ou de rouge à lèvres. Par ailleurs, l'apparition de ces traces inacceptables notamment sur les cols- de -chemisier- peut- écarter-certaines-femmes-de l'utilisation de -ce-type -de- maquillage.These compositions, when applied to the skin, have the drawback of transferring, that is to say of depositing at least in part, leaving traces, on certain supports with which they can be brought into contact. and in particular a glass, a cup, a cigarette, a garment or the skin. This results in poor hold of the applied film, requiring regular renewal of the application of the foundation or lipstick composition. Furthermore, the appearance of these unacceptable traces, in particular on the collars of the hem, may exclude certain women from the use of this type of make-up.
De plus, le sébum excrété par la peau au cours du temps modifie également les propriétés du maquillage. En particulier, le sébum ne favorise pas l'adhésion du maquillage sur la peau et le transfert du maquillage est encore plus important, engendrant une perte notable du maquillage restant sur la peau.In addition, the sebum excreted by the skin over time also changes the properties of makeup. In particular, sebum does not promote the adhesion of makeup on the skin and the transfer of makeup is even more important, causing a significant loss of the makeup remaining on the skin.
On recherche donc des compositions de maquillage de la peau « sans transfert » qui présentent l'avantage de former un dépôt résistant au transfert, en particulier en présence de sébum, notamment qui ne se dépose pas, au moins en partie, sur les supports avec lesquels elles sont mises en contact (verre, vêtements, cigarette, tissus).We are therefore looking for “makeup-free” makeup compositions for the skin which have the advantage of forming a deposit resistant to transfer, in particular in the presence of sebum, in particular which does not deposit, at least in part, on the supports with which they are put in contact (glass, clothes, cigarette, fabrics).
Pour améliorer la tenue des produits de maquillage, il est connu d'utiliser des polymères filmogènes. Par exemple, les documents US-6074654 et WO02/067877 proposent d'employer des résines de silicones.To improve the hold of make-up products, it is known to use film-forming polymers. For example, documents US-6074654 and WO02 / 067877 propose to use silicone resins.
La présente invention a donc pour but de fournir une nouvelle voie de formulation d'un produit cosmétique qui permette d'obtenir de bonnes propriétés de résistance au transfert, notamment en présence de sébum.The present invention therefore aims to provide a new way of formulating a cosmetic product which makes it possible to obtain good transfer resistance properties, in particular in the presence of sebum.
Les inventeurs ont découvert qu'il est possible d'obtenir une telle composition en utilisant un polymère particulier.The inventors have discovered that it is possible to obtain such a composition using a particular polymer.
De façon plus précise, la présente invention a donc pour objet une composition cosmétique de maquillage ou de soin de la peau comprenant une dispersion de particules, de préférence solides, d'un polymère éthylénique greffé dans une phase grasse liquide telle que décrite ci-après, la composition étant notamment telle que définie ci-après.More specifically, the present invention therefore relates to a cosmetic composition for making up or caring for the skin comprising a dispersion of particles, preferably solid, of an ethylenic polymer grafted in a liquid fatty phase as described below. , the composition being in particular as defined below.
Avantageusement, le polymère éthylénique greffé est tel que, lorsqu'il est présent en quantité suffisante dans la composition, cette dernière est apte à former un dépôt-ayant-un-indiee de transfert en présenee-de sébum-inférieure à-4. -Advantageously, the grafted ethylenic polymer is such that, when it is present in a sufficient amount in the composition, the latter is capable of forming a deposit-having-an indie transfer in the presence of sebum-less than-4. -
L'invention a également pour objet un procédé de maquillage de la peau, comprenant l'application sur les matières kératiniques, notamment sur la peau d'une composition telle que définie précédemment. L'invention a aussi pour objet l'utilisation d'une composition telle que définie précédemment pour obtenir un dépôt, notamment un maquillage sur la peau ayant une bonne résistance au transfert, notamment en présence de sébum.The subject of the invention is also a method for making up the skin, comprising the application to keratin materials, in particular to the skin, of a composition as defined above. The invention also relates to the use of a composition as defined above for obtaining a deposit, in particular a make-up on the skin having good resistance to transfer, in particular in the presence of sebum.
L'invention a encore pour objet l'utilisation, dans une composition cosmétique d'une dispersion de particules (de préférence solides) d'un polymère éthylénique greffé en dispersion dans une phase grasse liquide, la composition étant notamment apte à former un dépôt ayant un indice de transfert en présence de sébum inférieure à 4, pour obtenir un dépôt, notamment un maquillage, sur la peau présentant une bonne résistance au transfert, notamment en présence de sébum.Another subject of the invention is the use, in a cosmetic composition, of a dispersion of (preferably solid) particles of an ethylenic polymer grafted in dispersion in a liquid fatty phase, the composition being in particular capable of forming a deposit having a transfer index in the presence of sebum of less than 4, to obtain a deposit, in particular make-up, on the skin having good resistance to transfer, in particular in the presence of sebum.
Avantageusement, le polymère éthylénique greffé utilisé dans la composition selon l'invention est tel que lorsqu'il est présent en quantité suffisante dans la composition, cette dernière est apte à former un dépôt ayant un indice de transfert en présence de sébum inférieur à 4, notamment inférieur ou égal à 3,5 , de préférence inférieur ou égal à 3, notamment inférieur ou égal à 2,5 , préférentiellement inférieur ou égal à 2, plus préférentiellement inférieur ou égal 1 ,5 , et notamment inférieur ou égal à 1.Advantageously, the grafted ethylenic polymer used in the composition according to the invention is such that when it is present in a sufficient amount in the composition, the latter is capable of forming a deposit having a transfer index in the presence of sebum of less than 4, in particular less than or equal to 3.5, preferably less than or equal to 3, in particular less than or equal to 2.5, preferably less than or equal to 2, more preferably less than or equal to 1.5, and in particular less than or equal to 1.
L'indice de transfert en présence de sébum du dépôt obtenu avec la composition selon l'invention est déterminé selon le protocole de mesure décrit ci-après.The transfer index in the presence of sebum of the deposit obtained with the composition according to the invention is determined according to the measurement protocol described below.
On prépare un support (carré de 40 mm X 40 mm) constitué d'une couche de mousse de néoprène adhésif sur une de ses faces (vendue sous la dénomination RE70X40 212B de la société JOINT TECHNIQUE LYONNAIS IND). Sur la face non adhésive du support on fixe une couronne adhésive ayant un diamètre -interne -de —24 mm -et dont l'épaisseur- est d'environ -250- μm--Θn -applique- à l'intérieur de la couronne la composition que l'on arase avec une lame de verre pour obtenir un dépôt de la composition d'environ 250 μm d'épaisseur puis on retire la couronne et on laisse sécher pendant 20 heures à l'étuve à 37 °C. Le support est ensuite collé par sa face adhésive sur un embout d'un diamètre de 27 mm fixé sur une presse (STATIF MANUEL SV-1 de la société IMADA Co LTD) équipée d'un dynanomètre (DPS-5R de la société IMADA Co LTD).A support is prepared (square 40 mm X 40 mm) consisting of a layer of adhesive neoprene foam on one of its faces (sold under the name RE70X40 212B from the company JOINT TECHNIQUE LYONNAIS IND). On the non-adhesive side of the support, an adhesive crown is fixed having an internal diameter of -24 mm and the thickness of which is approximately -250 μm - Θn -applies- inside the crown the composition which is leveled off with a glass slide to obtain a deposit of the composition of approximately 250 μm thick, then the crown is removed and left to dry for 20 hours in an oven at 37 ° C. The support is then bonded by its adhesive side to a tip with a diameter of 27 mm fixed on a press (MANUAL STATIF SV-1 from the company IMADA Co LTD) equipped with a dynanometer (DPS-5R from the company IMADA Co LTD).
Sur un papier couché qualité photo (référence EPSON S041061 de 102g/m2) , on dessine une bande de 4 cm de largeur et 21 cm de longueur et dans cette bande on dessine 5 cases ayant chacune une longueur de 4,2 cm selon l'axe longitudinal de la bande. Le papier est placé sur le socle de la presse.On a photo quality coated paper (EPSON reference S041061 of 102g / m2), we draw a strip 4 cm wide and 21 cm long and in this strip we draw 5 boxes each having a length of 4.2 cm depending on the longitudinal axis of the strip. The paper is placed on the base of the press.
On dépose au centre de la première case une goutte de 10 μl de sébum artificiel ayant la composition suivante :A drop of 10 μl of artificial sebum having the following composition is placed in the center of the first box:
- trioléine 29 %- triolein 29%
- acide oléïque 28,5 %- oleic acid 28.5%
- oléate d'oléyle 18,5 %- 18.5% oleyl oleate
- squalène 14 %- squalene 14%
- cholestérol 7 %- cholesterol 7%
- palmitate de cholestérol 3 %- cholesterol palmitate 3%
Puis on presse le support (comportant l'échantillon de composition) sur la première case de la bande de papier à une force d'environ 4 kg exercée pendant 5 secondes. Puis on déplace de manière rectiligne et régulière le papier sur toute la longueur de la bande de telle sorte que le support soit en contact avec toute la longueur de la bande. La vitesse de déplacement de la bande est de l'ordre de 10 cm/s.Then the support (comprising the composition sample) is pressed on the first box of the paper strip at a force of approximately 4 kg exerted for 5 seconds. Then the paper is moved in a rectilinear and regular fashion over the entire length of the strip so that the support is in contact with the entire length of the strip. The speed of movement of the strip is of the order of 10 cm / s.
On observe alors visuellement la traînée de produit déposée sur la bande de papier. On attribue une note allant de Oà 5 par incréments de 0,5 en fonction du nombre de cases, de la première à la cinquième, traversées en tout ou partie par l-éventuelle-traînée de produit.The product trail deposited on the paper strip is then visually observed. A score ranging from 0 to 5 is assigned in increments of 0.5 depending on the number of boxes, from the first to the fifth, crossed in whole or in part by the possible streak of product.
Pour certains produits, non colorés, une étape de révélation peut être nécessaire de manière à rendre visible la traînée de produit. A titre d'exemple on utilise un composé apte à produire une réaction colorée au contact du produit transféré. Selon un autre exemple, on incorpore au produit à tester un actif qui émet dans le visible au moins une partie d'un rayonnement UV (lampe de Wood).For certain non-colored products, a revealing step may be necessary in order to make the product trail visible. By way of example, a compound is used which is capable of producing a colored reaction on contact with the transferred product. According to another example, an active ingredient which emits at least part of the UV radiation (Wood lamp) is incorporated into the product to be tested.
La note 5 est attribuée lorsqu'à l'observation, après avoir fait le déplacement relatif entre le papier et le support, il ne subsiste sur le support sensiblement aucun produit (moins de 10%). Dans ce dernier cas, le transfert peut être qualifié de total.A score of 5 is awarded when, upon observation, after having made the relative displacement between the paper and the support, substantially no product remains on the support (less than 10%). In the latter case, the transfer can be qualified as total.
La note 5 est également attribuée lorsque la traînée de produit s'étend au delà de la cinquième case, indépendamment de la quantité de produit subsistant sur le support.A score of 5 is also awarded when the product trail extends beyond the fifth box, regardless of the amount of product remaining on the support.
La note 0 est attribuée dans le cas où aucun produit présent sur le support n'est transféré sur la bande de papier. Aucune trace visible ne peut être observée sur la feuille. Le transfert peut être qualifié de nul.A score of 0 is assigned in the event that no product present on the support is transferred to the paper strip. No visible trace can be observed on the sheet. The transfer can be called null.
Par convention, le trait de séparation entre la case n et la case n+1 fait partie de la case n.By convention, the dividing line between box n and box n + 1 is part of box n.
Le tableau ci dessous illustre la façon dont sont attribuées les autres notes en fonction de l'endroit sur les cases 1 à 5 où s'arrête la traînée de produit. Pour ces notes, il reste une quantité plus ou moins grande de produit sur le support. Le transfert est partiel.The table below illustrates how the other scores are assigned based on the location in boxes 1 to 5 where the product streak ends. For these notes, there remains a greater or lesser quantity of product on the support. The transfer is partial.
La composition cosmétique selon l'invention comprend une dispersion de particules, de préférence solides, d'un polymère éthylénique greffé dans une phase grasse liquide.The cosmetic composition according to the invention comprises a dispersion of particles, preferably solid, of an ethylenic polymer grafted in a liquid fatty phase.
La composition cosmétique selon l'invention est une composition compatible avec les matières kératiniques, notamment la peau.The cosmetic composition according to the invention is a composition compatible with keratin materials, in particular the skin.
Par polymère "éthylénique", on entend un polymère obtenu par polymérisation de monomères comprenant une insaturation éthylénique.By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.
La dispersion de polymère éthylénique greffé est notamment exempte de polymère stabilisant distinct dudit polymère greffé, tels que ceux décrits dans EP749747, et les particules de polymère éthylénique greffé ne sont donc pas stabilisées en surface par de tels polymères stabilisants additionnels. Le polymère greffé est donc dispersé dans~la phase grasse liquide en l'absence de stabilisant additionnel en surface des particules du polymère grefféThe dispersion of grafted ethylenic polymer is in particular free of stabilizing polymer distinct from said grafted polymer, such as those described in EP749747, and the particles of grafted ethylenic polymer are therefore not surface stabilized by such additional stabilizing polymers. The graft polymer is dispersed in ~ the liquid fatty phase in the absence of additional surface stabilizer particles of the graft polymer
Par polymère greffé, on entend un polymère ayant un squelette comprenant au moins une chaîne latérale pendante ou située en bout de chaîne, et de préférence pendante.By grafted polymer is meant a polymer having a skeleton comprising at least one side chain hanging or located at the end of the chain, and preferably pending.
Avantageusement, le polymère éthylénique greffé comprend un squelette éthylénique insoluble dans ladite phase grasse liquide, et des chaînes latérales liées de manière covalente audit squelette et solubles dans ledit milieu de dispersion.Advantageously, the grafted ethylenic polymer comprises an ethylenic skeleton insoluble in said liquid fatty phase, and side chains covalently linked to said skeleton and soluble in said dispersion medium.
Le polymère éthylénique greffé est notamment un polymère non réticulé. En particulier, le polymère est obtenu par polymérisation de monomères comprenant un seul groupement polymérisable.The grafted ethylenic polymer is in particular a non-crosslinked polymer. In particular, the polymer is obtained by polymerization of monomers comprising a single polymerizable group.
De préférence, le polymère éthylénique greffé est un polymère filmogène. Par polymère "filmogène", on entend un polymère apte à former à lui seul ou en présence d'un agent auxiliaire de filmification, un film continu et adhérent sur un support, notamment sur les matières kératiniques.Preferably, the grafted ethylenic polymer is a film-forming polymer. By “film-forming” polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.
Selon un mode de réalisation de l'invention, le polymère éthylénique greffé est un polymère acrylique greffé.According to one embodiment of the invention, the grafted ethylenic polymer is a grafted acrylic polymer.
Le polymère éthylénique greffé est notamment susceptible d'être obtenu par polymérisation radicalaire dans un milieu organique de polymérisation :The grafted ethylenic polymer is in particular capable of being obtained by radical polymerization in an organic polymerization medium:
- d'au moins un monomère éthylénique, en particulier d'au moins un monomère acrylique et éventuellement d'au moins un monomère additionnel vinylique non acrylique, pour former ledit squelette insoluble ; et- At least one ethylenic monomer, in particular at least one acrylic monomer and optionally at least one additional non-acrylic vinyl monomer, to form said insoluble skeleton; and
- d'au moins un macromonomère comportant un groupe terminal polymérisable pour former les chaînes latérales, ledit macromonomère ayant une masse moléculaire moyenne en poids supérieure ou égale à 200 et la teneur en macromonomère polymérisé représentant de 0,05 à 20 % en poids du polymère.- At least one macromonomer comprising a polymerizable end group to form the side chains, said macromonomer having a weight average molecular weight greater than or equal to 200 and the content of polymerized macromonomer representing from 0.05 to 20% by weight of the polymer .
La phase grasse liquide peut contenir le milieu organique de polymérisation.The liquid fatty phase may contain the organic polymerization medium.
