ANHYDROUS COMPOSITION COMPRISING A NON-VOLATILE OIL, A VOLATILE HYDROCARBON OIL, A PARTICULAR LIPOPH

专利摘要:
The invention relates to an anhydrous composition, especially for the care and / or makeup of keratinous substances, in particular the skin, comprising, preferably in a physiologically acceptable medium: a) an oily phase comprising: i) at least one oil non-volatile and ii) at least one hydrocarbon-based volatile oil, and b) at least one monoalcohol containing from 2 to 8 carbon atoms and c) at least one lipophilic film-forming polymer chosen from: (i) silicone resins of the type MQ; (ii) silsesquioxane resins; (iii) vinyl polymers grafted with a carbosiloxane dendrimer; (iv) their mixtures; and d) at least one particulate material; said composition comprising at least 15% by weight of non-volatile oil (s) relative to the total weight of the composition. The invention also relates to a process for coating keratin materials, more particularly for makeup and / or care of keratin materials, such as the skin, characterized in that it comprises the application to keratin materials of an emulsion such as as previously defined
公开号:FR3041530A1
申请号:FR1559041
申请日:2015-09-25
公开日:2017-03-31
发明作者:Euriel Clavel
申请人:LOreal SA；
IPC主号:

专利说明:

ANHYDROUS COMPOSITION COMPRISING A NON-VOLATILE OIL, A VOLATILE HYDROCARBON OIL, A PARTICULAR LIPOPHILIC FILMOGENIC POLYMER, A MONO-ALCOHOL AND A PARTICULATE MATERIAL The invention relates to an anhydrous composition, especially for the care and / or makeup of keratin materials, in particular of the skin, comprising, preferably in a physiologically acceptable medium: a) an oily phase comprising: i) at least one nonvolatile oil and ii) at least one volatile hydrocarbon oil, and b) at least one monoalcohol comprising 2 to 8 carbon atoms and c) at least one lipophilic film-forming polymer chosen from: (i) silicone resins of MQ type; (ii) silsesquioxane resins; (iii) vinyl polymers grafted with a carbosiloxane dendrimer; (iv) their mixtures; and d) at least one particulate material; said composition comprising at least 15% by weight of non-volatile oil (s) relative to the total weight of the composition. The invention also relates to a process for coating keratin materials, more particularly for makeup and / or care of keratin materials, such as the skin, characterized in that it comprises the application to keratin materials of an emulsion such as as previously defined
Consumers are increasingly looking for make-up or skincare cosmetics that spread easily and quickly on the skin in the form of a deposit that should not be thick but instead blend as much as possible with the support.
It is known to those skilled in the art that especially liquid makeup and / or skincare products containing a high content of nonvolatile oils and especially of high refractive index (n> 1.450) make it possible to obtain good properties of spreading and penetration into the skin and comfort and good shine.
Examples of make-up products include liquid foundations, liquid lip glosses, and in the care field moisturizing and emollient oily products or solar oils.
This high content of non-volatile oils tends to lead to a feeling of greasiness and stickiness during application and to a poor performance of the deposit on the skin over time.
In particularly liquid formulas with a high oil content and based on particulate material such as pigments, it is difficult to maintain said materials in suspension over time; these will sediment and form a block very difficult to re-disperse ("cake").
In application EP2699636, there are known make-up compositions rich in monoalcohol and comprising a lipophilic film-forming polymer chosen from vinyl polymers grafted with a carbosiloxane dendrimer in order to obtain a better resistance to dullness. Alcoholic makeup compositions based on red organic pigments are also known in patent FR3005857. These documents do not mention the problems of using volatile oils at high levels in the presence of pigments. These compositions contain low levels of non-volatile oil in the composition and are not fully satisfactory in terms of application comfort.
There is therefore a need to search for novel skincare and / or make-up compositions based on a particulate material and with a high content of non-volatile oils, making it possible to substantially reduce or even eliminate the sticky effect on application. to obtain good properties of spreading and penetration into the skin and of comfort and good gloss, to obtain good holding properties over time and / or to obtain a "clean" sedimentation of the particles, resulting in a transparent release (without suspended particle) and an easy and homogeneous re-dispersion of the cake.
In the course of its research, the Applicant has unexpectedly discovered that these objectives can be achieved by using an anhydrous composition, preferably comprising in a physiologically acceptable medium: a) an oily phase comprising: i) at least one non-volatile oil and ii) at least one volatile hydrocarbon oil, and b) at least one monoalcohol containing from 2 to 8 carbon atoms relative to the total weight of the composition, and c) at least one lipophilic film-forming polymer chosen from: ) Silicone resins of MQ type; (ii) silsesquioxane resins; (iii) vinyl polymers grafted with a carbosiloxane dendrimer; (iv) their mixtures; and d) at least one particulate material; said composition comprising at least 15% by weight of non-volatile oil (s) relative to the total weight of the composition.
This discovery is the basis of the invention.
Thus, the invention firstly relates to an anhydrous composition, especially for the care and / or makeup of keratinous substances, in particular the skin, comprising, preferably in a physiologically acceptable medium: a) an oily phase comprising: at least one non-volatile oil and ii) at least one hydrocarbon-based volatile oil, and b) at least one monoalcohol containing from 2 to 8 carbon atoms relative to the total weight of the composition, and c) at least one film-forming polymer. lipophilic material selected from: (i) silicone resins of the MQ type; (ii) silsesquioxane resins; (iii) vinyl polymers grafted with a carbosiloxane dendrimer; (iv) their mixtures; and d) at least one particulate material; said composition comprising at least 15% by weight of non-volatile oil (s) relative to the total weight of the composition. The invention also relates to a process for coating keratin materials, more particularly makeup and / or care of keratin materials, such as the skin, characterized in that it comprises the application to keratin materials of a composition such as as defined previously Definitions
In the context of the present invention, the term "keratin materials" means the eyelashes, the lips and preferably the skin and more particularly the face, the cheeks, the eye contour, the eyelids.
By "physiologically acceptable" is meant compatible with the skin and / or its integuments, which has a pleasant color, smell and feel and which does not generate unacceptable discomfort (tingling, tightness, redness), which can divert the consumer to use this composition.
For the purposes of the invention, the expression "anhydrous composition" denotes, respectively, a composition which contains less than 5% by weight of water, preferably less than 2% by weight of water, or even less than 0.5% of water. water relative to its total weight, and in particular a composition free of water.
By "particulate material" is meant any compound in the form of insoluble and dispersible particles in the composition of the invention. Said material being different from the lipophilic film-forming polymer.
OIL PHASE
The compositions according to the invention comprise an oily phase.
The oily phase comprises at least one nonvolatile oil in a proportion of at least 15.0% by weight, preferably at least 30.0% by weight, more preferably at least 45.0% by weight relative to the total weight of the composition and at least one volatile hydrocarbon oil.
The term "oil" means any fatty substance in liquid form at ambient temperature (20-25 ° C.) and at atmospheric pressure. These oils can be of animal, vegetable, mineral or synthetic origin.
Non-volatile oils
By "non-volatile oil" is meant an oil remaining on the skin or the keratin fiber at room temperature (20-25 ° C.) and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 10 -3 mm. Hg (0.13 Pa). The oil may be chosen from all the oils, which are preferably physiologically acceptable, in particular mineral, animal, vegetable and synthetic oils; in particular the nonvolatile and / or silicone nonvolatile and / or fluorinated nonvolatile hydrocarbon oils and mixtures thereof.
By "hydrocarbon oil" is meant an oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and / or alcohol groups. As an example of a non-volatile hydrocarbon oil which can be used in the invention include: hydrocarbon oils of plant origin such as triglycerides of fatty acids of 4 to 24 carbon atoms such as triglycerides of caprylic / capric acids such as those sold by Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel; triglycerides of branched C18-C36 fatty acids and of glycerol, such as that sold under the name DUB TGI 24® by the company STEARINERIE DUBOIS (INCI name C18-36 ACID TRIGLYCERIDE); linear or branched hydrocarbons of mineral or synthetic origin such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, polybutenes, hydrogenated polyisobutene such as Parleam, squalane; synthetic ethers having from 10 to 40 carbon atoms such as dicaprylyl ether; synthetic esters, especially of fatty acids, isononyl isononanoate, isopropyl myristate, isopropyl palmitate, C12-C15 alcohol benzoate, hexyl laurate, diisopropyl adipate, ethyl 2-hexyl palmitate, octyl 2-dodecyl stearate, octyl 2-dodecyl erucate, isostearyl isostearate, diisostearyl malate, tridecyl trimellitate; branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, 2-butyloctanol, 2-hexyl decanol and 2-undecyl; pentadecanol, oleic alcohol; higher fatty acids such as oleic acid, linoleic acid, linolenic acid; carbonates, such as dicapryl carbonate; - acetates; - citrates; fluorinated oils which may be partially hydrocarbon-based and / or silicone-based, such as fluorosilicone oils, fluorinated polyethers or fluorinated silicones as described in document EP-A-847752; silicone oils, such as non-volatile polydimethylsiloxanes (PDMS); phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates, and mixtures thereof.
Preferably, the oily phase of the composition according to the invention comprises at least one non-volatile oil having a refractive index n greater than or equal to 1.450. The refractive index is measured at room temperature (20 ° C) and atmospheric pressure. Said non-volatile oil is in particular chosen from: non-volatile hydrocarbon oils having a refractive index greater than or equal to 1.450; non-volatile phenyl silicones having a refractive index greater than or equal to 1.450; and - their mixtures.
As hydrocarbon oils of refractive index n greater than or equal to 1.450, mention may be made in particular of:
linear or branched hydrocarbons of mineral or synthetic origin, in particular polybutenes such as the commercial products INDOPOL H 100 (n = 1.49), INDOPOL H 1500® (n = 1.5) from INEOS, and hydrogenated polyisobutenes; such as PARLEAM HV® commercial products (n = 1.456), PARLEAM SV® (n = 1.458) from NOF CORPORATION - fatty acid synthesis esters such as iso-stearyl lactate, isostearyl palmitate , octyldodecyl neodecanoate, isocetyl stearate, propylene glycol monoisostearate, 2-ethyl hexyl isostearate, octyldodecyl stearate, octyldodecyl myristate, di-isostearyl adipate, octyl hydroxystearate, glyceryl tri isostearate, octyl dodecyl stearoyl stearate, diisocetyl dodecane di-oate, dipentaerythrityl hexacaprylate / hexacaprate, octyl-2-dodecyl hydroxy stearate, tetraoctyldodecanoate of pentaerythrityl, tri-isostea citrate ryl, pentaerythrityl tetra-2-hexyldecanoate, propylene glycol di-iso-stearate, tridecyltetradecanoine, isostearyl isostearate, isofol 24 isostearate, triisocetyl citrate, diisopropyl dimer dilinoleate , pentaerythrityl tetra-decyltetradecanoate, diisostearyl malate, di-iso-arachidyl dodecane-di-oate, octyldodecyl erucate, tri-iso arachidyl citrate, hexyldecyl myristoylmethylaminopropionate, tetraisostearate, pentaerythrityl, trimethylolpropane triisostearate, oleyl erucate, ditrymethylolpropane tetraisostearate, dioctyldodecyl dimer dilinoleate, ethyl panthenol, sucrose 6-8 soybean fatty chains, triisostearyl trilinoleate, octyl-2-dodecyl benzoate 2-ethylhexyl benzoate, 12 isofol trimellitate, C 12 -C 15 alkylbenzoate, the hydrogenated dimer dilinoleyl / dimethylcarbonate copolymer, the tri-iso-decyl tri-mellitate, the tri-decyl tri-mellitate, tri-ethyl-2-hexyl trimellitate, castor oil benzoate, dipropylene glycol dibenzoate, 2-ethyl hexyl glyceryl ether palmitate; hydrocarbon-based oils of vegetable origin, such as branched-chain fatty acid triglycerides of C 18 -C 36 and of glycerol (n = 1.454 -1.458), arara oil, jojoba oil, coconut oil, praxium, virgin olive oil, meadowfoam oil, sesame oil, ximenia oil, soybean oil, macadamia oil, castor oil, oils containing polyoxypropylenated (POP) or polyoxethylenated (POE) groups, such as oxypropylenated myristyl diadipate (3 OP), oxyethylenated glyceryl triacetate (7 EO), PEG-4 (40E), PEG-6 (60E) PEG (8 EO), octyldodecyl PPG-3 myristyl ether dimer dilinoleate, - their mixtures Oil or hydrocarbon-based oils with a refractive index n greater than or equal to 1.450 will be selected more particularly among - branched C18-C36 fatty acid triglycerides (n = 1.46) and glycerol such as the commercial product such as the commercial product cial DUB TGI 24® by STEARINE DUBOIS, - diisostearyl malate (n = 1.46) as the commercial product SCHERCEMOL DISM ESTER® from LUBRIZOL, - tridecyl trimellitate (n = 1.48) as the commercial product LIPONATE TDTM® from VANTAGE SPECIALTY CHEMICALS, and mixtures thereof.
