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    • 专利摘要:
    The method comprises the following steps: (a) providing at least one cosmetic material and providing at least one photoactivatable material; (b) forming a layer (19) having on at least a first region of the layer (19) a photoactivatable material provided in step (a); (c) illuminating at least the first region of the layer (19) to activate the photoactivatable material; (d) forming an additional layer (19) on at least a second region of the additional layer (19), a photoactivatable material provided in step (a), (e) illuminating at least the second region of the additional layer (19) for activating the photoactivatable material; (f) repeating steps (d) through (e) until formation of the three-dimensional object. The cosmetic composition included in the three-dimensional object or constituting the three-dimensional object can be restored after formation of the three-dimensional object.
    公开号:FR3024659A1
    申请号:FR1457619
    申请日:2014-08-05
    公开日:2016-02-12
    发明作者:Clement Jaunet；Gonzalez Sonia Lorente
    申请人:LOreal SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for producing a three-dimensional object containing or constituting a cosmetic composition. The cosmetic composition contains at least one cosmetic product, in particular a makeup product, a care product, a washing product or a perfume, the cosmetic product being intended to be applied to a body surface of a user. More generally, "cosmetic product" is understood in particular for the purposes of the present invention, a product as defined in Regulation (EC) No. 1223/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic products. According to the invention, the three-dimensional object advantageously forms a lipstick, a stick, a hybrid powder, a deodorant and / or antiperspirant product, a soap, a face mask, a styling wax, and / or a perfume. solid.
    [0002] To manufacture a three-dimensional object comprising a cosmetic composition, it is known to use forming processes such as molding, filling, compacting, multi-compaction, injection of a wet powder, extrusion etc. Such manufacturing processes impose constraints on manufactured objects. In molding, objects generally have a draft limit, with as much undercut as possible when molded, even in a flexible mold. Molding processes also limit the complexity of the shapes, since it is impossible to make one piece in another, or to nest a piece in another. In all the aforementioned methods, the height of the product is a limiting factor. Complex shapes, especially three-dimensional are very difficult, if not impossible to achieve, and often very expensive. There are also limits in the coloration of the cosmetic composition, in particular in the number of colors that can be used, and in the control of the different colors in the cast mass. In particular, it is tedious to produce objects having distinct colors and / or color gradients, and / or graphic inscriptions, for example alphanumeric characters and / or juxtapositions of colors. The aforementioned methods are also limited in the use of different precursor materials to constitute the cosmetic composition. It is for example tedious to create via the same process an object consisting of cosmetic products of different natures and compositions.
    [0003] Another difficulty results from the fact that the processes of the aforementioned type are intended solely for shaping the three-dimensional object. In some cases, it is necessary to prepare upstream of the shaping at least one leg, commonly called "bulk", which complicates the manufacture in some cases. Moreover, when new objects incorporating cosmetic compositions are developed, it is generally useful to make functional models to determine the feasibility and potential interest of the object. These models are complex to make, and require many steps including the development of the formula, the manufacture of the tab, the realization of a specific tool, and product conditioning tests or shaping. These tests must sometimes be performed several times before obtaining a satisfactory result, which increases the time and cost of development. An object of the invention is to provide a simple and versatile method of manufacturing three-dimensional objects comprising a cosmetic composition, the objects having shapes, natures, and complex appearances. To this end, the subject of the invention is a process of the aforementioned type, comprising the following steps: (a) supplying at least one cosmetic material and providing at least one photoactivatable material; (b) forming a layer comprising one or more cosmetic materials provided in step (a) and on at least a first region of the layer, a photoactivatable material provided in step (a); (c) illuminating at least the first region of the layer to activate the photoactivatable material; (d) forming an additional layer comprising one or more cosmetic materials provided in step (a) and, on at least a second region of the additional layer, a photoactivatable material provided in step (a), the layer additional at least partially covering the previous layer; (E) illuminating at least the second region of the additional layer to activate the photoactivatable material; (f) repeating steps (d) to (e) until formation of the three-dimensional object, the cosmetic composition included in the three-dimensional object or constituting the three-dimensional object being restorable after formation of the three-dimensional object.
    [0004] The process according to the invention may comprise one or more of the following characteristics, taken alone or in any technically possible combination: the photoactivatable material comprises a photoinitiator and a photocrosslinkable compound which can be activated by the photoinitiator. the photocrosslinkable compound comprises at least one monomer, and / or at least one prepolymer and / or at least one polymer, especially chosen from polyesters with unsaturation (s) or (meth) acrylate groups, polyurethanes and / or polyureas with (meth) acrylate groups, (meth) acrylate polyethers, epoxyacrylates, (meth) acrylate or (meth) acrylamide-containing polyorganosiloxanes, acrylate perfluoropolyethers, polyethylene-linked polyene, mixtures thereof or copolymers. the photoactivatable material is deposited in liquid form through a nozzle on the first region and / or on the second region. The deposition of the photoactivatable material comprises the positioning of the nozzle in a succession of given positions on the first region and / or on the second region, and, in each given position, the deposition of a given quantity of photoactivatable material, illuminating the photoactivatable material deposited in the given position, then moving the nozzle to another given position on the first region 20 and / or the second region. a first cosmetic material provided in step (a) has a first color, a second cosmetic material supplied in step (a) having a second color, the formed cosmetic composition comprising the first cosmetic material and the second cosmetic material on the same layer or on different layers. the photoactivatable material is included in or constitutes a cosmetic material intended to be deposited in liquid form. at least one layer comprises a photoactivatable support material capable of forming a support for the cosmetic composition, the support being non-returnable, the method comprising illuminating the photoactivatable support material to form at least a part of the support. in step (a), at least one cosmetic material contains at least one structuring agent in liquid form, the process comprising a preliminary step of heating the cosmetic material (s) provided in step (a) to melt the each structuring agent; Each layer formed in step (b) comprising one or more heated cosmetic materials, the or each structuring agent contained in the one or more cosmetic materials being deposited in the molten state; the layer being at least partially solidified by cooling the or each cosmetic material to a temperature lower than that of the or each cosmetic material deposited in step (b); each additional layer formed in step (d) comprising one or more heated cosmetic materials, the or each structuring agent contained in the one or more cosmetic materials being deposited in the molten state; The additional layer being at least partially solidified by cooling the or each cosmetic material to a temperature lower than that of the or each cosmetic material in step (c); the photoactivatable material being deposited in at least one at least partially liquid layer. The heating temperature of the or each cosmetic material in step (a) is greater than 50 ° C and is advantageously between 60 ° C and 110 ° C; the deposition temperature of the or each cosmetic material in step (b) and in step (d) is less than or equal to the heating temperature, advantageously being greater than the solidification temperature of the or each material Cosmetic plus 5 ° C. the cooling of the or each cosmetic material in step (b) and in step (d) is greater than 3 ° C, advantageously greater than 5 ° C; the structuring agent is chosen from waxes, organophilic clays, pyrogenic silicas, fatty acids, pasty compounds, gelling agents, thickening agents, glutamidal resins, hydrophobic celluloses, tackifying resins, and mixtures thereof; . the precursor material of the cosmetic composition comprises a mass content in wax greater than 10%. the three-dimensional object is a lipstick, a stick, a hybrid powder, a deodorant and / or antiperspirant product, a soap, a face mask, a styling wax, and / or a solid perfume. The invention also relates to an additive manufacturing apparatus of a three-dimensional object comprising or constituting a cosmetic composition, the apparatus comprising: a support surface; A series of formation of successive layers comprising at least one cosmetic material and for at least one layer, a photoactivatable material; a source of illumination of the photoactivatable material; a control unit capable of driving the training assembly and the illumination source for performing the following steps: (a) supplying at least one cosmetic material and providing at least one photoactivatable material; (b) forming a layer comprising one or more cosmetic materials provided in step (a) and on at least a first region of the layer, a photoactivatable material provided in step (a); (c) illuminating at least the first region of the layer to activate the photoactivatable material; (d) forming an additional layer comprising one or more cosmetic materials provided in step (a) and, on at least a second region of the additional layer, a photoactivatable material provided in step (a), the additional layer at least partially covering the previous layer; (e) illuminating at least the second region of the additional layer to activate the photoactivatable material; (f) repeating steps (d) through (e) until the three-dimensional object is formed, the cosmetic composition comprised in the three-dimensional object or constituting the three-dimensional object being releasable after formation of the three-dimensional object. The apparatus according to the invention may comprise one or more of the following characteristics, taken separately or in any technically possible combination: the light source is chosen from a lamp and a laser. The training assembly comprises at least one dispensing nozzle of each cosmetic material, the light source being movable together with the nozzle. The invention will be better understood on reading the following description, given solely by way of example, and with reference to the appended drawings, in which: FIG. 1 is a diagrammatic view of an example of a apparatus for the manufacture of a three-dimensional object comprising a cosmetic composition, by a method according to the invention; FIGS. 2 to 4 illustrate examples of three-dimensional objects produced by a method according to the invention, using the apparatus of FIG. 1; The present invention relates to a method for manufacturing three-dimensional objects comprising a cosmetic composition 12 or consisting of a cosmetic composition 12, using an apparatus for manufacturing by additive deposition in liquid form of layers An example of this is illustrated in FIG. 1. The method according to the invention is intended to manufacture three-dimensional objects 10 consisting of cosmetic composition 12, as illustrated for example in FIG. 2 to be supplied directly to the user. or to be inserted in a packaging 16 manufactured separately from the cosmetic composition 12 as illustrated in FIG. 4. In a variant, represented in FIG. 3, the method according to the invention is also intended to manufacture by additive deposition of the objects three-dimensional devices 10 comprising, in addition to the cosmetic composition 12, a support 18 carrying the cosmetic composition 12, the support 18 both manufactured simultaneously by additive deposition with the cosmetic composition 12. According to the invention, the cosmetic composition 12, and optionally the support 18, consist of a plurality of successive layers 19 formed from at least one photoactivatable material , deposited on each other.
