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    • 专利摘要:
    The method comprises the following steps: (a) forming a layer (19) of powder comprising at least one cosmetic powder; (b) providing a photoactivatable material on at least a first region of the layer (19); (c) illuminating at least the first region of the layer (19) to activate the photoactivatable material; (d) forming an additional layer (19) of powder comprising at least one cosmetic powder; (e) providing at least a second region of the additional layer (19) of a photoactivatable material; (f) illuminating at least the second region of the additional layer (19) to activate the photoactivatable material; (g) repeating steps (d) through (f) until formation of the three-dimensional object. The cosmetic composition included in the three-dimensional object or constituting the three-dimensional object is restorable after formation of the three-dimensional object.
    公开号:FR3024657A1
    申请号:FR1457616
    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 make-up powder, in particular an eyeshadow, a complexion, a tan, or a blush, in the form of a simple powder, a hybrid powder or a powder wet. Alternatively, the three-dimensional object forms a deodorant and / or antiperspirant product, a soap, a solid shampoo and / or a solid perfume. 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.
    [0002] 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. The compacting, multicompacting and slurry injection processes are also limited in terms of the height of the finished product.
    [0003] 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 various 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.
    [0004] The abovementioned 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.
    [0005] Another difficulty results from the fact that the methods of the aforementioned type are intended solely for shaping the three-dimensional object. In some cases, it is necessary to prepare upstream of shaping at least one leg, commonly called "bulk", which complicates the manufacture in some cases.
    [0006] Moreover, when new objects incorporating cosmetic compositions are developed, it is generally useful to make functional models for determining the feasibility and possible 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 tooling, and product conditioning or shaping tests. 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 for manufacturing three-dimensional objects comprising a cosmetic composition, the objects being able to have complex shapes, natures, and appearances. To this end, the object of the invention is a process of the aforementioned type, the process comprising the following steps: (a) forming a powder layer comprising at least one cosmetic powder; (B) providing a photoactivatable material on at least a first region of the layer; (c) illuminating at least the first region of the layer to activate the photoactivatable material; (d) forming an additional layer of powder comprising at least one cosmetic powder, the additional layer at least partially covering the previous layer; (e) providing at least a second region of the additional layer of a photoactivatable material; (f) illuminating at least the second region of the additional layer to activate the photoactivatable material; (g) repeating steps (d) to (f) 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. The method 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 activatable by the photoinitiator. the photo-crosslinkable compound comprises at least one monomer, and / or at least one prepolymer and / or at least one polymer, especially chosen from unsaturated polyesters or (meth) acrylate groups, polyurethanes and / or polyureas (meth) acrylate groups, polyethers with (meth) acrylate groups, 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 or printhead on the first region and / or the second region. the deposition of the photoactivatable material comprises the positioning of the nozzle or printing head 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, and then moving the nozzle or print head to another given position on the first region and / or the second region. the illumination comprises the positioning of a light source 25 advantageously coherent with respect to a succession of given points on the first region and / or on the second region, and for each given point, the illumination of the photoactivatable material to using the light source in the given position, and then moving the light source to another given position on the first region and / or on the second region. The photoactivatable material is included in or constitutes a binding activator for binding at least one cosmetic powder. 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. Step (a) comprises the formation of a planar layer of powder comprising at least one cosmetic powder; the application of a powder binding activator and the bonding of the powder in at least a first region of the powder layer; Step (e) comprising the formation of an additional planar layer of powder comprising at least one cosmetic powder, the additional layer covering the previous layer; the method comprising applying a powder binding activator to at least a second region of the additional powder layer, the photoactivatable material being advantageously contained in the binding enhancer. a first binding enhancer provided in the applying step has a first color, a second binding activator supplied to the applying step having a second color, the formed cosmetic composition comprising the first binding enhancer and the second binding activator on the same layer or on different layers. it comprises the provision of a plurality of binding activators having distinct basic colors, the method comprising a step of forming at least one pixel of a layer having a predefined color by mixing a plurality of binding activators of distinct basic colors; the binding activator is transparent or colored; - It comprises a step of depositing at least one ink from a print cartridge on at least one layer of powder formed in step (a) or step (d). the cosmetic powder contains fillers, pigments, dyes, polymers and / or fibers. the method comprises the following steps: defining a predetermined shape and / or color of a three-dimensional object; Determining the dimensions and local composition of the regions of each powder layer on which a powder binding activator is to be applied, based on the predetermined shape. the three-dimensional object is chosen from a make-up powder, a hybrid powder, or a wet powder, a powdered deodorant and / or antiperspirant product, a solid shampoo or a soap powder. the method comprises a preliminary step of determining the color characteristics of an element by means of a color analysis device, the determination of the local composition of at least one region of a layer of powder on which a powder binding activator is to be applied being made on the basis of the color characteristics determined with the aid of the color analysis device; the three-dimensional object defines a hollow region comprising an unbound powder delimited by a wall formed of cosmetic powder bonded by at least one binding activator. 