According to one particular form of the invention, a mixture of C 18 -C 36 branched fatty acid triglycerides and of glycerol, of diisostearyl malate, and of diisostearyl malate, is used as hydrocarbon-based oils having a refractive index n greater than or equal to 1.450. tridecyl trimellitate.
Non-volatile silicone oils having a refractive index greater than or equal to 1.450 include, in particular, phenyl silicones:
Phenylated silicone (also called phenyl silicone oil) is understood to mean an organopolysiloxane substituted with at least one phenyl group. The phenyl silicone oil may be chosen from phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, trimethyl pentaphenyl trisiloxane and 2-phenylethyl trimethylsiloxysilicates. The silicone oil can meet the formula:
wherein the R groups independently represent a methyl or a phenyl. Preferably in this formula, the silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.
According to another embodiment, the silicone oil corresponds to the formula
wherein the R groups independently represent a methyl or a phenyl. Preferably in this formula, said organopolysiloxane comprises at least three phenyl groups, for example at least four or at least five.
Mixtures of the phenyl organopolysiloxanes described above can be used.
Examples that may be mentioned are mixtures of triphenylated, tetra- or penta-phenylated organopolysiloxane.
According to another embodiment, the silicone oil corresponds to the formula
in which Me is methyl, Ph is phenyl. Such phenyl silicone is especially manufactured by Dow Corning under the reference Dow Corning 555 Cosmetic Fluid (INCI name: trimethyl pentaphenyl trisiloxane). The reference Dow Corning 554 Cosmetic Fluid can also be used.
According to another embodiment, the silicone oil corresponds to the formula
wherein Me is methyl, y is 1 to 1000, and X is -CH 2 -CH (CH 3) (Ph).
According to another embodiment, the silicone oil corresponds to the formula
in which -OR 'represents -O-SiMe3, y is between 1 and 1000 and z is between 1 and 1000. The phenyl silicone oil may be chosen from the phenyl silicones of formula (VI) below:
(VI) in which - Ri to Rio, independently of one another, are hydrocarbon radicals, saturated or unsaturated, linear, cyclic or branched, C1-C30,
- m, n, p and q are, independently of one another, integers between 0 and 900, provided that the sum 'm + n + q' is not 0.
Preferably, the sum 'm + n + q' is between 1 and 100. Preferably, the sum 'm + n + p + q' is between 1 and 900, more preferably between 1 and 800. Preferably, q is equal to 0. The phenyl silicone oil may be chosen from the phenyl silicones of formula (VII) below:
in which: R 1 to R 6, independently of one another, are cyclic or branched linear or branched C 1 -C 30 hydrocarbon radicals, m, n and p are, independently of one another, integers between 0 and 100, provided that the sum 'n + m' is between 1 and 100.
Preferably, R 1 to R 6, independently of each other, represent a saturated hydrocarbon radical, linear or branched, C 1 -C 30, especially C 1 -C 12, and in particular a methyl, ethyl, propyl or butyl radical.
In particular, R 1 to R 6 may be identical, and furthermore may be a methyl radical.
Preferably, one can have m = 1 or 2 or 3, and / or n = 0 and / or p = 0 or 1, in formula (VII).
A phenyl silicone oil of formula (VI) having a viscosity at 25 ° C. of between 5 and 1500 mm 2 / s (ie 5 to 1500 ° C.), preferably having a viscosity of between 5 and 1000 mm 2 / s ( 5 to 1000 East).
As phenyl silicone oil of formula (VII), phenyltrimethicones such as DC556 from Dow Corning (22.5 cSt), Silbione 70663V30 from Rhône Poulenc (28 cSt), or diphenyldimethicones can be used in particular.
that Belsil oils, including Belsil PDM1000 (1000 is), Belsil PDM 200 (200 is) and Belsil PDM 20 (20 is) from Wacker. Values in parentheses represent viscosities at 25 ° C.
According to one particular form of the invention, the non-volatile oily phase may contain a mixture of one or more non-volatile oils having a refractive index greater than or equal to 1.450 and one or more non-volatile refractive index oils. less than 1.450. By way of example, non-volatile oil having a refractive index of less than 1.450, mention may in particular be made of synthetic ethers having from 10 to 40 carbon atoms, such as dicaprylyl ether (n = 1.43).
According to one particular form of the invention, a mixture of C 18 -C 36 branched fatty acid triglycerides and of glycerol, of diisostearyl malate, of tridecyl trimellitate and of dicapryl ether is used as non-volatile hydrocarbon oils. The non-volatile oil or oils according to the invention are preferably present in a concentration ranging from 15 to 85% by weight and more preferably ranging from 30 to 60% by weight, and particularly from 45 to 55% by weight. weight relative to the total weight of the composition The non-volatile oil or oils of refractive index n greater than or equal to 1.450 according to the invention are preferably present in a concentration ranging from 15 to 65% by weight. and more preferably ranging from 30 to 60% by weight%, and particularly from 45 to 55% by weight relative to the total weight of the composition.
Volatile hydrocarbon oils
For the purposes of the invention, the term "volatile oil" means an oil capable of evaporating on contact with the skin or keratin fiber in less than one hour at ambient temperature (20-25 ° C.) and pressure atmospheric. The volatile oils of the invention are volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular from 0.13 Pa to 40 000 Pa (10 -3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg). ). By way of example of volatile hydrocarbon oil that may be used in the invention, mention may be made of volatile hydrocarbon oils chosen from hydrocarbon-based oils having 8 to 16 carbon atoms, and in particular C 8 -C 16 isoalkanes of petroleum origin ( also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names of Isopars or permetyls, branched C8-C16 esters, isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon oils such as petroleum distillates, especially those sold under the name Shell or by Shell, may also be used; volatile linear alkanes such as those described in the patent application of Cognis DE10 2008 012 457.
Among the volatile hydrocarbon oils, the C 6 -C 16 isoalkanes, in particular isododecane, are preferred. The volatile hydrocarbon oil or oils in accordance with the invention are preferably present in concentrations ranging from 10 to 30% by weight and more particularly ranging from 12 to 25% by weight relative to the total weight of the composition.
According to one particular form of the invention, the composition may additionally contain at least one volatile silicone oil.
As volatile silicone oils, mention may be made of volatile linear or cyclic silicone oils, in particular those having a viscosity of <8 centistokes (8 × 10 -6 m 2 / s), and having in particular from 2 to 7 silicon atoms, these silicones possibly comprising alkyl or alkoxy groups having 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, there may be mentioned in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethylisiloxane, octamethyltrisiloxane and decamethyl tetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.
More particularly, dodecamethyl pentasiloxane will be used.
SINGLE ALCOHOL
The compositions of the invention comprise at least one monoalcohol containing from 2 to 8 carbon atoms, especially from 2 to 6 carbon atoms, and in particular from 2 to 4 carbon atoms.
The compositions of the invention may comprise one or more monoalcohol (s).
This monoalcohol can be represented for example by the formula RaOH, in which Ra represents a linear or branched alkyl group comprising from 2 to 8 carbon atoms. As monoalcohol, mention may be made of ethanol, isopropanol, propanol or butanol.
According to one embodiment, the compositions of the invention comprise ethanol.
The amount of monoalcohol (s) is, preferably, at least 8% by weight, and more preferably at least 10% by weight relative to the total weight of said composition.
According to an advantageous embodiment, the amount of mono-alcohol (s) ranges from 8% to 40% by weight, preferably from 10% to 20% by weight, and even more preferably from 10% to 15% by weight. relative to the total weight of said composition.
According to an advantageous embodiment, the weight ratio mono-alcohol / volatile hydrocarbon oil is greater than 1/1, preferably ranging from 1.1 / 1 to 3/1, and more particularly from 1.2 / 1 to 1 , 5/1.
LIPOPHILE FILMOGENIC POLYMER
The lipophilic film-forming polymer that may be used in the compositions in accordance with the invention are chosen from: (i) silicone resins of the MQ type; (ii) silsesquioxane resins; (iii) vinyl polymers grafted with a carbosiloxane dendrimer; (iv) their mixtures
By "polymer" is meant here a compound having one or more repeating units and preferably at least 2 repeating units.
The term "film-forming polymer" means a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a film which is macroscopically continuous and adheres to the keratin materials, and preferably a cohesive film, and better still a film of which the cohesion and the mechanical properties are such that said film can be isolable and manipulable in isolation, for example when said film is produced by casting on an anti-adherent surface such as a Teflon or silicone surface.
The film-forming polymers of the invention are lipophilic, in particular liposoluble or lipo-dispersible, that is to say soluble or dispersible in oils.
Liposoluble or lipo-dispersible means the possibility of dissolving the polymer or dispersing homogeneously in at least one oil, at room temperature or by heating if necessary to a temperature below the flash point of said oil, and a mass percentage generally less than or equal to 80% by weight of film-forming polymer.
Silicone resins type MQ
More generally, the term "resin" means a compound whose structure is three-dimensional.
The term "silicone resins" is also referred to as "silicone resins" or "siloxane resins". Thus, within the meaning of the present invention, a polydimethylsiloxane is not a silicone resin.
The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known under the name of "MDTQ", the resin being described according to the different monomeric siloxane units that it comprises, each of the letters "MDTQ" characterizing a type of unit.
The letter "M" represents the monofunctional unit of formula R1R2R3SiOi / 2, the silicon atom being connected to a single oxygen atom in the polymer comprising this unit.
The letter "D" means a Difunctional unit R1R2Si02 / 2 in which the silicon atom is connected to two oxygen atoms
The letter "T" represents a trifunctional unit of formula R1Si03 / 2-
Finally, the letter "Q" means a tetrafunctional unit S104 / 2 in which the silicon atom is bonded to four oxygen atoms themselves linked to the rest of the polymer.
In the units M, D, T defined above, R1, R2 and R3 represents a hydrocarbon radical (especially alkyl) having 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group.
Such resins are described for example in "Encyclopedia of Polymer Science and Enginnering, vol. 15, John and Wiley and Sons, New York, (1989), p. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or US 5,082,706, US 5,319,040, US 5,302, 685 and US 4,935,484. By way of example of silicone resins of MQ type that may be used according to the invention, mention may be made of the alkylsiloxysilicates of formula [(R 1) 3 SiO 1/2] x (SiO 4/2) y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group R 1 represents a radical as defined above, and preferably is an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group.
Examples of solid silicone resins of MQ type trimethylsiloxysilicate type include those sold under the reference SR1000 by the company General Electric, under the reference TMS 803 by the company Wacker, under the name "KF-7312J" by the company Shin- Etsu, "DC 749", "DC 593" by Dow Corning.
As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151 sold by General Electric). The preparation of such resins is described in particular in US5817302. Silsesquioxane resins