    [0005] The successive layers 19 are deposited in liquid form, and solidify at least under the effect of light radiation, the photoactivatable material forming a cosmetic material included in the layer 19 in liquid form or constituting the layer 19 in liquid form. The photoactivatable material is therefore included in or constitutes a cosmetic material. As a variant, the photoactivatable material is therefore included in or constitutes a photoactivatable binder intended to bind at least one cosmetic material, in particular a powder. Advantageously, the photoactivatable material comprises at least one photoinitiator and at least one photocrosslinkable compound, activatable by the photoinitiator.
    [0006] The photo-crosslinkable compound generally comprises one or more polymers and / or prepolymers having polymerizable ethylenic double bonds and / or one or more reactive double bond monomers. The double bond reactive monomers, when present, are generally one or more vinyl monomers, for example acrylates or methacrylates, in particular esters of acrylic or methacrylic acid. Each reactive monomer comprises at least one ethylenic double bond, and preferably more than one ethylenic double bond. The one or more polymers and / or prepolymers having ethylenic double bonds have an average number of ethylenic double bonds per polymer molecule of greater than 1.
    [0007] Examples of photocrosslinkable polymers and prepolymers that can be used in the photocrosslinkable compound include: unsaturated polyesters; it is a polyester-type group of polymers having one or more ethylenic double bonds, randomly distributed in the main chain of the polymer. - polyesters with (meth) acrylate groups and / or terminal obtained by polycondensation of a mixture of linear or branched or cycloaliphatic aliphatic carboxylic diacids, linear or branched or cycloaliphatic aliphatic diols,; Polyurethanes and / or polyureas containing (meth) acrylate groups, obtained by polycondensation of cycloaliphatic and / or aromatic aliphatic diisocyanates, triisocyanates and / or polyisocyanates, of at least one (meth) acrylic acid ester and a diol or polyol, polyols, especially diols, free of polymerizable ethylenic unsaturations, and at least one (meth) acrylic acid ester and a diol or polyol; Polyethers with (meth) acrylate groups obtained by esterification, with (meth) acrylic acid, of the terminal hydroxyl groups of homopolymers or copolymers of C1-4 alkylene glycols; epoxyacrylates obtained by reaction between at least one diepoxide and one or more carboxylic acids or polycarboxylic acids containing at least one ethylenic double bond; polyorganosiloxanes containing (meth) acrylate or (meth) acrylamide groups obtained, respectively, by esterification, advantageously with (meth) acrylic acid, of polyorganosiloxanes, and by amidification, for example with (meth) acrylic acid, of carrier polyorganosiloxanes; primary or secondary side and / or terminal amine groups; perfluoropolyethers containing acrylate groups obtained by esterification, for example with (meth) acrylic acid, of perfluoropolyethers bearing lateral and / or terminal hydroxyl groups; a polyene as defined above combined with a polythiol; Their mixtures or copolymers. The photoinitiator (s) usable in the photoactivatable material of the present invention are described, for example in the following articles whose content is an integral part of the present application: "Photoinitiators in the crosslinking of coatings", G. Li Bassi, Double Liaison - Chemistry of Paints, No. 361, November 1985, 35 pages 34-41; industrials of photoinduced polymerization ", Henri Strub, Chemical News, February 2000, pages 5 - 13 and" Photopolymers: theoretical and reaction of 3024659 8 taken ", Marc, JM Abadie, Double Liaison - Chemistry of Paints, n 435 - 436.1992, pages 28 - 34. These photoinitiators include alpha-hydroxyketones, alpha-aminoketones, chloroacetophenones aromatic ketones, thioxanthones and quinones, benzoin ethers, acylphosphine oxides, and photoinitiators. copolymerizable copolymerizable photoinitiators are molecules comprising both a photoinitiator group capable of photoinduced radical scission and at least one ethylenic double bond.
    [0008] According to the first aspect of the invention, the photoactivatable material is included in at least one cosmetic material capable of being deposited in liquid form and at least partially solidifying by crosslinking under the effect of radiation and / or heat. Alternatively, the photoactivatable material forms a cosmetic material as such for partially forming the cosmetic composition. In the latter case, at least one other cosmetic material is adapted to be deposited in liquid form with the photoactivatable material and to solidify at least partially by cooling. The radiation suitable for crosslinking the cosmetic compositions of the present invention has a wavelength of between 210 nm and 600 nm, preferably between 250 nm and 400 nm. In a preferred embodiment of the invention, a UV lamp is used and in particular a mercury vapor lamp, possibly doped with other elements, such as gallium, making it possible to modify the emission spectrum of the source. light. Alternatively or in addition, a laser is used to cause the crosslinking.