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 set of formation of successive layers of powder comprising at least one cosmetic powder, for at least one layer, a photoactivatable material; a source of illumination of the photoactivatable material; a control unit, capable of driving the formation assembly, and the illumination source for performing the following steps: (a) forming a powder layer comprising at least one cosmetic powder; (b) providing a photoactivatable material on at least a first region of the layer; (c) illuminating at least the first region of the layer to activate the photoactivatable material; (d) forming an additional layer of powder comprising at least one cosmetic powder, the additional layer at least partially covering the previous layer; (e) providing on at least a second region of the additional layer a photoactivatable material; (f) illuminating at least the second region of the additional layer to activate the photoactivatable material; (g) repeating steps (d) to (f) until the three-dimensional object is formed, the cosmetic composition included 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 nozzle or print head 35 intended for dispensing the photoactivatable material and / or at least one powder-binding activator, the light source being movable together with the nozzle or print head. The invention will be better understood on reading the description which will follow, 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 made 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 10 comprising a cosmetic composition 12 or consisting of a cosmetic composition 12, using a powder binder deposition manufacturing apparatus, an example of which is illustrated in FIG. 1.
    [0007] The method according to the invention is intended to manufacture three-dimensional objects consisting of a cosmetic composition 12, as illustrated for example in FIG. 2, to be supplied directly to the user or to be inserted in a package 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 three-dimensional objects comprising, in addition to the cosmetic composition 12, a support 18 carrying the cosmetic composition 12, the support 18 being manufactured simultaneously by additive deposition with the cosmetic composition 12. According to the invention, the cosmetic composition 12, and optionally the support 18, 25 consist of a plurality of successive layers 19 formed from at least one photoactivatable material, deposited on each other. The cosmetic composition 12, and optionally the support 18, are formed of a plurality of successive layers 19 each comprising at least one powder and at least one activator for local bonding of the powder, the layers 19 being deposited on each the others, the photoactivatable material being included in the binding activator or forming the binding activator. 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.
    [0008] The photocrosslinkable compound generally comprises one or more polymers and / or prepolymers having polymerizable ethylenic double bonds, and / or one or more reactive double bond monomers. Reactive double bond 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 comprising ethylenic double bonds have an average number of ethylenic double bonds per polymer molecule of greater than 1. By way of examples of photocrosslinkable polymers and prepolymers that can be used in the photocrosslinkable compound, mention may be made of polyesters with unsaturation (s); it is a group of polyester 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 aliphatic or cycloaliphatic 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 containing (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 polyorganosiloxanes; carriers of primary or secondary secondary 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, pages 34-41; industrial processes of photoinduced polymerization ", Henri Strub, L'Actualité Chimique, February 2000, pages 5 - 13 and" Photopolymers: theoretical and reaction of setting ", Marc, JM Abadie, Double Liaison - Chemistry of the Paintings, n 435 - 436 1992, pp. 28-34. These photoinitiators include alpha-hydroxyketones, alpha-amino ketones, chloroacetophenones, aromatic ketones, thioxanthones and quinones, benzoin ethers, acylphosphine oxides, and copolymerizable photoinitiators. The copolymerizable photoinitiators are molecules comprising both a photoinitiator group capable of photoinduced free radical scission and at least one ethylenic double bond The radiation suitable for the crosslinking of the cosmetic compositions of the present invention has a wavelength between 210 and 600 nm, preferably between 250 and 400 nm, in a preferred embodiment of the invention, use is made of A UV lamp and in particular a mercury vapor lamp, optionally doped with other elements, such as gallium, for modifying the emission spectrum of the light source. Alternatively or in addition, a laser is used to cause the crosslinking. The cosmetic composition 12, and optionally the support 18, are formed of a plurality of successive layers 19 each comprising at least one powder and at least one local binder of the powder, the layers 19 being deposited on one another . In this example, the binder constitutes as such a binding activator of the powder. Alternatively, a portion of the binder is dispersed in powder form in the powder and is activated by an activator subsequently added to the powder and binder mixture.
