Device suitable for packaging a heterogeneous mixture and distributing it in the form of a spray of fluid composition
The device addresses the challenge of dispensing heterogeneous mixtures as a spray by optimizing the particle size and volume fraction within the device, ensuring consistent spray quality and homogeneity.
Patent Information
- Application Number
- FR2023014016
- Authority / Receiving Office
- FR · FR
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-12-12
- Publication Date
- 2025-06-13
- Estimated Expiration
- 2043-12-12
AI Technical Summary
Current devices are unable to effectively package and dispense heterogeneous mixtures in the form of a spray of fluid composition, particularly in the cosmetic sector where macroscopic emulsions are gaining popularity.
A device comprising a container with a guide conduit and a dispensing member that adjusts the particle size and volume fraction of particles within the heterogeneous mixture to ensure optimal spray quality and homogeneity, with a ratio of internal guide duct diameter to particle diameter between 1 and 1.25, and a particle volume fraction between 50% and 70%.
The device ensures consistent spray quality and homogeneity of the fluid composition throughout its use, effectively addressing the challenge of dispensing heterogeneous mixtures as a spray.
Smart Images

Figure 00000037_0000 
Figure 00000038_0000 
Figure 00000039_0000
Abstract
Description
Title of the invention: Device suitable for packaging a heterogeneous mixture and distributing it in the form of a spray of fluid composition
[0001] The present invention relates to a device suitable for packaging a composition, in particular a cosmetic composition, in the form of a heterogeneous mixture and for dispensing it in the form of a spray of fluid composition.
[0002] Devices for packaging and dispensing fluid compositions in spray form have been known for a long time. This type of device is widely used, for example, for packaging and dispensing perfumes. We are seeing the deployment of this type of spray device in other cosmetic segments, such as the sun, hair, and more recently skin care sectors.
[0003] These devices are suitable for delivering compositions of low viscosity and in single-phase or conventional emulsion form, that is to say for which the dispersed phase is in the form of particles not visible to the naked eye, and in particular having a diameter of less than 250 μm, or even less than 150 μm. Such conventional emulsions can be referred to indifferently as "microscopic emulsions" or "microscopic dispersions".
[0004] At the same time, there is a growing consumer demand for compositions in the form of heterogeneous mixtures. This is particularly the case in the cosmetics field, with the success of products in the form of macroscopic emulsions such as DIOR's rose micro-oil, CHANEL's hydrabeauty micro-serum, L'OCCITANE's Immortelle Night Reset Oil-in-Serum, NUXE's Super Serum, CHANEL's Les Beiges Eau de Teint, and La Prairie's Skin Caviar Harmony extract.
[0005] However, no devices are known which are suitable for packaging such heterogeneous mixtures and delivering them in the form of a spray of fluid composition.
[0006] There therefore remains a need for a device suitable for packaging compositions, particularly cosmetic compositions, in the form of a heterogeneous mixture and for distributing them in the form of a spray of fluid composition.
[0007] Thus, the present invention aims to propose a device suitable for packaging compositions, in particular cosmetic compositions, in the form of a heterogeneous mixture and for dispensing them in the form of a spray of fluid composition, and in particular to propose a device capable of guaranteeing spray quality and homogeneity of the fluid composition delivered throughout the use of said device.
[0008] As can be seen from the examples below, this objective can be achieved subject to adjusting:
[0009] - the particle size at the internal diameter of the guide duct of the device, or conversely, such that the ratio “internal diameter of the guide duct / diameter of the particles” is between 1 and 1.25, and preferably between 1.1 and 1.2; and
[0010] - the volume fraction of particles, such that said particles re have a volume fraction of between 50% and 70%, preferably between 55% and 65%, and better still between 57% and 63%, relative to the total volume of the heterogeneous mixture.
[0011] Thus, the present invention relates to a packaging and dispensing device in the form of a spray of fluid composition, in particular cosmetic, characterized in that it comprises at least:
[0012] - a container comprising at least one heterogeneous mixture;
[0013] - a guide conduit arranged in the container; and
[0014] - a dispensing member capable of sucking heterogeneous mixture from the container, transforming the heterogeneous mixture into the fluid composition and distributing the fluid composition in the form of a spray,
[0015] the heterogeneous mixture comprising particles, preferably monodisperse, dispersed in a continuous phase, the particles having a diameter greater than 250 pm, and preferably greater than 500 pm,
[0016] characterized in that:
[0017] - the ratio “internal diameter of the guide duct / diameter of the particles” is between 1 and 1.25, and preferably between 1.1 and 1.2; and
[0018] - the particles represent a volume fraction of between 50% and 70%, of preferably between 55% and 65%, and better between 57% and 63%, relative to the total volume of the heterogeneous mixture.
[0019] The present invention also relates to the use of at least one device according to the invention, for perfuming a keratin material or an item of clothing.
[0020] According to the invention, the pH of a heterogeneous mixture and of a fluid composition according to the invention is typically between 3.0 and 8.0, in particular between 4.0 and 7.0.
[0021] Unless otherwise indicated, in all that follows, it is considered that we are at room temperature (for example T=25°C ± 2°C) and atmospheric pressure (760 mm Hg, or 1,013.105 Pa or 1013 mbar).
[0022] Packaging and dispensing device in the form of a spray
[0023] A packaging and dispensing device according to the invention, also referred to as a “packaging article” or “device”, aims to dispense a heterogeneous mixture in the form of a spray of composition fluid. A device according to the invention can therefore also be designated as a “spray device”, “spraying device” or “sprayer”.
[0024] A device according to the invention may be an atmospheric device or an airless device, i.e. without air intake.
[0025] Preferably, a device according to the invention is not an airless device, and therefore is not a device without air intake.
[0026] A device according to the invention does not comprise a pressurized container, and in particular is not an aerosol.
[0027] Preferably, a device according to the invention is an atmospheric device.
[0028] A device according to the invention can be actuated mechanically or automatically, preferably mechanically, in particular by activating a push button or a trigger present at the level of the dispensing member, as described in more detail below.
[0029] A packaging and dispensing device according to the invention comprises at least one container comprising at least one heterogeneous mixture, a guide conduit arranged in the container and a dispensing member. Container
[0030] The container of a device according to the invention, also referred to as a "bottle", may have any shape. In particular, the container may be in the form of a cylinder, a cube, a parallelepiped, in particular a rectangle, a sphere, a cone, in particular a straight cone, or a pyramid.
[0031] A container may be formed from any material, in particular chosen from glass, plastic, in particular polyethylene terephthalate (PET), polypropylene (PP) or polyethylene (PE).
[0032] Preferably, a container is transparent or translucent, so as to see the heterogeneous mixture being packaged therein.
[0033] Preferably, a container is wholly or partly colorless or colored.
[0034] Preferably, a container has a capacity of between 5 ml and 1000 ml, preferably between 10 ml and 750 ml, in particular between 25 ml and 500 ml, and better between 50 ml and 250 ml.
[0035] A container comprises at least one orifice, in particular to ensure its filling with a heterogeneous mixture, the introduction of the guide conduit and the coupling of the container with the dispensing member.
[0036] Preferably, the orifice of the container comprises a neck, in particular to ensure the attachment of the dispensing member to the container. Guide duct
[0037] The guide duct corresponds to the element of the device according to the invention which immerses in the heterogeneous mixture present in the container, and which ensures a fluid connection between the container and the dispensing member.
[0038] A guide duct within the meaning of the invention may indifferently be designated by the expression “dip tube” (or “DIP tube” in English).
[0039] The guide duct can be formed from any material, preferably the guide duct is made of plastic, in particular polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), preferably polyethylene (PE), and better still low density polyethylene (LDPE).
[0040] Preferably, the guide duct has an internal diameter of between 250 qm and 3750 qm, preferably between 500 qm and 2500 qm, in particular between 1000 qm and 2000 qm, and better still between 1250 qm and 1700 qm.
[0041] Preferably, the guide duct has an external diameter between 1 mm and 4 mm, preferably between 1.25 mm and 2.75 mm, and more preferably between 1.5 mm and 2 mm. In particular, the guide duct has an external diameter between 1.5 mm and 3 mm, preferably between 1.75 mm and 2.75 mm.
[0042] In view of the above, the internal diameter of the guide duct is adjusted with respect to the diameter of the particles of the heterogeneous mixture, or vice versa, in such a way that the ratio “internal diameter of the guide duct / diameter of the particles” is between 1 and 1.25, and preferably between 1.1 and 1.2.
[0043] Preferably, the guide conduit is transparent or translucent, so as to see the heterogeneous mixture being conditioned therein.
[0044] Preferably, the guide conduit is wholly or partly colorless or colored.
[0045] Preferably, the guide duct is not capable of breaking / shearing the particles of the heterogeneous mixture. In other words, the internal diameter of the guide duct is adjusted to ensure the suction of the heterogeneous mixture without altering the integrity of the particles and without preferential suction of either the continuous phase or the particles.
[0046] Preferably, the guide duct has a length adapted to the distance between the lower part of the dispensing member and the lower internal wall of the container, in particular so as to guarantee the suction of all of the heterogeneous mixture packaged in the container.