    [0009] Advantageously, several different cosmetic materials are used to form the cosmetic composition, by being deposited within the same layer or in separate layers. The different cosmetic materials have, for example, distinct compositions, to constitute, within the cosmetic composition 12, regions 20, 22 of different composition and / or appearance, for example in terms of chemical nature, mechanical properties and / or colors, as illustrated for example in Figure 2 or 3, or gradients of composition and color. In particular, the different cosmetic materials have different colors. In one example, all the layers 19 are made from the same cosmetic material. Alternatively, a layer 19 is made from a first cosmetic material, and at least one additional layer 19 made from a second cosmetic material distinct from the first cosmetic material. In another variant, at least one layer 19 is made in part from the first cosmetic material, and partly from the second cosmetic material 5 distinct from the first cosmetic material. The thickness of each layer 19 forming the three-dimensional object 10 is, for example, less than 50 μm and is in particular between 10 μm and 30 μm. Each layer 19 comprises at least one solid zone formed of at least one cosmetic material. Optionally, each layer 19 has empty zones 10 delimited by adjacent solid zones, depending on the desired shape of the three-dimensional object 10. Each layer 19 comprises at least one solid zone formed of at least one cosmetic material. Optionally, each layer 19 has empty zones delimited by adjacent solid zones, depending on the desired shape of the three-dimensional object 10. At ambient temperature, for example at 25 ° C., the cosmetic composition is structured. By "structured" is meant especially in the sense of the present invention that the cosmetic composition has a clean mechanical strength, that is to say that it keeps its shape spontaneously, throughout the life of the product in the absence of external stress. This lifetime is for example at least one day, including at least one year. Thus, the cosmetic composition in the three-dimensional object formed at the end of the process according to the invention is not liquid at ambient temperature, and does not spontaneously flow visibly macroscopically for at least one minute and advantageously, for at least one day, in the absence of external solicitation. Preferably, the cosmetic composition is solid. In this case, it can be entered and moved by the user without flowing. According to the invention, the cosmetic composition is releasable. For the purposes of the present invention, the term "releasable" is intended to mean that at least a part of the cosmetic composition is applicable to a body surface of the user and that the composition is capable of detaching at least partially from the body. three-dimensional object to stay on the body surface. In particular, the crosslinking provided by the photoactivatable material is not complete and does not prevent the cosmetic material from being releasable.
    [0010] Advantageously, the cosmetic composition is releasable by friction between the body surface and the cosmetic composition, without physical deterioration of the body surface. Alternatively, the cosmetic composition is releasable by friction between an applicator and the cosmetic composition. Alternatively, the cosmetic composition is releasable by dipping into a biologically compatible liquid to detach it at least in part from the three-dimensional object and apply it to the body surface. In a variant, the cosmetic composition can be restored by preheating the three-dimensional object to a biologically compatible temperature, for example less than 60 ° C. Advantageously, the cosmetic composition is chosen from a colored cosmetic composition, and in particular a makeup composition for the skin and / or mucous membranes. In particular, such a composition may be a foundation, a blush, a powder, a blush or an eyeshadow, a concealer compound, a lipstick or a lip gloss, a transparent or non-transparent stick, a block deodorant and / or antiperspirant, soap, transparent bread, face mask, styling wax, solid perfume, optionally with care or treatment properties. It may be a colored make-up composition intended to correct the color of the complexion. A composition according to the invention may also constitute a composition for makeup or care of nails or eyelashes. A composition according to the invention may also be in the form of anhydrous gel, emulsion or oil-in-water or water-in-oil dispersion or in the form of a multiple emulsion. It can be in the form of paste, more or less rigid solid, cream, ointment. It may be in anhydrous form, and more especially in the form of anhydrous gel, especially cast in stick or cup. The or each cosmetic material is intended to be heated to be deposited in at least partially liquid form in a hot layer, then to solidify at least partially by cooling and / or by crosslinking, after its deposition in a layer.
    [0011] By "at least partially liquid" it is generally meant that the cosmetic material is able to flow under the effect of its own weight. In particular, the cosmetic material is able to flow through an extrusion nozzle or extrusion head. The "at least partially liquid" material is completely liquid, or includes a liquid phase in which solid elements are dispersed, which flow through the liquid phase.
    [0012] In particular, the cosmetic material is at least partially liquid because of the fusion of the or each structuring agent contained in the cosmetic material. The term "hot" includes in particular beyond the melting temperature of the or each structuring agent, as measured by the ISO 11357-3: 2011 standard.
    [0013] Advantageously, each material is deposited in the form of droplets of hot liquid which are projected from a nozzle on a support, or on a previous layer of the three-dimensional object in formation. The at least partially liquid cosmetic material is able to solidify at least partially by cooling and / or by crosslinking. By "at least partial solidification" is meant that the cosmetic material is able to be structured in the sense defined above. In particular, the viscosity of the material is able to increase. In particular, the material is able to become solid. Cooling advantageously passes each structuring agent contained in the cosmetic material at a temperature below the temperature it exhibited during its deposition. This temperature is preferably lower than the melting temperature of the cosmetic material. The loss of temperature of the cosmetic material during cooling is greater than 3 ° C, especially greater than 5 ° C. To ensure the structuring of the cosmetic material and to form the cosmetic composition, each cosmetic material comprises at least one structuring agent. In one example, each cosmetic material comprises a first structuring agent common to all the cosmetic materials. As a variant, a first cosmetic material comprises a first structuring agent, and a second cosmetic material distinct from the first cosmetic material 25 comprises a second structuring agent distinct from the first structuring agent. The structuring agent is capable of being melted at a temperature above its melting point to allow liquid deposition of the cosmetic material in a layer. It is capable of solidifying by cooling to a temperature below its melting temperature after deposition in a layer.
    [0014] By structuring agent is meant a compound capable of increasing the viscosity of the composition incorporating it. The structuring agent makes it possible in particular to obtain a composition that can present a texture ranging from fluid to solid textures. To ensure adequate deposition, the melting temperature of the cosmetic composition containing the or each structuring agent is, for example, greater than 50 ° C. and is advantageously between 60 ° C. and 110 ° C. For the purposes of the invention, the temperature melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described for example in the ISO 11357-3: 2011 standard. A person skilled in the art will be able to choose the appropriate protocol according to the composition of which In particular, the melting point of the composition can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "MDSC 2920" by the TA Instruments company. The measurement protocol is as follows: A sample of 5 mg of the composition placed in a crucible is subjected to a first temperature rise from -20 ° C. to 100 ° C. at a heating rate of 10 ° C. minute, then is cooled from 100 ° C to -20 ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise from -20 ° C to 100 ° C at a heating rate of 5 ° C / minute. During the second rise in temperature, the variation of the power difference absorbed by the empty crucible and the crucible containing the sample of the composition as a function of temperature is measured. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature. On the contrary, the solidification point is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature during the temperature reduction following the second rise in temperature. The softening point of the cosmetic composition containing the or each structuring agent is, for example, between 50 ° C. and 70 ° C. This softening point is measured according to the protocol described in standard NF T66-147. The density of the cosmetic composition containing the or each structuring agent, taken at its melting temperature according to ASTM D4164, is for example between 0.7 and 1, especially between 0.8 and 0.9. The volume shrinkage of the cosmetic composition containing the or each structuring agent, taken from 40 ° C. to room temperature, for example 25 ° C., is less than 3%, and is in particular between 1.5% and 2.5%. %. This volume shrinkage is measured according to the protocol described in standard NF EN ISO 294-4, May 2003. The or each structuring agent in each cosmetic material contained in the cosmetic composition, forms a network for maintaining the composition. This network breaks on the surface during the application of the cosmetic product, allowing the restitution of the composition.
    [0015] A structuring agent or mixture of structuring agents may be present in the composition in a content ranging from 4% to 40% by weight relative to the total weight of the composition, and preferably ranging from 4% to 30% by weight. weight. The structuring agent according to the invention is chosen for example from: - waxes, - organophilic clays, - pyrogenic silicas, - fatty acids, - pasty compounds; Gelling agents, in particular organogellants; thickening agents; glutamides resins; hydrophobic celluloses, tackifying resins, and mixtures thereof. A wax, within the meaning of the present invention, is a solid lipophilic fat compound, solid at room temperature (25 ° C.), with a reversible solid / liquid state change, having a melting temperature greater than about 45 ° C. (resorbed by DSC) and better than 50 ° C and up to 95 ° C, and present in the solid state, an anisotropic crystalline organization. The waxes that are suitable for the invention may be hydrocarbon-based, silicone-based and / or fluorinated, optionally comprising ester or hydroxyl functions. As waxes that may be used in the composition of the invention, mention may be made, for example, of mineral waxes such as microcrystalline waxes, paraffin, petrolatum, ozokerite, montan wax; waxes of animal origin such as beeswax, shellac wax, lanolin and its derivatives; waxes of vegetable origin such as Candelilla, Ouricury, Carnauba waxes; Sunflower, Japanese rice bran, cocoa butter, cork fiber waxes or sugar cane; hydrogenated oils concrete at 25 ° C; fatty esters and glycerins concrete at 25 ° C; synthetic waxes such as polyethylene waxes and waxes obtained by Fischer-Tropsch synthesis; silicone waxes, and mixtures thereof, glycoside waxes. There may also be mentioned waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains. Mention may also be made of silicone waxes, fluorinated waxes, waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol. Fatty acids that may be mentioned include fatty acids having a fatty chain comprising from 8 to 28 carbon atoms, the number of ethylene oxide or propylene oxide groups ranging from 2 to 50 and that of glycerol in particular from 2 to 30. As a gelling agent, mention may be made of glycerol alginates and propylene glycol alginates. , gelane gum and welane gum. For the purposes of the present invention, the term "pasty compound" is intended to mean a lipophilic fatty compound having a reversible solid / liquid state change, having in the solid state an anisotropic crystalline organization and having at 23.degree. liquid fraction and a solid fraction. The pasty compound is preferably chosen from synthetic compounds and compounds of plant origin. A pasty compound can be obtained synthetically from starting materials of plant origin.