Among the resins of silsesquioxane that may be used in the compositions in accordance with the invention, mention may be made of alkyl silsesquioxane resins which are homopolymers and / or copolymers of silsesquioxane having a siloxane average unit of formula RinSiO (4-n) / 2, where each R 1 independently denotes a hydrogen atom or a C 1 -C 10 alkyl group where more than 80 mol% of the R 1 radicals represent a C 3 -C 10 alkyl group, n is a number of from 1.0 to 1.4, and more particularly, will use a silsesquioxane copolymer in which more than 60 mol% comprises RiSiO 3/2 units in which R 1 has the definition indicated above.
Preferably, the silsesquioxane resin is chosen such that R 1 is a C 1 -C 10 alkyl group, preferably a C 1 -C 4 alkyl group, and more particularly a propyl group. A polypropylsilsesquioxane resin or tylpropyl silsesquioxane (INCI name, POLYPROPYLSILSESQUIOXANE (and) ISODODECANE such as the product sold under the trade name Dow Corning® 670 Fluid by the company Dow-Corning.
Vinyl polymers grafted with a carbosiloxane dendrimer
A vinyl polymer suitable for the preparation of a composition according to the invention comprises at least one unit derived from carbosiloxane dendrimer.
The vinyl polymer has a backbone and at least one side chain, which comprises a carbosiloxane dendrimer derived unit having a carbosiloxane dendrimer structure.
The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure having branched groups having high molecular weights, said structure having a high regularity in the radial direction from the skeleton bond. Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in Japanese Laid-open Patent Application Kokai 9-171,154.
A vinyl polymer according to the invention may contain units derived from carbosiloxane dendrimers which may be represented by the following general formula (I):
(I) wherein: - R1 represents an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms; X 1 represents a silylalkyl group which, when i = 1, is represented by the formula (II):
(II) wherein: R1 is as defined above in formula (I), R2 represents an alkylene radical of 2 to 10 carbon atoms, R3 represents an alkyl group of 1 to 10 carbon atoms, X 1 + is chosen from: a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 5 to 10 carbon atoms and a silylalkyl group defined above of formula (II) with i = i + 1,
. i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and a1 is an integer of 0 to 3; Y represents a radical-polymerizable organic group chosen from: organic groups containing a methacrylic group or an acrylic group, said organic groups being represented by the formulas: or in which: R 4 represents a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and R 5 represents an alkylene group of 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group, with methylene and propylene groups being preferred; and. organic groups containing a styryl group of formula:
wherein: R6 represents a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, the methyl group being preferred; R7 represents an alkyl group of 1 to 10 carbon atoms; R8 represents an alkylene group of 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, the ethylene group being preferred; * b is an integer from 0 to 4; and * c is 0 or 1, so that if c is 0, - (R8) c- represents a bond.
In one embodiment, R 1 may be an aryl group having 5 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. The alkyl group may preferably be methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl or cyclohexyl. The aryl group may preferably be represented by a phenyl group and a naphthyl group. The methyl and phenyl groups are more particularly preferred, and the methyl group is most preferred.
According to one embodiment, R2 represents an alkylene group having 2 to 10 carbon atoms, especially a linear alkylene group, such as an ethylene, propylene, butylene or hexylene group; or a branched alkylene group, such as a methylmethylene, methylethylene, 1-methylpentylene or 1,4-dimethylbutylene group.
Ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene are most preferred.
According to one embodiment, R3 is chosen from methyl, ethyl, propyl, butyl and isopropyl groups.
In formula (II), i indicates the number of generations and thus corresponds to the number of repetitions of the silylalkyl group.
For example, when the number of generations is equal to one, the carbosiloxane dendrimer may be represented by the general formula shown below, wherein Y, R 1, R 2 and R 3 are as defined above, R 12 represents a hydrogen or is identical to R1; a1 is identical to a1. Preferably, the total average number of OR3 groups in a molecule is in the range of 0 to 7.
When the number of generations is 2, the carbosiloxane dendrimer may be represented by the following general formula, wherein Y, R 1, R 2, R 3 and R 12 are the same as defined above; a1 and a2 represent the ai of the indicated generation. Preferably, the total average number of OR3 groups in a molecule is in the range of 0 to 25.
In the case where the number of generations is equal to 3, the carbosiloxane dendrimer is represented by the general formula below, in which Y,
R1, R2, R3 and R12 are the same as defined above; a1, a2 and a3 represent the ai of the indicated generation. Preferably, the total average number of OR3 groups in a molecule is in the range of 0 to 79.
A vinyl polymer having at least one carbosiloxane dendrimer derived unit has a side molecular chain containing a carbosiloxane dendrimer structure, and may be derived from the polymerization: (A) from 0 to 99.9 parts by weight of a vinyl monomer; and (B) from 100 to 0.1 parts by weight of a radical-polymerizable organic group-containing carbosiloxane dendrimer represented by the general formula (I) as defined above.
The vinyl monomer component (A) in the vinyl polymer having at least one carbosiloxane dendrimer-derived unit is a vinyl-type monomer that contains a radical-polymerizable vinyl group.
There is no particular limitation with respect to such a monomer.
The following are examples of this vinyl type monomer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a lower alkyl analogue methacrylate; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate , 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, or a higher analogous methacrylate; vinyl acetate, vinyl propionate, or a lower analogous fatty acid vinyl ester; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate, or a higher analogous fatty acid ester; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone, or analogous aromatic vinyl monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide,
risobutoxymethoxymethacrylamide, Ν, Ν-dimethylmethacrylamide, or analogous vinyl monomers which contain amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or vinyl-like monomers which contain hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or vinyl-like monomers which contain a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl ether and vinyl, or a vinyl-like monomer with ether linkages; methacryloxypropyltrimethoxysilane, polydimethylsiloxane having a methacrylic group on one of its molecular ends, polydimethylsiloxane having a styryl group on one of its molecular ends, or a silicone-like compound having unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutylfumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl ether and glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid ; an unsaturated monomer polymerizable with radicals having a sulfonic acid group such as a styrene sulfonic acid group; a quaternary ammonium salt derived from methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and an ester of methacrylic acid of an alcohol having a tertiary amine group such as an ester of methacrylic acid and diethylamine.
The multifunctional vinyl-type monomers can also be used.
The following are examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, dimethacrylate of 1, 6-hexanediol, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris- (2-hydroxyethyl) isocyanurate dimethacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, styryl-capped polydimethylsiloxane having divinylbenzene groups on two ends, or analogous silicone compounds having unsaturated groups.
A carbosiloxane dendrimer, which is the component (B), can be represented by the formula (I) as defined above.
The following is the preferred examples of group Y of formula (I): an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group, 2- (3-vinylphenyl) ethyl group, vinyl group, allyl group , a methallyl group, and a 5-hexenyl group.
A carbosiloxane dendrimer according to the present invention can be represented by the following average structural formulas:
Thus, according to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by the following formula:
wherein: Y, R1, R2 and R3 are as defined in formulas (I) and (II) above; . a1, a2 and a3 meet the definition of ai according to formula (II); and. R12 is H, an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms.
According to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by one of the following formulas:
The vinyl polymer comprising the carbosiloxane dendrimer according to the invention can be manufactured according to the process for producing a branched silalkane siloxane described in Japanese Patent Application Hei 9-171 154.
For example, it can be produced by subjecting a hydrosilylation reaction to an organosilicon compound which contains a hydrogen atom connected to a silicon atom represented by the following general formula (IV):
(IV)
Wherein R 1 is as defined above in formula (I), and an organosilicon compound which contains an alkenyl group.
In the above formula, the organosilicon compound may be represented by 3-methacryloxypropyltris- (dimethylsiloxy) silane, 3-acryloxypropyltris- (dimethylsiloxy) silane, and 4-vinylphenyltris- (dimethylsiloxy) silane. The organosilicon compound which contains an alkenyl group may be represented by vinyltris- (trimethylsiloxy) silane, vinyltris- (dimethylphenylsiloxy) silane, and 5-hexenyltris- (trimethylsiloxy) silane.
The hydrosilylation reaction is carried out in the presence of a chloroplatinic acid, a vinylsiloxane and platinum complex, or a transition metal-like catalyst.
A vinyl polymer having at least one unit derived from carbosiloxane dendrimer may be chosen from polymers such that the unit of a derivative of a carbosiloxane dendrimer is a carbosiloxane dendritic structure represented by formula (III):
(III) wherein Z is a divalent organic group, "p" is 0 or 1, R1 is as defined above in formula (IV) and X1 is a silylalkyl group represented by formula (II) as defined above.
In a vinyl polymer having at least one unit derived from a carbosiloxane dendrimer, the ratio of polymerization between components (A) and (B), in terms of weight ratio between (A) and (B), is in a range of 0 / 100 to 99.9 / 0.1, or even 0.1 / 99.9 to 99.9 / 0.1, and preferably in a range of 1/99 to 99/1. A ratio between components (A) and (B) of 0/100 means that the compound becomes a homopolymer of component (B).
A vinyl polymer having at least one unit derived from carbosiloxane dendrimer can be obtained by the copolymerization of the components (A) and (B), or by the polymerization of the single component (B).
The polymerization may be free-radical polymerization or ionic polymerization, however radical polymerization is preferred.
The polymerization can be carried out by causing a reaction between components (A) and (B) in a solution for a period of 3 to 20 hours in the presence of a radical initiator at a temperature of 50 ° C to 150 ° C.
A suitable solvent for this purpose is hexane, octane, decane, cyclohexane, or a similar aliphatic hydrocarbon; benzene, toluene, xylene, or a similar aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, or ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-isobutyl ketone, or similar ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, or analogous esters; methanol, ethanol, isopropanol, butanol, or similar alcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, or a similar organosiloxane oligomer.
A radical initiator may be any compound known in the art for conventional radical polymerization reactions. Specific examples of such radical initiators are 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) or compounds azobic analogues; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, or a similar organic peroxide. These radical initiators can be used alone or in a combination of two or more. The radical initiators may be used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of components (A) and (B). A chain transfer agent can be added. The chain transfer agent may be 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethylsiloxane having a mercaptopropyl group or a mercapto-like compound; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane, or a similar halogenated compound.
In the manufacture of the vinyl polymer, after the polymerization, the unreacted residual vinyl monomer can be removed under vacuum heating conditions.