[0047] Preferably, the guide duct has a length corresponding to the distance between the lower part of the dispensing member and the lower internal wall of the container, reduced by the largest diameter of the particles of the heterogeneous mixture, so as not to hinder the good suction of the particles. Distribution body
[0048] A dispensing member according to the invention is adapted to suck up a composition, in particular a cosmetic composition, in the form of a heterogeneous mixture and to dispense it in the form of a spray of fluid composition.
[0049] A dispensing member according to the invention may be represented by a spray pump or a trigger pump, preferably by a spray pump.
[0050] [Fig. 1] [Fig.2] Different models of spray pumps are illustrated in particular in Figures 1 and 2.
[0051] [Fig.3] [Fig.4] Different models of trigger pumps are illustrated in particular in Figures 3 and 4.
[0052] Such spray pumps or trigger pumps are well known to those skilled in the art and are notably marketed by the companies APTAR, ALBEA / SILGAN.
[0053] The dispensing member can be actuated mechanically or automatically, preferably mechanically, via activation of the push button for the spray pump or the trigger for the trigger pump.
[0054] Preferably, a distribution member according to the invention is an atmospheric distribution member.
[0055] A dispensing member according to the invention is preferably a spray pump.
[0056] As illustrated in [Fig.l], a spray pump type dispensing member comprises at least:
[0057] - a push button 3 (or “actuator” in English), comprising at least one nozzle spray 2 (or “insert” in English) which ensures the expulsion of the heterogeneous mixture in the form of a spray of fluid composition,
[0058] - a piston 4, the role of which is to transfer the movement of the push button to the tube stem,
[0059] - a stem tube 8 (or “stem”, “valve” or “poppet” in English), the die placement allows in particular to vary the volume of the room,
[0060] - a chamber or body 10 (or “housing” or “body” in English),
[0061] - a spring 9 (or "spring" in English), the role of which is to place the dis delivery to a rest position in the absence of activation of the push button,
[0062] - a sleeve or ring 5 (or “fixture” or “closure” in English), which has the role to ensure that the rosary 6 is held on the container, and in particular on the neck of the container,
[0063] - a rosary or turret 6 (or “housing cap”, “turret” or “chaplet” in English), which has the role of ensuring the maintenance of the suction elements formed by the piston, the rod tube and the chamber on the sleeve 5, and
[0064] - a seal 7 (or “gasket” in English), the role of which is in particular to ensure the seal between the string 6 and the container opening.
[0065] The combination of the piston, the rod tube, the chamber and the spring form the “pump motor”.
[0066] Optionally, a dispensing member according to the invention may further comprise:
[0067] - a cap or hood 1 (or “cap” or “overcap” in English), which has the role (i) of protect the push button, (ii) prevent any unwanted activation of the push button, (iii) avoid any contamination of the push button and in particular of residual fluid composition located at the spray nozzle and (iv) the drying of residual fluid composition located at the spray nozzle, and / or
[0068] - a sliding seal or cuff (or “sliding seal” or “cuff” in English), the role is in particular to ensure the seal between the chamber and the rod tube.
[0069] For obvious reasons, the cap is removable.
[0070] The dispensing member is advantageously fixed to the upper part of the container.
[0071] The dispensing member is advantageously fixed to the container using a screw-on or clip-on ring.
[0072] Preferably, the device is a bottle comprising a neck at the orifice and a dispensing member fixed to the neck by crimping or snap-fastening.
[0073] The dispensing member may be formed from any material, such as for example plastic, in particular polyethylene terephthalate (PET), polypropylene (PP) or polyethylene (PE), polyacetal (POM); stainless steel (in particular for the spring); elastomer (in particular for the seal), and in particular ethylene-vinyl acetate (EVA).
[0074] Preferably, the dispensing member comprises at least one outlet orifice.
[0075] According to a particular embodiment, the dispensing member comprises several outlet ports
[0076] Preferably, the dispensing member makes it possible to deliver a dose of fluid composition of between 50 μl and 750 μl, preferably between 75 μl and 500 μl, and better still between 100 μl and 250 μl.
[0077] By default, a device according to the invention is in a so-called "rest" position (or configuration), i.e. a position in which the device, and in particular the push button, is not (or no longer) activated. This rest position is notably possible thanks to the spring which by default (i.e. without activation of the device / push button) pushes back the rod tube, and therefore the push button, whereby the chamber is provided with its maximum volume. It is this rest configuration which is illustrated in [Fig.l].
[0078] The push button is movable along an axis x-x' shown in [Fig.l].
[0079] Activation of the push button will cause the push button to move downwards along the axis x-x' shown in [Fig.l]. Mechanically, this movement causes the piston and the rod tube to move downwards, causing the volume of the chamber to decrease, and thus forcing the heterogeneous mixture present in the chamber to rise. in the rod tube, then the piston and finally the spray nozzle. This sequence of movement of the elements of the dispensing member described above is called the "activation sequence".
[0080] Deactivation of the device / push button ensures a return to the rest position thanks to the spring. Indeed, the spring initiates a sequence of movement of the elements of the dispensing member reverse to the activation sequence described above. Thus, the release of the push button, under the effect of the spring, authorizes the upward movement of the rod tube along the axis x-x' shown in [Fig.l]. Mechanically, this movement will cause an increase in the volume of the chamber, and therefore a phenomenon of suction of a part of the heterogeneous mixture present in the guide conduit, or even in the container, whereby the chamber fills with heterogeneous mixture.
[0081] Simultaneously, this movement will drive the piston upwards, then the push button.
[0082] According to an advantageous embodiment, the dispensing member comprises at least one non-return system, making it possible to prevent a return (or release) of the heterogeneous mixture, or even the fluid composition, sucked into the dispensing member towards the guide duct, or even the container. The non-return system therefore has the objective of allowing the heterogeneous mixture to pass in a single direction, and therefore of preventing any return of the heterogeneous mixture, or even the fluid composition, towards the guide duct, or even the container.
[0083] Indeed, such releases are not desirable for at least the following reasons:
[0084] (a) they decrease the volume fraction of capsules in the heterogeneous mixture of the container, and alter the suspension of the particles, or even exacerbate the creaming of the particles which, mechanically, leads throughout the use of the device to an increasingly significant drift in the homogeneity of the sprayed fluid composition;
[0085] (b) when the particles consist in whole or in part of a less dense phase that the continuous phase of the heterogeneous mixture, they induce the formation of a supernatant, which exacerbates the aforementioned drawback (a); and
[0086] (c) they alter the visual appearance of the heterogeneous mixture present in the container, resulting in in particular by opacification of the continuous phase and the formation of a supernatant when the particles include oils and / or perfumes.
[0087] A non-return system can be represented by any system known to those skilled in the art, and can in particular be represented by a ball or a non-return valve.
[0088] In other words, this embodiment advantageously makes it possible to preserve the advantages of the invention, and in particular makes it possible to preserve the homogeneity of the fluid composition delivered throughout the use of the device and to preserve the aesthetic character of the heterogeneous mixture present in the container.
[0089] Optionally, a dispensing member according to the invention may further comprise a system for ensuring the delivery of a spray of fluid composition regardless of the position of the device, and in particular when the device is upside down. Such a device is designated by the expression “upside down dispensing” or “USD device”. Such a dispensing member according to the invention provided with a USD system is described in [Fig.5] below [Fig.5].
[0090] According to a particular embodiment, the distribution member further comprises at least one filtration member mounted in the distribution member or mounted at the interface between the guide conduit and the distribution member, the filtration member being configured to facilitate the transformation of the heterogeneous mixture into a fluid composition, the openings of the filtration member being of an extent less than the average diameter of the particles, advantageously less than a third of the average diameter of the particles. Other elements of the device
[0091] The dispensing member may advantageously comprise at least one hoop, which is positioned around the fixing sleeve.
[0092] By way of illustration, a dispensing member, or even a packaging and dispensing device according to the invention, is described in EP1878507, subject of course to adjusting the diameter of the guide conduit to the diameter of the particles so as to satisfy the ratio. Heterogeneous mixture / Fluid composition
[0093] The device according to the invention aims at the packaging of at least one heterogeneous mixture and its distribution (or delivery) in the form of a spray of fluid composition.
[0094] By “spray” in the sense of the present invention, we mean a fluid composition sprayed in the form of a spray or a mist (or “mist” in English).
[0095] Preferably, the heterogeneous mixture and the fluid composition are cosmetic compositions.
[0096] The transformation of the heterogeneous mixture into a fluid composition is made possible by the shears generated by the movement of the heterogeneous mixture through the constituent elements of the dispensing member, in particular through the chamber, the rod tube, the piston and / or the spray nozzle, and in particular the spray nozzle.
[0097] By "heterogeneous mixture" is meant, within the meaning of the present invention, a composition, in particular a cosmetic composition, comprising particles dispersed in a continuous phase, the particles being visible to the naked eye, and in particular having a diameter greater than 250 pm, and preferably greater than 500 pm. A heterogeneous mixture within the meaning of this may also be referred to as “macroscopic emulsions” or “macroscopic dispersions”.
[0098] Such particles can therefore be indifferently designated by the expression “macroscopic particles”.