Le milieu organique liquide de dispersion, correspondant au milieu dans lequel est fourni le polymère greffé, peut être identique au milieu de polymérisation. Toutefois, le milieu de polymérisation peut être substitué en tout ou partie par un autre milieu organique liquide. Cet autre milieu organique liquide peut être ajouté, après polymérisationj au milieu de polymérisation. Ce dernier est ensuite évaporé en tout ou partie.The liquid organic dispersion medium, corresponding to the medium in which the grafted polymer is supplied, may be identical to the polymerization medium. However, the polymerization medium can be substituted in whole or in part by another liquid organic medium. This other liquid organic medium can be added, after polymerization, to the polymerization medium. The latter is then evaporated in whole or in part.
La phase grasse liquide peut contenir des composés liquides organiques autres que ceux présents dans le milieu de dispersion. Ces autres composés sont choisis de manière à ce que le polymère greffé reste à l'état de dispersion dans la phase grasse liquide.The liquid fatty phase can contain organic liquid compounds other than those present in the dispersion medium. These other compounds are chosen so that the grafted polymer remains in the state of dispersion in the liquid fatty phase.
Le milieu liquide organique de dispersion est présent dans la phase grasse liquide de la composition selon l'invention du fait de l'introduction dans la composition de la dispersion de polymère greffé obtenue.The organic liquid dispersion medium is present in the liquid fatty phase of the composition according to the invention due to the introduction into the composition of the graft polymer dispersion obtained.
La phase grasse liquide comprend, de préférence majoritairement un ou plusieurs composés organiques liquides (ou huiles) tels que définis ci-après. En particulier, la phase grasse liquide est une phase organique liquide non aqueuse et non miscible à l'eau à la température ambiante (25 °C).The liquid fatty phase preferably comprises one or more liquid organic compounds (or oils) as defined below. In particular, the liquid fatty phase is a non-aqueous liquid organic phase which is immiscible with water at room temperature (25 ° C).
On entend par "composé organique liquide" un composé non aqueux qui est à l'état liquide à la température ambiante (25 °C) et qui s'écoule donc de son propre poids.The term “liquid organic compound” is understood to mean a non-aqueous compound which is in the liquid state at room temperature (25 ° C.) and which therefore flows from its own weight.
On entend par "composé siliconé" un composé contenant au moins un atome de silicium.The term “silicone compound” means a compound containing at least one silicon atom.
Parmi les composés organiques liquides ou huiles, notamment volatiles ou non volatiles, pouvant être présents dans le milieu organique liquide de dispersion, on peut citer : - les composés organiques liquides, notamment non siliconés ou siliconés, ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1 2, de préférence inférieur ou égal à 17 (MPa)1/2, - les monoalcools ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1/2 ; et - leurs mélanges.Among the liquid organic compounds or oils, in particular volatile or non-volatile, which may be present in the liquid organic dispersion medium, there may be mentioned: - liquid organic compounds, in particular non-silicone or silicone, having a global solubility parameter according to Hansen solubility space less than or equal to 18 (MPa) 1 2 , preferably less than or equal to 17 (MPa) 1/2 , - monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal at 20 (MPa) 1/2 ; and - their mixtures.
Le paramètre de solubilité global δ selon l'espace de solubilité de Hansen est défini dans l'article « Solubility parameter values » de Eric A.Grulke de l'ouvrage « Polymer Handbook », 3eme édition, Chapitre VII, p.519-559 par la relation : δ= (dD 2 + dp2 + dH 2)1/2 dans laquelleThe global solubility parameter δ according to Hansen's solubility space is defined in the article “Solubility parameter values” by Eric A. Grulke of the work “Polymer Handbook”, 3 rd edition, Chapter VII, p.519- 559 by the relation: δ = (d D 2 + dp 2 + d H 2 ) 1/2 in which
- do caractérise les forces de dispersion de LONDON issues de la formation de dipôles induits lors des chocs moléculaires, - dp caractérise les forces d'interactions de DEBYE entre dipôles permanents, et- do characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks, - dp characterizes the DEBYE interaction forces between permanent dipoles, and
- dH caractérise les forces d'interactions spécifiques (type liaisons hydrogène, acide/base, donneur/accepteur, etc.).- d H characterizes the specific interaction forces (such as hydrogen bonds, acid / base, donor / acceptor, etc.).
La définition des solvants dans l'espace de solubilité selon Hansen est décrite dans l'article de CM. Hansen « The three dimensional solubility parameters » J.Paint Technol. 39, 105 (1967).The definition of solvents in the solubility space according to Hansen is described in the article by CM. Hansen "The three dimensional solubility parameters" J.Paint Technol. 39, 105 (1967).
Parmi les composés liquides organiques, notamment non siliconés ou siliconés, ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (Mpa)1/2, on peut citer des corps gras liquides, notamment des huiles, qui peuvent être choisis parmi les huiles naturelles ou synthétiques, carbonées, hydrocarbonées, fluorées, siliconées, éventuellement ramifiées, seules ou en mélange.Among the organic liquid compounds, in particular non-silicone or silicone compounds, having a global solubility parameter according to the Hansen solubility space of less than or equal to 18 (Mpa) 1/2 , liquid fatty substances, in particular oils, may be mentioned which can be chosen from natural or synthetic, carbon, hydrocarbon, fluorinated, silicone oils, optionally branched, alone or as a mixture.
Par "huile", on entend tout milieu non aqueux liquide à température ambiante (25°C) et pression atmosphérique (760mm de Hg), compatible avec une application sur la peau, les muqueuses (lèvres) et/ou les phanères (ongles, cils, sourcils, cheveux)."Oil" means any non-aqueous medium which is liquid at room temperature (25 ° C) and atmospheric pressure (760mm Hg), compatible with application to the skin, mucous membranes (lips) and / or integuments (nails, eyelashes, eyebrows, hair).
Parmi ces -huiles, on peut citer les huiles végétales formées -par des esters- d'acides gras et de polyols, en particulier les triglycérides, telles que l'huile de tournesol, de sésame ou de colza, ou les esters dérivés d'acides ou d'alcools à longue chaîne (c'est-à-dire ayant de 6 à 20 atomes de carbone), notamment les esters de formule RCOOR' dans laquelle R représente le reste d'un acide gras supérieur comportant de 7 à 19 atomes de carbone et R' représente une chaîne hydrocarbonée comportant de 3 à 20 atomes de carbone, tels que les palmitates, les adipates et les benzoates, notamment l'adipate de diisopropyle. On peut également citer les alcanes linéaires, ramifiés et/ou cycliques éventuellement volatils et notamment des huiles de paraffine, de vaseline, ou le polyisobutylène hydrogéné, l'isododécane, ou encore les 'ISOPARS', les isoparaffines volatiles. On peut citer également les esters, les éthers, les cétones. On peut encore citer les huiles siliconées telles que les polydiméthylsiloxanes et les polyméthylphénylsiloxanes, éventuellement substitués par des groupements aliphatiques et/ou aromatiques, éventuellement fluorés, ou par des groupements fonctionnels tels que des groupements hydroxyles, thiols et/ou aminés, et les huiles siliconées volatiles, notamment cycliques.Among these oils, vegetable oils formed by esters of fatty acids and polyols, in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or long-chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR 'in which R represents the remainder of a fatty acid higher comprising from 7 to 19 carbon atoms and R ′ represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, such as palmitates, adipates and benzoates, in particular diisopropyl adipate. Mention may also be made of linear, branched and / or cyclic alkanes which may be volatile and in particular paraffin oils, of petrolatum, or hydrogenated polyisobutylene, isododecane, or also 'ISOPARS', volatile isoparaffins. Mention may also be made of esters, ethers and ketones. Mention may also be made of silicone oils such as polydimethylsiloxanes and polymethylphenylsiloxanes, optionally substituted by aliphatic and / or aromatic groups, optionally fluorinated, or by functional groups such as hydroxyl, thiol and / or amino groups, and silicone oils volatile, especially cyclical.
En particulier, on peut citer les huiles de silicone, éventuellement ramifiées, volatiles et/ou non volatiles.In particular, mention may be made of silicone oils, optionally branched, volatile and / or non-volatile.
Par huile volatile, on entend tout milieu non aqueux susceptible de s'évaporer de la peau ou des lèvres, en moins d'une heure, ayant notamment une pression de vapeur, à température ambiante et pression atmosphérique allant de 10"3 à 300 mm de Hg (0,13 Pa à 40 000 Pa).By volatile oil is meant any non-aqueous medium capable of evaporating from the skin or the lips, in less than an hour, having in particular a vapor pressure, at ambient temperature and atmospheric pressure ranging from 10 "3 to 300 mm of Hg (0.13 Pa to 40,000 Pa).
Comme huile siliconée volatile utilisable dans l'invention, on peut citer les siliconés linéaires ou cycliques ayant de 2 à 7 atomes de silicium, ces siliconés comportant éventuellement des groupes alkyle ou alkoxy ayant de 1 à 10 atomes de carbone. En particulier, on peut citer l'octaméthylcyclotétrasiloxane, le décaméthylcyclopentasiloxane, le dodécaméthylcyclohexasiloxane, l'heptaméthylhexyltrisiloxane, l'heptaméthyloctyltrisiloxane, l'octaméthyltrisiloxane, le décaméthyltétrasiloxane et leurs mélanges.As volatile silicone oil which can be used in the invention, mention may be made of linear or cyclic silicones having from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. In particular, there may be mentioned octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and their mixtures.
Comme huile siliconée non volatile, on peut citer les polydialkylsiloxanes non -v0.ati.s7-— tels- -que --les polydiméthylsiloxanes (-P-DMS) — non- volatilsf -les- polydiméthylsiloxanes comportant des groupements alkyle, alcoxy ou phényle, pendant ou en bout de chaîne siliconée, groupements ayant de 2 à 24 atomes de carbone; les siliconés phénylées comme les phényl triméthicones, les phényl diméthicones, les phényl triméthylsiloxy diphénylsiloxanes, les diphényl diméthicones, les diphényl méthyldiphényl trisiloxanes, les polyméthylphénylsiloxanes; les polysiloxanes modifiés par des acides gras (notamment en C8-C20), des alcools gras (notamment en C8-C20) ou des polyoxyalkylènes (notamment polyoxyéthyléne et/ou polyoxypropylène); les polysiloxanes aminées ; les polysiloxanes à groupement hydroxyles; les polysiloxanes fluorés comportant un groupement fluoré pendant ou en bout de chaîne siliconée ayant de 1 à 12 atomes de carbone dont tout ou partie des hydrogène sont substitués par des atomes de fluor ; et leurs mélanges.Mention may be made, as non-volatile silicone oil, of polydialkylsiloxanes which are not -v0.ati.s 7 - such as - polydimethylsiloxanes (-P-DMS) - non-volatile - polydimethylsiloxanes comprising alkyl, alkoxy or phenyl, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyls dimethicones, diphenyl methyldiphenyl trisiloxanes, polymethylphenylsiloxanes; polysiloxanes modified with fatty acids (especially C8-C20), fatty alcohols (especially C8-C20) or polyoxyalkylenes (especially polyoxyethylene and / or polyoxypropylene); amino polysiloxanes; polysiloxanes containing hydroxyl groups; fluorinated polysiloxanes comprising a fluorinated group during or at the end of the silicone chain having from 1 to 12 carbon atoms of which all or part of the hydrogen are substituted by fluorine atoms; and their mixtures.
On peut citer, en particulier, comme composés organiques liquides non siliconés ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (Mpa)1/2 :Mention may be made, in particular, as non-silicone liquid organic compounds having an overall solubility parameter according to the Hansen solubility space of less than or equal to 18 (Mpa) 1/2 :
- les esters linéaires, ramifiés ou cycliques, ayant au moins 6 atomes de carbone, notamment de 6 à 30 atomes de carbone;- linear, branched or cyclic esters, having at least 6 carbon atoms, in particular from 6 to 30 carbon atoms;
- les éthers ayant au moins 6 atomes de carbone, notamment de 6 à 30 atomes de carbone ; et- ethers having at least 6 carbon atoms, in particular from 6 to 30 carbon atoms; and
- les cétones ayant au moins 6 atomes de carbone, notamment de 6 à 30 atomes de carbone.- ketones having at least 6 carbon atoms, in particular from 6 to 30 carbon atoms.
Par monoalcools liquides ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1/2, on entend les monoalcools liquides gras aliphatiques ayant de 6 à 30 atomes de carbone, la chaîne hydrocarbonée ne comportant pas de groupement de substitution. Comme monoalcools selon l'invention, on peut citer l'alcool oléique, le décanol et l'alcool linoléique.By liquid monoalcohols having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 , is meant aliphatic fatty liquid monoalcohols having from 6 to 30 carbon atoms, the hydrocarbon chain not comprising no substitution group. As monoalcohols according to the invention, there may be mentioned oleic alcohol, decanol and linoleic alcohol.
Avantageusement, la composition selon l'invention peut comprendre une huile volatile en une teneur allant de 1 % à 90 % en poids, par rapport au poids total de -la-composition,-et-da.pr-éféπence-allant.de_5..%_à_70 % en-poids. ___ . ....Advantageously, the composition according to the invention may comprise a volatile oil in a content ranging from 1% to 90% by weight, relative to the total weight of -the-composition, -and-da.pr-éféπence-ranging.de_5. .% _ to_70% by weight. ___. ....
La composition peut comprendre une huile non volatile en une teneur allant de 0,1 % à 80 % en poids, par rapport au poids total de la composition, et de préférence allant de 3 % à 50 % en poids. Selon un premier mode de réalisation de l'invention, la phase grasse liquide peut être une phase grasse liquide non siliconée.The composition may comprise a non-volatile oil in a content ranging from 0.1% to 80% by weight, relative to the total weight of the composition, and preferably ranging from 3% to 50% by weight. According to a first embodiment of the invention, the liquid fatty phase can be a non-silicone liquid fatty phase.
On entend par "phase grasse liquide non siliconée" une phase grasse comprenant un ou plusieurs composés organiques liquides ou huiles non siliconé(e)s, tels que ceux cités précédemment, lesdits composés non siliconés étant présents majoritairement dans la phase grasse liquide, c'est-à-dire à au moins 50 % en poids, notamment de 50 à 100 % en poids, de préférence de 60 % à 100 % en poids (par exemple de 60 à 99 % en poids), ou encore de 65 % à 100 % en poids (par exemple de 65 à 95 % en poids), par rapport au poids total de la phase grasse liquide.The term “non-silicone liquid fatty phase” means a fatty phase comprising one or more liquid organic compounds or non-silicone oils, such as those mentioned above, said non-silicone compounds being present mainly in the liquid fatty phase, it that is to say at least 50% by weight, in particular from 50 to 100% by weight, preferably from 60% to 100% by weight (for example from 60 to 99% by weight), or even from 65% to 100% by weight (for example from 65 to 95% by weight), relative to the total weight of the liquid fatty phase.
Les composés organiques liquides non siliconés peuvent être notamment choisis parmi :The non-silicone-based liquid organic compounds can in particular be chosen from:
- les composés organiques liquides non siliconés ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1/2, les monoalcools ayant un paramètre de solubilité global selon l'espace de so illuubbiilliittéé ddee HHaannssen inférieur ou égal à 20 (MPa)1/2 ; et leurs mélanges.- non-silicone-based liquid organic compounds having a global solubility parameter according to the Hansen solubility space less than or equal to 18 (MPa) 1/2 , the monoalcohols having a global solubility parameter according to the space of so illuubbiilliitté ddee HHaannssen less than or equal to 20 (MPa) 1/2 ; and their mixtures.
Ladite phase grasse liquide non siliconée peut donc éventuellement comprendre des composés organiques liquide ou huiles siliconé(e)s, tels que ceux cités précédemment, qui peuvent être présents en une quantité inférieure à 50 % en poids, notamment allant de 0,1 à 40 % en poids, voire allant de 1 à 35 % en poids, ou encore allant de 5 à 30 % en poids, par rapport au poids total de la phase grasse liquide.Said non-silicone-based liquid fatty phase may therefore optionally comprise liquid organic compounds or silicone oils, such as those mentioned above, which may be present in an amount of less than 50% by weight, in particular ranging from 0.1 to 40 % by weight, or even ranging from 1 to 35% by weight, or even ranging from 5 to 30% by weight, relative to the total weight of the liquid fatty phase.
Selon un mode particulier de réalisation de l'invention, la phase grasse liquide non siliconée ne contient pas de composés organiques liquides ou huiles siliconé(e)s.According to a particular embodiment of the invention, the non-silicone liquid fatty phase does not contain liquid organic compounds or silicone oils.