    [0009] Advantageously, several separate binders are used to form the cosmetic composition, being deposited in the same layer or in separate layers. The distinct binders 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 or colors, as illustrated for example in Figure 6 or 7, or gradients of composition and color. In particular, the separate binders have distinct colors. These colors are in particular basic colors (for example black, yellow, cyan, magenta) making it possible to mix a whole range of distinct colors. Alternatively, the binders or binders have a monochrome color, or an absence of color. The color of each point of the cosmetic composition is then provided by spraying droplets of an ink or a plurality of different color inks from one or more print cartridges. The thickness of each layer 19 forming the three-dimensional object 10 is for example less than 1 mm and is in particular between 50 microns and 200 microns. Each layer 19 comprises at least one solid zone formed of at least one powder and at least one binder of the powder. 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, it keeps its shape spontaneously, throughout the life of the product in l absence of external solicitation. 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 throughout the life of the product. , in the absence of external solicitation. This lifetime is for example for example of at least one day, including at least one year. Preferably, the cosmetic composition is solid. In this case, it can be entered and moved by the user without flowing.
    [0010] 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 portion 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 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 restored. 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.
    [0011] Alternatively, the cosmetic composition is biodegradable by being soaked in 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. The cosmetic composition is preferably délitable, that is to say that a portion of the powder, possibly carrying binder is likely to detach from the rest of the cosmetic composition under the effect of a mechanical action. Advantageously, the cosmetic composition is chosen from a colored cosmetic composition, and in particular a makeup composition for the skin and / or mucous membranes. The cosmetic composition is for example in the form of a makeup powder, a hybrid powder or a wet powder. Alternatively, the three-dimensional object forms a deodorant and / or antiperspirant product, a soap, a solid shampoo and / or a solid perfume. 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, optionally having care or treatment properties. treatment. It may be a colored makeup composition (beige or green) 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. The powder present in the cosmetic composition advantageously has an average particle size of, for example, between 0.1 μm and 150 μm, preferably between 0.1 μm and 100 μm. Equipment for carrying out this measurement is the Mastersizer 3000 from Malvern, as described in US 6,778,271 or GB2340932. This technique consists in measuring the intensity of the light scattered during the passage of a laser beam through a sample of dispersed particles. This data is then analyzed to calculate the size of the particles that created the diffraction pattern. It can be used for the liquid route and the dry route. The choice of the method depends on the powder to be analyzed. The skilled person uses the module that corresponds to the chosen method and performs the measurement.
    [0012] These grains may be spheroids or irregularly shaped particles, ranging in size from 0.1 microns to 100 microns. The mass content of cosmetic powder in the cosmetic composition, after formation of the three-dimensional object, is greater than 40%, in particular greater than 85%, advantageously greater than 90%.
    [0013] In the case of a make-up powder, the mass content of cosmetic powder is greater than 80%, and is in particular between 85% and 95% by weight. In the context of a hybrid powder, the mass content of cosmetic powder is advantageously between 60% and 90%. The powder includes, for example, fillers, polymers, pigments, and / or fibers. 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 can be mineral or organic of any shape, platelet, spherical or oblong, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide, poly-6-alanine and polyethylene powders, tetrafluoroethylene polymer powders, lauroyl-lysine, starch, nitrile of boron, 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 from 8 to 22 carbon atoms, preferably from 12 to 18 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. The powder may comprise generally spherical particles of at least one surface-stabilized polymer, especially in the form of nanoparticles of polymers. The nanoparticles are preferably of a size between 5 nm and 600 nm. 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 room temperature. It is also possible to use non-film-forming polymers, optionally crosslinked, which can be used as stably dispersed fillers in an oil.
    [0014] The polymers usable 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 -100 ° C to 300 ° C. When the polymer has a Tg too high for the desired application, it can be associated with a plasticizer so as to lower the Tg of the mixture used. The plasticizer may be chosen from plasticizers usually used in the field of application and in particular from 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, mention may be made of homopolymers or radical copolymers, vinylic 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 pigments are for example chosen from organic pigments, mineral pigments and pearlescent agents.
    [0015] 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.
    [0016] The fibers are for example selected from polyamide fibers such as nylon fibers. The binder mass content in the cosmetic composition is preferably between 5% and 60%. In the case of a makeup powder, this mass content is advantageously between 5% and 15%. In the context of a hybrid powder, the mass content of the binder in the cosmetic composition is advantageously between 10% and 40%. Advantageously, the binder is able to bind the powder by simple contact with the powder and / or after crosslinking, when the binder comprises or forms a photoactivatable material as defined above. The binder is then at least partially liquid at room temperature, for example at 25 ° C. By "at least partially liquid" is generally meant that the binder is able to flow under the effect of its own weight. In particular, the binder is able to flow through an extrusion nozzle or a print head. An extrusion nozzle is an elementary metering element, for example cylindrical. A printhead is an element of a printer responsible for projecting drops of ink. A print head has a multitude of nozzles. Generally, the projection of the drops in a print head is caused by an active moving means, such as a piezoelectric element.