[0099] Thus, a heterogeneous mixture according to the invention can be described as a macroscopically inhomogeneous mixture.
[0100] By "fluid composition" is meant a composition in the form of a heterogeneous mixture in which the particles have been broken and / or sheared, whereby a fluid composition is obtained in which the particles are no longer visible to the naked eye or felt when applied to the skin.
[0101] For the purposes of the present invention, the term "fluid" is intended to denote a composition which, at room temperature and atmospheric pressure, retains the ability to flow under its own weight and to be sprayed in the form of a spray or a mist. In other words, a fluid composition according to the invention is not in the form of a solid block, and in particular is not in the form of a solid gel.
[0102] By "sprayable" or "sprayable", within the meaning of the invention, is meant the capacity of a composition to be able to be sprayed in the form of fine droplets by means of a spray device according to the invention.
[0103] In other words, a fluid composition according to the invention is a vaporizable composition.
[0104] A heterogeneous mixture and a fluid composition according to the invention is not a gaseous composition.
[0105] The particles of the heterogeneous mixture are advantageously substantially spherical.
[0106] Preferably, the particles have a diameter of between 250 pm and 3000 pm, preferably between 500 pm and 2000 pm, better still between 750 pm and 1800 pm, very particularly between 1000 pm and 1600 pm, or even between 1200 pm and 1600 pm.
[0107] In a heterogeneous mixture according to the invention, the particles represent a volume fraction of between 50% and 70%, preferably between 55% and 65%, and better still between 57% and 63%, relative to the total volume of the heterogeneous mixture.
[0108] Without wishing to be bound by any theory, the inventors believe that the minimum volume fraction required in particles makes it possible to place the heterogeneous mixture according to the invention in a regime close to close packing (or "compact stacking"), which minimizes, or even makes negligible, the instabilities linked to the phenomena of creaming or sedimentation, in particular creaming, of the particles. We can therefore speak of "steric suspension" or "autonomous suspension", each macroscopic particle participating in the suspension of adjacent particles.
[0109] This observation is all the more advantageous since it is possible even when the continuous phase of the heterogeneous mixture is not suspensive with respect to the particles.
[0110] As is clear from Example 1 below, this observation is even more unexpected since a heterogeneous mixture according to the invention, despite a high particle volume fraction, remains compatible with its packaging and delivery with a spray device.
[0111] Preferably, a heterogeneous mixture and a fluid composition according to the invention comprise less than 10%, preferably less than 5%, in particular less than 2.5%, or even is free of alcohol(s), in particular ethanol, relative to the total weight of the heterogeneous mixture / of the fluid composition.
[0112] The term "alcohol" is understood to mean, in particular, a lower alkyl alcohol, with the exception of any alcohol(s) present as perfuming agent(s). A lower alkyl alcohol may be an aliphatic monoalcohol comprising from 2 to 6 carbon atoms. Such a lower alkyl alcohol may be ethanol.
[0113] The heterogeneous mixture / fluid composition is preferably free of any lower alkyl alcohol.
[0114] For the purposes of the present invention, "ethanol-free" or "alcohol-free" may also refer to a composition which is prepared by a preparation process preferably comprising no step of adding a lower alkyl alcohol and no step of mixing an alkyl alcohol with other ingredients.
[0115] However, it cannot be excluded that traces of lower alkyl alcohol, in particular traces of ethanol, may be present in some of the ingredients used in the preparation of the heterogeneous mixture of the invention, in particular in certain perfuming agents.
[0116] A heterogeneous mixture therefore comprises a continuous phase and a dispersed phase in the form of particles. Continuous phase
[0117] The continuous phase may be an aqueous phase or a fatty phase, and preferably the continuous phase is an aqueous phase.
[0118] The continuous phase of the heterogeneous mixture is liquid and may or may not be suspensive with respect to the particles, preferably the continuous phase of the heterogeneous mixture is liquid and not suspensive with respect to the particles.
[0119] Advantageously, the continuous phase is transparent so that the consumer can visualize the particles.
[0120] Preferably, the continuous phase of the heterogeneous mixture has a high shear viscosity, as measured at 25°C and under a shear stress of 100 s1, of less than or equal to 100 mPa.s, preferably less than or equal to 50 mPa.s., in par particular less than or equal to 25 mPa.s., and better less than or equal to 10 mPa.s.
[0121] Advantageously, the continuous phase, or even the fluid composition, has a flow threshold value less than or equal to 1 Pa, in particular less than or equal to 0.1 Pa, very particularly less than or equal to 0.01 Pa, or even has no flow threshold value.
[0122] Viscosity and yield value are measured by the following method: All measurements are carried out with a Ta instrument DHR10 rheometer equipped with a 40mm diameter spindle forming a 1° cone - the measuring gap being 29pm. The rheometer is controlled by Trios software. Measurements are carried out at 18°C, the temperature being controlled by a Peltier device. Rheological behavior is measured here using a shear sweep protocol (Flow sweep). Once the sample is in place and the temperature of 18°C is reached, the sample is left to rest for 60 seconds so that it can relax its constraints. It is then subjected to a logarithmic shear sweep between 0.01 and 500 s 1 with 5 points per decade. Viscosity (mPa.s) and stress (Pa) curves are plotted using Trios software.The analysis of the stress curve by the software applying the Herschel-Bulkley model allows to express the rheological behavior according to the following equation.
[0123] t- TQ + kÿ", sir> Tq
[0124] where r is the shear stress; is the yield threshold value; k is the consistency coefficient; T is the shear rate and tl is the yield index.
[0125] According to a particular embodiment, the continuous phase may further comprise at least one depolymerizing agent, in particular when the particles comprise at least one polyelectrolyte in the gelled state, and in particular at least one polyelectrolyte reactive to multivalent ions, as described below. This is in particular the case when the particles are in the form of capsules whose shell comprises at least one polyelectrolyte in the gelled state.
[0126] In the context of the present description, the term "depolymerizing agent" means a compound capable of weakening the polyelectrolyte in the gelled state to facilitate the formation of the fluid composition and prevent the appearance of a residual shell during application. A depolymerizing agent is notably described in WO2013 / 132082. According to one embodiment, the polyelectrolyte is chosen from polyelectrolytes reactive to calcium ions, such as a sodium alginate, and the depolymerizing agent is chosen from calcium chelating agents and salts capable of exchanging with calcium, such as EDTA. Particles
[0127] In particular, the particles have a diameter and mechanical resistance adjusted for (i) allow their movement through the guide duct without breaking them and (ii) ensure their ruptures / shears in and by the various constituent elements of the dispensing member, and thus ensure satisfactory transformation of the heterogeneous mixture into a fluid composition upon activation of the device, and therefore satisfactory delivery of the heterogeneous mixture in the form of a spray of fluid composition.
[0128] The particles may be single-phase or multi-phase.
[0129] According to a first embodiment, a particle according to the invention is a solid (or single-phase) particle, also indifferently designated by “bead”, “solid bead”, “balls” or “spheres”.
[0130] According to a second embodiment, a particle according to the invention is a core / shell type particle, also indifferently designated by “capsule”.
[0131] For the purposes of the present invention, the term "capsule" means a substantially spherical macroscopic element of the core / shell type, in which the shell completely encapsulates the core and the core comprises at least one drop of aqueous and / or fatty phase, preferably fatty phase.
[0132] The bark can be referred to indifferently by the terms “membrane” or “envelope”. Monodispersity
[0133] Preferably, the particles have a monodisperse distribution.
[0134] This monodispersity advantageously contributes to the aforementioned steric suspension and sprayability. Indeed, the inventors have observed that with a heterogeneous mixture comprising polydisperse particles, the smaller particles tend to occupy the spaces between the larger particles. This phenomenon leads to a local increase in particle density and therefore mechanically to creaming of the particles. These disadvantages impact the visual appearance of the heterogeneous mixture and the homogeneity during application, and even the sprayability.
[0135] By "monodisperse" is therefore meant, within the meaning of the present invention, a composition whose polydispersity in particle size, measured by the coefficient of variation Cv consisting of the ratio of the standard deviation to the average, is less than 10%, and in particular between 1% and 10%.
[0136] This ratio can be measured for example on the basis of the diameters measured on at least seven particles using the image processing software “Image J”, on the basis of a photograph of the particles taken from above with a digital camera.
[0137] Alternatively, the mass polydispersity of the particles can be calculated, based on at least fifty measurements of the mass of fifty particles made using a Mettler-Toledo type balance with an accuracy of 0.1 mg. Bark
[0138] The bark totally encapsulating the core is advantageously a gelled envelope and / or an envelope deriving from a complex coacervation reaction.
[0139] Preferably, the bark is an aqueous phase.
[0140] Advantageously, the bark is transparent. This transparency of the bark is particularly advantageous insofar as it gives a heterogeneous mixture according to the invention an impression according to which the cores of the capsules do not touch each other and are perfectly suspended in the continuous phase.
[0141] In the context of the present description, the term “gelled envelope” means an external phase surrounding the core of the capsules, and comprising at least one compound in the gelled state or in gel form.
[0142] The gelled envelope is generally formed by a monolayer of a homogeneous material.