-Lorsque-la phase grasse liquide est une phase grasse liquide non siliconée,-les macromonomères présents dans le polymère greffé sont avantageusement des macromonomères carbonés tels que décrits ci-après.When the liquid fatty phase is a non-silicone liquid fatty phase, the macromonomers present in the grafted polymer are advantageously carbon macromonomers as described below.
Lorsque la phase grasse liquide est une phase grasse liquide non siliconée, les macromonomères présents dans le polymère greffé sont avantageusement des macromonomères carbonés tels que décrits ci-après.When the liquid fatty phase is a non-silicone liquid fatty phase, the macromonomers present in the grafted polymer are advantageously carbon macromonomers as described below.
Par polymère greffé non siliconé, on entend un polymère greffé contenant majoritairement un macromonomère carboné et contenant éventuellement au plus 7 % en poids du poids total du polymère, de préférence au plus 5 % en poids, voire est exempt, de macromonomère siliconé.The term “non-silicone grafted polymer” is intended to mean a grafted polymer mainly containing a carbon macromonomer and optionally containing at most 7% by weight of the total weight of the polymer, preferably at most 5% by weight, or even is free, of silicone macromonomer.
Selon un deuxième mode de réalisation de l'invention, la phase grasse liquide peut être une phase grasse liquide siliconée.According to a second embodiment of the invention, the liquid fatty phase can be a silicone liquid fatty phase.
On entend par "phase grasse liquide siliconée" une phase grasse comprenant un ou plusieurs composés organiques liquides siliconés ou huiles siliconées tels que ceux décrits précédemment, lesdits composés siliconés étant présents majoritairement dans la phase grasse liquide, c'est-à-dire à au moins 50 % en poids, notamment de 50 à 100 % en poids, de préférence de 60 % à 100 % en poids (par exemple de 60 à 99 % en poids), ou encore de 65 % à 100 % en poids (par exemple de 65 à 95 % en poids), par rapport au poids total de la phase grasse liquide.The term “silicone liquid fatty phase” means a fatty phase comprising one or more silicone liquid organic compounds or silicone oils such as those described above, said silicone compounds being present mainly in the liquid fatty phase, that is to say at least at least 50% by weight, in particular from 50 to 100% by weight, preferably from 60% to 100% by weight (for example from 60 to 99% by weight), or also from 65% to 100% by weight (for example from 65 to 95% by weight), relative to the total weight of the liquid fatty phase.
Les composés organiques liquides siliconés peuvent être notamment choisis parmi :The liquid organic silicone compounds can be chosen in particular from:
- les composés organiques liquides, notamment non siliconés ou siliconés, ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1/2.- liquid organic compounds, in particular non-silicone or silicone compounds, having an overall solubility parameter according to the Hansen solubility space less than or equal to 18 (MPa) 1/2 .
Ladite phase grasse liquide siliconée peut donc éventuellement comprendre des composés organiques liquides ou huiles non siliconé(e)s, tels que décritsSaid liquid silicone fatty phase can therefore optionally comprise liquid organic compounds or non-silicone oils, as described
-précédemment! qui peuvent-être présents en une-quantité-inférieure à-50 %-eh poids, notamment allant de 0,1 à 40 % en poids, voire allant de 1 à 35 % en poids, ou encore allant de 5 à 30 % en poids, par rapport au poids total da la phase grasse liquide. Selon un mode particulier de réalisation de l'invention, la phase grasse liquide siliconée ne contient pas de composés organiques liquides non siliconés.- previously ! which may be present in an amount of less than -50% by weight, in particular ranging from 0.1 to 40% by weight, or even ranging from 1 to 35% by weight, or even ranging from 5 to 30% by weight. weight, relative to the total weight of the liquid fatty phase. According to a particular embodiment of the invention, the silicone liquid fatty phase does not contain non-silicone liquid organic compounds.
Lorsque la phase grasse liquide est une phase grasse liquide siliconée, les macromonomères présents dans le polymère greffé sont avantageusement des macromonomères Lorsque la phase grasse liquide est une phase grasse liquide siliconée, les macromonomères présents dans le polymère greffé sont avantageusement des macromonomères siliconés tels que décrits ci-après.When the liquid fatty phase is a liquid silicone fatty phase, the macromonomers present in the grafted polymer are advantageously macromonomers When the liquid fatty phase is a liquid silicone fatty phase, the macromonomers present in the grafted polymer are advantageously silicone macromonomers as described below.
En particulier, lorsque la phase grasse liquide est une phase grasse liquide siliconée, le polymère greffé présent dans la composition est avantageusement un polymère greffé siliconé.In particular, when the liquid fatty phase is a silicone liquid fatty phase, the grafted polymer present in the composition is advantageously a silicone grafted polymer.
Par polymère greffé siliconé, on entend un polymère greffé contenant majoritairement un macromonomère siliconé et contenant éventuellement au plus 7 % en poids du poids total du polymère, de préférence au plus 5 % en poids, voire est exempt, de macromonomère carboné, siliconés tels que décrits ci-après.The term “grafted silicone polymer” is intended to mean a grafted polymer mainly containing a silicone macromonomer and optionally containing at most 7% by weight of the total weight of the polymer, preferably at most 5% by weight, or even is free, of carbonaceous macromonomer, silicone such as described below.
Le choix des monomères constituant le squelette du polymère, des macromonomères, le poids moléculaire du polymère, la proportion des monomères et des macromonomères peut être fait en fonction du milieu organique liquide de dispersion de manière à obtenir avantageusement une dispersion de particules de polymères greffés en particulier une dispersion stable, ce choix pouvant être effectué par l'homme du métier.The choice of monomers constituting the backbone of the polymer, of the macromonomers, the molecular weight of the polymer, the proportion of the monomers and of the macromonomers can be made as a function of the liquid organic dispersion medium so as to advantageously obtain a dispersion of polymer particles grafted in particularly a stable dispersion, this choice can be made by a person skilled in the art.
Par "dispersion stable", on entend une dispersion qui n'est pas susceptible de former de dépôt solide ou de déphasage liquide/solide notamment après une - --centrifugation, par-exemple;-à 4000 tours/minute pendant-15 minutesBy "stable dispersion" is meant a dispersion which is not liable to form a solid deposit or a liquid / solid phase shift, in particular after - - centrifugation, for example; - at 4000 rpm for -15 minutes
Le polymère éthylénique greffé formant les particules en dispersion comprend donc un squelette insoluble dans ledit milieu de dispersion et une partie soluble dans ledit milieu de dispersion. Le polymère éthylénique greffé peut être un polymère statistique.The grafted ethylenic polymer forming the particles in dispersion therefore comprises a skeleton insoluble in said dispersion medium and a part soluble in said dispersion medium. The grafted ethylenic polymer can be a random polymer.
Selon l'invention, on entend par "polymère éthylénique greffé " un polymère susceptible d'être obtenu par polymérisation radicalaire :According to the invention, the term “grafted ethylenic polymer” means a polymer capable of being obtained by radical polymerization:
- d'un ou plusieurs monomère(s) éthylénique(s),- one or more ethylenic monomer (s),
- avec un ou plusieurs macromonomère(s), dans un milieu organique de polymérisation.- with one or more macromonomer (s), in an organic polymerization medium.
Selon l'invention, on entend par "polymère acrylique greffé " un polymère susceptible d'être obtenu par polymérisation radicalaire :According to the invention, the term “grafted acrylic polymer” means a polymer capable of being obtained by radical polymerization:
- d'un ou plusieurs monomère(s) acrylique(s), et éventuellement d'un ou plusieurs monomère(s) additionnel(s) vinylique(s) non acrylique(s),- one or more acrylic monomer (s), and optionally one or more additional non-acrylic vinyl monomer (s),
- avec un ou plusieurs macromonomère(s), dans un milieu organique de polymérisation.- with one or more macromonomer (s), in an organic polymerization medium.
Avantageusement, les monomères acryliques représentent de 50 à 100 % en poids, de préférence de 55 à 100 % en poids (notamment de 55 à 95 %.en poids), préférentiellement de 60 à 100 % en poids (notamment de 60 à 90 % en poids) du mélange monomères acryliques + monomères vinyliques non acryliques éventuels.Advantageously, the acrylic monomers represent from 50 to 100% by weight, preferably from 55 to 100% by weight (in particular from 55 to 95% by weight), preferably from 60 to 100% by weight (in particular from 60 to 90% by weight) of the mixture of acrylic monomers + optional non-acrylic vinyl monomers.
De préférence, les monomères acryliques sont choisis parmi les monomères dont l'homopolymère est insoluble dans le milieu de dispersion considéré, c'est-à-dire que l'homopolymère est sous forme solide (ou non dissous) à une concentration supérieure ou égale à 5% en poids à température ambiante (20°C) dans ledit milieu de dispersion.Preferably, the acrylic monomers are chosen from monomers whose homopolymer is insoluble in the dispersion medium under consideration, that is to say that the homopolymer is in solid form (or not dissolved) at a greater or equal concentration. at 5% by weight at room temperature (20 ° C) in said dispersion medium.
Selon-l'invention,-on-entend-par-"macr-omonomère ayant un grαupe-terminal polymérisable" tout polymère comportant sur une seule de ses extrémités un groupe terminal polymérisable apte à réagir lors de la réaction de polymérisation avec les monomères acryliques et éventuellement les monomères vinyliques non acryliques additionnels constituant le squelette. Le macromonomère permet de former les chaînes latérales du polymère acrylique greffé. Le groupe polymérisable du macromonomère peut être avantageusement un groupe à insaturation éthylénique susceptible de se polymériser par voie radicalaire avec les monomères constituant le squelette.According to the invention, - we mean - "macr-omonomer having a polymerizable grαupe-terminal" any polymer comprising on one of its ends a polymerizable terminal group capable of reacting during the polymerization reaction with acrylic monomers and optionally the additional non-acrylic vinyl monomers constituting the backbone. The macromonomer makes it possible to form the side chains of the grafted acrylic polymer. The group The polymerizable macromonomer can advantageously be an ethylenically unsaturated group capable of polymerizing by the radical route with the monomers constituting the skeleton.
Par "macromonomère carboné" on entend un macromonomère non siliconé, et notamment un macromonomère oligomère obtenu par polymérisation de monomère(s) non siliconé(s) à insaturation éthylénique, et principalement par polymérisation de monomères acryliques et/ou vinyliques non acryliques.By “carbon macromonomer” is meant a non-silicone macromonomer, and in particular an oligomeric macromonomer obtained by polymerization of non-silicone monomer (s) with ethylenic unsaturation, and mainly by polymerization of acrylic and / or non-acrylic vinyl monomers.
Par "macromonomère siliconé" on entend un macromonomère organopolysiloxane, et en particulier un macromonomère polydiméthylsiloxane.By "silicone macromonomer" is meant an organopolysiloxane macromonomer, and in particular a polydimethylsiloxane macromonomer.
De préférence, le macromonomère est choisi parmi les macromonomères dont l'homopolymère est soluble dans le milieu de dispersion considéré, c'est-à-dire complètement dissous à une concentration supérieure ou égale à 5 % en poids et à température ambiante dans ledit milieu de dispersion.Preferably, the macromonomer is chosen from macromonomers whose homopolymer is soluble in the dispersion medium under consideration, that is to say completely dissolved at a concentration greater than or equal to 5% by weight and at room temperature in said medium of dispersion.
Ainsi, le polymère acrylique greffé comprend un squelette (ou chaîne principale) constitué par un enchaînement de motifs acryliques résultant de la polymérisation notamment d'un ou plusieurs monomères acryliques et des chaînes latérales (ou greffons) issus de la réaction des macromonomères, lesdites chaînes latérales étant liées de manière covalente à ladite chaîne principale. Le squelette (ou chaîne principale) est insoluble dans le milieu de dispersion considéré alors que les chaînes latérales (ou greffons) sont solubles dans ledit milieu de dispersion.Thus, the grafted acrylic polymer comprises a skeleton (or main chain) consisting of a chain of acrylic units resulting from the polymerization in particular of one or more acrylic monomers and side chains (or grafts) resulting from the reaction of the macromonomers, said chains side being covalently linked to said main chain. The skeleton (or main chain) is insoluble in the dispersion medium considered while the side chains (or grafts) are soluble in said dispersion medium.
Par "monomères acryliques", on entend dans la présente demande des monomères choisis parmi l'acide (méth)acrylique, les esters de l'acide (méth)acrylique (appelés- également les-(méth)acrylates), les amides de l'acide (méthacrylique) (appelés également les (méth)acrylamides).By "acrylic monomers" is meant in the present application monomers chosen from (meth) acrylic acid, esters of (meth) acrylic acid (also called - (meth) acrylates), amides of l (methacrylic acid) (also called (meth) acrylamides).
Comme monomère acrylique susceptible d'être employé pour former le squelette insoluble du polymère, on peut citer, seul ou en mélange, les monomères suivants, ainsi que leurs sels :As acrylic monomer capable of being used to form the insoluble backbone of the polymer, there may be mentioned, alone or as a mixture, the monomers following, as well as their salts:
-(i) les (méth)acrylates de formule- (i) the (meth) acrylates of formula
CH, COOR2 CH, COOR 2
Ri dans laquelle :Ri in which:
- Ri désigne un atome d'hydrogène ou un groupe méthyle ;- Ri denotes a hydrogen atom or a methyl group;
- R2 représente un groupe choisi parmi :- R 2 represents a group chosen from:
- un groupe alkyle linéaire ou ramifié, comprenant de 1 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs hétéroatomes choisis parmi O, N et S; et/ou pouvant comporter un ou plusieurs substituants choisis parmi -OH, les atomes d'halogène (F, Cl, Br, I) et - NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en C1-C4; et/ou pouvant être substitué par au moins un groupe polyoxyalkylene, en particulier avec alkylène en C2-C4, notamment polyoxyéthylène et/ou polyoxypropylène, ledit groupe polyoxyalkylene étant constitué par la répétition de 5 à 30 motifs oxyalkylène;- a linear or branched alkyl group, comprising from 1 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S; and / or possibly comprising one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and - NR'R "with R 'and R" identical or different chosen from linear or branched alkyls in C1-C4; and / or may be substituted by at least one polyoxyalkylene group, in particular with C2-C4 alkylene, in particular polyoxyethylene and / or polyoxypropylene, said polyoxyalkylene group consisting of the repetition of 5 to 30 oxyalkylene units;
- un groupe alkyle cyclique comprenant de 3 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs hétéroatomes choisis parmi O, N et S, et/ou pouvant comporter un ou plusieurs substituants choisis parmi OH et les atomes d'halogène (F, Cl, Br, I);a cyclic alkyl group comprising from 3 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S, and / or possibly comprising one or more substituents chosen from OH and the atoms of halogen (F, Cl, Br, I);
A titre d'exemples de R2, on peut citer le groupe méthyle, éthyle, propyle, butyle, isobutyle, méthoxyéthyle, éthoxyéthyle, méthoxy-polyoxyéthylène 350 OE , trifluoroéthyle, 2-hydroxyéthyle, 2-hydroxypropyle, diméthylaminoéthyle, diéthylaminoéthyle, diméthylaminopropyle.As examples of R 2 , mention may be made of the methyl, ethyl, propyl, butyl, isobutyl, methoxyethyl, ethoxyethyl, methoxy-polyoxyethylene 350 EO, trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl group.
-(ii) les (méth)acrylamides de formule :- (ii) the (meth) acrylamides of formula:
dans laquelle : - R3 désigne un atome d'hydrogène ou un groupe méthyle ; in which : - R 3 denotes a hydrogen atom or a methyl group;
- R et R5, identiques ou différents, représentent un atome d'hydrogène ou un groupe alkyle, linéaire ou ramifié, comportant de 1 à 6 atomes de carbone, pouvant comporter un ou plusieurs substituants choisis parmi -OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en Cι-C4;ou- R and R 5 , identical or different, represent a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms, which may comprise one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched Cι-C4 alkyls, or
- R représente un atome d'hydrogène et R5 représente un groupe 1 ,1-diméthyl-3- oxobutyle.- R represents a hydrogen atom and R 5 represents a group 1, 1-dimethyl-3-oxobutyl.
A titre d'exemples de groupes alkyles pouvant constituer R4 et R5, on peut citer n- butyle, t-butyle, n-propyle, diméthylaminoéthyle, diéthylaminoéthyle, diméthylaminopropyle.As examples of alkyl groups which may constitute R 4 and R 5 , there may be mentioned n-butyl, t-butyl, n-propyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
les monomères (méth)acryliques comprenant au moins une fonction acide carboxylique, phosphorique ou sulfonique, tels que l'acide acrylique, l'acide méthacrylique, l'acide acrylamidopropanesulfonique.(meth) acrylic monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid.