To facilitate the preparation of raw material for cosmetics, the number average molecular weight of the vinyl polymer which contains a carbosiloxane dendrimer may be selected in the range of from 3,000 to 2,000,000, preferably from 5,000 to 800,000. It can be a liquid, an eraser, a paste, a solid, a powder, or any other form. Preferred forms are solutions consisting of dilution in solvents, a dispersion, or a powder.
The vinyl polymer may be a dispersion of a vinyl polymer having a carbosiloxane dendrimer structure in its side molecular chain, in a liquid such as a silicone oil, an organic oil, an alcohol, or water. The silicone oil may be a dimethylpolysiloxane having both trimethylsiloxy-capped molecular ends, a copolymer of methylphenylsiloxane and dimethylsiloxane having both trimethylsiloxy-terminated molecular ends, a methyl-3,3,3-trifluoropropylsiloxane copolymer and dimethylsiloxane having both trimethylsiloxy-terminated molecular ends, or analogous non-reactive linear silicone oils, as well as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, or a similar cyclic compound. In addition to the nonreactive silicone oils, modified polysiloxanes having functional groups such as silanol groups, amino groups, and polyether groups on the ends or within the side molecular chains may be used.
The organic oils may be isododecane, paraffin oil, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearic alcohol, cetostearyl alcohol, oleic alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum, sunflower oil, soybean oil, camellia oil, squalane, castor oil, cottonseed oil, coconut oil, yellow oil egg, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate, or a similar glycol ester oil; triglyceryl isostearate, triglyceride of a coconut oil fatty acid, or a similar polyhydric alcohol ester oil; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether, or a similar polyoxyalkylene ether. The alcohol may be of any type suitable for use in conjunction with a raw material of cosmetics. For example, it may be methanol, ethanol, butanol, isopropanol or lower alcohols.
A solution or dispersion of the alcohol should have a viscosity in the range of 10 to 109 mPa at 25 ° C. To improve the feel properties of use in a cosmetic product, the viscosity should be in the range of 100 to 5 x 108 mPa.s.
The solutions and dispersions can easily be prepared by mixing a vinyl polymer having at least one carbosiloxane dendrimer derived unit, a silicone oil, an organic oil, an alcohol, or water. The liquids may be present in the polymerization step. In this case, the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric or reduced pressure.
In the case of a dispersion, the dispersity of the vinyl polymer can be improved by adding a surfactant.
Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid, or anionic surfactants of the sodium salts. of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyl dimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow hydroxide trimethylammonium, coconut trimethylammonium oil hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether, a polyoxyalkylenealkylphenol, a polyoxyalkylene alkyl ester, polyoxyalkylene sorbitol ester, polyethylene glycol, polypropylene glycol, a diethylene glycol trimethylnonanol ethylene oxide additive, and surfactants; Nonionic, polyester-type actives, as well as mixtures.
In the dispersion, a mean diameter of the vinyl polymer particles may be in the range of 0.001 to 100 microns, preferably 0.01 to 50 microns. Indeed, beyond the recommended range, a cosmetic product mixed with the emulsion will not have a sufficiently good sensation on the skin or touch, nor sufficient spreading properties nor a pleasant sensation.
A vinyl polymer contained in the dispersion or solution may have a concentration in a range of between 0.1% and 95% by weight, preferably between 5% and 85% by weight. However, for ease of handling and mixing, the range should preferably be between 10% and 75% by weight.
A vinyl polymer that is suitable for the invention may also be one of the polymers described in the examples of application EP 0 963 751.
According to a preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer may be derived from the polymerization: from 0 to 99.9 parts by weight of one or more monomer (s) acrylate or methacrylate; and from 100 to 0.1 parts by weight of an acrylate or methacrylate monomer of a tri [tri (trimethylsiloxy) silylethyl dimethylsiloxy] silylpropyl carbosiloxane dendrimer.
The monomers (A1) and (B1) correspond to particular monomers (A) and (B), respectively.
According to one embodiment, a vinyl polymer having at least one unit derived from carbosiloxane dendrimer may comprise a unit derived from tri [tri (trimethylsiloxy) silylethyl dimethylsiloxy] silylpropyl carbosiloxane dendrimer, corresponding to one of the formulas:
According to one preferred embodiment, a vinyl polymer having at least one carbosiloxane dendrimer derived unit used in the invention comprises at least one butyl acrylate monomer.
According to one embodiment, a vinyl polymer may further comprise at least one fluorinated organic group.
Particularly preferred are structures in which the vinyl polymerized units constitute the backbone and carbosiloxane dendritic structures as well as fluorinated organic groups are attached to side chains. The fluorinated organic groups may be obtained by substituting with fluorine atoms all or part of the hydrogen atoms of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl and heptyl groups, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, and other alkyl groups from 1 to 20
carbon atoms, as well as alkyloxyalkylene groups of 6 to 22 carbon atoms.
The groups represented by the formula - (CFI2) x- (CF2) y-R13 are suggested by way of example of fluoroalkyl groups, obtained by substituting fluorine atoms for hydrogen atoms of alkyl groups. In the formula, the index "x" and 0, 1,2 or 3 and "y" and an integer of 1 to 20. R13 is an atom or a group selected from a hydrogen atom, a fluorine atom, -CH (CF3) 2-or CF (CF3) 2. Such fluorine-substituted alkyl groups are exemplified by linear or branched polyfluoroalkyl or perfluoroalkyl groups represented by the formulas presented below: -CF 3, -C 2 F 5, -nC 3 F 7, -CF (CF 3) 2, -nC 4 F 9, CF 2 CF (CF 3 ) 2, -NCsFn, -NCeFi3, -NC8F-17, CH2CF3, - (CH (CF3) 2, CH2CH (CF3) 2-CH2 (CF2) 2F, -CH2 (CF2) 3F, -CH2 (CF2) 4F, -CH2 (CF2) 6F, -CH2 (CF2) 8F, -CH2CH2CF3, -CH2CH2 (CF2) 2F, -CH2CH2 (CF2) 3F, -CH2CH2 (CF2) 4F, -CH2CH2 (CF2) 6F, -CH2CH2 (CF2) 8F, -CH2CH2 (CF2) ioF, -CH2CH2 (CF2) 12F, -CH2CH2 (CF2) uF, -CH2CH2 (CF2) 16F, -CH2CH2CH2CF3, -CH2CH2CH2 (CF2) 2F, -CH2CH2CH2 (CF2) 2H, -CH2 ( CF2) 4H and -CH2CH2 (CF2) 3H.
The groups represented by -CH2CH2- (CF2) m-CFR14- [OCF2CF (CF3)] n-OC3F7 are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkoxyoxyalkylene groups. In the formula, the index "m" is 0 or 1, "n" is 0, 1,2, 3, 4, or 5, and R14 is a fluorine atom or CF3. Such fluoroalkyloxyfluoroalkylene groups are exemplified by perfluoroalkyloxyfluoroalkylene groups represented by the formulas set forth below: -CH2CH2CF (CF3) - [OCF2CF (CF3)] n-OC3F7, -CH2CH2CF2CF2- [OCF2CF (CF3)] n-OC3F7.
The number average molecular weight of the vinyl polymer used in the present invention may range from about 3,000 to about 2,000,000, and more preferably from about 5,000 to about 800,000.
This type of fluorinated vinyl polymer can be obtained by adding: a vinyl monomer (M2) without a fluorinated organic group, on a vinyl monomer (M1) containing fluorinated organic groups, and a carbosiloxane dendrimer (B) such as defined above of general formula (I) as defined above, subjecting them to copolymerization.
Thus, according to one embodiment, a composition of the invention may comprise a vinyl polymer having at least one unit derived from carbosiloxane dendrimer and resulting from the copolymerization of a vinyl monomer (M1) as defined above, optionally a vinyl monomer (M2) as defined above, and a carbosiloxane dendrimer (B) as defined above, said vinyl polymer having a copolymerization ratio between the monomer (M1) and the monomer (M2 ) from 0.1 to 100: 99.9 to 0% by weight, and a copolymerization ratio between the sum of the monomers (M1) and (M2) and the monomer (B) from 0.1 to 99.9: 99 , 9 to 0.1% by weight.
The vinyl monomers (M1) containing fluorinated organic groups in the molecule are preferably monomers represented by the general formula: (CH2) = CR15COORf.
In this formula, R15 is a hydrogen atom or a methyl group, Rf is a fluorinated organic group exemplified by the fluoroalkyl and fluoroalkyloxyfluoroalkylene groups described above. The compounds represented by the formulas presented below are suggested as specific examples of the component (M1). In the formulas present below, "z" is an integer of 1 to 4. CH 2 = CCH 3 COO-CF 3, CH 2 = CCH 3 COO-C 2 F 5, CH 2 = CCH 3 COO-nC 3 F 7, CH 2 = CCH 3 COO-CF (CF 3) 2, CH 2 = CCH 3 COO -NC4F9, CH2 = CCH3COO-CF (CF3) 2, CH2 = CCH3COO-nC5Fn, CH2 = CCH3COO-nC6F13, CH2 = CCH3COO-nC8F17, CH2 = CCH3COO-CH2CF3, CH2 = CCH3COO-CH (CF3) 2, CH2 = CCH3COO -CH2CH (CF3) 2, CH2 = CCH3COO-CH2 (CF2) 2F, CH2 = CCH3COO-CH2 (CF2) 2F, CH2 = CCH3COO-CH2 (CF2) 4F, CH2 = CCH3COO-CH2 (CF2) 6F, CH2 = CCH3COO -CH2 (CF2) 8F, CH2 = CH3COO-CH2CH2CF3, CH2 = CH3COO-CH2CH2 (CF2) 2F, CH2 = CH3COO-CH2CH2 (CF2) 3F, CH2 = CH3COO-CH2CH2 (CF2) 4F, CH2 = CH3COO-CH2CH2 (CF2 ) 6F, CH2 = CCH3COO-CH2CH2 (CF2) 8F, CH2 = CCH3COO-CH2CH2 (CF2) ioF, CH2 = CCH3COO-CH2CH2 (CF2) 12F, CH2 = CCH3COO-CH2CH2 (CF2) uF, CH2 = CCH3COO-CH2-CH2 - (CF2) 16F, CH2 = CH3COO-CH2CH2CH2CF3, CH2 = CH3COO-CH2CH2CH2 (CF2) 2F, CH2 = CH3COO-CH2CH2CH2 (CF2) 2H, CH2 = CH3COO-CH2 (CF2) 4H, CH2 = CH3COO- (CF2) 3H , CH2 = CCH3COO-CH2CH2CF (CF3) - [OCF2-CF (CF3)] z-OC3F7, CH2 = CCH3COO-CH2CH2CF2CF2- [OCF2-CF (CF3)] z-OC3F7, CH2 = CHCOO-CF3i CH2 = CHCOO-C2F5 , CH2 = CHCOO-nC3F7, CH2 = CHCOO-CF (CF3 ) 2, CH2 = CHCOO-nC4F9, CH2 = CHCOO-CF2CF (CF3) 2, CH2 = CHCOO-nC5Fn, CH2 = CHCOO-nC6F13, CH2 = CHCOO-nC8F7, CH2 = CHCOO-CH2CF3, CH2 = CHCOO-CH (CF3 CH2 = CHCOO-CH2CH (CF3) 2i CH2 = CHCOO-CH2 (CF2) 2F, CH2 = CHCOO-CH2 (CF2) 3F, CH2 = CHCOO-CH2 (CF2) 4F, CH2 = CHCOO-CH2 (CF2) 6F , CH2 = CHCOO-CH2 (CF2) 8F, CH2 = CHCOOCH2CH2CF3, CH2 = CHCOO-CH2CH2 (CF2) 2F, CH2 = CHCOO-CH2CH2 (CF2) 3F, CH2 = CHCOO-CH2CH2 (CF2) 4F, CH2 = CHCOO -CH2CH2 (CF2) 6F, CH2 = CHCOO-CH2CH2 (CF2) 8F, CH2 = HCOO-CH2CH2 (CF2) ioF, CH2-CHCOO-CH2CH2- (CF2) 12F, CH2 = CHCOO-CH2CH2 (CF2) uF, CH2 = CHCOO-CH2CH2 (CF2) 16F, CH2 = CHCOCH2CH2CHF3, CH2 = CHCOO-CH2CH2CH2 (CF2) 2F, CH2 = CHCOO-CH2CH2CH2 (CF) 2H, CH2 = CHCOO-CH2 (CF2) 4H, CH2 = CHCOO-CH2CH2 ( CF2) 3H, CH2 = CHCOO-CH2CH2CF (CF3) -, [OCF2-CF (CF3)] z-OC3Ft, CH2 = CHCOO-CH2CH2CF2CF2 (CF3) - [OCF2-CF (CF3)] 2-OC3F7.
Of these, the vinyl polymers represented by the formulas presented below are preferred: CH 2 = CHCOO-CH 2 CH 2 (CF 2) 6F, CH 2 = CHCOO-CH 2 CH 2 (CF 2) 8F, CH 2 = CCH 3 COO-CH 2 CH 2 (CF 2) 6F, CH 2 = CCH3COO-CH2CH2 (CF2) 8F, ch2 = chcoo-ch2cf3, ch2 = cch3coo-ch2cf3.
The vinyl polymers represented by the formulas presented below are particularly preferred: CH2 = CHCOO-CH2CF3, CH2 = CCHCOO-CH2CF3.
The vinyl monomers (M2) which do not contain fluorinated organic groups in the molecule may be any monomers having radical-polymerizable vinyl groups which are exemplified, for example, by methyl acrylate, methyl methacrylate or acrylate. ethyl, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and other lower alkyl acrylates or methacrylates; glycidyl acrylate, glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate , n-hexyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, and other higher acrylates and methacrylates; vinyl acetate, vinyl propionate, and other lower fatty acid vinyl esters; vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, and other higher fatty acid esters; styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone, and other vinyl aromatic monomers; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and other amino vinyl monomers, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N methoxymethylacrylamide, N-methoxymethacrylamide, isobutoxymethoxyacrylamide, isobutoxymethoxy-methacrylamide, Ν, Ν-dimethylacrylamide, Ν, Ν-dimethylmethacrylamide, and other vinyl amide monomers; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylic acid alcohol, methacrylic acid hydroxypropyl alcohol and other hydroxy vinyl monomers; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and other carboxylic acid vinyl monomers; tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethyleneglycol acrylate, ethoxydiethyleneglycol methacrylate, polyethyleneglycol acrylate, polyethyleneglycol methacrylate, polypropyleneglycol monoacrylate polypropylene glycol monomethacrylate, hydroxybutylvinylether, cetylvinylether, 2-ethylhexylvinylether and other ether-linked vinyl monomers; acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, polydimethylsiloxanes containing acrylic or methacryl groups at one of the ends, polydimethylsiloxanes containing alkenylaryl groups at one of the ends and other silicone compounds containing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride, acrylonitrile, methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecylsuccinic anhydride; acrylglycidyl ether, methacrylglycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, alkali metal salts, ammonium salts and organic amine salts of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and other radical-polymerizable unsaturated carboxylic acids, radical-polymerizable unsaturated monomers containing sulfonic acid groups such as styrenesulfonic acid as well as their alkali metal salts, their ammonium salts and their organic amine salts; quaternary ammonium salts derived from acrylic acid or methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, methacrylic acid esters of a tertiary amine alcohol such as diethylamine ester, methacrylic acid and their quaternary ammonium salts.