[0143] Typically, the envelope is:
[0144] - a gelled envelope completely encapsulating the core, said gelled envelope comprising at least one polyelectrolyte in gelled state and / or at least one thermosensitive hydrophilic gelling agent; and / or
[0145] - an envelope that derives from a complex coacervation reaction between two oppositely charged polymers capable of coacerbating.
[0146] Advantageously, the bark has a homogeneous thickness. By "homogeneous thickness", for the purposes of the present invention, is meant capsules whose bark thickness varies according to a standard deviation of less than or equal to 20%, preferably less than or equal to 10%.
[0147] Preferably, the shell of the capsules has a thickness of between 50 microns and 1200 microns, preferably between 100 microns and 1000 microns, better still between 200 microns and 750 microns, particularly between 300 microns and 500 microns, or even between 100 microns and 200 microns.
[0148] In particular, the shell of the capsules has a thickness greater than 80 microns, preferably greater than 120 microns, and very particularly greater than 170 microns.
[0149] The presence of a shell of minimal thickness advantageously makes it possible to adjust, in particular to reduce, the content of polyelectrolyte(s) in the gelled state, thermosensitive hydrophilic gelling agent(s) and / or oppositely charged polymers capable of coacerbating. This makes it possible to obtain heterogeneous mixtures with optimized properties in terms of sprayability and sensoriality, while guaranteeing satisfactory mechanical strength of the capsules in the container of the device.
[0150] When transparent, the presence of a bark of minimal thickness is further advantageous in that it also contributes to the aforementioned visual impression. according to which the cores of the capsules do not touch each other and are perfectly suspended in the continuous phase of the heterogeneous mixture.
[0151] Preferably, the shell of the capsules has a thickness different from the values between 80 microns and 200 microns, preferably between 100 microns and 180 microns, better between 120 microns and 170 microns.
[0152] Preferably, the shell of the capsules is a gelled envelope comprising a gel containing water and at least one polyelectrolyte advantageously chosen from proteins, natural polysaccharides and polyelectrolytes reactive to multivalent ions, and mixtures thereof.
[0153] By "polyvalent ion-reactive polyelectrolyte" is meant, within the meaning of the present invention, a polyelectrolyte capable of passing from a liquid state in an aqueous solution to a gelled state under the effect of contact with a gelling solution containing multivalent ions such as ions of an alkaline-earth metal chosen for example from calcium ions, barium ions, magnesium ions.
[0154] In the liquid state, the individual polyelectrolyte chains are substantially free to flow relative to each other. An aqueous solution of 2% by mass of polyelectrolyte then exhibits purely viscous behavior at the shear gradients characteristic of the shaping process. The viscosity of this solution at zero shear is between 50 mPa.s and 10,000 mPa.s, advantageously between 3,000 mPa.s and 7,000 mPa.s. This viscosity at the shear gradients characteristic of the flows involved during the manufacture of the capsules is, for example, measured using a stress or strain rheometer imposed at the manufacturing temperature, 25°C for example. For the measurements, a cone-plane geometry with a diameter of 10 to 50 mm and a cone angle of 1° maximum will be used.
[0155] The individual polyelectrolyte chains in the liquid state advantageously have a molar mass greater than 65000 g / mol.
[0156] In the gelled state, the individual polyelectrolyte chains form, together with the multivalent ions, a coherent three-dimensional network which retains the liquid core and prevents its flow. The individual chains are held relative to each other and cannot flow freely relative to each other. In this state, the viscosity of the formed gel is infinite.
[0157] The three-dimensional polyelectrolyte gel contained in the envelope traps water and the surfactant when present.
[0158] Advantageously, the polyelectrolyte is chosen from polysaccharides, synthetic polyelectrolytes based on acrylates (sodium, lithium, potassium or ammonium polyacrylate, or polyacrylamide), synthetic polyelectrolytes based on sulfonates (sodium poly(styrene sulfonate), for example). More particularly Typically, the polyelectrolyte is chosen from alkaline earth alginates, such as sodium alginate or potassium alginate, gellan or pectin.
[0159] Preferably, the polyelectrolyte is selected from a protein such as collagen; a natural polysaccharide such as heparan sulfate; a polyelectrolyte reactive to multivalent ions, in particular a polysaccharide reactive to multivalent ions such as alginate, pectin, in particular Low Methoxyl pectin, carrageenan, in particular kappa and iota-carrageenan, gellan gum, diutan gum, fur-cellaran, or one of their derivatives, and their mixtures; and preferably a polyelectrolyte reactive to multivalent ions.
[0160] According to one embodiment of the invention, the polyelectrolyte is a sodium alginate.
[0161] Alginates are produced from brown algae called "laminaria", designated by the English term "sea weed".
[0162] By “heat-sensitive gelling agent” is meant a gelling agent which reacts to heat, and in particular is a gelling agent which is solid at room temperature and liquid at a temperature above 40°C, preferably above 50°C.
[0163] Preferably, the thermosensitive hydrophilic gelling agent is chosen from agar, kappa carrageenan, konjac, gelatin, and mixtures thereof.
[0164] Preferably, the thermosensitive hydrophilic gelling agent is not a hydrophilic gelling agent capable of gelling in the presence of at least one salt.
[0165] The oppositely charged, coacerbated polymers comprise at least one first cationic polymer and at least one second anionic polymer.
[0166] In view of the above, these oppositely charged polymers capable of coacerving are advantageously hydrophilic.
[0167] According to a particular embodiment, the anionic polymer is hydrophilic and the cationic polymer is lipophilic, or vice versa. This embodiment is notably illustrated in WO2012120043.
[0168] The oppositely charged polymers capable of coacerbating may be chosen from the pairs “gum arabic (or acacia gum) / gelatin”, “albumin / alginate”, “gelatin / alginate” or “carbomere / amodimethicone”.
[0169] Of course, the person skilled in the art will take care to choose the polyelectrolyte(s) and / or the thermosensitive hydrophilic gelling agent(s) and / or the oppositely charged polymers capable of coacerbating and / or their quantity in such a way that the advantageous properties of the invention are not or are not substantially altered by the envisaged addition. These adjustments fall within the general knowledge of the person skilled in the art.
[0170] A composition according to the invention may advantageously comprise between 0.1% and 5%, preferably between 0.15% and 3%, and better still between 0.2% and 1%, by weight of poly- electrolyte(s) and / or thermosensitive hydrophilic gelling agent(s) and / or oppositely charged polymers capable of coacerbating, relative to the total weight of the bark.
[0171] Advantageously, the bark, in particular when represented by a gelled envelope as described above, may also comprise at least one surfactant.
[0172] The surfactant is advantageously an anionic surfactant, a non-nionic surfactant, a cationic surfactant, or a mixture thereof. The molecular mass of the surfactant is advantageously between 150 g / mol and 10000 g / mol, preferably between 250 g / mol and 1500 g / mol.
[0173] In the case where the surfactant is an anionic surfactant, it is for example chosen from alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkali metal alkyl phosphates, dialkyl sulfosuccinates, alkaline earth metal salts of saturated or unsaturated fatty acids, or a mixture thereof. These surfactants advantageously have at least one hydrophobic hydrocarbon chain having a number of carbons greater than 5, or even 10, and at least one hydrophilic anionic group, such as a sulfate, a sulfonate or a carboxylate linked to one end of the hydrophobic chain.
[0174] In the case where the surfactant is a cationic surfactant, it is for example chosen from alkylpyridium or alkylammonium halide salts such as n-ethyldodecylammonium chloride or bromide, cetylammonium chloride or bromide (CTAB), or a mixture thereof. These surfactants advantageously have at least one hydrophobic hydrocarbon chain having a number of carbon atoms greater than 5, or even 10, and at least one hydrophilic cationic group, such as a quaternary ammonium cation.
[0175] In the case where the surfactant is a nonionic surfactant, it is for example chosen from polyoxyethylenated and / or polyoxypropylenated derivatives of fatty alcohols, fatty acids, alkylphenols, alkylpolyglycerols, arylphenols, alkylglucosides, polysorbates, cocamides, or a mixture thereof.
[0176] According to one embodiment of the invention, the surfactant is sodium lauryl sulfate (SLS or SDS) or sodium lauryl glutamate.
[0177] The mass content of surfactant(s) in the bark is advantageously greater than 0.001%, preferably greater than 0.1%, in particular between 0.001% and 1%, and better still between 0.01% and 0.5%, relative to the total weight of the bark. Heart
[0178] The capsules comprise a liquid or at least partly gelled or at least partly thixotropic core, and preferably liquid.
[0179] According to a first embodiment, the capsule is a so-called “simple” capsule, meaning that the core is monophasic, that is to say made up of a single phase, this phase being placed in whole or in part in contact with the bark. A simple capsule is for example a capsule as described in WO2010 / 063937.
[0180] According to a first variant, a simple capsule comprises two distinct phases, namely a first phase forming the core and a second phase in the gelled state forming the shell and surrounding the first phase. This first variant of a simple capsule is illustrated in [Fig.6] [Fig.6] (18: capsule; 14: shell; 12: fatty phase).