Parmi ces monomères acryliques, on peut tout particulièrement citer les (méth)acrylates de méthyle, d'éthyle, de propyle, de butyle, d'isobutyle; les (méth)acrylates de méthoxyéthyle ou d'éthoxyéthyle; le méthacrylate de trifluoroéthyle; le méthacrylate de diméthylaminoéthyle, le méthacrylate de diéthylaminoéthyle, le méthacrylate de 2-hydroxypropyle, le méthacrylate de 2- hydroxyéthyle, l'acrylate de 2-hydroxypropyle, l'acrylate de 2-hydroxyéthyle ; le diméthylaminopropylméthacrylamide, l'acide (méth)acrylique ; et leurs sels ; et leurs mélanges.Among these acrylic monomers, mention may very particularly be made of methyl, ethyl, propyl, butyl and isobutyl (meth) acrylates; methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate; dimethylaminopropylmethacrylamide, (meth) acrylic acid; and their salts; and their mixtures.
De préférence, les monomères acryliques sont choisis parmi l'acrylate de méthyle, l'acrylate de méthoxyéthyle, le méthacrylate de méthyle, le méthacrylate de 2- hydroxyéthyle, l'acide (méth)acrylique, le méthacrylate de diméthylaminoéthyle, et leurs mélanges.Preferably, the acrylic monomers are chosen from methyl acrylate, methoxyethyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, (meth) acrylic acid, dimethylaminoethyl methacrylate, and their mixtures.
Parmi les monomères additionnels vinyliques non acryliques, on peut citer : - les esters vinylique de formule : R6-COO-CH=CH2 dans laquelle RQ représente un groupe alkyle linéaire ou ramifié, comprenant de 1 à 6 atomes, ou un groupe alkyle cyclique comportant de 3 à 6 atomes de carbone et/ou un groupe aromatique, par exemple de type benzénique, anthracenique, et naphtalénique ;Among the additional non-acrylic vinyl monomers, mention may be made of: - vinyl esters of formula: R 6 -COO-CH = CH 2 in which RQ represents a linear or branched alkyl group, comprising from 1 to 6 atoms, or an alkyl group cyclic with 3 to 6 carbon atoms and / or an aromatic group, for example of the benzene, anthracene and naphthalene type;
- les monomères vinyliques non acryliques comprenant au moins une fonction acide carboxyiique, phosphorique ou sulfonique, tels que l'acide crotonique, l'anhydride maléique, l'acide itaconique, l'acide fumarique, l'acide maléique, l'acide styrènesulfonique, l'acide vinylbenzoïque, l'acide vinylphosphorique, et leurs sels ;non-acrylic vinyl monomers comprising at least one carboxyic, phosphoric or sulfonic acid function, such as crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, and their salts;
- les monomères vinyliques non acryliques comprenant au moins une fonction aminé tertiaire, tels que la 2-vinylpyridine, la 4-vinylpyridine ; - et leurs mélangeas.- non-acrylic vinyl monomers comprising at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine; - and their mixes.
Selon un mode de réalisation de l'invention, le polymère greffé comprend de l'acide (méth)acryiique.According to one embodiment of the invention, the grafted polymer comprises (meth) acrylic acid.
Avantageusement, les monomères acryliques présents dans le polymère greffé comprennent au moins l'acide (méth)acrylique, et en particulier au moins l'acide (méth)acrylique et au moins un monomère choisi parmi les (méth)acrylates et les (méth)acrylamides décrits précédemment aux points (i) et (ii). De préférence, les monomères acryliques comprennent au moins l'acide (méth)acrylique et au moins un monomère choisi parmi les (méth)acrylates d'alkyle en C-1-C3. L'acide (méth)acrylique peut être présent en une teneur d'au moins 5 % en poids, par rapport au poids total du polymère (notamment allant de 5 % à 80 % en poids), de préférence d'au moins 10 % en poids (notamment allant de 10 % en poids à 70 % en poids) , préférentiellement d'au moins 15 % en poids (notamment allant de 15 % à 60 % en poids).Advantageously, the acrylic monomers present in the grafted polymer comprise at least (meth) acrylic acid, and in particular at least (meth) acrylic acid and at least one monomer chosen from (meth) acrylates and (meth) acrylamides described above in points (i) and (ii). Preferably, the acrylic monomers comprise at least (meth) acrylic acid and at least one monomer chosen from C-1-C3 alkyl (meth) acrylates. The (meth) acrylic acid may be present in a content of at least 5% by weight, relative to the total weight of the polymer (in particular ranging from 5% to 80% by weight), preferably at least 10% by weight (in particular ranging from 10% by weight to 70% by weight), preferably at least 15% by weight (in particular ranging from 15% to 60% by weight).
Parmi les sels, on peut citer ceux obtenus par neutralisation des groupements acides à l'aide de base inorganiques telles que l'hydroxyde de sodium, l'hydroxyde de potassiumH'hydroxyde-d^ammonium ou de -bases organiques-de type aleanols- aminés comme la monoethanolamine, la diéthanolamine, la triethanolamine, la 2- méthyl-2-amino-1 -propanol.Among the salts, mention may be made of those obtained by neutralization of acid groups using inorganic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or organic bases of the aleanol type. amines such as monoethanolamine, diethanolamine, triethanolamine, 2-methyl-2-amino-1-propanol.
On peut également citer les sels formés par neutralisation des motifs aminé tertiaire, par exemple à l'aide d'acide minéral ou organique. Parmi les acides minéraux, on peut citer l'acide sulfurique ou l'acide chlorhydrique, l'acide bromhydrique, iodhydrique, l'acide phosphorique, l'acide borique. Parmi les acides organiques, on peut citer les acides comportant un ou plusieurs groupes carboxylique, sulfonique, ou phosphonique. Il peut s'agir d'acides aliphatiques linéaires, ramifiés ou cycliques ou encore d'acides aromatiques. Ces acides peuvent comporter, en outre, un ou plusieurs hétéroatomes choisis parmi O et N, par exemple sous la forme de groupes hydroxyles. On peut notamment citer l'acide acétique ou l'acide propionique, l'acide téréphtalique, ainsi que l'acide citrique et l'acide tartrique.Mention may also be made of the salts formed by neutralization of the tertiary amine units, for example using mineral or organic acid. Among the acids minerals, there may be mentioned sulfuric acid or hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, boric acid. Among the organic acids, mention may be made of acids comprising one or more carboxylic, sulphonic or phosphonic groups. They can be linear, branched or cyclic aliphatic acids or even aromatic acids. These acids may also contain one or more heteroatoms chosen from O and N, for example in the form of hydroxyl groups. Mention may in particular be made of acetic acid or propionic acid, terephthalic acid, as well as citric acid and tartaric acid.
Selon un mode de réalisation de l'invention, le polymère éthylénique greffé ne contient pas de monomères vinyliques non acryliques additionnels tels que décrits précédemment. Dans ce mode de réalisation, le squelette insoluble du polymère éthylénique greffé est formé uniquement de monomères acryliques tels que décrits précédemment.According to one embodiment of the invention, the grafted ethylenic polymer does not contain additional non-acrylic vinyl monomers as described above. In this embodiment, the insoluble skeleton of the grafted ethylenic polymer is formed only from acrylic monomers as described above.
Il est entendu que ces monomères acryliques non polymérisés peuvent être solubles dans le milieu de dispersion considéré, mais le polymère formé avec ces monomères est insoluble dans le milieu de dispersion.It is understood that these non-polymerized acrylic monomers may be soluble in the dispersion medium under consideration, but the polymer formed with these monomers is insoluble in the dispersion medium.
Selon un mode particulier de réalisation de l'invention, le polymère éthylénique greffé est susceptible d'être obtenu par polymérisation radicalaire dans un milieu organique de polymérisation : - d'un monomère acrylique principal choisi parmi les (méth)acrylates d'alkyle en C1-C3, seul ou en mélange, et éventuellement d'un ou plusieurs monomères acryliques additionnels choisis parmi l'acide acrylique, l'acide méthacrylique et les (méth)acrylates d'alkyle de formule (I) définie ci-après, et leurs sels, pour former ledit squelette insoluble ; etAccording to a particular embodiment of the invention, the grafted ethylenic polymer is capable of being obtained by radical polymerization in an organic polymerization medium: - of a main acrylic monomer chosen from C1 (meth) acrylates -C3, alone or as a mixture, and optionally of one or more additional acrylic monomers chosen from acrylic acid, methacrylic acid and the alkyl (meth) acrylates of formula (I) defined below, and their salts, to form said insoluble skeleton; and
- et d^u moins-un-macromonomère siliconé comportant un groupe terminal- polymérisable, tel que défini précédemment.- And of at least one silicone macromonomer comprising a terminal- polymerizable group, as defined above.
Comme monomère acrylique principal, on peut utiliser l'acrylate de méthyle, le méthacrylate de méthyle, l'acrylate d'éthyle, le méthacrylate d'éthyle, l'acrylate de n-propyle, le méthacrylate de n-propyle, l'acrylate d'iso-propyle et le méthacrylate d'iso-propyle, et leurs mélanges.As the main acrylic monomer, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl acrylate can be used. n-propyl, n-propyl methacrylate, isopropyl acrylate and isopropyl methacrylate, and mixtures thereof.
On préfère tout particulièrement l'acrylate de méthyle, le méthacrylate de méthyle, le méthacrylate d'éthyle.Particular preference is given to methyl acrylate, methyl methacrylate and ethyl methacrylate.
Les monomères acryliques additionnels peuvent être choisis parmi :The additional acrylic monomers can be chosen from:
- l'acide (méth)acrylique et ses sels,- (meth) acrylic acid and its salts,
- les (méth)acrylates de formule (I) et leurs sels :- the (meth) acrylates of formula (I) and their salts:
H,C=C COOR'H, C = C COOR '
| (i)| (I)
dans laquelle :in which :
- R'i désigne un atome d'hydrogène ou un groupe méthyle ;- R'i denotes a hydrogen atom or a methyl group;
- R 2 représente- R 2 represents
- un groupe alkyle linéaire ou ramifié comprenant de 1 à 6 atomes de carbone, ledit groupe comportant dans sa chaîne un ou plusieurs atomes d'oxygène et/ou comportant un ou plusieurs substituants choisis parmia linear or branched alkyl group comprising from 1 to 6 carbon atoms, said group comprising in its chain one or more oxygen atoms and / or comprising one or more substituents chosen from
-OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en C-1-C3 ;-OH, halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched C-1-C3 alkyl;
- un groupe alkyle cyclique comprenant de 3 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs atomes d'oxygène et/ou pouvant comporter un ou plusieurs substituants choisis parmi OH et les atomes d'halogène (F, Cl, Br, I) ;a cyclic alkyl group comprising from 3 to 6 carbon atoms, said group possibly comprising in its chain one or more oxygen atoms and / or possibly comprising one or more substituents chosen from OH and the halogen atoms (F, Cl , Br, I);
- et leurs mélanges.- and their mixtures.
A. titre ^exemples de R2, on peut citer le groupe méthoxyéthyle,_éthoxyéthyle,_ trifluoroéthyle; 2-hydroxyéthyle, 2-hydroxypropyle, diméthylaminoéthyle, diéthylaminoéthyle, diméthylaminopropyle. A. Title ^ examples of R 2 , there may be mentioned the methoxyethyl, _ethoxyethyl, _ trifluoroethyl group; 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
Parmi ces monomères acryliques additionnels, on peut tout particulièrement citer l'acide (méth)acrylique, les (méth)acrylates de méthoxyéthyle ou d'éthoxyéthyle; le méthacrylate de trifluoroéthyle; le méthacrylate de diméthylaminoéthyle, le méthacrylate de diéthylaminoéthyle, le méthacrylate de 2-hydroxypropyle, le méthacrylate de 2-hydroxyéthyle, l'acrylate de 2-hydroxypropyle, l'acrylate de 2- hydroxyéthyle, leurs sels, et leurs mélanges. On préfère tout particulièrement l'acide acrylique, l'acide méthylacrylique.Among these additional acrylic monomers, mention may very particularly be made of (meth) acrylic acid, methoxyethyl or ethoxyethyl (meth) acrylates; the trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, their salts, and mixtures thereof. Particularly preferred is acrylic acid, methylacrylic acid.
Les macromonomères comportent à une des extrémités de la chaîne un groupe terminal polymérisable apte à réagir au cours de la polymérisation avec les monomères acryliques et éventuellement les monomères vinyliques additionnels, pour former les chaînes latérales du polymère éthylénique greffé. Ledit groupe terminal polymérisable peut être en particulier un groupe vinyle ou (méth)acrylate (ou (méth)acryl), et de préférence un groupe (méth)acrylate.The macromonomers comprise at one end of the chain a polymerizable end group capable of reacting during the polymerization with the acrylic monomers and optionally the additional vinyl monomers, to form the side chains of the grafted ethylenic polymer. Said polymerizable end group may in particular be a vinyl or (meth) acrylate (or (meth) acryl) group, and preferably a (meth) acrylate group.
Les macromonomères sont choisis préférentiellement parmi les macromonomères dont l'homopolymère a une température de transition vitreuse (Tg) inférieure ou égale à 25°C, notamment allant de - 100°C à 25°C, de préférence allant de - 80°C à 0°C.The macromonomers are preferably chosen from macromonomers whose homopolymer has a glass transition temperature (Tg) less than or equal to 25 ° C, in particular ranging from - 100 ° C to 25 ° C, preferably ranging from - 80 ° C to 0 ° C.
Les macromonomères ont une masse moléculaire moyenne en poids supérieure ou égale à 200, de préférence supérieure ou égale à 300, préférentiellement supérieure ou égale à 500, et plus préférentiellement supérieure à 600. De préférence, les macromonomères ont une niasse moléculaire moyenne en poids (Mw) allant de 200 à 100 000, de préférence allant de 500 à 50 000, préférentiellement allant de 800 à 20 000, plus préférentiellement allant de 800 à 10000, et encore plus préférentiellement allant de 800 à 6000.The macromonomers have a weight average molecular weight greater than or equal to 200, preferably greater than or equal to 300, preferably greater than or equal to 500, and more preferably greater than 600. Preferably, the macromonomers have a weight average molecular mass ( Mw) ranging from 200 to 100,000, preferably ranging from 500 to 50,000, preferably ranging from 800 to 20,000, more preferably ranging from 800 to 10,000, and even more preferably ranging from 800 to 6,000.
Dans la présente demande, les masses molaires moyennes en poids (Mw) et en nombre (Mn) sont déterminées par chromatographie liquide par perméation de gel (solvant - THF,- -courbe- d'étalonnage établie -avec des étalons de polystyrène- linéaire, détecteur réfractométrique).In the present application, the average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (solvent - THF, - - curve - of established calibration - with polystyrene standards - linear , refractometric detector).
Comme macromonomères carbonés, on peut en particulier citer : -(i) les homopolymères et les copolymères (méth)acrylate d'alkyle linéaire ou ramifié en C8-C22, présentant un groupe terminal polymérisable choisi parmi les groupes vinyle ou (méth)acrylate parmi lesquels on peut citer en particulier : les macromonomères de poly(acrylate d'éthyl-2 hexyle) à extrémité mono(méth)acrylate ; les macromonomères de poly(acrylate de dodécyle) ou de poly(méthacrylate de dodécyle) à extrémité mono(méth)acrylate ; les macromonomères de poly(acrylate de stéaryle) ou de poly (méthacrylate de stéaryle) à extrémité mono(méth)acrylate.As carbon macromonomers, mention may in particular be made of: (i) linear or branched C8-C22 homopolymers and copolymers (meth) acrylate of alkyl, having a polymerizable end group chosen from vinyl or (meth) acrylate groups among which mention may be made in particular of: macromonomers of poly (2-ethylhexyl acrylate) with mono (meth) acrylate end; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers with mono (meth) acrylate end; poly (stearyl acrylate) or poly (stearyl methacrylate) macromonomers with mono (meth) acrylate end.
De tels macromonomères sont notamment décrits dans les brevets EP895467 et EP96459 et dans l'article Gillman K.F., Polymer Letters, Vol 5, page 477-481 (1967).Such macromonomers are in particular described in patents EP895467 and EP96459 and in the article Gillman K.F., Polymer Letters, Vol 5, page 477-481 (1967).