    [0017] The "at least partially liquid" binder is completely liquid, or comprises a liquid phase in which solid elements are dispersed, which flow through the liquid phase. Advantageously, the binder is deposited in the form of liquid droplets which are projected from a nozzle or print head onto a layer of powder free of binder. The viscosity of the binder, taken at its deposition temperature at the nozzle or print head is for example less than 5 mPa.s and in particular between 0.5 mPa.s and 3 mPa.s.
    [0018] Alternatively, the binder is at least partially in hot liquid form. It is for example intended to be heated to be deposited in liquid form in a powder layer, then to solidify at least partially, after it has been deposited in a layer of powder, and / or after crosslinking, when the binder comprises or forms a photoactivatable material as defined above.
    [0019] The term "hot" includes in particular beyond the melting temperature of the binder. For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in ISO 11357-3: 2011.
    [0020] In this embodiment, the at least partially liquid binder is capable of solidifying at least partially by cooling and / or crosslinking. By "at least partial solidification" is meant that the binder is able to be structured in the sense defined above. In particular, the viscosity of the binder is able to increase. In particular, the binder is able to become solid.
    [0021] Cooling advantageously passes the binder at a temperature below the temperature it exhibited during its deposition. This temperature is preferably lower than the melting temperature of the binder. The temperature loss of the binder during cooling is greater than 3 ° C., especially greater than 5 ° C.
    [0022] Alternatively, the binder is activatable by solvent evaporation. In a first embodiment, the binder comprises a main binding agent for giving a structure to the powder. It advantageously comprises a secondary binding agent in addition to the main agent. It also comprises a photoactivatable material as defined above.
    [0023] In a second embodiment, a first binder comprises a main binding agent for providing a structure to the powder. It advantageously comprises a secondary binding agent in addition to the main agent. A second binder is made of photoactivatable material as defined above. In this case, the first binder and the second binder are deposited on the same powder layer in the same positions or in separate positions. The main binding agent is preferably chosen from oils, especially silicone oils, or esters. It is thus possible to mention hydrocarbon-based oils such as liquid paraffin or petrolatum; mink oil, turtle oil, soybean oil, perhydrosqualene; almond oil, calophyllum, palm oil, grape seed oil, sesame oil, corn oil, rapeseed oil, sunflower oil, cotton, castor oil, avocado, jojoba, olive or cereal sprouts; esters of lanolic acid, oleic acid, (auric) acid, stearic acid, fatty esters, such as isopropyl myristate, isopropyl palmitate, butyl stearate, laurate, hexyl, diisopropyl adipate, isononyl isononate, 2-ethylhexyl palmitate, 2-hexyl-decyl laurate, 2-octyldecyl palmitate, myristate or 2-octyl lactate dodecyl, 2-diethylhexyl succinate, diisostearyl malate, glycerol or diglycerine triisostearate, higher fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid, higher fatty alcohols such as cetanol, stearyl alcohol or oleic alcohol, linoleic or linolenic alcohol, isostearic alcohol or octyl dodecanol, silicone oils such as PDMS, optionally phenylated such as phenyltrimethicones or optionally substituted with aliphatic and / or aromatic groups, optionally fluorinated, or with functional groups such as hydroxyl, thiol and / or amine groups; polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, fluorinated silicones, perfluorinated oils. It is also possible to use volatile oils, such as cyclotetradimethylsiloxane, cyclopentadimethylsiloxane, cyclohexadimethylsiloxane, methylhexyldimethylsiloxane or isoparaffins such as ISOPARs, in particular isododecane. The or each binder contained in the cosmetic composition forms a network for maintaining the composition, in particular of the powder contained in the composition. This network breaks on the surface during the application of the cosmetic product, allowing the restitution of the composition.
    [0024] The additional agent is chosen from water, an alcohol, especially methanol, ethanol, propanol, a polymer, especially a polyvinyl alcohol, or a polymer resin, a ceramic precursor, such as a polycarbisilazane or a mineral precursor, in particular based on silica.
    [0025] The manufacturing method according to the invention is implemented in a binder deposition manufacturing apparatus 150 on successive layers of powders, an example of which is illustrated schematically in FIG. 1. The apparatus 150 comprises a set 151 of formation of successive layers of powder.
