Packaging and dispensing device suitable for packaging a composition sensitive to oxidation

Abstract

Packaging and dispensing device adapted for packaging an oxidation-sensitive composition. Device comprising: A container having a body defining at least partially a chamber for containing the composition, a piston (20) capable of moving within said chamber, comprising: A piston body (21) made of a first material, in particular thermoplastic, having a central portion (29) and at least one sealing lip (24) bearing on the inner surface of the body (11), a portion (91) made of a second material having lower oxygen permeability than the first material, extending along said longitudinal axis (X) over more than the greater part of the inner cross-section of the container body. Figure for the abbreviation: Fig. 2

Description

Title of the invention: Packaging and dispensing device adapted for packaging an oxidation-sensitive composition technical field

[0001] The present invention relates to devices for conditioning and distributing a fluid composition, and more particularly those adapted to receive a composition sensitive to oxidation. Previous technique

[0002] In the cosmetic field, a number of active ingredients are susceptible to degradation by an oxidation mechanism. By way of illustration and without limitation of these active ingredients susceptible to oxidation, we can mention in particular ascorbic acid and its derivatives such as 5,6-di-O-dimethylsilylascorbate, the potassium salt of dl-alpha-tocopheryl-21-ascorbyl-phosphate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, phloroglucinol, enzymes, ferulic acid, retinol, retinol derivatives such as [3-carotene, palmitate or retinyl acetate; flavonoids in particular resveratrol and polyunsaturated fatty acids.

[0003] Specific packaging has thus been developed for these compositions, in particular tubes made with multilayer films comprising at least one layer forming an oxygen barrier, for example in Ethylene Vinyl Alcohol (EVOH) or in aluminium.

[0004] However, these tubes have the disadvantage of becoming difficult to empty when little of the product remains inside, and the yield is often lower than desired. Furthermore, this type of packaging and distribution is well-established and remains unattractive to consumers, failing to convey the codes of luxury.

[0005] There are also devices with a flexible inner pocket of relatively complex and expensive construction.

[0006] Devices comprising a glass container equipped with a pipette have also been proposed, but these devices are not suitable for creamy or pasty compositions.

[0007] Publications KR102413886B1, WO2021125513A1, WO2017060631A1, KR101422069B1, KR101021611B1, KR200421315Y1 and WO2009151188A1 are known of conditioning devices comprising a cylindrical body defining at least partially a chamber containing the composition, A pump equipping the device has a suction conduit opening into this chamber. A piston is mounted in the body to define the bottom of the chamber and can move upwards towards the pump as the chamber is emptied. These known devices are not designed for the effective and lasting protection of an oxidation-sensitive composition.

[0008] Application KR 2018 0078806 describes a polyketone film having oxygen barrier and mechanical properties.

[0009] Application KR 2021 0004661 aims to provide a cosmetic container with resistance to shocks and abrasion and preventing the manifestation of undesirable odors that may be generated by certain materials in contact with the cosmetic contents. Description of the invention

[0010] There is therefore a need for a conditioning and distribution device suitable for conditioning and protecting a composition sensitive to oxidation, and remedying all or part of the drawbacks of the devices proposed to date for this purpose. Summary of the invention

[0011] The invention aims to meet this need, and it achieves this in one of its aspects by proposing a device for conditioning and distributing a fluid composition, comprising: - A container having a cylindrical body, of circular or other cross-section, particularly oblong, for example oval, extending along a longitudinal axis and defining at least partially a chamber intended to contain the composition, - A movable piston inside said body, capable of moving axially within it in response to the extraction of the composition from said chamber, this piston comprising: • A piston body made of a first material, in particular thermoplastic, comprising a central portion and at least one sealing lip applying to the inner surface of the cylindrical body of the container and having a flexibility allowing it to conform to the shape of the cross-section of said body, • An oxygen barrier portion, made of a second material having lower oxygen permeability than said first material, extending in projection along said longitudinal axis over more than the major part of the internal cross-section of the cylindrical body of the container, and preferably over more than 60%, better 70%, even better 80%, or even 90% or 95% of said interior section, even better more than 99%, or even the entirety of said section.

[0012] Oxygen permeabilities are compared under the same conditions, representative of the behavior with respect to oxygen diffusion through these materials during storage under typical conditions, for example in air at 20°C and atmospheric pressure (1013.25 hPa) and at 40% relative humidity. To compare the permeabilities, their oxygen transmission rate (OTR) measured according to ASTM D3985 or ISO 15105 standards can be compared.