On peut en particulier citer les macromonomères à base de poly(acrylate d'éthyl- 2-hexyle) ou de poly(acrylate de dodécyle) à extrémité mono(méth)acryiate.Mention may in particular be made of macromonomers based on poly (ethyl-2-hexyl acrylate) or poly (dodecyl acrylate) with a mono (meth) acryiate end.
-(ii) les polyoléfines ayant un groupe terminal à insaturation éthylénique , en particulier ayant un groupement terminal (méth)acrylate. Comme exemple de telles polyoléfines, on peut citer en particulier les macromonomères suivants, étant entendu qu'ils ont un groupe terminal (méth)acrylate : les macromonomères de polyethylene, les macromonomères de polypropylene, les macromonomères de copolymère polyéthylène/polypropylène, les macromonomères de copolymère polyéthylène/polybutylène, les macromonomères de polyisobutylène ; les macromonomères de polybutadiène; les macromonomères de polyisoprène ; les macromonomères de polybutadiène; les macromonomères de poly(éthylène/butylène)-polyisoprène ;- (ii) polyolefins having an ethylenically unsaturated end group, in particular having a (meth) acrylate end group. As an example of such polyolefins, mention may be made in particular of the following macromonomers, it being understood that they have a terminal (meth) acrylate group: polyethylene macromonomers, polypropylene macromonomers, polyethylene / polypropylene copolymer macromonomers, macromonomers of polyethylene / polybutylene copolymer, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; polybutadiene macromonomers; poly (ethylene / butylene) -polyisoprene macromonomers;
De tels macromonomères sont en particulier décrits dans US5625005 qui mentionne des macromonomères éthylène/butylène et éthylène/propylène à groupement terminal réactif (méth)acrylate.Such macromonomers are in particular described in US5625005 which mentions ethylene / butylene and ethylene / propylene macromonomers with reactive (meth) acrylate end group.
On peut en particulier citer le méthacrylate de poly(éthylène/butylène), tel que celui commercialisé sous la dénomination Kraton Liquid L-1253 par Kraton Polymers. Comme macromonomères siliconés, on peut en particulier citer les polydiméthylsiloxanes à groupement terminal mono (méth)acrylate, et notamment ceux de formule (II) suivante :Mention may in particular be made of poly (ethylene / butylene) methacrylate, such as that marketed under the name Kraton Liquid L-1253 by Kraton Polymers. As silicone macromonomers, mention may in particular be made of polydimethylsiloxanes with a mono (meth) acrylate end group, and in particular those of formula (II) below:
dans laquelle Rβ désigne un atome d'hydrogène ou un groupement méthyle ; Rg désigne un groupe hydrocarboné divalent ayant de 1 à 10 atomes de carbone et contient éventuellement une ou deux liaisons éther -O- ; R10 désigne un groupe alkyl ayant de 1 à 10 atomes de carbone, notamment de 2 à 8 atomes de carbone ; n désigne un nombre entier allant de 1 à 300, de préférence allant de 3 à 200, et préférentiellement allant de 5 à 100.in which Rβ denotes a hydrogen atom or a methyl group; Rg denotes a divalent hydrocarbon group having from 1 to 10 carbon atoms and optionally contains one or two ether bonds -O-; R10 denotes an alkyl group having from 1 to 10 carbon atoms, in particular from 2 to 8 carbon atoms; n denotes an integer ranging from 1 to 300, preferably ranging from 3 to 200, and preferably ranging from 5 to 100.
Comme macromonomères siliconés, on peut utiliser les monométhacryloxypropyl polydiméthylsiloxanes tels que ceux commercialisés sous la dénomination PS560- K6 par la société United Chemical Technologies Inc. (UCT) ou sous la dénomination MCR-M17 par la société Gelest Inc.As silicone macromonomers, use may be made of monomethacryloxypropyl polydimethylsiloxanes such as those sold under the name PS560-K6 by the company United Chemical Technologies Inc. (UCT) or under the name MCR-M17 by the company Gelest Inc.
De préférence, le macromonomère polymérisé (constituant les chaînes latérales du polymère greffé) représente de 0,1 à 15 % en poids du poids total du polymère, préférentiellement de 0,2 à 10 % en poids, et plus préférentiellement de 0,3 à 8 % en poids.Preferably, the polymerized macromonomer (constituting the side chains of the grafted polymer) represents from 0.1 to 15% by weight of the total weight of the polymer, preferably from 0.2 to 10% by weight, and more preferably from 0.3 to 8% by weight.
Comme polymère éthylénique greffé particulièrement préféré dispersé dans une phase grasse liquide non siliconée, on peut utiliser ceux obtenus par polyméiisation __:As a particularly preferred grafted ethylenic polymer dispersed in a non-silicone liquid fatty phase, those obtained by polymerization can be used:
- de l'acrylate de méthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans un solvant choisi parmi l'isododécane, l'isononanoate d'isononyle, l'octyldodécanol , le malate de diisostéaryle, un benzoate d'alkyl Cι2-C15 (tel que Finsolv TN) ; - de l'acrylate de méthoxyéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans l'isododécane ;- methyl acrylate and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in a solvent chosen from isododecane, isononyl isononanoate, octyldodecanol, diisostearyl, a Cι 2 -C 15 alkyl benzoate (such as Finsolv TN); - methoxyethyl acrylate and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane;
- des monomères acrylate de méthyle / méthacrylate de méthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans l'isododécane ;- Methyl acrylate / methyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane;
- des monomères acrylate de méthyle / acide acrylique et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans l'isododécane ; - des monomères acrylate de méthyle / méthacrylate de diméthylaminoéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans l'isododécane ;- Methyl acrylate / acrylic acid monomers and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane; - Methyl acrylate / dimethylaminoethyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane;
- des monomères acrylate de méthyle / méthacrylate de 2-hydroxyéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans l'isododécane.- Methyl acrylate / 2-hydroxyethyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane.
Comme polymère acrylique greffé particulièrement préféré dispersé dans une phase grasse liquide siliconée, on peut utiliser ceux obtenus par polymérisation : de l'acrylate de méthyle et du macromonomère monométhacryloxypropylpolydiméthylsiloxane ayant un poids moléculaire moyen en poids allant de 800 à 6000, en particulier dans le décaméthylcyclopentasiloxane ou le phényltriméthicone ;As particularly preferred grafted acrylic polymer dispersed in a silicone liquid fatty phase, those obtained by polymerization can be used: methyl acrylate and the monomethacryloxypropylpolydimethylsiloxane macromonomer having a weight average molecular weight ranging from 800 to 6000, in particular in decamethylcyclopentasiloxane or phenyltrimethicone;
- de l'acrylate de méthyle, d'acide acrylique et du màcromonomère monométhacryloxypropylpolydiméthylsiloxane ayant un poids moléculaire moyen en poids allant de 800 à 6000, en particulier dans le décaméthylcyclopentasiloxane ou le phényltriméthicone.- Methyl acrylate, acrylic acid and monomethacryloxypropylpolydimethylsiloxane monomonomer having a weight average molecular weight ranging from 800 to 6000, in particular in decamethylcyclopentasiloxane or phenyltrimethicone.
De préférence, le polymère greffé a une masse moléculaire moyenne en poids (Mw) -comprise -entre 10-000 -et-300 000, notamment entre 20 000- et 2-00- 000, mieux encore entre 25 000 et 150 000Preferably, the grafted polymer has a weight-average molecular mass (Mw) -comprises -between 10-000 -and-300 000, in particular between 20 000- and 2-00- 000, better still between 25 000 and 150 000
Grâce aux caractéristiques susmentionnées, dans un milieu organique de dispersion donné, les polymères ont la capacité de se replier sur eux-mêmes, formant ainsi des particules de forme sensiblement sphérique, avec sur le pourtour de ces particules les chaînes latérales déployées, qui assurent la stabilité de ces particules. De telles particules résultant des caractéristiques du polymère greffé ont la particularité de ne pas s'agglomérer dans ledit milieu et donc de s'autostabiliser et de former une dispersion de particules de polymère particulièrement stable.Thanks to the above-mentioned characteristics, in a given organic dispersion medium, the polymers have the capacity to fold in on themselves, thus forming particles of substantially spherical shape, with around the periphery of these particles the deployed side chains, which ensure the stability of these particles. Such particles resulting from the characteristics of the grafted polymer have the particularity of not agglomerating in said medium and therefore of self-stabilizing and of forming a dispersion of particularly stable polymer particles.
En particulier, les polymères éthyléniques greffés de la dispersion peuvent former des particules nanométriques, de taille moyenne allant de 10 à 400 nm, de préférence de 20 à 200 nm. Du fait de cette taille très faible, les particules de polymère greffé en dispersion sont particulièrement stables et donc peu susceptibles de former des agglomérats.In particular, the grafted ethylenic polymers of the dispersion can form nanometric particles, of average size ranging from 10 to 400 nm, preferably from 20 to 200 nm. Because of this very small size, the particles of polymer grafted in dispersion are particularly stable and therefore unlikely to form agglomerates.
La dispersion de polymère greffé peut donc être une dispersion stable et ne forme pas de sédiments, lorsqu'elle est placée pendant une durée prolongée (par exemple 24 heures) à température ambiante (25 °C).The dispersion of grafted polymer can therefore be a stable dispersion and does not form sediments, when it is placed for a prolonged period (for example 24 hours) at room temperature (25 ° C).
De préférence, la dispersion de particules' de polymère greffé présente un taux de matière sèche (ou extrait sec) en polymère pouvant aller de 40 % à 70 % en poids de matière sèche, notamment allant de 45 % à 65 % en poids.Preferably, the dispersion of particles of grafted polymer has a content of dry matter (or dry extract) in polymer which can range from 40% to 70% by weight of dry matter, in particular ranging from 45% to 65% by weight.
On peut préparer la dispersion de particules de polymère greffé par un procédé comprenant une étape de copolymérisation radicalaire, dans un milieu organique de polymérisation, d'un ou plusieurs monomères acryliques tels que définis précédemment avec un ou plusieurs macromonomères tels que définis précédemment.The dispersion of grafted polymer particles can be prepared by a process comprising a step of radical copolymerization, in an organic polymerization medium, of one or more acrylic monomers as defined above with one or more macromonomers as defined above.
Comme indiqué précédemment, le milieu organique liquide de dispersion peut être identique ou différent du milieu de polymérisation.As indicated above, the liquid organic dispersion medium can be identical to or different from the polymerization medium.
D'une- manière classique,- la copolymérisation peut être effectuée- en présence- d'un initiateur de polymérisation. Les initiateurs de polymérisation peuvent être des amorceurs radicalaires. De manière générale, un tel initiateur de polymérisation peut être choisi parmi les composés organiques peroxydes tels que le dilauroyl peroxyde, le dibenzoyl peroxyde, le tert-butyl peroxy-2- éthylhexanoate ; les composés diazotés tels que azobisisobutyronitrile, l'azobisdiméthylvalero-nitrile.In a conventional manner, the copolymerization can be carried out in the presence of a polymerization initiator. The polymerization initiators can be radical initiators. In general, such a polymerization initiator can be chosen from organic peroxide compounds such as dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2- ethylhexanoate; diazotized compounds such as azobisisobutyronitrile, azobisdimethylvalero-nitrile.
La réaction peut être également initiée à l'aide de photoinitiateurs ou par une radiation telle que des UV, des neutrons ou par plasma.The reaction can also be initiated using photoinitiators or by radiation such as UV, neutrons or plasma.
D'une manière générale, pour mettre en œuvre ce procédé, on introduit, dans un réacteur de taille appropriée à la quantité de polymère que l'on va réaliser, au moins une partie du milieu organique de polymérisation, une partie des monomères acryliques et/ou vinyliques additionnels, qui constituera, après polymérisation, le squelette insoluble, la totalité du macromonomère (qui constituera les chaînes latérales du polymère) et une partie de l'initiateur de polymérisation. A ce stade d'introduction, le milieu réactionnel forme un milieu relativement homogène.In general, to carry out this process, at least part of the organic polymerization medium is introduced into a reactor of a size appropriate to the quantity of polymer that is to be produced, and / or additional vinyls, which will constitute, after polymerization, the insoluble skeleton, all of the macromonomer (which will constitute the side chains of the polymer) and part of the polymerization initiator. At this stage of introduction, the reaction medium forms a relatively homogeneous medium.
Le milieu réactionnel est ensuite agité et chauffé jusqu'à une température pour obtenir une polymérisation des monomères et macromonomeres. Après un certain temps, le milieu initialement homogène et limpide conduit-à une dispersion d'aspect laiteux. On ajoute ensuite un mélange constitué de la partie restante de monomères et de l'initiateur de polymérisation. Après un temps adéquat pendant lequel le mélange est chauffé sous agitation, le milieu se stabilise sous forme d'une dispersion laiteuse, la dispersion comprenant des particules de polymères stabilisés dans le milieu dans lequel elles ont été créées, ladite stabilisation étant due à la présence, dans le polymère, de chaînes latérales solubles dans ledit milieu de dispersion.The reaction medium is then stirred and heated to a temperature to obtain a polymerization of the monomers and macromonomers. After a certain time, the initially homogeneous and clear medium leads to a dispersion of milky appearance. A mixture consisting of the remaining part of the monomers and of the polymerization initiator is then added. After an adequate time during which the mixture is heated with stirring, the medium stabilizes in the form of a milky dispersion, the dispersion comprising particles of polymers stabilized in the medium in which they were created, said stabilization being due to the presence , in the polymer, of side chains soluble in said dispersion medium.
Le polymère greffé décrit précédemment peut être présent dans la composition selon l'invention en une teneur allant de 0,5 % à 45 % en poids, par rapport au poids total de la composition, de préférence allant de 1 % à 30 % en poids, et préférentiellement allant de 2 % à 25 % en poids.The graft polymer described above can be present in the composition according to the invention in a content ranging from 0.5% to 45% by weight, relative to the total weight of the composition, preferably ranging from 1% to 30% by weight , and preferably ranging from 2% to 25% by weight.
— La composition -selon-l'invention-peut comprendre une ou des matières colorantes. choisies parmi les colorants hydrosolubles, et les matières colorantes pulvérulentes comme les pigments, les nacres, et les paillettes bien connues de l'homme du métier. Les matières colorantes peuvent être présentes, dans la composition, en une teneur allant de 0,01 % à 50 % en poids, par rapport au poids de la composition, de préférence de 0,01 % à 30 % en poids.- The composition - according to the invention - may comprise one or more coloring matters. chosen from water-soluble dyes, and pulverulent dyestuffs such as pigments, nacres and flakes well known to those skilled in the art. Dyestuffs may be present in the composition, in a content ranging from 0.01% to 50% by weight, relative to the weight of the composition, preferably from 0.01% to 30% by weight.
Par pigments, il faut comprendre des particules de toute forme, blanches ou colorées, minérales - ou organiques, insolubles dans le milieu physiologique, destinées à colorer la composition.The term “pigments” should be understood to mean particles of any shape, white or colored, mineral - or organic, insoluble in the physiological medium, intended to color the composition.
Par nacres, il faut comprendre des particules de toute forme irisées, notamment produites par certains mollusques dans leur coquille ou bien synthétisées.By nacres, it is necessary to understand particles of any iridescent shape, in particular produced by certain molluscs in their shell or else synthesized.
10 Les pigments peuvent être blancs ou colorés, minéraux et/ou organiques. On peut citer, parmi les pigments minéraux, le dioxyde de titane, éventuellement traité en surface, les oxydes de zirconium ou de cérium, ainsi que les oxydes de zinc, de fer (noir, jaune ou rouge) ou de chrome, le violet de manganèse, le bleu outremer, l'hydrate de chrome et le bleu ferrique, les poudres métalliques comme la poudre d'aluminium, la poudre de cuivre.The pigments can be white or colored, mineral and / or organic. Among the mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red) or chromium, violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metallic powders such as aluminum powder, copper powder.
Parmi les pigments organiques, on peut citer le noir de carbone, les pigments de type D & C, et les laques à base de carmin de cochenille, de baryum, strontium, calcium, aluminium.Among the organic pigments, mention may be made of carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.