    [0026] The apparatus 150 includes at least one nozzle or printhead 152 for dispensing at least one powder-binding activator in liquid form, and for each binding activator dispensed by the nozzle or head of the printing 152, a container 154 for conditioning the binding activator, and a set 156 for conveying the activator for connection between the tank 154 and the nozzle or print head 152.
    [0027] For example, when several different color bonding activators are used, the apparatus 150 advantageously includes a color print nozzle or printhead. The apparatus 150 includes a support surface 158 adapted to bear the successive layers of powder, and an assembly 160 for relative displacement of the nozzle or print head 152 relative to the support surface 158. The apparatus 150 also comprises a control unit 162 of the training assembly 151, the displacement assembly 160 and the conveyor assembly 156. It advantageously comprises a man-machine interface 164. According to the invention, the apparatus 150 comprises a radiation source 190 for activating the photoactivatable material present in each layer 19 containing it. The radiation source 190 is for example movable together with the nozzle or print head 152, advantageously being carried by the nozzle or print head 152. In this case, the radiation source 190 is preferably activatable by pulses before each movement of the nozzle or print head 152 between two positions facing the layer 19 in formation. As indicated above, the source 190 is capable of emitting radiation suitable for crosslinking at a wavelength of between 210 and 600 nm, preferably between 250 and 400 nm. In one embodiment of the invention, the source 190 is a UV lamp and in particular a mercury vapor lamp, optionally doped with other elements, such as gallium, for modifying the spectrum of In a variant or in addition, the source 190 comprises a laser movable together with the nozzle or print head 152 or movable independently of the nozzle or print head 152. It is thus suitable for irradiating the photoinitiator at a wavelength suitable for its decomposition or / and to cause a local heating of the binder generating a thermal decomposition of the photoinitiator. The training assembly 151 includes a powder reservoir 165, and a powder dispensing member 166 to the support surface 158 or to a previous powder layer 19. In the example illustrated in FIG. 1, the powder reservoir 165 is delimited downwards by a movable piston 167, able to move upwards in order to maintain the level of powder in the reservoir 165, after the application of a layer 19.
    [0028] The powder dispensing member 166 here comprises a roller movably mounted in the reservoir 165, at the top surface of the powder, for pushing a layer of powder laterally facing the support surface 158, directly on this surface. 158, or on a previous powder layer 19 carried by the support surface 158.
    [0029] Each layer of powder 19 thus formed is thus flat. It is devoid of macroscopic relief of height greater than 4 times the average thickness of the layer 19. The average thickness of the powder layer 19 is less than 1 mm and is generally between 50 microns and 200 microns. In this example, the apparatus 150 includes at least one nozzle or print head 152 dispensing a plurality of separate link activators from a plurality of respective reservoirs 154. The nozzle or print head 152 defines at least one dispensing orifice of the bonding activator. Advantageously, it is suitable for distributing the binding activator in the form of successive droplets which are projected towards the support surface 158, on a layer of powder 19 that has just been deposited. 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 powder layer 19 is preferably less than 5 mm, and is in particular between 0.5 mm and 1.5 mm.
    [0030] Thus, each droplet or set of droplets projected at a given position of the nozzle or print head 152 is able to define an area of the layer 19 forming a "pixel" on the powder layer 19. The composition and or the appearance of each pixel, in particular its color, can thus be defined by the nature of the binding enhancer (s) added in the pixel. In the particular case where the binder is hot liquid, each tank 154 is advantageously provided with a heating system 168 adapted to maintain the binding activator in liquid form in the tank 154. The conveyor assembly 156 comprises a Binding activator supply line 170, connecting tank 154 to nozzle or printhead 152, a system (not shown) for pumping binding activator through line 170, and preferably, at less a control member 172 of the flow of the link activator flowing through the supply line 170, controlled by the unit 162. The control member 172 is for example a valve controlled between a blocking configuration the flow of the binding enhancer and a distribution pattern of the binding enhancer.
    [0031] In a variant, the conveyor assembly 156 is devoid of a control member 172, the flow of the cosmetic material being controlled by the pumping system. In the particular case where the binder is hot liquid, the pipe 170 and the nozzle or printhead 152 are heat insulated to maintain the bonding activator in liquid form during its conveying. In this example, the support surface 158 is defined on a piston 173 movable vertically. After the formation of each layer 19, and the application of a bonding activator in at least one region of the layer 19, the piston 173 is able to move downwards, to lower the newly formed layer 19 below the upper surface of the powder present in the reservoir. This allows the application of a new layer of powder free of binding activator on that coming to receive the binding activator through the powder dispenser 166. The displacement assembly 160 is clean to allow three-axis relative positioning of the nozzle or print head 152 relative to the support surface 158, or relative to the previous layer 19 deposited on the support surface 158. The displacement assembly 160 is driven by the unit 162 to horizontally move the nozzle or printhead 152 relative to the previous layer 19 or relative to the support surface 158, to selectively deposit at least one link activator droplet at a location predetermined on the forming layer, corresponding to a pixel as defined above.