    [0016] The pasty compound may advantageously be chosen from: lanolin and its derivatives, polymeric or non-polymeric silicone compounds, fluorinated polymeric or non-polymeric compounds, vinyl polymers, in particular: homopolymers of olefins, copolymers olefins, homopolymers and copolymers of hydrogenated dienes, linear or branched oligomers, homo or copolymers of alkyl (meth) acrylates preferably having a C 8 -C 30 alkyl group, homo and copolymer oligomers of vinyl esters having C 8 -C 30 alkyl groups; and homo- and copolymer oligomers of vinyl ethers having C 8 -C 30 alkyl groups; liposoluble polyethers resulting from the polyetherification between one or more C2-C100 diols; preferably C2-050; esters, - mixtures thereof. Gelling agents that may be mentioned include mineral and organic lipophilic gelling agents.
    [0017] As thickening agents, mention may be made of carboxyvinyl polymers, polyacrylamides, optionally crosslinked and / or neutralized 2-acrylamido-2-methylpropanesulphonic acid polymers and copolymers, and 2-acrylamido-2-methylpropanesulphonic acid copolymers, and hydroxyethyl acrylate cellulose derivatives; polysaccharides and especially gums such as Xanthan gum, hydroxypropyl guar gums; the silicas. The thickeners may also be cationic.
    [0018] For the purposes of the present invention, the term "glutamide resin" is intended to mean an N, N'-dialkylacrylamide. By tackifying resin is meant a resin having a number average molecular weight of less than or equal to 10,000 g / mol, in particular ranging from 250 to 10,000 g / mol, preferably less than or equal to 5,000 g / mol, in particular ranging from 250 to 5,000 g / mol, better still, less than or equal to 2,000 g / mol, especially ranging from 250 to 2,000 g / mol and even more preferably less than or equal to 1,000 g / mol, especially ranging from 250 to 1,000 g / mol; mol. The number average molecular weights (Mn) were determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector). The resin of the composition according to the invention is advantageously a so-called tackifying resin. Such resins are especially described in the Handbook of Pressure Sensitive Adhesive, edited by Donatas Satas, 3rd ed., 1989, p. 609-619. The resin of the composition according to the invention is chosen from rosin, rosin derivatives, hydrocarbon resins and their mixtures, and preferably from hydrocarbon resins. Rosin is a mixture comprising mainly organic acids called rosin acids (mainly abietic and pimaric type acids).
    [0019] There are three types of rosin: rosin ("gum rosin") obtained by incision on live trees, wood rosin ("wood rosin") which is extracted from stumps or pine wood, and tall ("tall oil rosin") which is obtained from a by-product from the production of paper. The rosin derivatives may be derived in particular from the polymerization, hydrogenation and / or esterification (for example with polyhydric alcohols such as ethylene glycol, glycerol, pentaerythritol) of rosin acids. The hydrocarbon resins are chosen from low molecular weight polymers which can be classified, according to the type of monomer they comprise, into: o hydrocarbon-based indene resins. Aliphatic pentanediene resins; mixed pentanediene and indene resins; diene resins of cyclopentanediene dimers; diene resins of isoprene dimers. hydrogenated C6-C20 polyolefins.
    [0020] The resin may be chosen from indene hydrocarbon resins, preferably hydrogenated resins. Preferably, the indene hydrocarbon resin is derived from the polymerization of indene monomer and monomer selected from styrene, methylindene, methylstyrene and mixtures thereof. Advantageously, the cosmetic material has a wax content by weight greater than 10%, and especially between 10% and 30%, particularly between 5% and 20%. Advantageously, the structuring agent comprises at least one wax, and preferably a mixture of waxes. Preferably, the mixture of waxes comprises a first wax having a melting point greater than 80 ° C., at least one second wax having a temperature. melting point of between 60 ° C and 80 ° C and at least one third wax having a melting point of between 50 ° C and 60 ° C. The mass content of the first wax in the cosmetic material is for example between 6% and 10%, especially between 7% and 8%. The mass content of the second wax is, for example, between 2% and 5%, in particular between 3% and 4%. The mass content of the third wax is in particular between 2% and 7%, for example between 3% and 5%. In addition to the structuring agent, the cosmetic material comprises ingredients that are compatible with the skin, the lips and the integuments, such as keratinous fibers.
    [0021] Advantageously, the cosmetic material comprises, in addition to the structuring agent, an additional agent chosen, for example, from oils, pastes, coloring agents, fillers, surfactants, sequestering agents, neutralizers, antioxidants and softeners. , opacifiers, stabilizers, dyes, perfumes, cosmetic active ingredients, reducing agents, essential oils, preservatives, bactericides, moisturizers, vitamins, essential fatty acids, sphingolipids, self-tanning agents, as Examples include DHA, sunscreens, defoamers, sequestering agents, thickening or suspending agents, any other ingredient usually used in cosmetics. A coloring agent may be chosen from water-soluble or fat-soluble dyes, pigments, pearlescent agents and mixtures thereof. The composition according to the invention may further comprise one or more dyestuffs chosen from water-soluble dyes and pulverulent dyestuffs such as pigments, nacres and flakes well known to those skilled in the art. The pigments are, for example, inorganic pigments such as metal oxides, in particular iron and titanium, or organic pigments.
    [0022] By "nacres", it is necessary to include colored particles of any shape, iridescent or not, in particular produced by certain shellfish in their shell or else synthesized and which exhibit a color effect by optical interference. The nacres may be chosen from pearlescent pigments such as titanium mica coated with an iron oxide, titanium mica covered with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with a organic dye and 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. The nacres may more particularly have a color or a yellow, pink, red, bronze, orange, brown, gold and / or coppery reflection.
    [0023] By "dyes" are meant generally organic compounds soluble in fatty substances such as oils or in a hydroalcoholic phase. The liposo lubies may be chosen from Sudan Red, DC Red 17, DC Green 6, 6-carotene, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, quinoline yellow. Water-soluble dyes are, for example, beet juice, methylene blue. The cosmetic composition according to the invention may also contain at least one material with a specific optical effect. This effect is different from a simple conventional hue effect, i.e. unified and stabilized as produced by conventional dyestuffs such as 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 fibers, especially interferential fibers. Of course, these different materials can be combined to provide the simultaneous manifestation of two effects. 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, the particles comprising a substrate, organic or inorganic, 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 their mixtures or alloys (e.g. bronzes and brasses) are preferred metals. The term "metal derivatives" denotes compounds derived from metals, in particular oxides, fluorides, chlorides and sulphides. A composition according to the invention may comprise a filler. For the purposes of the present invention, the term "filler" is understood to mean particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or the texture of the composition. The fillers may be inorganic or organic in any form, platelet-shaped, spherical or oblong, irrespective of the crystallographic form (for example, sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, clays, bentonite, kaolin, polyamide, poly-6-alanine and polyethylene powders, tetrafluoroethylene polymer powders, lauroyl lysine, starch, boron nitride, polymeric hollow microspheres such as polyvinylidene chloride / acrylonitrile copolymers of acrylic acid and silicone resin microbeads, elastomeric polyorganosiloxane particles, precipitated calcium carbonate, carbonate and magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres, glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate. It may also be particles comprising a copolymer, said copolymer comprising trimethylol hexyl lactone. In particular, it may be a hexamethylene diisocyanate / trimethylol hexyllactone copolymer.