In addition, it is also possible to use, as vinyl monomers (M2), the polyfunctional vinyl monomers which are exemplified for example by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate and diacrylate. ethylene glycol, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, diacrylate 1,6-hexanediol, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl acrylate, trimethylolpropanetrioxyethyl methacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, dimethacrylate tris (2-hydroxyethyl) isocyanate urate, tris (2-hydroxyethyl) isocyanurate triacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, polydimethylsiloxane whose both ends of the molecular chain are blocked by alkenylaryl groups, and other silicone compounds with unsaturated groups .
With respect to the above-mentioned ratio in which (M1) and (M2) are copolymerized, the weight ratio between (M1) and (M2) is preferably in the range 1:99 to 100: 0. Y may be chosen, for example, from organic groups containing acrylic or methacrylic groups, organic groups containing alkenylaryl groups, or alkenyl groups of 2 to 10 carbon atoms.
The organic groups with acrylic or methacrylic groups and the alkenylaryl groups are as defined above.
Among the compounds (B), there may be mentioned, for example, the following compounds:
The carbosiloxane dendrimers (B) can be prepared using the preparation method for the branched siloxane / silakylene copolymers described in EP 1 055 674.
For example, they may be prepared by subjecting organic silicone compounds to alkenyl and silicone compounds comprising silicon-bonded hydrogen atoms, represented by the formula (IV) as defined above, to a hydrosilylation reaction.
The copolymerization ratio (by weight) between the monomer (B) and the monomers (M1) and (M2) is preferably in the range of 1:99 to 99: 1, and even more preferably in the range of from 5:95 to at 95: 5.
Amino groups may be introduced into the side chains of the vinyl polymer using, included in the component (M2), vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, followed by modification with potassium acetate monochloride, ammonium acetate monochloride, monochloroacetic acid aminomethylpropanol salt, monobromoacetic acid triethanolamine salt, sodium monochloropropionate, and other alkali metal salts of halogenated fatty acids; otherwise, carboxylic acid groups can be introduced into the side chains of the vinyl polymer by using, included in the component (M2), vinyl monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid. , crotonic acid, fumaric acid and maleic acid, and the like, then neutralizing the product with triethylamine, diethylamine, triethanolamine, and other amines.
A fluorinated vinyl polymer may be one of the polymers described in the examples of application WO 03/045337.
According to a preferred embodiment, a grafted vinyl polymer in the sense of the present invention may be carried in an oil or a mixture of oil (s), preferably volatile (s) in particular, chosen (s) from the oils of silicones and hydrocarbon oils and mixtures thereof.
According to a particular embodiment, a silicone oil that is suitable for the invention may be cyclopentasiloxane.
According to another particular embodiment, a hydrocarbon oil suitable for the invention may be isododecane.
The vinyl polymers grafted with at least one carbosiloxane dendrimer-derived unit that may be particularly suitable for the present invention are the polymers sold under the names TIB 4-100, TIB 4-101, TIB 4-120, TIB 4-130, TIB 4- 200, FA 4002 ID (TIB 4-202), TIB 4-220, FA 4001 CM (TIB 4-230) by Dow Corning.
According to one particular form of the invention, the lipophilic film-forming polymer or polymers are chosen from: a silicone resin of MQ type of trimethylsiloxysilicate type; a phenylalkylsiloxysilicate type MQ resin,
a polypropylsilsesquioxane or t-propyl silsesquioxane resin (INCI name: POLYPROPYLSILSESQUIOXANE (and) ISODODECANE
a vinyl polymer grafted with at least one unit derived from carbosiloxane dendrimer (INCI name ACRYLATES / POLYTRIMETHYLSILOXYMETHACRYLATE).
According to one particular form of the invention, the lipophilic film-forming polymer is a polypropylsilsesquioxane or t-propyl silsesquioxane resin (INCI name: POLYPROPYLSILSESQUIOXANE (and) ISODODECANE).
According to one embodiment, the composition according to the present invention comprises the lipophilic film-forming polymer with an active material content of from 0.1% to 20%, in particular from 0.5% to 15%, more particularly from 0.5% to 15% by weight. % to 10%, and preferably from 0.5% to 4% by weight relative to the total weight of said composition.
According to a particularly preferred form, the composition according to the invention comprises at least a) at least 15.0% by weight relative to the total weight of the composition of at least one non-volatile hydrocarbon oil of higher refractive index or equal to 1.450 chosen from C 18 -C 36 branched fatty acid triglycerides, diisosteale malate, tridecyl trimellitate and mixtures thereof and optionally at least one non-volatile oil having a refractive index of less than 1.450, in particular, chosen from synthetic ethers containing from 10 to 40 carbon atoms, in particular dicaprylyl ether; and b) at least one hydrocarbonaceous volatile oil chosen from C8-C16 isoalkanes, in particular isododecane, and c) at least 8% by weight of ethanol relative to the total weight of the composition, and d) at least one lipophilic film-forming polymer chosen from a trimethylsiloxysilicate type MQ silicone resin, a polypropylsilsesquioxane or t-propyl silsesquioxane resin, a vinyl polymer grafted with at least one unit derived from a carbosiloxane dendrimer, and e) at least one pigment.
PARTICULATE MATERIAL
The particulate materials that can be used in the compositions according to the invention can be chosen from pigments, fillers and their mixtures.
The term "pigments" is intended to mean white or colored particles, mineral or organic, insoluble in an aqueous solution, intended to color and / or opacify the resulting film.
By "charge" is meant colorless or white, solid particles of all shapes, which are in an insoluble form and dispersed in the medium of the composition. Of mineral or organic nature, they make it possible to confer body or rigidity on the composition and / or on the softness, and on the uniformity of the makeup
pigments
The pigments may be present in a proportion of from 0.1% to 40% by weight, in particular from 1% to 30% by weight, and in particular from 5% to 15% by weight, relative to the total weight of the composition. cosmetic.
As inorganic pigments that may be used in the invention, mention may be made of titanium, zirconium or cerium oxides, as well as zinc, iron or chromium oxides, ferric blue, manganese violet, ultramarine blue and Chromium hydrate. Preferably, the composition of the invention comprises at least titanium oxides and iron oxides.
As inorganic pigments that can be used in the invention, mention may be made in particular of nacres.
By "nacres", it is necessary to include colored particles of any shape, iridescent or otherwise, in particular, produced by certain shellfish in their shell or else synthesized and which exhibit a color effect by optical interference.
The nacres can be chosen from pearlescent pigments, such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic dyestuffs.
Mention may also be made, by way of example of nacres, of natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride. Among the nacres available on the market, mention may be made of mother-of-pearl TIMICA, FLAMENCO and DUOCHROME (based on mica) marketed by ENGELHARD, TIMIRON pearls marketed by MERCK, mother-of-pearl containing PRESTIGE mica marketed by the company. ECKART and nacres based on SUNSHINE synthetic mica sold by the company SUN CHEMICAL.
The nacres may more particularly have a color or a yellow, pink, red, bronze, orange, brown, gold and / or coppery reflection. As an illustration of the pearlescent agents that can be used in the context of the present invention, mention may be made, in particular, of gold-colored pearlescent agents, sold in particular by ENGELHARD, under the name Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze nacres, in particular, sold by the company Merck under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by Engelhard under the name Super Bronze (Cloisonne); orange nacres, in particular, sold by ENGELHARD under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); brown-colored pearlescent agents, in particular, sold by ENGELHARD under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacres with a copper sheen, in particular, marketed by Engelhard under the name Copper 340A (Timica); the red-colored pearlescent agents, in particular, marketed by MERCK under the name Sienna fine (17386) (Colorona); yellow-colored pearlescent agents, in particular, marketed by Engelhard under the name Yellow (4502) (Chromalite); nacres of red hue with gold glare, in particular, sold by ENGELHARD under the name Sunstone G012 (Gemtone); pink nacres, in particular, sold by ENGELHARD under the name Tan opal G005 (Gemtone); black nacres with gold reflection, sold by the company Engelhard under the name Nu antique bronze 240 AB (Timica), blue pearls, in particular, sold by MERCK under the name Matte Blue (17433) (Microna), white nacres with silvery reflection, in particular, sold by the company Merck under the name Xirona Silver and the golden-green orange-colored mother-of-pearl, in particular, marketed by MERCK under the name Indian summer (Xirona) and their mixtures.
Among the pigments that can be used according to the invention, mention may be made of those that have an optical effect other than a simple effect of conventional hue, that is to say unified and stabilized as produced by conventional dyestuffs, such as, for example, monochromatic pigments. For the purposes of the invention, "stabilized" means devoid of effect of color variability with the angle of observation or in response to a change in temperature.
For example, this material may be chosen from particles with a metallic sheen, goniochromatic coloring agents, diffractive pigments, thermochromic agents, optical brighteners, and especially interferential fibers. Of course, these different materials can be combined to provide the simultaneous manifestation of two effects, or even a new effect according to the invention.
The particles with a metallic sheen that can be used in the invention are in particular chosen from: particles of at least one metal and / or at least one metal derivative, particles comprising an organic or inorganic substrate, monomaterial or multimaterial, at least partially covered by at least one metal-reflecting layer comprising at least one metal and / or at least one metal derivative, and mixtures of said particles.
Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te. Se and their mixtures or alloys. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr, and mixtures or alloys thereof (e.g., bronzes and brasses) are preferred metals.
The term "metal derivatives" denotes compounds derived from metals, in particular oxides, fluorides, chlorides and sulphides. As an illustration of these particles, mention may be made of aluminum particles, such as those sold under the names STARBRITE 1200 EAC® by SIBERLINE and METALURE® by ECKART.
Mention may also be made of copper metal powders or mixtures of alloys, such as the references 2844 sold by the company Radium Bronze, metallic pigments, such as aluminum or bronze, such as those sold under the trade names ROTOSAFE 700 ECKART company, the silica-coated aluminum particles marketed under the name VISIONAIRE BRIGHT SILVER by the company ECKART and the metal alloy particles, such as bronze powders (alloy copper and zinc) coated with silica marketed under the name of Visionaire Bright Natural Gold from Eckart.
It may also be particles comprising a glass substrate such as those sold by the company NIPPON SHEET GLASS under the names MICROGLASS METASHINE. The goniochromatic coloring agent may be selected from, for example, interfering multilayer structures and liquid crystal coloring agents.
Examples of symmetrical interferential multilayer structures that can be used in compositions produced in accordance with the invention are, for example, the following structures: Al / SiO 2 / Al / SiO 2 / Al, pigments having this structure being marketed by DuPont de Nemours; Cr / MgF 2 / Al / MgF 2 / Cr, pigments having this structure being marketed under the name CHROMAFLAIR by the company FLEX; M0S2 / SiO2 / AI / S102 / M0S2; Fe 2 O 3 / SiO 2 / Al / SiO 2 / Fe 2 O 3, and