[0181] According to a second variant, a simple capsule comprises two distinct phases, namely a first phase forming the core in the form of several drops and a second phase in the gelled state forming the shell and surrounding all the drops of the first phase. This second variant of a simple capsule is illustrated in [Fig.7] [Fig.7] (18: capsule; 14: shell; 12: fatty phase).
[0182] According to another embodiment, the capsule is a so-called “complex” capsule, meaning that the core comprises an intermediate phase, the intermediate phase being placed in whole or in part in contact with the shell, and at least one drop of first phase placed in the intermediate phase.
[0183] According to a first variant, a complex capsule is such that the core comprises a single intermediate drop of an intermediate phase, the intermediate phase being placed in whole or in part in contact with the bark, and at least one internal drop of a first phase arranged in the intermediate phase. This second variant of a simple capsule is illustrated in [Fig.8][Fig.8] (18: capsule; 14: bark; 12: fatty phase; 16: internal phase).
[0184] According to a second variant (not illustrated), a complex capsule is such that the core comprises several intermediate drops of intermediate phase, the intermediate phase being placed in whole or in part in contact with the shell, and each intermediate drop comprises at least one internal drop of an internal phase arranged in each intermediate drop.
[0185] For obvious reasons, the shell-forming phase and the core-forming phase are immiscible.
[0186] Advantageously, the phase forming the core of the capsules and the continuous phase of the heterogeneous mixture are immiscible.
[0187] By "immiscible" or "non-miscible" within the meaning of the present invention, it is meant that the solubility of a first phase in a second phase is advantageously less than 5% by mass, and vice versa.
[0188] For obvious reasons, in complex capsules, the intermediate phase and the internal phase are immiscible.
[0189] Thus, according to a first variant of complex capsules, the intermediate phase is a fatty phase and the internal phase is an aqueous phase. According to a second variant, the intermediate phase is a first fatty phase and the internal phase is a second fatty phase immiscible with the first fatty phase. Pairs of immiscible oils are described in particular in FR3063893.
[0190] The drops of internal phase of complex capsules are advantageously macroscopic, and advantageously have a size (or diameter) greater than 150 pm, and preferably greater than or equal to 200 pm, but in all cases necessarily less than the diameter of the core of the capsules.
[0191] Determining the size of the particles falls within the general knowledge of those skilled in the art, and can in particular be measured by a method using the “Image J” image processing software.
[0192] The minimum volume of the core is advantageously between 5% and 80%, preferably between 10% and 70%, better between 20% and 60%, and very particularly between 30% and 50%, relative to the total volume of the capsule.
[0193] In particular, the inventors have observed that the nature and / or content of polyelectrolyte(s) and / or thermosensitive hydrophilic gelling agent(s) forming the shell of the capsules makes it possible to modulate the mechanical resistance (or compressive strength), and therefore the deformability, of the capsules, thus making it possible to further increase the volume fraction of the capsules relative to the total volume of the composition.
[0194] Thus, and as indicated previously, the capsules of the heterogeneous mixture advantageously comprise a Ri / Rc ratio of between 0.5 and 0.8, preferably between 0.6 and 0.8, and better still between 0.6 and 0.7, in which:
[0195] - Ri corresponds to the radius of the core of the capsules; and
[0196] - Rc corresponds to the radius of the capsule, namely resulting from the sum of the radius of the core of the capsules and the thickness of the bark.
[0197] In cases where the capsules are complex capsules, Rc also includes the radius of the internal phase internal particles.
[0198] Preferably, the capsules according to the invention comprise a ratio (e) / Ri of between 0.2 and 1, preferably between 0.3 and 0.8, and very particularly between 0.4 and 0.7, in which:
[0199] - (e) corresponds to the thickness of the bark; and
[0200] - Ri corresponds to the radius of the core of the capsules.
[0201] These values of ratio Ri / Rc or ratio (e) / Ri correspond to a compromise satisfactory and not obvious between mechanical resistance, sprayability and sensoriality.
[0202] According to a particular embodiment, a heterogeneous mixture according to the invention may comprise between 45% and 85%, preferably between 45% and 70%, better still between 50% and 65%, very particularly between 55% and 60%, by weight of particles relative to the total weight of the heterogeneous mixture.
[0203] Advantageously, a heterogeneous mixture in which the particles are in the form of capsules may comprise between 5% and 40%, preferably between 10% and 30%, and better still between 15% and 20%, by weight of the constituent phase of the core of the capsules relative to the total weight of the heterogeneous mixture. Active agents
[0204] Preferably, the particles comprise at least one fatty phase comprising at least one active agent, in particular at least one perfuming agent.
[0205] When the particles are in the form of capsules, the core of the capsules comprises at least one active agent.
[0206] An active agent is in particular chosen from a biological active agent and / or cosmetic active agent, preferably chosen from moisturizing agents, healing agents, depigmenting agents, UV filters, desquamating agents, antioxidant agents, active agents stimulating the synthesis of dermal and / or epidermal macromolecular agents, dermo-contracting agents, antiperspirant agents, soothing agents, anti-aging agents, perfuming agents, anticoagulants, anti-thrombogenic agents, anti-mitotic agents, anti-proliferation, anti-adhesion, anti-migration agents, cell adhesion promoters, growth factors, antiparasitic molecules, anti-inflammatories, angiogenic agents, angiogenesis inhibitors, vitamins, hormones, proteins, antifungals, antimicrobial molecules, antiseptics or antibiotics, and mixtures thereof. Such assets are described in particular in FR 1 558 849.Preferably, the active agent is chosen from perfuming agents. Fragrances
[0207] A perfuming agent according to the invention is preferably a lipophilic agent, that is to say soluble or dispersible in an organic solvent, in particular an oil.
[0208] A “perfuming agent”, also indifferently designated by “perfume”, “perfume juice” or “perfume concentrate”, within the meaning of the present invention, may be chosen from compounds having the INCI name “Perfume” or “Fragrance”. Thus, within the meaning of the present invention, the term “perfume” does not designate a mixture comprising a perfume concentrate and alcohol.
[0209] The perfuming agents that can be used according to the invention are ingredients commonly used in perfumery. Their nature does not require a more detailed description here, which cannot be exhaustive, since a person skilled in the art is able to choose them based on his general knowledge and according to the desired olfactory effect. These perfuming agents belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, nitrogenous or sulfurous heterocyclic compounds, as well as essential oils of natural or synthetic origin. Many of these ingredients are also listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in more recent scientific and patent literature relating to the art of perfumery.
[0210] For example, a perfuming agent is a compound or mixture of compounds that is at least partially volatile at room temperature and whose odor can be detected. A perfuming agent composed of essential oils is generally diluted in order to express its full olfactory potential, that is to say a perception that evolves during the day after application to the surface to be treated, thanks to the presence of several odorous organic compounds having different volatilities from one another. The development of a perfume includes a step of combining several perfuming raw materials to give a top note, a heart note and a base note to the perfuming composition.
[0211] A perfuming agent may be prepared from natural or synthetic organic perfumed materials.
[0212] Examples of natural fragrance materials are extracts of flowers, leaf stems, fruits, barks, roots, woods, herbs, grasses, resins, balsams, and mixtures thereof.
[0213] These plant-based fragrance materials may be essential oils, such as bergamot, rose, lavender, sandalwood, cardamom, sage, chamomile, clove, lemon balm, mint, cinnamon leaf, juniper, vetiver, frankincense, galbanum, labdanum, and mixtures thereof.
[0214] Examples of synthetically derived fragrance materials are hedione, ethylene brassilate, habanolide, benzyl acetate, benzyl benzoate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, citronellyl acetate, citronellyl formate, geranyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate. , benzyl formate, ethyl methyl phenyl glycinate alkylcyclohexyl propionate, styralyl propionate and benzyl salicylate, benzyl ethyl ether, linear alkanals of 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, ionones such as alpha-isomethylionone, methylcedrylketone, anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol, terpineol, terpenes, and mixtures thereof.
[0215] These compounds often occur as a mixture of two or more of these odorous substances.
[0216] The characteristics of a heterogeneous mixture according to the invention, in particular those of the particles, are such that they allow high contents of agent(s) perfuming agent(s), without prejudice to the kinetic stability of the heterogeneous mixture and in particular without prejudice to the suspension of the particles in the continuous phase.
[0217] Thus, the heterogeneous mixture can advantageously comprise from 2.5% to 40%, preferably from 5% to 30%, better still from 10% to 20%, by weight of active agent(s), in particular perfuming agent(s), relative to the total weight of the heterogeneous mixture.
[0218] Also, the heterogeneous mixture may advantageously comprise from 5% to 90%, preferably from 10% to 70%, in particular from 20% to 60%, or even from 30% to 50%, by weight of active agent(s), in particular perfuming agent(s), relative to the total weight of the particles, in particular when in the form of solid beads.
[0219] Also, when the particles are in the form of capsules, the heterogeneous mixture may advantageously comprise from 5% to 100%, preferably from 10% to 90%, in particular from 25% to 80%, or even from 50% to 70%, by weight of active agent(s), in particular perfuming agent(s), relative to the total weight of the core of the particles. Aqueous phase
[0220] According to the invention, an aqueous phase comprises at least water. In addition to distilled or deionized water, water suitable for the invention may also be natural spring water or floral water.