    [0032] The displacement assembly 160 is further controlled by the unit 162 to vertically maintain the vertical distance between the nozzle or print head 152 and the support surface 158 or the previous layer. In this example, the displacement assembly 160 includes a mechanism 174 for three-dimensional displacement of the nozzle or printhead 152, and a mechanism 176 for vertical displacement of the support surface 158. The control unit 162 is clean. to calculate, from a digital model of the three-dimensional object, the spatial arrangement of the binding activator within each layer of powder 19, to deposit it with each nozzle or print head 10 152, and, within each layer 19 to be formed, the exact composition of the binding activator in each zone of the layer 19. On this basis, the control unit 162 is able to control the corresponding relative displacement of each nozzle or printhead 152 relative to the support surface 158 for depositing a given binding activator on each zone to be formed of each layer 19, and controlling the control of the conveying assembly 156, in particular of the pumping system and from control member 172, at each position of the nozzle or print head 152, depending on the desired activator in this area. The human-machine interface 164, 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 digital mockups, or by importing a predefined digital mock-up file, for use by the control unit 162. An example of a manufacturing method according to the invention will now be described. Advantageously, the user initially defines using the man-machine interface 164 the shape and composition of the object to be produced, for example by choosing a digital mock-up file in a database of digital mockups or by importing this file. Then, the digital mockup file is transmitted to the control unit 162. The control unit 162 then defines the shape of the various layers 19 intended to constitute the three-dimensional object, and within each layer the activator composition connecting each zone of the layer defining a "pixel". The control unit 162 then calculates the necessary displacement of the or each nozzle or print head 152 during the construction of each layer 19, and determines whether a link activator is to be added at a given position of the nozzle or If so, which print head (s) 152 must be added in each given position of the nozzle or print head 152.
    [0033] Each binding activator is prepared in a reservoir 154. At least one reservoir 154 then contains a binding enhancer comprising at least one binder. According to the invention, at least one binder comprises photoactivatable material as defined above. Alternatively, at least one binder is made of photoactivatable material as defined above. Then, the control unit 162 controls the training assembly 151, the displacement assembly 160 and the conveyor assembly 150 on the basis of the calculations made previously to successively form the different layers 19 on each other.
    [0034] For each layer 19 to be formed, the control unit 162 first drives the forming assembly 151 to deposit a layer of powder facing the previous layer 19 or the support surface 158 where appropriate. The powder layer is flat and free of binder. The control unit moves the nozzle or print head 152 in each zone 15 to be formed of the layer 19 and projects at least one binding activator, advantageously in the form of liquid droplets, against the powder layer 19 which has just been formed. filed. The droplets are projected directly onto the powder layer 19 or against the support surface 158.
    [0035] In this operation, the control unit 162 maintains substantially the vertical distance between the nozzle or printhead 152 and the previous layer 19 and / or the support surface 158. In a first embodiment, between each moving the nozzle or print head 152 opposite the newly formed layer of powder, after the deposition of at least one binder droplet, the radiation source 190 is activated to cause the activation of the material photoactivatable by photochemical and / or thermal decomposition of the photoinitiator and radical reaction of the monomer (s) and / or the prepolymer (s) and / or the polymer (s). Alternatively, the radiation source 190 is activated after the nozzle or print head 152 has finished moving relative to the newly formed layer of powder after deposition of the entire binder to be placed. on the powder layer. The binding activator binds the powder, for example by crosslinking in the selected regions of layer 19.
    [0036] In this example, the color of each pixel of the layer 19 is defined in particular by the color of the binding activator or the mixture of binding enhancers projected on this pixel. Once the layer 19 has been formed, the displacement assembly 160 is driven to move the layer 19 previously formed from the nozzle or print head 152. A new layer of powder is applied to the previous layer by the dispensing member. The preceding operations are repeated to add the different layers 19 to one another.
    [0037] Once all the layers 19 of the three-dimensional object have been formed, the unbound powder present in the areas lacking binding activator is removed from the three-dimensional object 10. The three-dimensional object 10 is thus cleaned. According to the invention, at least one binding activator is applied to selected areas of several layers 19, and in some cases all layers 19 are formed to additively build the structured cosmetic composition within the three-dimensional object 10. It is thus possible to construct three-dimensional objects comprising or consisting of a cosmetic composition having selected and complex shapes, compositions and appearances which are distinct depending on the zone, and gradients of appearance and composition, by simple local control of the link activator to be added in each zone of a given layer 19 of the three-dimensional object 10. In a variant (not shown), the apparatus 150 comprises an additional printing head, capable of projecting a or more inks contained in at least one print cartridge.