Fe 2 O 3 / SiO 2 / Fe 2 O 3 / SiO 2 / Fe 2 O 3, pigments having these structures being sold under the name SICOPEARL by the company BASF; MoS2 / SiO2 / mica-oxide / SiO2 / MoS2; Fe 2 O 3 / SiO 2 / mica-oxide / SiO 2 / Fe 2 O 3;
TiO 2 / SiO 2 / TiO 2 and TiO 2 / Al 2 O 3 / TiO 2; SnO / TiCVSiCVTiCVSnO; Fe 2 O 3 / SiO 2 / Fe 2 O 3; Sn0 / mica / TiO 2 / SiO 2 / TiO 2 / mica / SnO, pigments having these structures being sold under the name XIRONA by the company Merck (Darmstadt). By way of example, these pigments may be the pigments of silica / titania / tin oxide structure sold under the name Xirona Magic by the company Merck, the silica / brown iron oxide structural pigments marketed under the name XIRONA. INDIAN SUMMER by the company MERCK and the silica / titanium oxide / mica / tin oxide structural pigments marketed under the name XIRONA CARRIBEAN BLUE by the company MERCK. Mention may also be made of the INFINITE COLORS pigments from SHISEIDO. Depending on the thickness and nature of the different layers, different effects are obtained. Thus, with the Fe.sub.2 O.sub.3 / SiO.sub.2 / Al.sub.2 / Fe.sub.2 O.sub.3 structure, grey-green to gray-red is passed for SiO.sub.2 layers of 320 to 350 nm; from red to golden for S1O2 layers of 380 to 400 nm; from violet to green for SiO2 layers from 410 to 420 nm; from copper to red for SiO2 layers from 430 to 440 nm.
Mention may be made, by way of example of pigments with a polymeric multilayer structure, those marketed by the company 3M under the name COLOR GLITTER.
As liquid crystal goniochromatic particles, it is possible to use, for example, those sold by the company CFIENIX, as well as those marketed under the name FIELICONE® HC by the company WACKER.
loads
The fillers that can be used in the compositions of the invention can be of organic or mineral nature and make it possible, in particular, to impart to it additional properties of dullness, coverage, strength and / or improved stability.
The filler content may range from 2% to 20% by weight, especially from 4% to 12% by weight, relative to the total weight of said composition.
The fillers used in the compositions according to the present invention may be of lamellar, globular, spherical, fiber or any other intermediate form between these defined forms.
The fillers according to the invention may or may not be superficially coated, and in particular they may be surface-treated with silicones, amino acids, fluorinated derivatives or any other substance which promotes dispersion and compatibility of the filler in the process. composition.
Examples of mineral fillers that may be mentioned include clays, talc, mica, silica, hollow silica microspheres, kaolin, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, glass or ceramic microcapsules, silica and titanium dioxide composites, such as the TSG series marketed by Nippon Sheet Glass, hydrophobic silica airgel particles surface-modified with trimethylsilyl groups.
According to one particular form of the invention, the composition of the invention comprises, as filler, at least hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups and / or lipophilic clay. Examples of hydrophobic silica aerogels that can be used in the invention include, for example, the airgel marketed under the name VM-2260® (INCI name SILICA SILYLATE), by the company Dow Corning, whose particles have a size average of about 1000 microns and a specific surface area per unit mass of 600 to 800 m2 / g.
The aerogels marketed by Cabot under the references AEROGEL TLD 201, AEROGEL OGD 201, AEROGEL TLD 203, ENOVA® AEROGEL MT 1100 and ENOVA AEROGEL MT 1200 may also be mentioned.
The airgel marketed under the name VM-2270 (INCI name Silica silylate), by the company Dow Corning, whose particles have an average size ranging from 5 to 15 microns and a specific surface per unit mass ranging from 600 to 800 m2 / g.
The clays can be natural or synthetic and are rendered lipophilic by treatment with an alkylammonium salt such as a C 10 -C 22 ammonium chloride, for example di-stearyl dimethyl ammonium chloride.
They may be chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.
Preferably, they are chosen from hectorites.
In particular, use will be made of a hectorite modified with di-stearyl dimethyl ammonium chloride, such as the commercial product sold under the name Bentone GEL ISD V® by the company ELEMENTIS.
Examples of organic fillers that may be mentioned are polyamide powders (Nylon® Orgasol from Atochem), polyethylene, poly methyl methacrylate, polytetrafluoroethylene (Teflon) powders, copolymers of acrylic acid (Polytrap from the company). Dow Corning), lauroyl lysine, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel (Nobel Industry), hexamethylene diisocyanate / Trimethylol hexyllactone copolymer powder (Toshiki Plastic Powder), microbeads silicone resins other than those previously defined (Toshiba Tospearl, for example) synthetic or natural micronized waxes, metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms for example, zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate, lypore ® L 200 (Chemdal Corporation), polyurethane powders, in particular, crosslinked polyurethane powders comprising a copolymer, said copolymer comprising trimethylol hexyl lactone. In particular, it may be a hexamethylene diisocyanate / trimethylol hexyllactone polymer. Such particles are in particular commercially available, for example, under the name PLASTIC POWDER D-400® or PLASTIC POWDER D-800® from TOSHIKI, and mixtures thereof.
Additives
The compositions according to the invention may also contain additional cosmetic ingredients conventionally used for the formulation of particular galenics generally adjusted with respect to the targeted keratin material. This or these additional cosmetic ingredients may be chosen in particular from waxes, pasty fatty substances, surfactants, lipophilic gelling agents, dispersing agents, actives, preservatives, antioxidants, solvents, perfumes, sunscreens, bactericides, odor absorbers, fat-soluble dyes, and mixtures thereof.
The amounts of additional cosmetic ingredients are those conventionally used in the field under consideration, and for example from 0.01 to 20% of the total weight of the composition, and preferably from 0.01 to 10% of the total weight of the composition.
Of course, those skilled in the art will take care to choose any additional ingredients and / or their quantity so that the advantageous properties of the composition according to the invention are not or substantially not impaired by the addition envisaged.
Liposoluble dyes are, for example, Sudan Red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, Orange DC 5 and yellow quinoline
Silicone surfactant
According to a particular form, the compositions in accordance with the invention may additionally comprise a silicone surfactant, especially chosen from oxyalkylenated and preferably oxyethylenated polydimethylsiloxanes.
Preferably, the silicone surfactant comprises polyoxyethylene chains on the main chain (side or pendant polyoxyethylene chains).
The number of alkylene oxide units may range from 2 to 50 and preferably from 5 to 20.
Such silicone surfactants are especially those referred to as PEG-10 dimethicone sold by Shinetsu under the name KF-6017.
The silicone surfactant may be present in the composition according to the invention in an amount ranging from 0.01 to 5% by weight, relative to the total weight of the composition, and preferably from 0.1 to 3% by weight.
Dispersing agent
Advantageously, a composition according to the invention may further comprise a dispersing agent.
Such a dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them.
According to a particular embodiment, a dispersing agent according to the invention is a surfactant.
Active
For a particular care application, a composition according to the invention may comprise at least one moisturizing agent (also called humectant).
Preferably, the moisturizing agent is glycerin.
The moisturizing agent (s) may be present in the composition in a content ranging from 0.1% to 15% by weight, especially from 0.5% to 10% by weight, or even from 1% to 6% by weight, relative to to the total weight of said composition.
Other active agents which may be used in the composition of the invention include, for example, vitamins, sunscreens and mixtures thereof.
Preferably, a composition according to the invention comprises at least one active agent.
It is routine for those skilled in the art to adjust the nature and quantity of the additives present in the compositions according to the invention, so that the desired cosmetic properties thereof are not not affected.
Galenic forms
The compositions according to the invention can be in the form of a foundation, eyeshadow, blush, concealer, mascara, lipstick.
A cosmetic composition of the invention may be in the form of an anhydrous liquid product, an anhydrous gel, in the form of an anhydrous stick or in the form of an anhydrous soft paste. In particular, a cosmetic composition of the invention can be in the form of a liquid foundation, a hot-melt foundation product, a body make-up product, a concealer or an eyeshadow. , a makeup base.
According to one embodiment, a composition of the invention may advantageously be in the form of a skincare composition for the body or face, in particular the face.
According to another embodiment, a composition of the invention may advantageously be in the form of a makeup base composition.
According to another embodiment, a composition of the invention may advantageously be in the form of a foundation.
According to one embodiment, a composition of the invention may advantageously be in the form of an eyeshadow or a blush.
Such compositions are especially prepared according to the general knowledge of those skilled in the art.
Expressions "understood" from ... to ... "must be understood as inclusive terms unless otherwise specified. The invention is illustrated in more detail by the examples and figures presented hereinafter. Unless otherwise indicated, the quantities indicated are expressed as a percentage by mass.
Examples
Both anhydrous formulas were produced:
M.A. * = active ingredient Procedure:
The constituents of phase A were weighed into the main beaker and stirred while keeping at room temperature at Moritz. The stirring speed was adapted according to the amount of manufacture and the viscosity of the mixture. Stirring was maintained until a homogeneous mixture was obtained. Phase B was added with stirring. Stirring was maintained until a homogeneous mixture (absence of clusters) was obtained. Phase C was prepared separately by dispersing the Silica Sylilate in the mixture of the two oils in a beaker using a spatula. Mixture C was added with Moritz stirring. Stirring was maintained until a homogeneous mixture was obtained. Phases D and E were added with stirring. Stirring was maintained for 10 minutes. The stirring speed was adapted according to the quantity manufactured and the viscosity of the mixture. Finally phase F was added with Moritz stirring. Stirring was maintained until a homogeneous mixture and a good pigment dispersion (absence of clusters) were obtained. We then conditioned quickly.
It has been observed that Example 1 according to the invention comprising the lipophilic film-forming polymer of the silsesquioxane resin type allows, after centrifugation at 1000 rpm for one hour, at room temperature and at room temperature for 24 hours, in a bottle of 30 ml. ml, gives a "clean" sedimentation of the pigments resulting in a transparent release and easy and homogeneous re-dispersion of the cake unlike Example 2 without lipophilic film-forming polymer.
The composition of Example 1 also presented an oily sensory non-greasy and non-sticky.
Examples 3 to 7
Examples 3 and 4 of the invention and Examples 5, 6 and 7 (outside the invention) were prepared under the same conditions as Examples 1 and 2.
M.A. * = active ingredient
The results of the appearance of the compositions after centrifugation for 1 hour at 1000 rpm and rest for 24 h in a 30 ml flask are indicated in the following table:
It was observed that Example 3 according to the invention comprising the lipophilic film-forming polymer of the MQ resin type and Example 4 according to the invention comprising the vinylophilic film-forming polymer of the vinyl polymer type grafted with a carbosiloxane dendrimer allow after centrifugation at 1000 rpm one hour, at room temperature and rest for 24 hours, at room temperature, in a 30 ml flask, give a "clean" sedimentation of the pigments resulting in a transparent release and an easy and homogeneous re-dispersion of the cake unlike: - Example 5 comprising the film-forming polymer. ACRYLIC ACID / ISOBUTYL ACRYLATE / ISOBORNYL ACRYLATE COPOLYMER,
- Example 6 comprising the film forming polymer POLYDIENE / POLYBUTADIENE HYDROGEN - Example 7 comprising the film forming polymer ACRYLATES / DIMETHICONE COPOLYMER.
Examples 3 and 4 of the invention also presented an oily sensory non-greasy and non-sticky.