[0221] The continuous aqueous phase can serve as a dispersion medium for the particles and when the particles are in the form of capsules, ensure permanent hydration of their shell.
[0222] The continuous aqueous phase may comprise a physiologically acceptable medium, generally adapted to the nature of the support on which the heterogeneous mixture is to be applied, as well as to the aspect in which the heterogeneous mixture is to be packaged.
[0223] According to one embodiment, the physiologically acceptable medium is represented directly by the continuous phase of the heterogeneous mixture.
[0224] In the context of the invention, and unless otherwise stated, the term "physiologically acceptable medium" means a medium suitable for cosmetic applications, and particularly suitable for the application of a composition of the invention to a keratin material, particularly the skin and / or the hair, and more particularly the skin.
[0225] According to a particular embodiment, the aqueous phase may comprise at least water and optionally at least one hydrophilic gelling agent, and thus be described as an “aqueous gel”.
[0226] By “hydrophilic” is meant a gelling agent that is soluble or dispersible in water.
[0227] A hydrophilic gelling agent makes it possible in particular to modulate the fluidity of the aqueous phase, and therefore the texture and / or the sensoriality of the composition comprising it.
[0228] Preferably, the mass percentage of water in the aqueous phase is at least 70%, in particular from 70% to 98%, preferably from 80% to 95%, relative to the total mass of the aqueous phase.
[0229] Preferably, the continuous aqueous phase represents a volume fraction of less than 50%, preferably between 15% and 49%, and in particular between 30% and 40%, relative to the total volume of the composition. Hydrophilic gelling agents
[0230] As additional hydrophilic gelling agent, mention may be made of:
[0231] - natural gelling agents, in particular chosen from algae extracts, plant exudates, seed extracts, exudates of microorganisms, such as alcasealan (INCI: Alcaligenes Polysaccharides), and other natural agents, in particular hyaluronic acid,
[0232] - semi-synthetic gelling agents, in particular chosen from derivatives of cellulose and modified starches,
[0233] - synthetic gelling agents, in particular chosen from homopolymers of (meth)acrylic acid or one of their esters, copolymers of (meth)acrylic acid or one of their esters, copolymers of AMPS (2-acrylamido-2-methylpropane sulfonic acid), associative polymers, for example those described in FR2999921,
[0234] - other gelling agents, in particular chosen from clays, silicas such as those marketed under the names Aérosil® 90 / 130 / 150 / 200 / 300 / 380), and
[0235] - their mixtures.
[0236] These hydrophilic gelling agents are described in more detail in FR3041251.
[0237] In particular, the hydrophilic gelling agents are preferably chosen from the group consisting of polysaccharides, galactomannans, polysaccharides, glycosaminoglycans, polyols, and mixtures thereof.
[0238] Advantageously, the hydrophilic gelling agents are chosen from the group consisting of xanthan, carrageenan, carob, guar, gellan, hyaluronic acid, cellulose derivatives, and mixtures thereof.
[0239] Of course, a person skilled in the art will take care to choose the possible hydrophilic gelling agents and / or their quantity in such a way that the advantageous properties of the invention are not or are not substantially altered by the envisaged addition. These adjustments fall within the general knowledge of a person skilled in the art.
[0240] Preferably, the aqueous phase does not comprise carbomer (or acrylic polymer).
[0241] Preferably, the aqueous phase does not comprise a base, in particular alkali metal hydroxide, and in particular NaOH (or sodium hydroxide). Fat phase
[0242] A fatty phase may comprise at least one oil and optionally at least a lipophilic gelling agent. Oils
[0243] The term "oil" means a fatty substance which is liquid at room temperature and atmospheric pressure. Examples of oils which can be used in a dispersion of the invention include:
[0244] - hydrocarbon oils of vegetable origin, such as jojoba oil hy drogenated, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil;
[0245] - hydrocarbon oils of animal origin, such as perhydrosqualene and squalane;
[0246] - synthetic esters and ethers, in particular of fatty acids, such as oils of formulas R1COOR2 and R1OR2 in which RI represents the residue of a C8 to C29 fatty acid, and R2 represents a branched or unbranched C3 to C30 hydrocarbon chain, such as for example Purcellin oil, isononyl isononanoate, isodecyl neopentanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, fatty alcohol heptanoates, octanoates, decanoates; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetrabehenate (DUB PTB) or pentaerythrityl tetraisostearate (Prisorine 3631);
[0247] - linear or branched hydrocarbons, of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam oil;
[0248] - silicone oils, such as polymethylsiloxanes (PDMS) volatile or not with a linear or cyclic silicone chain, liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane and cyclopentasiloxane; polydimethylsiloxanes (or dimethicones) comprising alkyl, alkoxy or phenyl groups, pendant or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldimethicones, diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes;
[0249] - fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), or octyldodecanol;
[0250] - partially hydrocarbon and / or silicone fluorinated oils such as those described in document JP-A-2-295912;
[0251] - and mixtures thereof.
[0252] According to another preferred embodiment, the fatty phase does not comprise silicone oil, and preferably does not comprise polydimethylsiloxane (PDMS).
[0253] Of course, the person skilled in the art will take care to choose the possible oils and / or their quantity in such a way that the advantageous properties of the invention are not or are not substantially altered by the envisaged addition. These adjustments fall within the general knowledge of the person skilled in the art. Lipophilic gelling agents
[0254] A lipophilic gelling agent, i.e. soluble or dispersible in a fatty phase, may be chosen from organic or mineral, polymeric or molecular gelling agents; fatty substances which are solid at room temperature and pressure, in particular chosen from waxes, pasty fatty substances, butters; and mixtures thereof, and preferably from polymeric gelling agents. Such lipophilic gelling agents are described in particular in WO2019002308.
[0255] Among the lipophilic gelling agents that can be used in the present invention, mention may be made of dextrin and fatty acid esters, such as dextrin palmitates. Among the dextrin and fatty acid esters, mention may be made, for example, of dextrin palmitates, dextrin myristates, dextrin palmitates / ethylhexanoates and mixtures thereof. Mention may in particular be made of the dextrin and fatty acid esters marketed under the names Rheopearl® KL2 (INCI name: dextrin palmitate), Rheopearl® TT2 (INCI name: dextrin palmitate ethylhexanoate), and Rheopearl® MKL2 (INCI name: dextrin myristate) by the company Miyoshi Europe, also dextrin palmitate marketed by The Innovation Company.
[0256] Mention may also be made of THIXCIN® R from Elementis Specialties (INCI: Trihy-droxystearin), OILKEMIA™ 5S polymer from Lubrizol (INCI: Caprylic / Capric Triglyceride (and) Polyurethane-79), Oilkemia™ 5S CC polymer, (INCI: INCI: Caprylic / Capric Triglyceride (and) Hydrogenated Poly(C6-20 Olefin) (and) HDI / Trimethylol Hexyllactone Crosspolymer), Estogel M from PolymerExpert (INCI: CASTOR OIL / IPDI COPOLYMER & CAPRYLIC / CAPRIC TRIGLYCERIDE), TEMC30 (INCI: Caprylic / Capric Triglyceride (and) Castor Oil / IPDI Copolymer), THydrogenated Castor Oil / Sebacic Acid Copolymer and its derivatives, notably marketed respectively under the names Estogel Green (or Estogel G) and Estogel Green 40 by PolymerExpert, and their blends.
[0257] Advantageously, a lipophilic gelling agent is a heat-sensitive gelling agent.
[0258] According to the invention, a heterogeneous mixture according to the invention may comprise from 0.5% to 30%, preferably from 1% to 25%, in particular from 1.5% to 20%, better still from 2% to 15%, and in particular from 5% to 12%, by weight of lipophilic gelling agent(s) relative to the total weight of the fatty phase comprising it.
[0259] Of course, a person skilled in the art will take care to choose the possible lipophilic gelling agent(s) and / or their quantity in such a way that the advantageous properties of the invention are not or are not substantially altered by the envisaged addition. These adjustments fall within the general knowledge of a person skilled in the art. Additional compound(s)
[0260] According to the invention, a heterogeneous mixture according to the invention, in particular the continuous phase and / or the dispersed phase, may further comprise at least one additional compound different from the oils, hydrophilic and lipophilic gelling agents, and active agents mentioned above.
[0261] The heterogeneous mixture according to the invention may thus also comprise powders; reflective particles, in particular glitter, in particular as defined in FR3082731; coloring agents, in particular chosen from water-soluble or non-water-soluble, fat-soluble or non-fatty, organic or inorganic coloring agents, materials with an optical effect, liquid crystals, and mixtures thereof; fillers, in particular as described in FR1755907; emulsifying and / or non-emulsifying silicone elastomers, in particular as described in EP2353577; “soft focus” fillers; texturizing agents, in particular polyethylene glycols (eg sold under the name Carbowax) or glycerin; preservatives; humectants; stabilizers; chelating agents; emollients; pH modifying agents, osmotic force modifying agents and / or refractive index modifiers, etc., or any usual cosmetic additive; and their mixtures.