20 On peut également citer les pigments à effet tels les particules comportant un substrat organique ou minéral, naturel ou synthétique, par exemple le verre, les résines acrylique, le polyester, le polyuréthane, le polyethylene téréphtalate, les céramiques ou les alumines, ledit substrat étant recouvert ou non de substances métalliques comme l'aluminium, l'or, l'argent, le platine, le cuivre, le bronze, ou d'oxydes métalliques comme le dioxyde de titane, l'oxyde de fer, l'oxyde de chrome et leurs mélanges.Mention may also be made of effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being or not covered with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metallic oxides such as titanium dioxide, iron oxide, chromium and their mixtures.
Les pigments nacrés peuvent être choisis parmi les pigments nacrés blancs telsThe pearlescent pigments can be chosen from white pearlescent pigments such as
- - - -que-le-mica recouvert-deJitane, ou d'oxychlorure de.bismuth, les pigments._nacr_és_- - - -that-the-mica covered-withJitane, or with oxychloride de.bismuth, the pigments._nacr_és_
30 colorés tels que le mica titane recouvert avec des oxydes de fer, le mica titane recouvert avec notamment du bleu ferrique ou de l'oxyde de chrome, le mica titane recouvert avec un pigment organique du type précité ainsi que les pigments nacrés à base d'oxychlorure de bismuth. . On peut également utiliser les pigments interférentiels, notamment à cristaux liquides ou multicouches.30 colors such as titanium mica coated with iron oxides, titanium mica coated with in particular ferric blue or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pigments pearlescent based on bismuth oxychloride. . It is also possible to use interference pigments, in particular liquid crystal or multilayer pigments.
Avantageusement, le polymère greffé présent dans la composition selon l'invention permet d'obtenir une bonne dispersion homogène des matières colorantes pulvérulents comme les pigments ou les nacres.Advantageously, the grafted polymer present in the composition according to the invention makes it possible to obtain a good homogeneous dispersion of the pulverulent dyestuffs such as pigments or nacres.
L'invention a donc également pour objet une composition de fond de teint comprenant une dispersion de particules de polymère éthylénique greffé dans une phase grasse liquide, telle que décrite précédemment, et au moins une matière colorante, notamment des pigments, des nacres, ou toute autre charge à effet optique.The invention therefore also relates to a foundation composition comprising a dispersion of particles of ethylenic polymer grafted in a liquid fatty phase, as described above, and at least one coloring matter, in particular pigments, nacres, or any other charge with optical effect.
Les colorants hydrosolubles sont par exemple le jus de betterave, le bleu de méthylène.The water-soluble dyes are, for example, beet juice, methylene blue.
La composition selon l'invention peut comprendre en outre en outre une ou plusieurs charges, notamment en une teneur allant de 0,01 % à 50 % en poids, par rapport au poids total de la composition, de préférence allant de 0,01 % à 30 % en poids. Par charges, il faut comprendre des particules de toute forme, incolores ou blanches, minérales ou de synthèse, insolubles dans le milieu de la composition quelle que soit la température à laquelle la composition est fabriquée. Ces charges servent notamment à modifier la rhéologie ou la texture de la composition.The composition according to the invention may also further comprise one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% at 30% by weight. By fillers, it is necessary to understand particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is produced. These charges are used in particular to modify the rheology or the texture of the composition.
Les charges peuvent être minérales ou organiques de toute forme, plaquettaires, sphériques ou oblongues, quelle que soit la forme cristallographique ( par exemple feuillet, cubique, hexagonale, orthorombique, etc). On peut citer le talc, le mica, la silice, le kaolin, les poudres de polyamide (Nylon®) (Orgasol® de chez Atochem), -de poly-β-alanine et-de polyethylene, les poudres de -polymères -de- tétrafluoroéthylène (Téflon®), la lauroyl-lysine, l'amidon, le nitrure de bore, les microsphères creuses polymériques telles que celles de chlorure de polyvinylidène/acrylonitrile comme l'Expancel® (Nobel Industrie), de copolymères d'acide acrylique (Polytrap® de la société Dow Corning) et les microbilles de résine de siliconé (Tospearls® de Toshiba, par exemple), les particules de polyorganosiloxanes élastomères, le carbonate de calcium précipité, le carbonate et l'hydro-carbonate de magnésium, l'hydroxyapatite, les microsphères de silice creuses (Silica Beads® de Maprecos), les microcapsules de verre ou de céramique, les savons métalliques dérivés d'acides organiques carboxyliques ayant de 8 à 22 atomes de carbone, de préférence de 12 à 18 atomes de carbone, par exemple le stéarate de zinc, de magnésium ou de lithium, le laurate de zinc, le myristate de magnésium.The fillers can be mineral or organic of any shape, platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorombic, etc.). Mention may be made of talc, mica, silica, kaolin, powders of polyamide (Nylon®) (Orgasol® from Atochem), -of poly-β-alanine and -of polyethylene, powders of -polymers -of - tetrafluoroethylene (Teflon®), lauroyl-lysine, starch, boron nitride, hollow polymeric microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), of acrylic acid copolymers (Polytrap® from Dow Corning) and microbeads silicone resin (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, metallic soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium or lithium, zinc laurate, magnesium myristate.
0 La composition selon l'invention peut également contenir des ingrédients couramment utilisés en cosmétique, tels que les vitamines, les agents hydratants, les émollients, les agents anti-radicaux libres, les épaississants, les oligoéléments, les adoucissants, les séquestrants, les parfums, les agents alcalinisants ou acidifiants, les conservateurs, les filtres solaires, les tensioactifs, les antioxydants, les gommes, les cires, les agents propulseurs, ou leurs mélanges.0 The composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, moisturizers, emollients, anti-free radical agents, thickeners, trace elements, softeners, sequestrants, perfumes , basifying or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, gums, waxes, propellants, or mixtures thereof.
Bien entendu, l'homme du métier veillera à choisir ce ou ces éventuels composés complémentaires, et/ou leur quantité, de manière telle que les propriétés avantageuses de la composition correspondante selon l'invention ne soient pas, 0 ou substantiellement pas, altérées par l'adjonction envisagée.Of course, a person skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the corresponding composition according to the invention are not, 0 or substantially not, affected by the proposed addition.
La composition selon l'invention peut se présenter notamment sous forme de suspension, de dispersion, de solution, de gel, d'émulsion, notamment émulsion huile-dans-eau (H/E) ou eau-dans-huile (E/H), ou multiple (E/H/E ou polyol/H/E ou H/E/H), sous forme de crème, de pâte, de mousse, de dispersion de vésicules notamment de lipides ioniques ou non, de lotion biphasé ou multiphase, de spray, de poudre, de pâte. La composition peut être anhydre, par exemple il peut s'agir d'un stick ou d'une pâte anhydre. La composition peut être une composition non - - rincée.- - 0The composition according to the invention can be in particular in the form of a suspension, dispersion, solution, gel, emulsion, in particular oil-in-water (O / W) or water-in-oil (W / O) emulsion ), or multiple (W / O / W or polyol / O / W or O / W / O), in the form of a cream, paste, foam, vesicle dispersion, in particular of ionic lipids or not, of two-phase lotion or multiphase, spray, powder, paste. The composition can be anhydrous, for example it can be a stick or an anhydrous paste. The composition can be a leave-in composition - - 0
L'homme du métier pourra choisir la forme galénique appropriée, ainsi que sa méthode de préparation, sur la base de ses connaissances générales, en tenant compte d'une part de la nature des constituants utilisés, notamment de leur solubilité dans le support, et d'autre part de l'application envisagée pour la composition.Those skilled in the art will be able to choose the appropriate dosage form, as well as its preparation method, on the basis of his general knowledge, taking into account on the one hand the nature of the constituents used, in particular their solubility in the support, and on the other hand of the application envisaged for the composition.
Selon un autre aspect, l'invention concerne également un ensemble cosmétique comprenant : i) un récipient délimitant au moins un compartiment, ledit récipient étant fermé par un élément de fermeture ; et ii) une composition disposée à l'intérieur dudit compartiment, la composition étant conforme à l'invention.According to another aspect, the invention also relates to a cosmetic assembly comprising: i) a container delimiting at least one compartment, said container being closed by a closing element; and ii) a composition placed inside said compartment, the composition being in accordance with the invention.
Le récipient peut être sous toute forme adéquate. Il peut être notamment sous forme d'un flacon, d'un tube, d'un pot, d'un étui, d'une boite, d'un sachet ou d'un boîtier.The container can be in any suitable form. It can in particular be in the form of a bottle, a tube, a pot, a case, a box, a sachet or a case.
L'élément de fermeture peut être sous forme d'un bouchon amovible, d'un couvercle, d'un opercule, d'une bande déchirable, ou d'une capsule, notamment du type comportant un corps fixé au récipient et une casquette articulée sur le corps. Il peut être également sous forme d'un élément assurant la fermeture sélective du récipient, notamment une pompe, une valve, ou un clapet.The closure element may be in the form of a removable stopper, a cover, a cover, a tearable strip, or a capsule, in particular of the type comprising a body fixed to the container and an articulated cap. on the body. It can also be in the form of an element ensuring the selective closure of the container, in particular a pump, a valve, or a valve.
Le récipient peut être associé à un applicateur, notamment sous forme d'un bloc de mousse ou d'élastomère, d'un feutre, ou d'une spatule. L'applicateur peut être libre (houppette ou éponge) ou solidaire d'une tige portée par l'élément de fermeture, tel que décrit par exemple dans le brevet US 5 492 426. L'applicateur peut être solidaire du récipient, tel que décrit par exemple le brevet FR 2 761 959.The container can be associated with an applicator, in particular in the form of a block of foam or of elastomer, of a felt, or of a spatula. The applicator can be free (puff or sponge) or integral with a rod carried by the closure element, as described for example in US patent 5,492,426. The applicator can be integral with the container, as described for example the patent FR 2 761 959.
Le produit peut être contenu directement dans le récipient, ou indirectement. A titre d'exemple, le produit peut être disposé sur un support imprégné, notamment sous-forme d'une lingette-ou d'un tampon,- et-disposé (à l'unité ou plusieurs)-dans- une boîte ou dans un sachet. Un tel support incorporant le produit est décrit par exemple dans la demande WO 01/03538. L'élément de fermeture peut être couplé au récipient par vissage. Alternativement, le couplage entre l'élément de fermeture et le récipient se fait autrement que par vissage, notamment via un mécanisme à baïonnette, par encliquetage, serrage, soudage, collage, ou par attraction magnétique. Par "encliquetage" on entend en particulier tout système impliquant le franchissement d'un bourrelet ou d'un cordon de matière par déformation élastique d'une portion, notamment de l'élément de fermeture, puis par retour en position non contrainte élastiquement de ladite portion après le franchissement du bourrelet ou du cordon.The product can be contained directly in the container, or indirectly. For example, the product can be placed on an impregnated support, in particular in the form of a wipe-or pad, -and-arranged (individually or several) -in- a box or in A sachet. Such a support incorporating the product is described for example in application WO 01/03538. The closure element can be coupled to the container by screwing. Alternatively, the coupling between the closure element and the container is done other than by screwing, in particular via a bayonet mechanism, by snap-fastening, tightening, welding, bonding, or by magnetic attraction. By "snap-fastening" is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the closure element, then by return to the non-elastically constrained position of said portion after crossing the bead or cord.
Le récipient peut être au moins pour partie réalisé en matériau thermoplastique. A titre d'exemples de matériaux thermoplastiques, on peut citer le polypropylene ou le polyethylene.The container can be at least partly made of thermoplastic material. As examples of thermoplastic materials, mention may be made of polypropylene or polyethylene.
Alternativement, le récipient est réalisé en matériau non thermoplastique, notamment en verre ou en métal (ou alliage).Alternatively, the container is made of non-thermoplastic material, in particular glass or metal (or alloy).
Le récipient peut être à parois rigides ou à parois déformables, notamment sous forme d'un tube ou d'un flacon tube.The container may have rigid walls or deformable walls, in particular in the form of a tube or a tube bottle.
Le récipient peut comprendre des moyens destinés à provoquer ou faciliter la distribution de la composition. A titre d'exemple, le récipient peut être à parois déformables de manière à provoquer la sortie de la composition en réponse à une surpression à l'intérieur du récipient, laquelle surpression est provoquée par écrasement élastique (ou non élastique) des parois du récipient. Alternativement, notamment lorsque le produit est sous forme d'un stick, ce dernier peut être entraîné par un mécanisme à piston. Toujours dans le cas d'un stick, notamment de produit de maquillage (rouge à lèvres, fond de teint, etc.), le récipient peut comporter un mécanisme, notamment à crémaillère, ou avec une tige filetée, ou avec une rampe hélicoïdale, et apte à déplacer un stick en direction de ladite ouverture.- Un tel mécanisme est décrit par-exemple dans le brevet FR-2 806-273 ou dans le brevet FR 2 775 566. Un tel mécanisme pour un produit liquide est décrit dans le brevet FR 2 727 609. Le récipient peut être constitué d'un boîtier avec un fond délimitant au moins un logement contenant la composition, et un couvercle, notamment articulé sur le fond, et apte à recouvrir au moins en partie ledit fond. Un tel boîtier est décrit par exemple dans la demande WO 03/018423 ou dans le brevet FR 2 791 042.The container may include means for causing or facilitating the distribution of the composition. For example, the container may have deformable walls so as to cause the exit of the composition in response to an overpressure inside the container, which overpressure is caused by elastic (or inelastic) crushing of the walls of the container. . Alternatively, especially when the product is in the form of a stick, the latter can be driven by a piston mechanism. Still in the case of a stick, in particular of makeup product (lipstick, foundation, etc.), the container may include a mechanism, in particular rack and pinion, or with a threaded rod, or with a helical ramp, and able to move a stick in the direction of said opening. Such a mechanism is described for example in patent FR-2 806-273 or in patent FR 2 775 566. Such a mechanism for a liquid product is described in Patent FR 2,727,609. The container may consist of a housing with a bottom delimiting at least one housing containing the composition, and a cover, in particular articulated on the bottom, and capable of covering said bottom at least in part. Such a case is described, for example, in application WO 03/018423 or in patent FR 2,791,042.
Le récipient peut être équipé d'un essoreur disposé au voisinage de l'ouverture du récipient. Un tel essoreur permet d'essuyer l'applicateur et éventuellement, la tige dont il peut être solidaire. Un tel essoreur est décrit par exemple dans le brevet FR 2 792 618.The container can be equipped with a wringer disposed near the opening of the container. Such a wringer makes it possible to wipe the applicator and possibly, the rod of which it may be integral. Such a wringer is described for example in patent FR 2 792 618.
La composition peut être à la pression atmosphérique à l'intérieur du récipient (à température ambiante) ou pressurisée, notamment au moyen d'un gaz propulseur (aérosol). Dans ce dernier cas, le récipient est équipé d'une valve (du type de celles utilisées pour les aérosols).The composition can be at atmospheric pressure inside the container (at room temperature) or pressurized, in particular by means of a propellant gas (aerosol). In the latter case, the container is fitted with a valve (of the type used for aerosols).
Le contenu des brevets ou demandes de brevets cités précédemment sont incorporés par référence dans la présente demande.The content of the patents or patent applications cited above are incorporated by reference into the present application.
L'invention va maintenant être décrite plus en détail à la lumière des exemples suivants donnés à titre illustratif et non limitatif.The invention will now be described in more detail in the light of the following examples given by way of illustration and not limitation.
Les présents exemples illustrent la préparation de polymères conformes à l'invention, aptes à former une dispersion de particules dans un milieu organique considéré.The present examples illustrate the preparation of polymers in accordance with the invention, capable of forming a dispersion of particles in a considered organic medium.
Dans ces exemples, on détermine, après préparation de ladite dispersion, les masses molaires moyennes en poids (Mw) et en nombre (Mn) du polymère, la température de transition vitreuse du polymère, le taux de matière sèche (ou extrait sec) de la dispersion et la taille des particules de polymères.In these examples, after preparation of said dispersion, the average molar masses by weight (Mw) and by number (Mn) of the polymer are determined, the glass transition temperature of the polymer, the dry matter (or dry extract) content of the dispersion and size of the polymer particles.