    [0038] The ink or inks are projected on each pixel, in addition to the binding activator and possibly the photoactivatable material projected onto this pixel. The color of each pixel is thus obtained by mixing the binding activator (s) projected on the pixel, possibly the photoactivatable material and by the inking or projected on the pixel.
    [0039] The color of each pixel of each layer 19 of the cosmetic composition can therefore be predefined, and obtained precisely on the cosmetic composition manufactured by the process according to the invention. In particular, each region of the cosmetic composition can be manufactured with a color chosen by the user. For example, the apparatus 150 may comprise a color analysis device, including a spectrophotometer capable of determining data characteristic of a color chosen by the user, taken for example over a range of colors or on a color chart. accessory such as a garment. The spectrophotometer is for example of the type sold by the company "X-Rite".
    [0040] The apparatus 150 is then adapted to use the data to construct a cosmetic composition having at least one color region similar to that determined by the color analysis device, either using a mixture of appropriate binding enhancers or using a mixture of inks contained in a print cartridge.
    [0041] In a variant, at least one bonding activator added in at least one layer 19 is intended to form a support 18 of the cosmetic composition that forms part of the three-dimensional object. Advantageously, the support 18 thus formed is not restorable. after solidification, in contrast to the cosmetic composition. Examples of activators for carrier 18 are binders containing a polymer soluble in alcohols, in water and / or in ketones, such as polyvinyl butyral (PVB), polyvinyl acetate (PVAC) or polyvinyl alcohol (PVAL). Alternatively, these binders are glues or thermosetting materials. The bonding activator for forming the carrier 18 is then projected from a specific nozzle or print head 152. In this variant, at least one partially liquid binding activator for forming the support is deposited during the formation of the three-dimensional object. On at least one layer of powder is added either exclusively a first binding activator for forming a region of the support, or a second binding activator for forming a region of the cosmetic composition and a first binding activator for forming a support region. In this case, the apparatus 150 comprises at least one reservoir 154 for conditioning the support material and a set 156 for conveying the support material between the reservoir 154 and the nozzle or printhead 152.
    [0042] The control unit 162 is capable of determining whether the support material is to be added at a given position of the nozzle or printhead 152, in addition to or in substitution for a cosmetic material. The binding activator for forming a region of the support is for example a polymer, in particular a thermoplastic polymer or a non-restorable photoactivatable polymer, taken from a family as defined above.
    [0043] The support material crosslinks under the effect of illumination and / or heating generated by the source 190 to form the support 18. In a particular example, the support material is made of a non-releasable photoactivatable material, As defined above, which crosslinks during the formation of the three-dimensional object 10. The cosmetic composition 12 may then contain at least one restorable photoactivatable material or may not contain it. In another variant, the cosmetic composition delimits at least one hollow central region containing free powder free of binding activator, encapsulated in a region of bound powder.
    [0044] Advantageously, the manufacturing method according to the invention is implemented for producing 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.
    权利要求:
    Claims (16)
    [0001]
    CLAIMS1.- A method of additive manufacturing of a three-dimensional object (10) comprising or constituting a cosmetic composition, the process comprising the following steps: (a) forming a layer (19) of powder comprising at least one cosmetic powder; (b) providing a photoactivatable material on at least a first region of the layer (19); (c) illuminating at least the first region of the layer (19) to activate the photoactivatable material; (d) forming an additional layer (19) of powder comprising at least one cosmetic powder, the additional layer (19) at least partially covering the layer (19) above; (e) providing at least a second region of the additional layer (19) of a photoactivatable material; (f) illuminating at least the second region of the additional layer (19) to activate the photoactivatable material; (g) repeating steps (d) to (f) 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. - A method according to any one of the preceding claims, wherein the photoactivatable material is deposited in liquid form through a nozzle or printhead (152) on the first region and / or the second region. 3024657 25
    [0005]
    5. - The method of claim 4, wherein the deposition of the photoactivatable material comprises the positioning of the nozzle or print head (152) in a succession of given positions on the first region and / or on the second region, and, in each given position, depositing a given quantity of photoactivatable material, illuminating the photoactivatable material deposited in the given position, and then moving the nozzle or print head (152) to another given position on the first region and / or the second region.