    [0024] As indicated above, in one variant, the cosmetic composition is a lipstick. Lipsticks may, in a known manner, be in two forms: in the form of a stick or in the form of a flexible paste. In this case, the cosmetic material comprises at least one wax in a fatty phase. A conventional form associates about 7 to 8% of hard wax (melt temperature above 80 ° C), 3-4% of intermediate wax (melt temperature of 60 to 80 ° C), and 3 to 5% of soft wax (melting temperature between 50 and 60 ° C).
    [0025] For pasty types there are two types, the solid crystalline type at room temperature, characterized by a melting temperature of between 30 and 50 degrees C, and pasty soft paste. Lipsticks may include oils. By "oil" is meant a liquid fatty substance at room temperature (25 ° C.) and atmospheric pressure (760 mm Hg, ie 1.05 × 10 5 Pa). The oil may be chosen from all physiologically acceptable and in particular cosmetically acceptable oils, in particular mineral, animal, vegetable, and synthetic oils; in particular volatile and / or nonvolatile hydrocarbon and / or silicone and / or fluorinated oils and mixtures thereof.
    [0026] The oil may comprise a gelling agent, such as a polymer, especially a modified sugar. For the preparation of lipstick, the cosmetic material may comprise at least one polymeric system which comprises at least one film-forming polymer. Among the film-forming polymers that may be mentioned are radical-type synthetic polymers resulting from the copolymerization of C1-C8 alkyl methacrylate monomers, optionally combined with acrylic acid, styrene and α-methyl styrene. Radical polymer is understood to mean a polymer obtained by polymerization of unsaturated monomers, in particular ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates). Radical-type polymers may especially be polymers or copolymers. vinyls, especially acrylic polymers. Among the alkyl (meth) acrylates, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate and 2-ethylhexyl methacrylate. According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, that is, some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms. According to the invention, a copolymer chosen from acrylic acid / methacrylate, acrylic acid / methacrylate / styrene and copolymers of (meth) acrylates is preferably used as the film-forming polymer.
    [0027] When the polymer used according to the invention comprises monomers bearing a salt-forming group (for example a carboxylic acid group), it may be neutralized, totally or partially with the aid of a neutralizing agent (in this case a base). to neutralize the acid group) well known to those skilled in the art. The neutralization may, in addition, promote the dispersion, especially in water, of the polymer, or even stabilize said dispersion.
    [0028] Advantageously, the radical-forming film-forming polymer of the polymeric system is present in the composition according to the invention either in solubilized (dissolved) form or in dispersed form, ie in the form of a dispersion of particles, in particular in a cosmetically or dermatologically acceptable medium. Preferably, the radical-forming film-forming polymer is in the form of an aqueous dispersion of particles of said polymer. For the preparation of lipstick, the cosmetic material may comprise at least one plasticizer and / or a coalescing agent. In particular, mention may be made, alone or as a mixture, of the usual plasticizers or coalescence agents, such as: o glycols and their derivatives; the glycerol esters, the propylene glycol derivatives, the carboxylic acid esters, the oxyethylenated derivatives, the water-soluble polymers having a low glass transition temperature, less than 25 ° C., preferably less than 25 ° C., 15 ° C. Lipstick compositions also include fillers, pigment or nacre as defined above. In another variant, the cosmetic composition is a stick, in particular an aqueous or alcoholic stick, or a dry stick and / or an anhydrous cream. A cosmetic composition in the form of a stick or a loaf may advantageously comprise a gel containing a compound chosen from the group consisting of: polyols, dibenzylidene-oses, hardening agents, such as those of the sulphosuccinate type, and any of their mixtures .
    [0029] The solid stick or bread compositions may comprise a mixture of various anhydrous and / or lipophilic constituents such as waxes (natural, vegetable, mineral or synthetic), oils (vegetable or mineral) and other fatty substances (fatty esters). liquids, synthetic triglycerides and solid fatty esters). The solid stick or bread compositions may be aqueous and comprise an active ingredient dissolved in a water / gelled polyol phase gelled by a gelling agent such as, for example, dibenzylidene sorbitol. The solid stick or bread compositions may be transparent. Among the sticks or solid breads may be mentioned aqueous or alcoholic types, and dry and anhydrous types.
    [0030] In another variant, the cosmetic composition is a cosmetic cleaning and / or make-up removing composition are commonly used to clean keratin materials, especially the skin, in particular when they are covered with makeup products such as the bottom complexion. These compositions generally contain a base of liquid or solid soap. The term "soap" thus denotes the fatty acid neutralized with a mineral base or the fatty acid salt. The fatty acid is often a carboxylic acid comprising a linear or branched, saturated or unsaturated alkyl chain having 6 to 30 carbon atoms, preferably 12 to 22 carbon atoms. Soaps are generally fatty soaps of tallow and / or copra and / or castor oil. Preferably, these soaps are chosen from sodium salts, in particular from C 16 -C 20 fatty acid sodium salts and C 10 -C 14 fatty acid sodium salts, or mixtures thereof. In particular, the soap contains a sodium sterate. In yet another variant, the cosmetic composition is a hybrid powder. The composition according to the invention may be a cast powder.
    [0031] Hybrid powders may comprise a dispersion of generally spherical particles of at least one surface-stabilized polymer in a physiologically or cosmetically acceptable liquid fatty substance. These dispersions can in particular be in the form of nanoparticles of polymers in stable dispersion in said fatty substance. The nanoparticles are preferably between 5 nm and 600 nm in size. It is thus possible to use radical polymers, polycondensates or even polymers of natural origin. The polymer may be selected by those skilled in the art depending on its properties, depending on the subsequent application desired for the composition. Thus, the polymer may be film-forming or non-film-forming; in this second case, it may in particular be in the form of a crosslinked polymer. It is therefore possible to use film-forming polymers, preferably having a low glass transition temperature (Tg), less than or equal to the ambient temperature. It is also possible to use non-film-forming, optionally cross-linked, polymers which can be used as stably dispersed fillers in an oil. The polymers which can be used in the context of the present invention preferably have a molecular weight of the order of 2000 to 10,000,000, and a glass transition temperature of from -100 ° C. to 300 ° C. When the polymer has a Tg too high for the desired application, a plasticizer can be added to lower the Tg of the mixture used. The plasticizer may be chosen from the plasticizers usually used in the field of application and in particular from the compounds which may be solvents of the polymer. Among the non-crosslinked film-forming polymers that may be mentioned are homopolymers or radical copolymers, acrylic or vinyl, preferably having a Tg of less than or equal to 30 ° C. Among the non-film-forming polymers, there may be mentioned homopolymers or radical copolymers, vinyl or acrylic, optionally crosslinked, preferably having a Tg greater than or equal to 40 ° C, such as polymethyl methacrylate, polystyrene or tert-butyl polyacrylate. The liquid fatty substance in which the polymer particles are dispersed may consist of any cosmetic or dermatologically acceptable oil, especially chosen from oils of mineral, animal, vegetable or synthetic origin, carbonaceous, hydrocarbon-based, fluorinated and / or silicone-based. , alone or as a mixture in that they form a homogeneous and stable mixture and where they are compatible with the intended use.