Les masses molaires moyennes en poids (Mw) et en nombre (Mn) sont déterminées par chromatographie liquide par perméation de gel (solvant THF, courbe d'étalonnage établie avec des étalons de polystyrène linéaire, détecteur réfractométrique). La mesure de la température de transition vitreuse (Tg) est effectuée selon la norme ASTM D3418-97, par analyse enthalpique différentielle (DSC "Differential Scanning Calorimetry") sur calorimètre, sur une plage de température comprise entre -100°C et +150°C à une vitesse de chauffe de 10°C/min dans des creusets en aluminium de 150 μl.The average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector). The measurement of the glass transition temperature (Tg) is carried out according to standard ASTM D3418-97, by differential enthalpy analysis (DSC "Differential Scanning Calorimetry") on a calorimeter, over a temperature range between -100 ° C and +150 ° C at a heating rate of 10 ° C / min in 150 μl aluminum crucibles.
La préparation des creusets se fait de la manière suivante : dans un creuset en aluminium de 150 μl on introduit 100 μl de la dispersion obtenue et on laisse le solvant s'évaporer pendant 24h à température ambiante et à 50% d'humidité relative. On renouvelle l'opération puis on introduit le creuset dans le calorimètre Mettler DSC30.The crucibles are prepared as follows: 100 μl of the dispersion obtained is introduced into an aluminum crucible of 150 μl and the solvent is allowed to evaporate for 24 hours at room temperature and at 50% relative humidity. The operation is repeated and then the crucible is introduced into the Mettler DSC30 calorimeter.
Le taux de matière sèche (ou extrait sec), c'est à dire la teneur en matière non volatile, peut être mesurée de différentes manières : on peut citer par exemple les méthodes par séchage à l'étuve ou les méthodes par séchage par exposition à un rayonnement infrarouge.The rate of dry matter (or dry extract), that is to say the content of non-volatile matter, can be measured in different ways: there may be mentioned, for example, methods by drying in an oven or methods by drying by exposure. to infrared radiation.
De préférence, le taux de matière sèche est mesuré par échauffement de l'échantillon par des rayons infrarouges de 2 μm à 3,5 μm de longueur d'onde. Les substances contenues dans la composition qui possèdent une pression de vapeur élevée s'évaporent sous l'effet de ce rayonnement. La mesure de la perte de poids de l'échantillon permet de déterminer l'extrait sec de la composition. Ces mesures sont réalisées au moyen d'un dessiccateur à infrarouges commercial LP16 de chez Mettler. Cette technique est parfaitement décrite dans la documentation de l'appareil fournie par Mettler.Preferably, the dry matter content is measured by heating the sample by infrared rays from 2 μm to 3.5 μm in wavelength. The substances contained in the composition which have a high vapor pressure evaporate under the effect of this radiation. Measuring the weight loss of the sample makes it possible to determine the dry extract of the composition. These measurements are carried out using a commercial infrared dryer LP16 from Mettler. This technique is fully described in the device documentation provided by Mettler.
Le protocole de mesure est le suivant : on étale environ 1g de la composition sur une coupelle métallique. Celle-ci, après introduction dans le dessiccateur, est soumise à une consigne de température de 120°C pendant une heure. La masse humide de l'échantillon, correspondant à la masse initiale et la masse sèche de échantillon.-correspondant-à la masse après exposition au rayonnement,- sont- mesurées au moyen d'une balance de précision.The measurement protocol is as follows: approximately 1 g of the composition is spread over a metal dish. This, after introduction into the desiccator, is subjected to a temperature set point of 120 ° C for one hour. The wet mass of the sample, corresponding to the initial mass and the dry mass of the sample. - corresponding to the mass after exposure to radiation, - are measured using a precision balance.
Le taux de matière sèche est calculée de la manière suivante : Extrait Sec = 100 x (masse sèche / masse humide). Les tailles de particules peuvent être mesurées par différentes techniques : on peut citer en particulier les techniques de diffusion de la lumière (dynamiques et statiques), les méthodes par compteur Coulter, les mesures par vitesse de sédimentation (reliée à la taille via la loi de Stokes) et la microscopie. Ces techniques permettent de mesurer un diamètre de particules et pour certaines d'entre elles une distribution granulométrique.The dry matter content is calculated as follows: Dry extract = 100 x (dry mass / wet mass). Particle sizes can be measured by different techniques: we can cite in particular light scattering techniques (dynamic and static), Coulter counter methods, measurements by sedimentation speed (related to size via the law of Stokes) and microscopy. These techniques make it possible to measure a particle diameter and for some of them a particle size distribution.
De préférence, les tailles et les distributions de tailles des particules des compositions selon l'invention, sont mesurées par diffusion statique de la lumière au moyen d'un granuiomètre commercial de type MasterSizer 2000 de chez Malvern. Les données sont traitées sur la base de la théorie de diffusion de Mie. Cette théorie, exacte pour des particules isotropes, permet de déterminer dans le cas de particules non sphériques, un diamètre « effectif » de particules. Cette théorie est notamment décrite dans l'ouvrage de Van de Hulst, H.C., "Light Scattering by Small Particles," Chapitres 9 et 10, Wiley, New York, 1957. La composition est caractérisée par son diamètre « effectif » moyen en volume D[4,3], défini de la manière suivante :Preferably, the sizes and size distributions of the particles of the compositions according to the invention are measured by static light scattering using a commercial granuiometer of the MasterSizer 2000 type from Malvern. The data is processed on the basis of Mie diffusion theory. This theory, exact for isotropic particles, makes it possible to determine in the case of non-spherical particles, an "effective" diameter of particles. This theory is notably described in the work of Van de Hulst, HC, "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957. The composition is characterized by its "effective" average diameter in volume D [4.3], defined as follows:
où Vj représente le volume des particules de diamètre effectif dj. Ce paramètre est notamment décrit dans la documentation technique du granuiomètre. Les mesures sont réalisées à 25 °C, sur une dispersion de particules diluée, obtenue à partir de la composition de la manière suivante : 1) dilution d'un facteur 100 avec de l'eau, 2) homogénéisation de la solution, 3) repos de la solution durant 18 heures, 4) récupération du surnageant homogène blanchâtre. Le diamètre « effectif » est obtenu en prenant un indice de réfraction de 1 ,33 pour l'eau et un indice de réfraction moyen de 1 ,42 pour les particules. where Vj represents the volume of particles of effective diameter dj. This parameter is described in particular in the technical documentation of the granuiometer. The measurements are carried out at 25 ° C., on a dispersion of dilute particles, obtained from the composition as follows: 1) dilution by a factor of 100 with water, 2) homogenization of the solution, 3) rest of the solution for 18 hours, 4) recovery of the whitish homogeneous supernatant. The "effective" diameter is obtained by taking a refractive index of 1.33 for water and an average refractive index of 1.42 for particles.
L'invention est illustrée plus en détails par les exemples décrits ci-après.The invention is illustrated in more detail by the examples described below.
Exemple 1 Cet exemple illustre la préparation d'un polymère formant une dispersion de particules dans un solvant carboné, ledit polymère étant obtenu par polymérisation d'acrylate de méthyle, d'acide acrylique et le macromonomère correspondant à un copolymère polyéthylène/polybutylène (Kraton L-1253).Example 1 This example illustrates the preparation of a polymer forming a dispersion of particles in a carbon solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the macromonomer corresponding to a polyethylene / polybutylene copolymer (Kraton L-1253 ).
Dans un réacteur de 1 litre, on charge 200 g d'heptane, 200 g d'isododécane, 14g d'acrylate de méthyle, 10 g d'acide acrylique, 16 g de macromonomère du type copolymère de polyéthylène/polybutylène à groupement terminal méthacrylate (Kraton L-1253) et 3,2 g de tertio butyl péroxy-2-éthylhexanoate (Trigonox 21 S). On agite et on chauffe le mélange réactionnel à température ambiante à 90°C en 1 heure. Après 15 minutes à 90°C, on observe un changement d'aspect du milieu réactionnel, qui passe d'un aspect transparent à un aspect laiteux. On maintient le chauffage sous agitation pendant 15 minutes supplémentaires puis on ajoute goutte à goutte pendant 1 heure un mélange constitué par 130 g d'acrylate de méthyle, 30g d'acide acrylique et 2 g de Trigonox 21 S.200 g of heptane, 200 g of isododecane, 14 g of methyl acrylate, 10 g of acrylic acid, 16 g of macromonomer of the polyethylene / polybutylene copolymer type with methacrylate end group are charged into a 1 liter reactor. (Kraton L-1253) and 3.2 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21 S). Stir and heat the reaction mixture to room temperature at 90 ° C in 1 hour. After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. Heating is continued with stirring for an additional 15 minutes, then a mixture consisting of 130 g of methyl acrylate, 30 g of acrylic acid and 2 g of Trigonox 21 S is added dropwise for 1 hour.
On laisse ensuite le chauffage pendant 4 heures à 90°C puis on distille l'heptane du milieu réactionnel. A l'issue de cette opération de distillation, on obtient une dispersion de particules de polymère ainsi préparé stable dans l'isododécaneThe heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium. At the end of this distillation operation, a dispersion of particles of polymer thus prepared, stable in isododecane, is obtained.
Les caractéristiques du polymère et des particules formées par ledit polymère sont les suivantes :The characteristics of the polymer and of the particles formed by said polymer are as follows:
- Masse moléculaire poids Mw= 175294- molecular weight Mw = 175294
- Masse moléculaire nombre Mn=28265- Molecular mass number Mn = 28265
- Indice de polydispersité (Mw/Mn)= 6.2- Polydispersity index (Mw / Mn) = 6.2
Extrait sec théorique : 54.9% dans l'isododécaneTheoretical dry extract: 54.9% in isododecane
- Granulométrie : 85 nm avec polydispersité de 0,04 réalisée sur Malvern Autosizer Lo-C à 25°C ;- Grain size: 85 nm with polydispersity of 0.04 carried out on Malvern Autosizer Lo-C at 25 ° C;
Le polymère greffé comprend 8 % en poids de macromonomère par rapport au poids du polymère.The grafted polymer comprises 8% by weight of macromonomer relative to the weight of the polymer.
La stabilité de la dispersion obtenue est mise en évidence par la mise en œuvre du protocole de stabilité suivant : dans un tube à hémolyse, on place 8 ml de la dispersion réalisée et on centrifuge à 4000 tours/min pendant 15 minutes à l'aide d'une centrifugeuse Jouan C100-S5. Au bout de 15 minutes, on constate qu'il n'y a pas de déphasage ce qui démontre que la dispersion est stable.The stability of the dispersion obtained is demonstrated by the implementation of the following stability protocol: in a hemolysis tube, 8 ml of the dispersion carried out and centrifuged at 4000 rpm for 15 minutes using a Jouan C100-S5 centrifuge. After 15 minutes, we see that there is no phase shift, which shows that the dispersion is stable.
EXEMPLE 2 :EXAMPLE 2:
Cet exemple illustre la préparation d'un polymère formant une dispersion de particules dans un solvant siliconé, ledit polymère étant obtenu par polymérisation d'acrylate de méthyle, d'acide acrylique et de macromonomère monométhacryloxypropyl polydiméthylsiloxane ayant un poids moléculaire moyen en poids de 5000 vendu sous la dénomination MCR-M17 par la société Gelest Inc.This example illustrates the preparation of a polymer forming a dispersion of particles in a silicone solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and of monomethacryloxypropyl polydimethylsiloxane macromonomer having a weight average molecular weight of 5000 sold under the name MCR-M17 by the company Gelest Inc.
Dans un réacteur de 1 litre, on charge 200 g d'heptane, 200 g de décaméthylcyclopentasiloxane, 26 g d'acrylate de méthyle, 14 g de monométhacryloxypropylpolydiméthylsiloxane MCR-M17 et 3,2 g de tertiobutylperoxy-2-éthyIhexanoate (Trigonox 21 S).200 g of heptane, 200 g of decamethylcyclopentasiloxane, 26 g of methyl acrylate, 14 g of monomethacryloxypropylpolydimethylsiloxane MCR-M17 and 3.2 g of tert-butylperoxy-2-ethyhexanoate (Trigonox 21 S) are charged to a 1 liter reactor. ).
On agite et on chauffe le mélange réactionnel à 90°C en 1 heure. Après 15 minutes à 90°C, on observe un changement d'aspect du milieu réactionnel, qui passe d'un aspect transparent à un aspect laiteux. On maintient le chauffage sous agitation pendant 15 minutes supplémentaires puis on ajoute goutte à goutte pendant 1 heure un mélange constitué par 120 g d'acrylate de méthyle, 40g d'acide acrylique et 2 g de Trigonox 21 S. On laisse ensuite le chauffage pendant 4 heures à 90°C puis on distille l'heptane du milieu réactionnel. A l'issue de cette opération de distillation, on obtient une dispersion de particules de polymère ainsi préparé stable dans le décaméthylcyclopentasiloxaneStir and heat the reaction mixture to 90 ° C in 1 hour. After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. The heating is kept under stirring for an additional 15 minutes, then a mixture consisting of 120 g of methyl acrylate, 40 g of acrylic acid and 2 g of Trigonox 21 S is added dropwise for 1 hour. 4 hours at 90 ° C. then the heptane is distilled from the reaction medium. At the end of this distillation operation, a dispersion of particles of polymer thus prepared, stable in decamethylcyclopentasiloxane, is obtained.
(donc de chaîne latérale solubie dans la D5) par rapport au poids du polymère. (therefore of side chain solubied in D5) relative to the weight of the polymer.
Les caractéristiques du polymère et des particules formées par ledit polymère sont les suivantes : - Extrait sec : 50 % dans le décaméthylcyclopentasiloxane réalisé par thermobalanceThe characteristics of the polymer and of the particles formed by said polymer are as follows: - Dry extract: 50% in decamethylcyclopentasiloxane produced by thermobalance
- Transition vitreuse : 12°C par DSC Mettler- Glass transition: 12 ° C by DSC Mettler
- Granulométrie : 170 nm avec polydispersité de 0,04 réalisée sur Malvern Autosizer Lo-C à 25°C- Granulometry: 170 nm with polydispersity of 0.04 carried out on Malvern Autosizer Lo-C at 25 ° C
Exemple 3 :Example 3:
Cet exemple illustre la préparation d'un polymère formant une dispersion de particules dans un solvant carboné, ledit polymère étant obtenu par polymérisation d'acrylate de méthyle, d'acide acrylique et le macromonomère correspondant à un copolymère polyéthylène/polybutylène (Kraton L-1253).This example illustrates the preparation of a polymer forming a dispersion of particles in a carbon solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the macromonomer corresponding to a polyethylene / polybutylene copolymer (Kraton L-1253 ).
Dans un réacteur de 1 litre, on charge 200 g d'heptane, 200 g d'isododécane, 14g d'acrylate de méthyle, 10g d'acide acrylique et 16 g de macromonomère du type copolymère de polyéthylène/polybutylène (Kraton L-1253) et 3.2 g de tertio butyl peroxy-2-éthylhexanoate (Trigonox 21 S).200 g of heptane, 200 g of isododecane, 14 g of methyl acrylate, 10 g of acrylic acid and 16 g of macromonomer of the polyethylene / polybutylene copolymer type (Kraton L-1253) are charged to a 1 liter reactor. ) and 3.2 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21 S).
On agite et on chauffe le mélange réactionnel à température ambiante à 90°C en 1 heure. Après 15 minutes à 90°C, on observe un changement d'aspect du milieu réactionnel, qui passe d'un aspect transparent à un aspect laiteux. On maintient le chauffage sous agitation pendant 15 minutes supplémentaires puis on ajoute goutte à goutte pendant 1 heure un mélange constitué par 70 g d'acrylate de méthyle, 90g d'acide acrylique et 2 g de Trigonox 21 S.Stir and heat the reaction mixture to room temperature at 90 ° C in 1 hour. After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. The heating is kept under stirring for an additional 15 minutes, then a mixture consisting of 70 g of methyl acrylate, 90 g of acrylic acid and 2 g of Trigonox 21 S is added dropwise for 1 hour.
On laisse ensuite le chauffage pendant 4 heures à 90°C puis on distille l'heptane du milieu réactionnel. A l'issue de cette opération de distillation, on obtient une dispersion de particules de polymère ainsi préparé stable dans l'isododécaneThe heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium. At the end of this distillation operation, a dispersion of particles of polymer thus prepared, stable in isododecane, is obtained.