    [0006]
    6. - Method according to any one of the preceding claims, wherein the illumination comprises the positioning of a light source (190) advantageously coherent with respect to a succession of points given on the first region and / or on the second region, and for each given point, the illumination of the photoactivatable material by means of the light source (190) in the given position, then the displacement of the light source (190) to another given position on the first region and / or the second region. 15
    [0007]
    7. - Method according to any one of the preceding claims, wherein the photoactivatable material is included in or constitutes a binding activator for binding at least one cosmetic powder.
    [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. A process according to any one of the preceding claims wherein step (a) comprises forming a planar powder layer (19) comprising at least one cosmetic powder; the method comprising applying a powder binding activator and bonding the powder in at least a first region of the powder layer (19); step (e) comprising the formation of an additional planar powder layer (19) comprising at least one cosmetic powder, the additional layer (19) covering the preceding layer (19); the method comprising the application of a powder binding activator on at least a second region of the layer (19) of additional powder, the photoactivatable material being advantageously contained in the binding activator. 3024657 26
    [0010]
    The method of any of the preceding claims, wherein a first link activator provided in the applying step has a first color, a second link activator provided in the applying step having a second color. the formed cosmetic composition comprising the first binding activator and the second binding activator on the same layer (19) or on different layers (19).
    [0011]
    11. - Method according to any one of the preceding claims, comprising a step of depositing at least one ink from a print cartridge on at least one layer of powder (19) formed in step (a) or at step 10 (d).
    [0012]
    12. - Method according to any one of the preceding claims, wherein the cosmetic powder contains fillers, pigments, dyes, polymers and / or fibers.
    [0013]
    13. A process according to any one of the preceding claims wherein the three-dimensional object (10) is selected from a makeup powder, a hybrid powder, or a wet powder, a deodorant and / or antiperspirant product. powder, a solid shampoo or soap powder.
    [0014]
    14. Apparatus (150) for the additive manufacturing of a three-dimensional object (10) comprising or constituting a cosmetic composition, the apparatus (150) comprising: a support surface (158); an assembly (151) for forming successive layers (19) of powder comprising at least one cosmetic powder, for at least one layer (19), a photoactivatable material; a source (190) for illuminating the photoactivatable material; A control unit (162) for controlling the forming assembly (151) and the illumination source (190) for performing the following steps: (a) forming a powder layer (19) comprising at least one cosmetic powder; (b) providing a photoactivatable material on at least a first region of the layer (19); (c) illuminating at least the first region of the layer (19) to activate the photoactivatable material; (d) forming an additional layer (19) of powder comprising at least one cosmetic powder, the additional layer (19) at least partially covering the layer (19) above; (E) providing on at least a second region of the additional layer (19) of a photoactivatable material; (f) illuminating at least the second region of the additional layer (19) to activate the photoactivatable material; (G) repeating steps (d) to (f) 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).
    [0015]
    15. Apparatus (150) according to claim 14, wherein the light source (190) is selected from a lamp and a laser.
    [0016]
    Apparatus (150) according to claim 15, wherein the forming assembly (151) comprises at least one nozzle or printhead (152) for dispensing the photoactivatable material and / or at least one a powder binding activator, the light source (190) being movable together with the nozzle or print head (152). 15 20
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    同族专利:
    公开号 | 公开日
    EP3177451A1|2017-06-14|
    US20170232675A1|2017-08-17|
    ES2835599T3|2021-06-22|
    FR3024657B1|2016-09-02|
    WO2016020447A1|2016-02-11|
    EP3177451B1|2020-11-04|
    US10413758B2|2019-09-17|
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    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 |
    2021-07-15| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1457616A|FR3024657B1|2014-08-05|2014-08-05|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|FR1457616A| FR3024657B1|2014-08-05|2014-08-05|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|
    EP15752976.9A| EP3177451B1|2014-08-05|2015-08-05|Method for the additive manufacture of a three-dimensional object comprising or forming a cosmetic composition by application of a photoactivatable material onto a powder|
    US15/501,454| US10413758B2|2014-08-05|2015-08-05|Method for the additive manufacture of a three-dimensional object comprising or forming a cosmetic composition by application of a photoactivatable material onto a powder, and associated apparatus|
    ES15752976T| ES2835599T3|2014-08-05|2015-08-05|Process for the additive manufacture of a three-dimensional object that comprises or forms a cosmetic composition by applying a photoactivatable material in a powder|
    PCT/EP2015/068082| WO2016020447A1|2014-08-05|2015-08-05|Method for the additive manufacture of a three-dimensional object comprising or forming a cosmetic composition by application of a photoactivatable material onto a powder, and associated apparatus|
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