权利要求:
Claims (22)
[1" id="c-fr-0001]
An anhydrous composition, comprising, preferably in a physiologically acceptable medium: a) an oily phase comprising: i) at least one nonvolatile oil; ii) at least one hydrocarbonaceous volatile oil; and b) at least one monoalcohol comprising 2 to 8 carbon atoms and c) at least one lipophilic polymeric polymer selected from: (i) iMQ-type silicone resins; (ii) silsesquioxane resins; (iii) vinyl polymers grafted with a carbosiloxane dendrimer; (iv) their mixtures; and d) at least one particulate material; said composition comprising at least 15% by weight of non-volatile oil (s) relative to the total weight of the "imposition.
[2" id="c-fr-0002]
2. Composition according to claim 1, wherein the oily phase according to the invention comprises at least one non-volatile oil having a refractive index n greater than or equal to 1.450; said nonvolatile oil being preferably chosen from nonvolatile hydrocarbon oils having a refractive index n greater than or equal to 1.450, phenyl silicones having a refractive index n greater than or equal to 1.450, and mixtures thereof.
[3" id="c-fr-0003]
3. Composition according to claim 2, wherein the non-volatile hydrocarbon oil of refractive index n greater than or equal to 1.450 is chosen from: linear or branched hydrocarbons of mineral or synthetic origin; fatty acid synthesis esters; hydrocarbon oils of vegetable origin; oils comprising polyoxypropylenated or polyoxethylenated groups, their mixtures
[4" id="c-fr-0004]
4. .Composition according to claim 2 or 3, wherein nonvolatile hydrocarbon oil of refractive index n greater than or equal to 1.450 is selected from Cie-Cæ branched fatty acid triglycerides, diisostearyl malate, trimellitate of tridecyl and mixtures thereof and in particular is a mixture of triglycerides of C 18 -C 18 branched fatty acids, of diisostearyl malate and of tridecyl trimellitate
[5" id="c-fr-0005]
5. Composition according to any one of claims 1 to 4, wherein the non-volatile oily phase contains a mixture of one or more non-oil. volatiles of refractive index n greater than or equal to 1.450 and of one or more non-volatile oils having a refractive index of less than 1.450.
[6" id="c-fr-0006]
6. Composition according to claim 5, wherein the non-volatile oil of refractive index n less than 1.450 is chosen from synthetic ethers containing from 10 to 40 carbon atoms, in particular dicaprylyl ether.
[7" id="c-fr-0007]
A composition according to any one of claims 1 to 6, wherein the non-volatile oil is a mixture of Cta-C 8 branched fatty acid triglycerides and glycerol, diisostearyl malate, tridecyl trimellitate and dicapryl. ether.
[8" id="c-fr-0008]
A composition according to any one of claims 1 to 7, wherein the non-volatile oil or oils are present in a concentration of at least 30% by weight, preferably at least 45% by weight., And especially ranging from 15 to 85% by weight, and more particularly ranging from 30 to 60% by weight, and even more particularly from 45 to 55% by weight relative to the total weight of the composition.
[9" id="c-fr-0009]
9. Composition according to any one of claims 2 to 7, wherein the non-volatile oil or oils of refractive index n greater than or equal to 1.450 are present in a range of 15 to 65% by weight, and more particularly ranging from 30 to 60% by weight, and even more particularly from 45 to 55% by weight relative to the total weight of the composition
[10" id="c-fr-0010]
10. Composition according to any one of claims 1 to 9, wherein the volatile hydrocarbon oil is selected from C8-C16 isoalkanes, in particular isododecane.
[11" id="c-fr-0011]
11. Composition according to any one of claims 1 to 10, wherein the volatile hydrocarbon oil or oils are present in concentrations ranging from 10 to 30% by weight and more particularly ranging from 12 to 25% by weight relative to total weight of the composition.
[12" id="c-fr-0012]
12. Composition according to any one of claims 1 to 11, further comprising at least one volatile silicone oil, in particular dodecamethyl pentasiloxane.
[13" id="c-fr-0013]
13. Composition according to any one of claims 1 to 12, wherein the mono-alcohol having 2 to 8 carbon atoms is ethanol.
[14" id="c-fr-0014]
14. Composition according to any one of claims 1 to 13, wherein the amount of mono-alcohol (s) is, preferably, at least 8% by weight, and more preferably at least 10% by weight relative to to the total weight of said composition, particularly varies from 8% to 40% by weight, more particularly from 10% to 20% by weight, and even more particularly from 10% to 15% by weight, relative to the total weight of said composition .
[15" id="c-fr-0015]
15. Composition according to any one of claims 1 to 14, wherein the lipophilic film-forming polymer (s) is (are) chosen from: a silicone resin of MQ type of trimethylsiloxysilicate type; a phenylalkylsiloxysilicate type MQ resin; a polypropylsilsesquioxane or t-propyl silsesquioxane resin; a vinyl polymer grafted with at least one unit derived from a carbosiloxane dendrimer.
[16" id="c-fr-0016]
16. Composition according to any one of claims 1 to 15, wherein the lipophilic film-forming polymer is a polypropylsilsesquioxane or t-propyl silsesquioxane resin.
[17" id="c-fr-0017]
17. Composition according to any one of claims 1 to 16, wherein the lipophilic film-forming polymer is present in an active material content of from 0.1% to 20%, in particular from 0.5% to 15%, more particularly from 0.5% to 10%, and preferably from 0.5% to 4%, by weight relative to the total weight of said composition.
[18" id="c-fr-0018]
18. Composition according to any one of claims 1 to 17, wherein the particulate material is selected from pigments, fillers and mixtures thereof.
[19" id="c-fr-0019]
19. Composition according to any one of claims 1 to 18, comprising: as a filler, at least hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups and / or. a lipophilic clay, in particular a hectorite modified with di-stearyl di-methyl ammonium chloride.
[20" id="c-fr-0020]
20. Composition according to any one of claims 1 to 19, comprising: in addition to at least one silicone surfactant, in particular chosen from oxyalkylenated and preferably oxyethylenated polyimoxysiloxanes.
[21" id="c-fr-0021]
21. Composition according to any one of claims 1 to 20, in the form of an anhydrous liquid product, an anhydrous gel, in the form of an anhydrous stick or in the form of anhydrous soft paste.
[22" id="c-fr-0022]
22. A process for coating keratin materials, more particularly for makeup and / or care of keratin materials, such as the skin, characterized in that it comprises the application to keratin materials of a composition as defined according to US Pat. any one of claims 1 to 21.