Les caractéristiques du polymère et des particules formées par ledit polymère sont les suivantes :The characteristics of the polymer and of the particles formed by said polymer are as follows:
- Masse moléculaire poids Mw= non caractérisable par GPC- Molecular mass weight Mw = not characterizable by GPC
- Masse moléculaire nombre Mn= non caractérisable par GPC- Molecular mass number Mn = not characterizable by GPC
- Indice de polydispersité (Mw/Mn)= non caractérisable par GPC Extrait sec théorique : 53.6% dans l'isododécane - Granulométrie : non mesurée- Polydispersity index (Mw / Mn) = not characterizable by GPC Theoretical dry extract: 53.6% in isododecane - Grain size: not measured
Le polymère greffé comprend 8 % en poids de macromonomère par rapport au poids du polymère.The grafted polymer comprises 8% by weight of macromonomer relative to the weight of the polymer.
Après la mise en œuvre du protocole de stabilité conformément à l'exemple 1 , on constate que la dispersion obtenue est stable.After the implementation of the stability protocol in accordance with Example 1, it is found that the dispersion obtained is stable.
Exemple 4 :Example 4:
Cet exemple illustre la préparation d'un polymère formant une dispersion de particules dans un solvant carboné, ledit polymère étant obtenu par polymérisation d'acrylate de méthyle, d'acide acrylique et le macromonomère correspondant à un copolymère polyéthylène/polybutylène à groupement terminal méthacrylate (Kraton L-1253).This example illustrates the preparation of a polymer forming a dispersion of particles in a carbonaceous solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the macromonomer corresponding to a polyethylene / polybutylene copolymer with methacrylate end group ( Kraton L-1253).
Dans un réacteur de 1 litre, on charge 200 g d'heptane, 200 g d'isododécane, 28 g d'acrylate de méthyle et 12 g de macromonomère du type copolymère de polyéthylène/polybutylène à groupement terminal méthacrylate (Kraton L-1253) et 3.2 g de tertio butyl peroxy-2-éthylhexanoate (Trigonox 21 S). On agite et on chauffe le mélange réactionnel à température ambiante à 90°C en 1 heure. Après 15 minutes à 90°C, on observe un changement d'aspect du milieu réactionnel, qui passe d'un aspect transparent à un aspect laiteux. On maintient le chauffage sous agitation pendant 15 minutes supplémentaires puis on ajoute goutte à goutte pendant 1 heure un mélange constitué par 150 g d'acrylate de méthyle, 10g d'acide acrylique et 2 g de Trigonox 21 S.200 g of heptane, 200 g of isododecane, 28 g of methyl acrylate and 12 g of macromonomer of the polyethylene / polybutylene copolymer type with methacrylate end group (Kraton L-1253) are loaded into a 1 liter reactor. and 3.2 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21 S). Stir and heat the reaction mixture to room temperature at 90 ° C in 1 hour. After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. Heating is continued with stirring for an additional 15 minutes, then a mixture consisting of 150 g of methyl acrylate, 10 g of acrylic acid and 2 g of Trigonox 21 S is added dropwise for 1 hour.
-On laisse ensuite le chauffage-pendant 4 heures à-90-G-puis on distille l'heptane - - du milieu réactionnel. A l'issue de cette opération de distillation, on obtient une dispersion de particules de polymère ainsi préparé stable dans l'isododécaneThe heating is then left for 4 hours at -90-G, then the heptane is distilled - from the reaction medium. At the end of this distillation operation, a dispersion of particles of polymer thus prepared, stable in isododecane, is obtained.
Le polymère greffé comprend 6 % en poids de macromonomère par rapport au poids du polymère.The grafted polymer comprises 6% by weight of macromonomer relative to the weight of the polymer.
Les caractéristiques du polymère et des particules formées par ledit polymère sont les suivantes :The characteristics of the polymer and of the particles formed by said polymer are as follows:
- Masse moléculaire poids Mw= 143639- molecular weight Mw = 143639
- Masse moléculaire nombre Mn=23965- Molecular mass number Mn = 23965
- Indice de polydispersité (Mw/Mn)= 5.99- Polydispersity index (Mw / Mn) = 5.99
- Extrait sec théorique : 51.3 % dans l'isododécane- Theoretical dry extract: 51.3% in isododecane
- Granulométrie : 48 nm avec polydispersité de 0,04 réalisée sur Malvern Autosizer Lo-C à 25°C ;- Grain size: 48 nm with polydispersity of 0.04 carried out on Malvern Autosizer Lo-C at 25 ° C;
Après la mise en œuvre du protocole de stabilité conformément à l'exemple 1 , on constate que la dispersion obtenue est stable.After the implementation of the stability protocol in accordance with Example 1, it is found that the dispersion obtained is stable.
Exemple 5 :Example 5:
Cet exemple illustre la préparation d'un polymère formant une dispersion de particules dans une huile siliconée, ledit polymère étant obtenu par polymérisation d'acrylate de méthyle et du macromonomère monométhacryloxypropylpolydiméthylsiloxane ayant un poids moléculaire moyen en poids de 5000 vendu sous la dénomination MCR-M17 par la société Gelest Inc.This example illustrates the preparation of a polymer forming a dispersion of particles in a silicone oil, said polymer being obtained by polymerization of methyl acrylate and of the macromonomer monométhacryloxypropylpolydiméthylsiloxane having a weight average molecular weight of 5000 sold under the name MCR-M17 by Gelest Inc.
Dans un réacteur de 1 litre, on charge 200 g d'heptane, 200 g de décaméthylcyclopentasiloxane, 30 g d'acrylate de méthyle, 10 g de monométhacryloxypropylpolydiméthylsiloxane MCR-M17 et 3,2 g de tertiobutyiperoxy-2-éthylhexanoate (Trigonox 21 S). 0n .. agjte -et on -chauffe-le- mélange réactionnel à 90°C en-1 -heure.- Après -15 minutes à 90°C, on observe un changement d'aspect du milieu réactionnel, qui passe d'un aspect transparent à un aspect laiteux. On maintient le chauffage sous agitation pendant 15 minutes supplémentaires puis on ajoute goutte à goutte pendant 1 heure un mélange constitué par 160 g d'acrylate de méthyle et 2 g de Trigonox 21 S. On laisse ensuite le chauffage pendant 4 heures à 90°C puis on distille l'heptane du milieu réactionnel.200 g of heptane, 200 g of decamethylcyclopentasiloxane, 30 g of methyl acrylate, 10 g of monomethacryloxypropylpolydimethylsiloxane MCR-M17 and 3.2 g of tertiobutyiperoxy-2-ethylhexanoate (Trigonox 21 S) are charged to a 1 liter reactor. ). 0 n .. a gjte -and -heat-the reaction mixture at 90 ° C in-1-hour.- After -15 minutes at 90 ° C, there is a change in appearance of the reaction medium, which passes from '' a transparent appearance to a milky appearance. The heating is maintained with stirring for an additional 15 minutes, then a mixture consisting of 160 g of methyl acrylate and 2 g of Trigonox 21 S. The heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium.
A l'issue de cette opération de distillation, on obtient une dispersion de particules de polymère ainsi préparé stable dans le décaméthylcyclopentasiloxane (D5).At the end of this distillation operation, a dispersion of particles of polymer thus prepared, stable in decamethylcyclopentasiloxane (D5), is obtained.
Le polymère greffé comprend 5 % en poids de macromonomère (donc de chaîne latérale soluble dans la D5) par rapport au poids du polymère.The grafted polymer comprises 5% by weight of macromonomer (therefore of side chain soluble in D5) relative to the weight of the polymer.
Les caractéristiques du polymère et des particules formées par ledit polymère sont les suivantes :The characteristics of the polymer and of the particles formed by said polymer are as follows:
- Masse moléculaire poids Mw=102347- molecular weight Mw = 102347
- Masse moléculaire nombre Mn=28283- Molecular mass number Mn = 28283
- Indice de polydispersité (Mw/Mn)= 3.62- Polydispersity index (Mw / Mn) = 3.62
- Extrait sec : 51 ,4 % dans le D5 réalisé par thermobalance- Dry extract: 51.4% in D5 produced by thermobalance
- Transition vitreuse : 12°C par DSC Mettler- Glass transition: 12 ° C by DSC Mettler
- Granulométrie : 160 nm avec polydispersité de 0,04 réalisée sur Malvern Autosizer Lo-C à 25°C- Granulometry: 160 nm with polydispersity of 0.04 carried out on Malvern Autosizer Lo-C at 25 ° C
Après mise en œuvre du protocole de stabilité conformément à l'exemple 1 , on constate que la dispersion est stable.After implementation of the stability protocol in accordance with Example 1, it is found that the dispersion is stable.
Les polymères des exemples 1 à 5 comprennent les monomères suivants , leurs taux étant indiqués en pourcentage en poids du polymère :The polymers of Examples 1 to 5 include the following monomers, their levels being indicated as a percentage by weight of the polymer:
Exemples 6 à 10EXAMPLES 6 TO 10
On a préparé 5 fonds de teint ayant les compositions suivantes (les teneurs sont indiquées en pourcentage par rapport au poids total de la composition) :5 foundations were prepared having the following compositions (the contents are indicated as a percentage relative to the total weight of the composition):
Chaque composition contient 2,1 % en poids de matière active de polymère greffé. --Each composition contains 2.1% by weight of graft polymer active material. -
ingrédients utilisés :ingredients used:
ABIL EM 97 : mélange siliconé oxyéthylénée oxypropylénée substituée en α-ω /cyclométhicone (85/15) vendu par la Société GoldschmidtABIL EM 97: substituted oxyethylenated oxypropylenated silicone mixture in α-ω / cyclomethicone (85/15) sold by the company Goldschmidt
Inwitor 780 K : Mono-diglycerides d'acide iso-steraique estérifiés par de l'acide succinique, vendu par la Société SasolInwitor 780 K: Mono-diglycerides of isosteroic acid esterified with succinic acid, sold by the company Sasol
D5 : cyclopentasiloxaneD5: cyclopentasiloxane
Gomme de siliconé : mélange de polydiphényl diméthylsiloxane et de cyclopentasiloxane (15/85) vendu sous la dénomination MIRASIL C(DPDM par la société RHODIASilicone gum: mixture of polydiphenyl dimethylsiloxane and cyclopentasiloxane (15/85) sold under the name Mirasil C (DPDM by the company RHODIA
Poudre de nylon vendue sous la dénomination Orgasol® 2002 extra D NAT COS par la société ATOFINANylon powder sold under the name Orgasol® 2002 extra D NAT COS by the company ATOFINA
les 10 % de pigments comprennent :the 10% of pigments include:
1 ,43 % d'oxydes de fer jaune enrobés de tri-isostéaroyl titanate d'isopropyle1.43% yellow iron oxides coated with isopropyl tri-isostearoyl titanate
(BYO-I 2 de Kobo)(BYO-I 2 from Kobo)
0,46 % d'oxydes de fer brun enrobés de tri-isostéaroyl titanate d'isopropyle (BRO-I0.46% brown iron oxides coated with isopropyl tri-isostearoyl titanate (BRO-I
2 de Kobo)2 of Kobo)
0,22 % d'oxydes de fer noir enrobés de tri-isostéaroyl titanate d'isopropyle (BBO-I0.22% black iron oxides coated with isopropyl tri-isostearoyl titanate (BBO-I
2 de Kobo)2 of Kobo)
7,89 % de dioxyde de titane enrobés de tri-isostéaroyl titanate d'isopropyle (BTD-7.89% titanium dioxide coated with isopropyl tri-isostearoyl titanate (BTD-
401 de Kobo)401 by Kobo)
Puis on a mesuré l'indice de transfert en présence de sébum de chaque composition selon le protocole de mesure décrit précédemment. On a obtenu les résultats suivants :Then the transfer index was measured in the presence of sebum of each composition according to the measurement protocol described above. The following results were obtained:
On constate que les compositions ont un indice de transfert en présence de sébum inférieur à 4. En outre, les compositions des exemples 6 à 8 ont une meilleure résistance au transfert en présence de sébum que les compositions des exemples 9 et 10. On constate donc que la présence d'acide acrylique dans le polymère greffé favorise la propriété non transfert du dépôt obtenu avec la composition. It is found that the compositions have a transfer index in the presence of sebum of less than 4. In addition, the compositions of Examples 6 to 8 have better resistance to transfer in the presence of sebum than the compositions of Examples 9 and 10. It is therefore found that the presence of acrylic acid in the grafted polymer promotes the non-transfer property of the deposit obtained with the composition.
Claims
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0215737 | 2002-12-12 | ||
| FR0215737A FR2848558B1 (en) | 2002-12-12 | 2002-12-12 | ACRYLIC POLYMER, DISPERSION OF SAID POLYMER STABLE IN A NONAQUEOUS ORGANIC MEDIUM AND COMPOSITION COMPRISING SAID DISPERSION |
| FR0215739A FR2848560B1 (en) | 2002-12-12 | 2002-12-12 | ACRYLIC POLYMER, DISPERSION OF SAID POLYMER STABLE IN A NONAQUEOUS SILICONE ORGANIC MEDIUM AND COMPOSITION COMPRISING SAID DISPERSION |
| FR0215739 | 2002-12-12 | ||
| FR0215738A FR2848559B1 (en) | 2002-12-12 | 2002-12-12 | ACRYLIC POLYMER, DISPERSION OF SAID POLYMER STABLE IN A NONAQUEOUS AND NON - SILICONE ORGANIC MEDIUM AND COMPOSITION COMPRISING SAID DISPERSION |
| FR0215738 | 2002-12-12 | ||
| PCT/FR2003/003708 WO2004055073A2 (en) | 2002-12-12 | 2003-12-12 | Cosmetic composition comprising a polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1585777A2 true EP1585777A2 (en) | 2005-10-19 |
Family
ID=32600653
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03813186A Withdrawn EP1583784A2 (en) | 2002-12-12 | 2003-12-12 | Non-transfer cosmetic composition comprising a dispersion of a grafted ethylene polymer |
| EP03813184A Withdrawn EP1585777A2 (en) | 2002-12-12 | 2003-12-12 | Cosmetic composition comprising a polymer |
| EP03813183A Withdrawn EP1572770A2 (en) | 2002-12-12 | 2003-12-12 | Cosmetic composition comprising a polymer |
| EP03813190.0A Expired - Lifetime EP1572137B1 (en) | 2002-12-12 | 2003-12-12 | Non-transfer cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03813186A Withdrawn EP1583784A2 (en) | 2002-12-12 | 2003-12-12 | Non-transfer cosmetic composition comprising a dispersion of a grafted ethylene polymer |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03813183A Withdrawn EP1572770A2 (en) | 2002-12-12 | 2003-12-12 | Cosmetic composition comprising a polymer |
| EP03813190.0A Expired - Lifetime EP1572137B1 (en) | 2002-12-12 | 2003-12-12 | Non-transfer cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase |
Country Status (6)
| Country | Link |
|---|---|
| US (3) | US7794695B2 (en) |
| EP (4) | EP1583784A2 (en) |
| JP (5) | JP4167229B2 (en) |
| AU (8) | AU2003300595A1 (en) |
| ES (1) | ES2627551T3 (en) |
| WO (8) | WO2004055073A2 (en) |
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- 2003-12-12 US US10/538,783 patent/US7794695B2/en not_active Expired - Fee Related
- 2003-12-12 JP JP2004559837A patent/JP4167229B2/en not_active Expired - Fee Related
- 2003-12-12 EP EP03813184A patent/EP1585777A2/en not_active Withdrawn
- 2003-12-12 AU AU2003300595A patent/AU2003300595A1/en not_active Abandoned
- 2003-12-12 WO PCT/FR2003/003708 patent/WO2004055073A2/en not_active Ceased
- 2003-12-12 WO PCT/FR2003/003710 patent/WO2004055079A2/en not_active Ceased
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- 2003-12-12 US US10/538,782 patent/US20060134034A1/en not_active Abandoned
- 2003-12-12 ES ES03813190.0T patent/ES2627551T3/en not_active Expired - Lifetime
- 2003-12-12 WO PCT/FR2003/003707 patent/WO2004055077A2/en not_active Ceased
- 2003-12-12 EP EP03813183A patent/EP1572770A2/en not_active Withdrawn
- 2003-12-12 US US10/538,016 patent/US20060251601A1/en not_active Abandoned
- 2003-12-12 AU AU2003300599A patent/AU2003300599A1/en not_active Abandoned
- 2003-12-12 WO PCT/FR2003/003713 patent/WO2004055081A2/en not_active Ceased
- 2003-12-12 EP EP03813190.0A patent/EP1572137B1/en not_active Expired - Lifetime
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- 2003-12-12 AU AU2003300601A patent/AU2003300601A1/en not_active Abandoned
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2008
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