    [0032] By liquid fatty substance is meant any nonaqueous liquid medium at room temperature. It is thus possible to mention hydrocarbon oils, acid esters, higher fatty acids, silicone oils which are optionally phenylated or optionally substituted with aliphatic and / or aromatic groups, optionally fluorinated, or with functional groups such as hydroxyl groups. thiols and / or amines; polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, fluorinated silicones, perfluorinated oils. Volatile oils can also be used. A hybrid powder may comprise at least one non-polymeric organic molecular gelling agent, also called an organogelling agent, which is a compound whose molecules are capable of establishing between them physical interactions leading to a self-aggregation of the molecules with formation of a network. supra-molecular three-dimensional which is responsible for the gelation of the oil (s) (also called liquid fatty phase). The supra-molecular network may result from the formation of a network of fibrils (due to stacks or aggregations of organogelling molecules), immobilizing the molecules of the liquid fatty phase. The ability to form this network of fibrils, and thus to gel, depends on the nature (or chemical class) of the organogelator, the nature of the substituents carried by its molecules for a given chemical class and the nature of the phase liquid fat. In general, each molecule of an organogelator can establish several types of physical interactions with a neighboring molecule. Also, advantageously, the molecules of the organogelators according to the invention comprise at least one group capable of establishing hydrogen bonds and better still at least two groups capable of establishing hydrogen bonds, at least one aromatic ring and better at least two aromatic rings, at least one or more ethylenically unsaturated bonds and / or at least one or more asymmetric carbons.
    [0033] Preferably, the groups capable of making hydrogen bonds are chosen from hydroxyl, carbonyl, amine, carboxylic acid, amide, urea and benzyl groups and their combinations. The organogelling organism (s) according to the invention are soluble in the liquid fatty phase after heating until a transparent homogeneous liquid phase is obtained. They can be solid or liquid at room temperature and atmospheric pressure. These organogelators include, in particular, amides of carboxylic acids, the diamides having hydrocarbon chains each containing from 1 to 22 carbon atoms, for example from 6 to 18 carbon atoms, said chains being unsubstituted or substituted with at least one substituent chosen from ester, urea and fluoro groups (see application EP-A-1086945) and in particular the diamines resulting from the reaction of diaminocyclohexane, the amides of N-acylamino acids and the diamides resulting from the reaction of an N-acylamino acid with amines having from 1 to 22 carbon atoms. It is also possible to use as organogellants compounds of bis-urea type.
    [0034] Examples of organogelators are dibutyl lauroyl glutamide and dibutyl ethylhexanoyl glutamide. The hybrid powder may be a fatty powder typically comprising 40 to 50% of fatty substances, 35 to 45% of nacre or pigment, and 5 to 20% of a polymer by weight relative to the total mass of the composition. .
    [0035] The expression "fatty binder" denotes a fatty substance or mixture of fatty substances constituting the binder of the compacted or cast powders, as well as a fatty substance or mixture of fatty substances present in the free powders, in particular to increase the softness of the application and promote adhesion to the skin. The use as binders in a compacted powder of silicone oils, which are linear polysiloxanes (polydimethylsiloxane or the like, abbreviated as PDMS) of low viscosity, in combination with high viscosity PDMSs (silicone gums) is described in patent application JP-61-180707. It has also been advocated the use as binders of silicone resins (three-dimensional polycondensation products) in combination with volatile silicones in cosmetic powders.
    [0036] The manufacturing method according to the invention is implemented in a device 50 for manufacturing by direct deposition of successive layers, an example of which is illustrated schematically in FIG. 1. The apparatus 50 comprises a layer forming assembly comprising at least one nozzle 52 dispensing at least one cosmetic material in liquid form, and, for each cosmetic material dispensed by the nozzle 52, a tank 54 for packaging the cosmetic material, and a set 56 for conveying the cosmetic material between the reservoir 54 and the nozzle 52. The apparatus 50 comprises a support surface 58, capable of carrying the layers of cosmetic material successively deposited on each other, and a set 60 of relative displacement of the nozzle 52 relative to the support surface 58. The apparatus 50 also comprises a control unit 62 of the displacement assembly 60 and the conveyor assembly 56. natively a man-machine interface 64.
    [0037] In this example, the apparatus 50 comprises a nozzle 52 associated with each reservoir 54, for delivering the cosmetic material contained in the reservoir 54. In a variant, at least two reservoirs 54 are connected to the same nozzle 52. The nozzle 52 defines at least one cosmetic material dispensing orifice. Advantageously, it is suitable for dispensing the cosmetic material in the form of successive droplets which are projected towards the support surface 58 on the support surface 58 or on a previous layer. Each droplet preferably has a mass less than 100 ng, for example between 30 ng and 100 ng. The distance separating the dispensing orifice from the preceding layer is preferably less than 5 mm, and is in particular between 0.5 mm and 1.5 mm. Thus, each droplet or set of droplets projected (s) in a given position of the nozzle 52 is able to define an area of the layer 19 forming a "pixel" on the layer to be deposited. The composition and / or the appearance of each pixel can thus be defined by the nature of the cosmetic material or materials added in the pixel.
    [0038] Each reservoir 54 is advantageously provided with a heating system 66 capable of keeping the cosmetic material in liquid form in the reservoir 54, and advantageously of a stirrer (not shown). The conveyor assembly 56 comprises a conduit 70 for supplying cosmetic material, connecting the reservoir 54 to the nozzle 52, a system (not shown) for pumping the cosmetic material through the pipe 70, and at least one The control 72 of the flow of cosmetic material circulating through the supply line 70, controlled by the unit 62. For example, the control member 72 is a valve controlled between a blocking configuration of the flow of flow. cosmetic material and a cosmetic material dispensing configuration. In a variant, the conveyor assembly 56 is devoid of a control member 72, the flow of the cosmetic material being controlled by the pumping system. Preferably, the pipe 70 and the nozzle 52 are insulated to maintain the cosmetic material in liquid form during its conveying.
    [0039] The displacement assembly 60 is adapted to allow the relative positioning of the nozzle 52 relative to the support surface 58 in three axes, or with respect to the previous layer 19 deposited on the support surface 58. The displacement 60 is driven by the unit 62 to horizontally move the nozzle 52 relative to the previous layer 19 or relative to the support surface 58, in order to selectively deposit at least one droplet of cosmetic material at a predetermined location on the layer in formation, corresponding to a pixel as defined above. The displacement assembly 60 is further controlled to maintain vertically the vertical distance between the nozzle 52 and the support surface 58 or the previous layer.
    [0040] In this example, the displacement assembly 60 comprises a mechanism 74 for three-dimensional displacement of the nozzle 52, and a mechanism 76 for vertical displacement of the support surface 58. The control unit 62 is able to calculate, from a numerical model of the three-dimensional object, the spatial arrangement of each layer 19 to be formed by depositing with the aid of the or each nozzle 52, and, within each layer 19 to be formed, the exact composition of each zone of the layer. On this basis, the control unit 62 is able to control the corresponding relative displacement of each nozzle 52 relative to the support surface 58 to deposit a given material on each zone to be formed of each layer 19, and to control the piloting. of the conveyor assembly 56, in particular the pumping system and the control member 72, at each position of the nozzle 52, depending on the desired material in this area. The human-machine interface 64, when present, is able to allow a user to define the shape of the three-dimensional object to be produced, for example by choosing a digital mock-up file in a database of data. digital models, or by importing a predefined digital mock-up file, for operation by the control unit 62. According to the invention, the apparatus 50 includes a source 90 of radiation adapted to activate the material. photoactivable present in each layer 19 containing.