类似技术:

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公开号 | 公开日 | 专利标题

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EP3352728B1|2019-12-04|Anhydrous liquid composition comprising oils, a film-forming polymer, a monoalcohol and a particulate material

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US20150290116A1|2015-10-15|Cosmetic process for making-up and/or caring for the skin and/or the lips

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JP2018531283A6|2018-12-13|Anhydrous liquid composition comprising oil, film-forming polymer, monoalcohol and particulate material

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FR2935269A1|2010-03-05|COSMETIC COMPOSITION COMPRISING A POLYMER WITH A DENDRIMERIC CARBOSILOXANE MOTIF.

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FR2974367A1|2012-10-26|COMPOSITIONS COMPRISING CARBOSILOXANE DENDRIMER-BASED POLYMER AND HIGH MONO-ALCOHOL QUANTITY

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FR3015251A1|2015-06-26|COSMETIC COMPOSITION COMPRISING A CARBOSILOXANE DENDRIMER-BASED POLYMER AND EXPANDED POLYMER PARTICLES

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FR2973245A1|2012-10-05|COMPOSITIONS COMPRISING PERLITE AND CARBOSILOXANE DENDRIMER-BASED POLYMER

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JP6199984B2|2017-09-20|Solid powdery cosmetic composition

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EP2512427B1|2013-11-06|Cosmetic composition comprising a supramolecular compound capable of establishing hydrogen bonds, and a particular additional ingredient

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FR2878738A1|2006-06-09|Cosmetic composition, e.g. lipstick, lip gloss, foundation, mascara, concealer, nail varnish, antisun composition, or hair make-up product, includes vinyl polymer| containing carbosiloxane dendrimer-based unit|

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FR2935268A1|2010-03-05|COSMETIC COMPOSITION COMPRISING A POLYMER WITH A DENDRIMERIC CARBOSILOXANE MOTIF.

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FR3041532A1|2017-03-31|LIQUID COSMETIC COMPOSITION COMPRISING A HIGH CONTENT OF NON-VOLATILE OILS AND METHOD OF TREATING LIP

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FR2988293A1|2013-09-27|Cosmetic composition, useful for making up and caring skin, comprises non-volatile ester, and emulsifying silicone elastomer, where composition is in form of water-in-oil emulsion including aqueous phase dispersed in fatty phase

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FR3041510A1|2017-03-31|PACKAGING AND APPLICATION ASSEMBLY OF A LIQUID COSMETIC PRODUCT

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FR3088201A1|2020-05-15|COMPOSITION COMPRISING POLYMER PARTICLES, A VOLATILE HYDROCARBON OIL, A FILM-FORMING SILICONE VINYL POLYMER, A PHENYLATED SILICONE NON-VOLATILE OIL

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FR2976805A1|2012-12-28|COSMETIC COMPOSITION COMPRISING A SUPRAMOLECULAR COMPOUND CAPABLE OF ESTABLISHING HYDROGEN BONDS, AND TWO SEPARATE PARTICULATE SILICONE OILS

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FR3015259A1|2015-06-26|COMPOSITION SOLID WITH CARBOSILOXANE DENDRIMER-BASED VINYL POLYMER, NON-VOLATILE ESTER ALCOHOL OIL, AND PROCESSING METHOD

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CN114191318A|2022-03-18|Anhydrous liquid composition comprising an oil, a film-forming polymer, a monol and a particulate material

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FR3111556A1|2021-12-24|Composition comprising polymer particles, a volatile hydrocarbon-based oil, a film-forming silicone vinyl polymer, a coconut oil

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FR2992213A1|2013-12-27|Cosmetic composition comprises pulverulent coloring materials, 0.1 wt.% of hydrophobic aerogel silica particles, and a vinyl polymer having unit derived from carbosiloxane dendrimer

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FR3041531A1|2017-03-31|LIQUID COSMETIC COMPOSITION COMPRISING A HIGH CONTENT OF NON-VOLATILE OILS, NON-IONIC SILICONE SURFACTANT AND METHOD OF TREATING LIP

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FR3067595A1|2018-12-21|WATER-IN-OIL EMULSION BASED ON NON-INTERFERENTIAL NON-THICKENING LOADS, NON-VOLATILE OIL, HYDROPHOBIC FILMOGENIC POLYMER, EMULSIFYING SILICONE ELASTOMER AND PIGMENTS

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FR3015254A1|2015-06-26|COMPOSITION SOLID WITH VINYLIC POLYMER WITH CARBOSILOXANE DENDRIMER PATTERN, PHENYLIC SILICONE OIL AND ORGANIC LOAD AND PROCESSING METHOD

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FR3015258A1|2015-06-26|SOLID COMPOSITION WITH CARBOSILOXANE DENDRIMER VINYLIC POLYMER, HYDROCARBONIC VOLATILE OILS AND PROCESSING METHOD

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FR2924935A1|2009-06-19|Cosmetic composition, useful for the care and make-up of lips, comprises filler, silicone compound, fatty phase, non-silicone wax, water or devoid of water, volatile oil or totally free of volatile oil, and dye

同族专利:

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公开号 | 公开日

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EP3352728A1|2018-08-01|

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ES2769073T3|2020-06-24|

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JP6657408B2|2020-03-04|

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US20180263890A1|2018-09-20|

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FR3041530B1|2020-01-17|

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JP2018531283A|2018-10-25|

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JP2020037583A|2020-03-12|

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EP3352728B1|2019-12-04|

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KR20180052737A|2018-05-18|

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CN108135807A|2018-06-08|

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WO2017050699A1|2017-03-30|

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KR102110270B1|2020-05-13|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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WO2002094182A2|2001-05-18|2002-11-28|Revlon Consumer Products Corporation|Long wearing composition for making up eyes, skin, and lips|

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FR2974367A1|2011-04-22|2012-10-26|Oreal|COMPOSITIONS COMPRISING CARBOSILOXANE DENDRIMER-BASED POLYMER AND HIGH MONO-ALCOHOL QUANTITY|

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FR3015259A1|2013-12-23|2015-06-26|Oreal|COMPOSITION SOLID WITH CARBOSILOXANE DENDRIMER-BASED VINYL POLYMER, NON-VOLATILE ESTER ALCOHOL OIL, AND PROCESSING METHOD|WO2020011540A1|2018-07-12|2020-01-16|L'oreal|Composition comprising a silicone/polyurea or silicone/polyurethane copolymer or silicone/polyurea/polyurethane copolymer, a silicone resin, a volatile alkane and a c2-c8 monoalcohol|US10047199B2|2009-12-24|2018-08-14|Dow Corning Toray Co., Ltd.|Copolymer having carbosiloxane dendrimer structure, and composition and cosmetic containing the same|

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KR102033017B1|2012-04-30|2019-10-16|아모레퍼시픽|Make-up cosmetic compositions comprising MQ silicone resins and propylsilsesquioxane|EP3787590A1|2018-05-04|2021-03-10|Johnson & Johnson Consumer Inc.|Cleansing compositions|

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US10940100B2|2018-05-30|2021-03-09|L'oréal|Cosmetic composition with long wear, metallic finish and cooling sensation|

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EP3906272A1|2018-12-31|2021-11-10|Dow Silicones Corporation|Branched organosilicon compound, method of preparing same, and copolymer formed therewith|

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CN113348199A|2018-12-31|2021-09-03|美国陶氏有机硅公司|Branched organosilicon compounds, methods of making branched organosilicon compounds, and copolymers formed therewith|

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WO2020142388A1|2018-12-31|2020-07-09|Dow Silicones Corporation|Composition, method of preparing copolymer, and methods and end uses thereof|

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EP3906274A1|2018-12-31|2021-11-10|Dow Silicones Corporation|Acrylate-functional branched organosilicon compound, method of preparing same, and copolymer formed therewith|

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FR3095758B1|2019-05-06|2021-11-26|Oreal|Oil-in-oil emulsion with at least one hydrophobic coated metal oxide and at least two immiscible oils comprising a non-volatile polar hydrocarbon oil and a non-volatile silicone oil|

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WO2021128055A1|2019-12-25|2021-07-01|L'oreal|Composition for conditioning keratain fibers|

法律状态:
2016-08-16| PLFP| Fee payment|Year of fee payment: 2 |

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2017-03-31| PLSC| Publication of the preliminary search report|Effective date: 20170331 |

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2017-08-10| PLFP| Fee payment|Year of fee payment: 3 |

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2018-08-13| PLFP| Fee payment|Year of fee payment: 4 |

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2019-08-15| PLFP| Fee payment|Year of fee payment: 5 |

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2020-08-12| PLFP| Fee payment|Year of fee payment: 6 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1559041A|FR3041530B1|2015-09-25|2015-09-25|ANHYDROUS COMPOSITION COMPRISING A NON-VOLATILE OIL, A VOLATILE HYDROCARBON OIL, A PARTICULAR LIPOPHILIC FILM-FORMING POLYMER, A MONO-ALCOHOL AND A PARTICULATE MATERIAL|

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FR1559041|2015-09-25|FR1559041A| FR3041530B1|2015-09-25|2015-09-25|ANHYDROUS COMPOSITION COMPRISING A NON-VOLATILE OIL, A VOLATILE HYDROCARBON OIL, A PARTICULAR LIPOPHILIC FILM-FORMING POLYMER, A MONO-ALCOHOL AND A PARTICULATE MATERIAL|

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KR1020187010509A| KR102110270B1|2015-09-25|2016-09-19|Anhydrous liquid composition comprising oil, film-forming polymer, monoalcohol and particulate matter|

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PCT/EP2016/072183| WO2017050699A1|2015-09-25|2016-09-19|Anhydrous liquid composition comprising oils, a film-forming polymer, a monoalcohol and a particulate material|

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US15/762,879| US20180263890A1|2015-09-25|2016-09-19|Anhydrous liquid composition comprising oils, a film-forming polymer, a monoalcohol and a particulate material|

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JP2018534015A| JP6657408B2|2015-09-25|2016-09-19|Anhydrous liquid composition comprising oil, film forming polymer, monoalcohol and particulate material|

---

EP16774466.3A| EP3352728B1|2015-09-25|2016-09-19|Anhydrous liquid composition comprising oils, a film-forming polymer, a monoalcohol and a particulate material|

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CN201680055172.6A| CN108135807A|2015-09-25|2016-09-19|Anhydrous liquid composition comprising oil, film forming polymer, single methanol and microparticle material|

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ES16774466T| ES2769073T3|2015-09-25|2016-09-19|Anhydrous liquid composition comprising oils, a film-forming polymer, a monoalcohol and a particulate material|

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JP2019206236A| JP2020037583A|2015-09-25|2019-11-14|Anhydrous liquid composition comprising oils, film-forming polymer, monoalcohol, and particulate material|