[0262] In particular, the continuous phase of the heterogeneous mixture may further comprise a pH corrector and / or a buffer, in particular so as to prevent any variation in pH when the particles comprise a perfuming agent.
[0263] Of course, a person skilled in the art will take care to choose the possible additional compound(s) and / or their quantity in such a way that the advantageous properties of the invention are not or are not substantially altered by the envisaged addition. These adjustments fall within the general knowledge of a person skilled in the art. Specific embodiments
[0264] A composition according to the invention may comprise a single population of particles among the different variants of solid beads, simple capsules and complex capsules described previously.
[0265] According to a first embodiment variant, a heterogeneous mixture according to the invention comprises at least two different populations of capsules chosen from the different variants of simple and complex capsules described previously.
[0266] According to another embodiment variant, a heterogeneous mixture according to the invention comprises at least one population of particles in the form of solid beads and at least one population of particles in the form of capsules chosen from the different variants of simple and complex capsules described previously.
[0267] All these variants are advantageous in that they allow in particular access to heterogeneous mixtures comprising macroscopic elements of different densities and / or sizes and / or mechanical resistance, thus being able to lead to different visual / aesthetic effects and / or cosmetic effects and / or sensory effects. Preparation process
[0268] The preparation of a heterogeneous mixture according to the invention, and in particular of the particles, falls within the general knowledge of those skilled in the art.
[0269] By way of illustration, solid beads can be obtained using any method known to those skilled in the art, for example those described in BRPI1001438 or FR2645439.
[0270] By way of illustration, capsules may be obtained by means of non-micro / milli-fluidic manufacturing processes, such as for example by Rayneri agitation, or by means of micro / milli-fluidic manufacturing processes, for example those described in WO2010063937, FR2964017, WO2012089820, WO2021037999, WO2022106361, EP2292752, EP0525731, EP1020177, EP1025842.
[0271] Preferably, the solid beads and the capsules can in particular be obtained with the BUCHI Encapsulators B-390 microfluidic device, as described in example 1.
[0272] A method for preparing particles in the form of capsules, or even a heterogeneous mixture, is described in WO2022106361.
[0273] Optionally, a method for preparing particles in the form of capsules, or even a heterogeneous mixture, as described in WO2022106361 can be coupled to the gelling device described in WO2023099530 and / or to the gelling extinction unit WO2023099536. Uses
[0274] A heterogeneous mixture according to the invention is oral or topical, preferably topical.
[0275] The device and the heterogeneous mixture according to the invention can in particular be used in the cosmetic, pharmaceutical, food, nutraceutical, and preferably cosmetic fields.
[0276] Preferably, a heterogeneous mixture according to the invention can be used, following activation of the device according to the invention, as a fluid composition to be sprayed, in particular a cosmetic composition.
[0277] A heterogeneous mixture according to the invention may be dedicated to the care and / or makeup and / or perfuming of a keratin material. The cosmetic destination of the heterogeneous mixture will be dictated in particular by the nature and / or the quantity of active agent(s).
[0278] Preferably, when the particles comprise at least one perfuming agent, a heterogeneous mixture according to the invention may be a perfuming composition and in particular may be an eau de toilette, an eau de Cologne, a perfume extract, a spirit of perfume, a veil of perfume, or an eau de parfum. Thus, when the particles comprise at least one perfuming agent, a heterogeneous mixture according to the invention is advantageously a perfuming composition, in particular an alcohol-free perfuming composition, in liquid form comprising macroscopic particles intended to perfume an individual after spraying or application to the skin, hair and / or clothing. Such a product is not rinsed after application.
[0279] A perfume composition will thus be distinguished from a scented composition. Indeed, a cosmetic composition can be perfumed without being perfumed.
[0280] Preferably, a heterogeneous mixture according to the invention is not dedicated to the care and / or makeup of a keratin material.
[0281] The present invention also relates to a method of non-therapeutic cosmetic treatment, in particular care and / or makeup and / or perfuming, and preferably perfuming, of a keratin material, or in the case of perfuming a garment, comprising at least one step of applying to the keratin material and / or said garment at least one heterogeneous mixture by means of activating a device according to the invention.
[0282] The present invention also relates to the use of at least one composition according to the invention, for the care and / or makeup and / or perfuming, and preferably perfuming, of a keratin material, or in the case of perfuming a garment, by means of the activation of a device according to the invention.
[0283] Throughout the description, the expression "comprising a" must be understood as being synonymous with "comprising at least one", unless otherwise specified. The expressions "between ... and ...", "from ... to ..." and "ranging from ... to ..." must be understood inclusively, unless otherwise specified.
[0284] EXAMPLE: Comparative study
[0285] 1.1. Preparation of particles in the form of capsules
[0286] Table 1 below indicates the composition of single capsules comprising a gelled shell based on gelled alginate (OF) completely encapsulating a core composed of a perfumed fatty phase (IF).
[0287] Table 1: Trade name INCI %mass %mass / e / phase capsule OF Eau Water 98.36 80.14 Protanal LF 200S Sodium alginate 1.5 1.22 SDS Sodium lauryl sulfate 0.14 0.11 IF Parfum Fragrance 90 16.67 DUB MCT55 / 45 MB Caprylic / Capric triglyceride 10 1.85 Total 100.00%
[0288] A. Preparation of the first liquid solution (IF)
[0289] The perfume and the oil were mixed, and stirring was continued until homogenized.
[0290] B. Preparation of the second liquid solution (OF)
[0291] SDS and sodium alginate were added to water under magnetic stirring. The solution was kept stirring for 24 hours to ensure that the alginate was completely dissolved and the solution was homogeneous.
[0292] C. Preparation of the gelling solution
[0293] 200 g of calcium chloride were dissolved in 1000 g of water.
[0294] D. Obtaining the capsules
[0295] The capsule manufacturing process is based on the concentric co-extrusion of two solutions (i.e. IF in OF) using the BUCHI Encap-sulators B-390 microfluidic device and nozzles with diameters of 450, 750 and 1000 pm. The parameters applied to obtain capsules of 800, 1400 and 2000 microns are described in Table 2 below. Those skilled in the art will know how to adjust the BUCHI frequency to prevent / avoid any coalescence phenomenon when the drops fall into the air.
[0296] Table 2: Capsule pack 1 2 3 BUCHI nozzle size (in pm) 450 750 1000 Flow rate (in ml / min) 12 OF: 9.78 IF: 2.22 21 OF: 17.11 IF: 3.89 32 OF: 26.07 IF: 5.93 Optimal frequency range (in Hz) 800 100 70 Capsule diameters 800 1400 2000 obtained (in pm)
[0297] The capsules obtained are monodisperse, namely that the polydispersity in size of the capsules, measured by the coefficient of variation Cv consisting of the ratio of the standard deviation to the mean, is less than 10%. 1.2. Preparation of the heterogeneous mixture
[0298] The capsules of batches 1 to 3 obtained in example 1.1 are collected, washed with osmosis water, then mixed with the composition described in table 3 below which is dedicated to forming the continuous aqueous phase of the different heterogeneous mixtures.
[0299] Table 3: Continuous non-suspensive aqueous phase Raw materials % by mass Water QSP* Glycerol 19.0 Propanediol (Zemea, Dupont Tate) 7.0 Microcare PE (Phenoxyethanol) 0.89 Microcare emollient PTG (Pentylene Glycol) 2.22 Total 100
[0300] * Sufficient Quantity For Preparation of the continuous aqueous phase
[0301] The preservatives were first dispersed in the glycols (glycerol and pro-panediol) by stirring using a paddle stirrer. Finally, water was added and the whole was mixed using a paddle stirrer for 1 hour.
[0302] The aqueous phase obtained is transparent and has a viscosity of less than 15 mPa.s and is not suspensive with respect to the capsules of batches 1, 2 and 3.
[0303] For each batch of capsules, 4 heterogeneous mixtures are prepared which differ in the volume fraction of capsules relative to the total volume of the heterogeneous mixture, as described in Table 4 below.
[0304] 1.3. Conditioning of heterogeneous mixtures in spray devices
[0305] The heterogeneous mixtures obtained in example 1.2 are packaged at different volume fractions in devices having a capacity of 50 ml and comprising a guide conduit (or dip tube) with an internal diameter of 1.66 mm and a spray pump type dispensing member as illustrated in [Fig.l].
[0306] We thus obtain 12 devices D1.1 to D-3.4 as described in table 4 below. below.