    [0041] The radiation source 90 is for example movable together with the nozzle 52, being advantageously carried by the nozzle 52. In this case, the radiation source 90 is preferably pulse-activatable before each movement of the nozzle 52 between two positions. facing the layer 19 in formation. As indicated previously, the source 90 is capable of emitting radiation suitable for crosslinking at a wavelength of between 210 nm and 600 nm, preferably between 250 nm and 400 nm. In a preferred embodiment of the invention, the source 90 is a UV lamp and in particular a mercury vapor lamp, optionally doped with other elements, such as gallium, making it possible to modify the emission spectrum of the light source 90. Alternatively or additionally, the source 90 comprises a laser. An example of a manufacturing method according to the invention will now be described. Advantageously, the user initially defines using the man-machine interface 64 the shape and composition of the object to be produced, for example by choosing a digital mock-up file in a database of digital mock-ups or 20 by importing this file. Then, the digital mockup file is transmitted to the control unit 62. The control unit 62 then defines the shape of the various layers 19 intended to constitute the three-dimensional object, and within each layer the composition of each zone. of the layer defining a "pixel".
    [0042] The control unit 62 then calculates the necessary displacement of the or each nozzle 52 during the construction of each layer 19, and determines whether a cosmetic material is to be added at a given position of the nozzle 52, if any. which cosmetic material (s) must be added at each given position of the nozzle 52. Each cosmetic material is prepared in a reservoir 54 by causing the structuring agent to melt. The cosmetic material is maintained in the liquid state, advantageously with the aid of the heating system 66. The photoactivatable material is joined to at least one cosmetic material introduced into a reservoir 54 or is prepared in the form of a particular material introduced into the a tank 54 specific to this material.
    [0043] Thereafter, the control unit 62 drives the displacement assembly 60 and the conveyor assembly 50 on the basis of the calculations made previously to successively form the different layers 19 on each other. For each layer 19 to be formed, the control unit moves the nozzle 52 in each zone to be formed of the layer 19 and projects at least one cosmetic material, advantageously in the form of liquid droplets, against the previous layer 19 or against the surface in particular, the or each structuring agent contained in each cosmetic material is deposited in the molten state to form the layer 19.
    [0044] At least a portion of the deposited droplets contain or consist of photoactivatable material. The droplets are projected directly onto the previous layer 19 or against the support surface 58. The space located between the orifice of the nozzle 52 and the previous layer 19 is then completely empty. In particular, this empty space is totally empty of matter. Between each displacement of the nozzle 52 facing the previous layer 19, the radiation source 90 is activated to cause the activation of the photoactivatable material, by photochemical and / or thermal decomposition of the photoinitiator and by radical reaction of the monomer (s) and / or or prepolymer (s) and / or polymer (s). During this operation, the control unit 62 keeps the vertical distance between the nozzle 52 and the previous layer 19 and / or the support surface 58 substantially constant. Thus, the layer 19 formed is flat. The term "plane" advantageously means that the maximum thickness of the layer 19 is less than 4 times the average thickness of the layer 19. The cosmetic material solidifies at least partially by cooling, and / or by crosslinking to solidify the layer 19. The cooling advantageously passes the cosmetic material at a temperature below the temperature it exhibited during its deposition. This temperature is preferably lower than the melting temperature of the cosmetic material. The loss of temperature of the cosmetic material during cooling is greater than 3 ° C, especially greater than 5 ° C.
    [0045] Once the layer 19 has been formed, the displacement assembly 60 is driven to move the nozzle 52 away from the layer 19 previously formed. The previous operations are repeated to add the different layers 19 to each other. It is thus possible to construct three-dimensional objects comprising or consisting of a cosmetic composition having selected and complex shapes, compositions and appearances that are distinct according to the zone, and gradients of appearance and composition, by simple order. of the cosmetic material to be added in each zone of a given layer 19 of the three-dimensional object 10. In a variant, at least one material is intended solely for the construction of the three-dimensional object 10, this cosmetic material being removed from the the three-dimensional object at the end of the additive process, for example by dissolving in a suitable solvent or by melting, without harming the three-dimensional object 10. This material is for example intended for the manufacture of parts undercut of the three-dimensional object 10.
    [0046] This carrier material is, for example, a hydroxyl wax or a paraffin, preferably having a melting point of less than 50 ° C. In a variant, this material is removed by mechanical action, for example by being broken or scraped off. Such material may be used to create empty areas of matter in the three-dimensional object 10 after it has been removed. In a variant, at least one support material added in at least one layer 19 is intended to form a support 18 of the cosmetic composition that is part of the three-dimensional object 10. Advantageously, the support 18 thus formed is not restorable after solidification, unlike the cosmetic composition.
    [0047] In this variant, at least one partially liquid layer comprising a support material is deposited during the formation of the three-dimensional object. This layer is either made of carrier material, or comprises areas made of carrier material and areas made of cosmetic material. In this case, the apparatus 50 comprises at least one reservoir 54 for packaging 30 of the support material and a set 56 for conveying the support material between the reservoir 54 and the nozzle 52. The control unit 62 is able to determine if the support material is to be added at a given position of the nozzle 52, in addition to or in replacement of a cosmetic material.
    [0048] The support material is, for example, a polymer, in particular a thermoplastic polymer, a hydroxylated wax, or a paraffin which is brought above its melting temperature during the deposition of the layer, or else a non-returnable photoactivatable polymer. , taken in a family as defined above. The support material crosslinks under the effect of illumination and / or heating generated by the source 90 to form the support 18.
    [0049] In a particular example, the support material consists of a non-restorable photoactivatable material as defined above, which crosslinks during the formation of the three-dimensional object 10. The cosmetic composition 12 can then contain at least one photoactivatable material The process of manufacture according to the invention is advantageously implemented for the production of prototypes of three-dimensional objects comprising or constituting a structured cosmetic composition. In a variant, the manufacturing method according to the invention is used to produce finished products in production, for example in a factory or in a shop. 15
    权利要求:
    Claims (15)
    [0001]
    CLAIMS1.- A method of additive manufacturing of a three-dimensional object (10) comprising or constituting a cosmetic composition, the method comprising the following steps: (a) providing at least one cosmetic material and providing at least one photoactivatable material; (b) forming a layer (19) comprising one or more cosmetic materials provided in step (a) and on at least a first region of the layer (19), a photoactivatable material provided in step (a) ; (c) illuminating at least the first region of the layer (19) to activate the photoactivatable material; (d) forming an additional layer (19) comprising one or more cosmetic materials provided in step (a) and, on at least a second region of the additional layer (19), a photoactivatable material provided at step (a), the additional layer (19) at least partially covering the previous layer (19); (e) illuminating at least the second region of the additional layer (19) to activate the photoactivatable material; (f) repeating steps (d) to (e) until formation of the three-dimensional object (10), the cosmetic composition included in the three-dimensional object (10) or constituting the three-dimensional object (10) being releasable after formation of the three-dimensional object (10).
    [0002]
    2. - Method according to claim 1, wherein the photoactivatable material comprises a photoinitiator and a photocrosslinkable compound activated by the photoinitiator.
    [0003]
    3. - Method according to claim 2, wherein the photocrosslinkable compound comprises at least one monomer, and / or at least one prepolymer and / or at least one polymer, especially chosen from polyesters with unsaturation (s) or groups (meth ) acrylate, polyurethanes and / or polyureas containing (meth) acrylate groups, polyethers containing (meth) acrylate groups, epoxyacrylates, polyorganosiloxanes containing (meth) acrylate or (meth) acrylamide groups, perfluoropolyethers containing acrylate groups, a polyene associated with a polythiol, their mixtures or copolymers.
    [0004]
    4. - Method according to any one of the preceding claims, wherein the photoactivatable material is deposited in liquid form through a nozzle (52) on the first region and / or the second region. 3024659 31
    [0005]
    5. - The method of claim 4, wherein the deposition of the photoactivatable material comprises the positioning of the nozzle (52) in a succession of given positions on the first region and / or on the second region, and in each given position, depositing a given amount of photoactivatable material, illuminating the photoactivatable material deposited in the given position, and then moving the nozzle (52) to another given position on the first region and / or the second region.