[0307] Table 4: Capsule batch 1 2 3 Device ref. Dl. 1 Dl .2 Dl .3 Dl .4 D-2. 1 D-2. 2 D-2. 3 D-2. 4 D-3. 1 D-3. 2 D-3. 3 D-3. 4 Ratio “internal diameter of the guide duct / particle diameter” 2.07 1.18 0.83 Volume fraction of capsules in relation to the total volume of the heterogeneous mixture 35 45 65 80 35 45 65 80 35 45 65 80 1.4. Restitution tests
[0308] Restitution tests are carried out with the 12 devices obtained in example 1.3. These tests consist of actuating the push button 4 times per hour for 8 hours for 5 days, and observing during this use the behavior of the heterogeneous mixture in the device in terms of suspensivity with respect to the capsules and the capacity of the devices to (i) suck up the capsules, (ii) deliver a homogeneous composition over time (the homogeneity is evaluated thanks to the homogeneity of the olfactory intensity perceived during use and by microscopic observation of the sprayed composition) and (iii) deliver a composition in the form of a spray. Rating criteria: 0 1 2 Suspension of capsules Creaming of capsules in less than 5 minutes Creaming of capsules in less than 1 hour No creaming Suction Poor suction; Average suction; Satisfactory suction capsules clogging of the TP(2) by particles preferential aspiration of PAC(1) making; aspirated mix “capsules” / PAC(1)” constant in use Homogeneity of delivery Poor delivery; delivery PAC(1) only Average delivery; Preferential delivery PAC(1) Satisfactory delivery; delivered mix “capsules” / PAC(1)” constant in use Sprayability Delivery impossible Delivery in the form of a jet Delivery in the form of a mist
[0310] (1) PAC: Continuous Aqueous Phase
[0311] (2) TP: Dip Tube (or guide conduit). Results and discussions:
[0312] Capsule batch Ref Capsule suspension Capsule suction Delivery homogeneity Sprayability 1 Dl.l 0 1 0 2** D-1.2 1 1 0 2** D-1.3 2 1 1 2** D-1.4 2 0 NA* 1 2 D-2.1 0 1 0 2** D-2.2 1 1 1 2** D-2.3 2 2 2 2 D-2.4 2 0 NA* NA* 3 D-3.1 0 1 0 2** D-3.2 1 1 0 2** D-3.3 2 0 NA* NA* D-3.4 2 0 NA* NA*
[0313] NA*: Not Applicable due to plugging of the dip tube.
[0314] ** Sprayability is satisfactory at the start of use only, due to the creaming of the capsules and therefore preferential aspiration of the continuous aqueous phase. After aspiration and delivery of the part of the continuous aqueous phase devoid of capsules, the end of the dip tube accesses the capsules. However, their density is such that the quality of the spray quickly collapses, or even the aspiration of the heterogeneous mixture obtained becomes impossible.
[0315] From the above results, it is observed that a capsule volume fraction of less than 50% does not allow a satisfactory steric suspension due to too rapid creaming of the capsules, and this is the case for the 3 batches of capsules. In use, this results in a preferential aspiration, and therefore distribution, of the continuous aqueous phase, leading to an increase in the capsule concentration as the product is used. Mechanically, the formulation of the dispensed liquid composition will be inhomogeneous during use, i.e. mainly composed of the continuous aqueous phase at the start of use, then increasingly concentrated in the dispersed phase as use progresses. This increase in capsule concentration even leads, after a while, to the suction / delivery device becoming blocked.
[0316] With a capsule volume fraction of less than 50%, it is therefore not possible to guarantee an exact and constant formulation of the composition delivered throughout its use, regardless of the size of the capsules.
[0317] From a volume fraction in capsules of 50%, a composition capable of ensuring suspension of the capsules in the continuous non-suspensive aqueous phase is obtained. However, it is noted that the capacity of the device to deliver a homogeneous composition throughout its use is only observed with test D-2.3. Finally, from a volume fraction in capsules greater than or equal to 70%, it is observed that the heterogeneous mixture becomes less and less fluid to be correctly pumped.
[0318] Also, from the above results, it is observed that the suction capacity of the device decreases as the size of the capsules increases, this disadvantage being exacerbated with the increase in the volume fraction of capsules. In particular, it is observed that the suction capacity of the device is optimal when the ratio "internal diameter of the guide duct / diameter of the particles" is between 1 and 1.25, and even more so when this ratio is between 1.1 and 1.2.
[0319] Finally, from the above results, it is observed that the sprayability quality of the device decreases as the size of the capsules increases, this disadvantage being exacerbated with the increase in the volume fraction of capsules, except for test D-2.3 which is the only one to combine high density of capsules, good sprayability and homogeneity of the liquid composition distributed in use, which are advantageous properties which are at first sight incompatible.
[0320] However, test D-2.3 is the only test to combine an “internal diameter of the guide duct / diameter of the particles” ratio of between 1.00 and 1.25 and a volume fraction of the capsules relative to the total volume of the heterogeneous mixture of between between 70% and 50%, which is particularly unexpected. Test D-2.3 is notably illustrated in [Fig.9][Fig.9].
[0321] Similar results were observed with capsule batch No. 1 subject to adjusting the dip tube and capsule volume fraction to meet the advantageous ranges described above for test D-2.3.
[0322] Similar results were also observed with a heterogeneous mixture for which the capsules were replaced by solid beads, the composition of which is described in Table 5 below.
[0323] Table 5: Solid pearls Raw materials INCI % by mass Water QSP* Protanal LF 200S Sodium alginate 1.22 Total 100
[0324] * Sufficient Quantity For
Claims
Claims
1. Device for packaging and dispensing in the form of a spray of a fluid composition, in particular a cosmetic composition, characterized in that it comprises at least: - a container comprising at least one heterogeneous mixture; - a guide duct arranged in the container; and - a dispensing member capable of sucking heterogeneous mixture from the container, transforming the heterogeneous mixture into the fluid composition and dispensing the fluid composition in the form of a spray, the heterogeneous mixture comprising particles, preferably monodisperse, dispersed in a continuous phase, the particles having a diameter greater than 250 pm, and preferably greater than 500 pm, characterized in that: - the ratio "internal diameter of the guide duct / diameter of the particles" is between 1 and 1.25, and preferably between 1.1 and 1.2;and - the particles represent a volume fraction of between 50% and 70%, preferably between 55% and 65%, and better still between 57% and 63%, relative to the total volume of the heterogeneous mixture.;
2. Device according to the preceding claim, in which the particles have a diameter of between 250 pm and 3000 pm, preferably between 500 pm and 2000 pm, better still between 750 pm and 1800 pm, and very particularly between 1000 pm and 1600 pm.
3. Device according to claim 1 or 2, in which the heterogeneous mixture comprises between 45% and 70%, preferably between 50% and 65%, and better still between 55% and 60%, by weight of particles relative to the total weight of the heterogeneous mixture.
4. Device according to any one of the preceding claims, in which the particles comprise at least one fatty phase comprising at least one active agent, in particular at least one perfuming agent.
5. Device according to the preceding claim, in which the particles comprise from 2.5% to 40%, preferably from 5% to 30%, and better still from 10% to 20%, by weight of active agent(s), preferably perfuming agent(s), relative to the total weight of the heterogeneous mixture.
6. Device according to any one of the preceding claims, wherein the particles comprise from 5% to 90%, preferably from 10% to 70%, in particular from 25% to 60%, or even from 30% to 50%, by weight of active agent(s), in particular of perfuming agent(s), relative to the total weight of the particles.
7. A device according to any preceding claim, wherein the particles further comprise at least one oil.
8. A device according to any preceding claim, wherein the particles are in the form of solid beads and / or capsules comprising a core and at least one shell.
9. Device according to the preceding claim, in which the particles in the form of capsules comprise a Ri / Rc ratio of between 0.5 and 0.9, preferably between 0.6 and 0.8, and better still between 0.6 and 0.7, in which: - Ri corresponds to the radius of the core of the capsules; and - Rc corresponds to the radius of the capsule.
10. Device according to any one of claims 8 and 9, wherein the envelope is: - a gelled envelope totally encapsulating the core, said gelled envelope comprising at least one polyelectrolyte in the gelled state and / or at least one thermosensitive hydrophilic gelling agent; and / or - an envelope which derives from a complex coacervation reaction between two oppositely charged polymers capable of coacerving.
11. Device according to any one of the preceding claims, in which the heterogeneous mixture comprises less than 10%, preferably less than 5%, in particular less than 2.5%, or even is free of alcohol(s), in particular ethanol, relative to the total weight of the heterogeneous mixture.
12. Device according to any one of the preceding claims, in which the continuous phase is liquid and suspensive with respect to the particles.
13. Device according to any one of claims 1 to 11, in which the continuous phase is liquid and not suspensive with respect to the capsules.
14. A device according to any preceding claim, wherein the continuous phase has a high shear viscosity, as measured at 25°C and under a shear stress of 100 s-1, of less than or equal to 100 mPa.s, preferably less than or equal to 50 mPa.s, in particular less than or equal to 25 mPa.s, and more preferably less than or equal to 10 mPa.s.
15. Device according to the preceding claim 13 or 14, in which the continuous phase, or even the fluid composition, has a flow threshold value less than or equal to 1 Pa, in particular less than or equal to 0.1 Pa, very particularly less than or equal to 0.01 Pa, or even has no flow threshold value.
16. A device according to any preceding claim, wherein the heterogeneous mixture / fluid composition is a perfuming composition.
17. Use of at least one device according to any one of the preceding claims, for perfuming a keratin material or an item of clothing.
Citation Information
Patent Citations
Seamless capsule and process for producing the same
EP0525731A2
Multilayered soft capsule for eliminating foul breath and process for producing the same
EP1020177A1
Capsular preparation containing unsaturated fatty acid or derivative thereof and process for producing the same
EP1025842A1
Spraying device and use of same
EP1878507A2
Seamless capsule
EP2292752A1