    [0006]
    6. A process according to any one of the preceding claims, wherein a first cosmetic material provided in step (a) has a first color, a second cosmetic material provided in step (a) having a second color, the formed cosmetic composition comprising the first cosmetic material and the second cosmetic material on the same layer (19) or on different layers (19).
    [0007]
    7. A process according to any one of the preceding claims, wherein the photoactivatable material is included in or constitutes a cosmetic material to be deposited in liquid form.
    [0008]
    8. - Process according to any one of the preceding claims, wherein at least one layer (19) comprises a photoactivatable support material adapted to form a support (18) of the cosmetic composition, the support (18) being non-releasable the method comprising illuminating the photoactivatable support material to form at least a portion of the support (18).
    [0009]
    9. - Method according to any one of the preceding claims, wherein, in step (a), at least one cosmetic material contains at least one structuring agent in liquid form, the method comprising a preliminary step of heating the Cosmetic materials provided in step (a) for melting the or each structuring agent; each layer (19) formed in step (b) comprising one or more heated cosmetic materials, the or each structuring agent contained in the one or more cosmetic materials being deposited in the molten state; The layer (19) being at least partially solidified by cooling the or each cosmetic material to a temperature lower than that of the or each cosmetic material deposited in step (b); each layer (19) additional formed in step (d) comprising one or more heated cosmetic materials, the or each structuring agent contained in the one or more cosmetic materials being deposited in the molten state; The additional layer (19) being at least partially solidified by cooling the or each cosmetic material to a temperature lower than that of the or each cosmetic material in step (c); the photoactivatable material being deposited in at least one at least partially liquid layer (19).
    [0010]
    10. - Process according to claim 9, wherein the structuring agent is chosen from waxes, organophilic clays, fumed silicas, fatty acids, pasty compounds gelling agents, thickeners, glutamides resins, celluloses hydrophobic, tackifying resins, and mixtures thereof. 10
    [0011]
    11. - The method of claim 10, wherein the precursor material of the cosmetic composition has a mass content of wax greater than 10%.
    [0012]
    12. - Method according to any one of claims 9 to 11, wherein the three-dimensional object (10) is a lipstick, a stick, a hybrid powder, a deodorant and / or antiperspirant product, a soap, a face mask, a styling wax, and / or a solid perfume.
    [0013]
    13. Apparatus (50) for the additive manufacturing of a three-dimensional object (10) comprising or constituting a cosmetic composition, the apparatus (50) comprising: a support surface (58); a formation assembly of successive layers (19) comprising at least one cosmetic material and for at least one layer (19) a photoactivatable material; a source (90) for illuminating the photoactivatable material; a control unit (64) for controlling the formation assembly and the illumination source (90) for performing the following steps: (a) providing at least one cosmetic material and providing at least one a photoactivatable material; (b) forming a layer (19) comprising one or more cosmetic materials provided in step (a) and on at least a first region of the layer (19), a photoactivatable material provided in step (a) ; (c) illuminating at least the first region of the layer (19) to activate the photoactivatable material; (d) forming an additional layer (19) comprising one or more cosmetic materials provided in step (a) and, on at least a second region of the additional layer (19), a photoactivatable material provided at step (a), the additional layer (19) at least partially covering the previous layer (19); (E) illuminating at least the second region of the additional layer (19) to activate the photoactivatable material; (F) repeating steps (d) through (e) until the three-dimensional object (10) is formed, the cosmetic composition comprised in the three-dimensional object (10) or constituting the three-dimensional object (10) being restorable after formation of the three-dimensional object (10). 5
    [0014]
    14. Apparatus (50) according to claim 13, wherein the light source (90) is selected from a lamp and a laser.
    [0015]
    15. Apparatus (50) according to claim 14, wherein the forming assembly comprises at least one nozzle (52) for dispensing each cosmetic material, the light source (90) being movable together with the nozzle (52). 10 15
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    同族专利:
    公开号 | 公开日
    EP3177450B1|2020-07-01|
    WO2016020442A1|2016-02-11|
    US10493690B2|2019-12-03|
    ES2808867T3|2021-03-02|
    FR3024659B1|2016-09-30|
    US20180186065A1|2018-07-05|
    EP3177450A1|2017-06-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1184156A1|2000-09-01|2002-03-06|Optoform Sarl Procedes de Prototypage Rapide|Photopolymerizable foam composition, rapid prototyping process and apparatus for making three dimensional articles, articles obtained therewith and their use|
    EP2636511A1|2010-11-01|2013-09-11|Keyence Corporation|Modeling material for forming photoshaped article by ink-jet photoshaping method, support material for shape supporting during formation of photoshaped article by the photoshaping method, and process for producing photoshaped article by the photoshaping method|
    US8377623B2|2007-11-27|2013-02-19|3D Systems, Inc.|Photocurable resin composition for producing three dimensional articles having high clarity|
    US9867449B2|2014-06-20|2018-01-16|Richard Joseph LaHood, SR.|System and method of manufacturing a three-dimensional cosmetic product|FR3024657B1|2014-08-05|2016-09-02|Oreal|PROCESS FOR THE ADDITIVE MANUFACTURE OF A THREE DIMENSIONAL OBJECT COMPRISING OR CONSTITUTING A COSMETIC COMPOSITION BY APPLYING A PHOTOACTIVABLE MATERIAL TO A POWDER, AND ASSOCIATED APPARATUS|
    US10486364B2|2016-05-03|2019-11-26|Xerox Corporation|System and method for forming integrated interfaces within a three-dimensionally printed object with different build materials|
    CN109759707B|2019-01-13|2020-08-14|大连理工大学|laser-TIG composite heat source additive manufacturing method for aluminum alloy annular part|
    CN110405138A|2019-07-02|2019-11-05|南京理工大学|A kind of moltening mold castings wax-pattern 3D printer|
    法律状态:
    2015-06-29| PLFP| Fee payment|Year of fee payment: 2 |
    2016-02-12| PLSC| Search report ready|Effective date: 20160212 |
    2016-07-12| PLFP| Fee payment|Year of fee payment: 3 |
    2017-07-14| PLFP| Fee payment|Year of fee payment: 4 |
    2018-07-12| PLFP| Fee payment|Year of fee payment: 5 |
    2020-07-15| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1457619A|FR3024659B1|2014-08-05|2014-08-05|METHOD FOR THE ADDITIVE MANUFACTURE OF A THREE DIMENSIONAL OBJECT COMPRISING OR CONSTITUTING A DIRECT PROJECTION COSMETIC COMPOSITION USING A PHOTOACTIVABLE MATERIAL, AND ASSOCIATED APPARATUS|FR1457619A| FR3024659B1|2014-08-05|2014-08-05|METHOD FOR THE ADDITIVE MANUFACTURE OF A THREE DIMENSIONAL OBJECT COMPRISING OR CONSTITUTING A DIRECT PROJECTION COSMETIC COMPOSITION USING A PHOTOACTIVABLE MATERIAL, AND ASSOCIATED APPARATUS|
    ES15750324T| ES2808867T3|2014-08-05|2015-08-05|Process for the additive manufacturing of a three-dimensional object that comprises or forms a cosmetic composition by direct projection using a photoactivatable material|
    EP15750324.4A| EP3177450B1|2014-08-05|2015-08-05|Method for the additive manufacture of a three-dimensional object comprising or forming a cosmetic composition by direct projection using a photoactivatable material.|
    US15/501,264| US10493690B2|2014-08-05|2015-08-05|Method for the additive manufacture of a three-dimensional object comprising or forming a cosmetic composition by direct projection using a photoactivatable material|
    PCT/EP2015/068062| WO2016020442A1|2014-08-05|2015-08-05|Method for the additive manufacture of a three-dimensional object comprising or forming a cosmetic composition by direct projection using a photoactivatable material, and associated apparatus|
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