[0013] Thanks to the invention, the permeability of the piston to oxygen from the air is reduced, which greatly improves the conditions of preservation of the oxidation-sensitive composition contained in the container, the latter being also made in such a way as not to be excessively permeable to oxygen.

[0014] The invention thus makes it possible to benefit from the advantages associated with packaging using a mobile piston, namely the possibility of packaging and distributing in a dosed manner creamy or pasty compositions with a high rate of restitution and great ease of use, while improving the preservation of the composition with respect to the effects of atmospheric oxygen, even with a total content of active ingredient(s) sensitive to oxidation relatively high, for example a vitamin C or retinol content greater than or equal to 0.1% by mass relative to the total mass of the composition.

[0015] The container is preferably made of glass, and even better of drawn glass, which allows for a reduction in its thickness and control of the internal diameter, particularly in soda-lime glass, thus facilitating its recycling. The glass acts as a barrier to atmospheric oxygen, and controlling its internal diameter allows the piston to move easily upon contact with it.

[0016] Preferably, the piston comprises at least one elastomeric seal applied to the inner surface of the container body; such a seal improves the piston's airtightness to oxygen by further reducing the passage of air downstream of the barrier portion. Better still, the piston comprises two such elastomeric seals, which further improves the airtightness to oxygen.

[0017] The elastomeric seal(s) are preferably added seals, and better still are O-rings (also called “O-ring” seals).

[0018] The elastomer seal(s) are preferably mounted on the piston body.

[0019] Preferably, this includes one or two annular grooves for receiving this or these elastomer seals, in particular toroidal seals.

[0020] The elastomer seals, especially when there are two of them, are preferably identical, which facilitates the making of the piston.

[0021] The elastomeric seal(s) are advantageously located axially between the sealing lip and the barrier part.

[0022] The elastomeric seal(s) are preferably made of butyl. Barrier part

[0023] The barrier part is preferably made of a thermoplastic material.

[0024] The barrier portion may include a peripheral lip that applies to the inner surface of the container body

[0025] The barrier portion can cover most of the lower face of the piston body, and in particular its entire central region.

[0026] The barrier portion may have openings through which the thermoplastic material of the piston body extends. This contributes to the adhesion of the barrier portion to the piston body, which is useful in cases of poor material compatibility resulting in weak adhesion during manufacturing. Other cooperating reliefs of the hollow / projection type, including hollows formed by non-through holes, may be provided to improve the adhesion of the body and the barrier portion.

[0027] The openings can be made in a tubular upright of the barrier portion, this upright preferably being extended below by said peripheral lip. The material bridges extending through said openings can be connected to each other by an inner ring within said upright.

[0028] The thickness of the material of the piston body at the location of said openings can be relatively high, in particular more than double that in the central part of the body, which limits the diffusion of oxygen at this level.

[0029] Said openings preferably have lateral faces oriented parallel to the same median plane M, which facilitates the demolding of the part forming the barrier.

[0030] Preferably, the barrier portion is made of a thermoplastic material that has a higher melting point than the body material, allowing the body to be overmolded onto the barrier portion. For example, the melting point difference between the two materials is at least 25°C, being, for example, between 160 and 210°C for LDPE or HDPE and on the order of 235 to 255°C for the Carilon® polyketone polymer from Shell Chemicals.

[0031] Preferably, the conditioning and distribution device includes a means for sampling the composition, and this sampling means is preferably a pump, the latter being preferably mounted on a neck extending superiorly from said cylindrical body.

[0032] The pump may include a central suction conduit, plunging into the chamber containing the composition.

[0033] The piston body then has in its center, preferably, a recess which closely follows the shape of this conduit, which makes it possible to limit the residual volume of composition present in the chamber when the piston has reached its end of stroke.

[0034] The piston body is preferably made of a thermoplastic material chosen from polyolefins, in particular polyethylene (PE), preferably low density (LDPE), polypropylene (PP), their copolymers and mixtures thereof.

[0035] The barrier portion is preferably made of a thermoplastic material, preferably a polyketone polymer (PK or sometimes also POK). Polyketone polymer (PK)

[0036] These polymers have the structural specificity of possessing a carbon skeleton made up of carbon monoxide and alpha olefin motifs.

[0037] Hydrocarbons with ethylenic unsaturation suitable for use as precursors of so-called polyketone polymers have up to 20, preferably up to 10, carbon atoms. Examples of such hydrocarbons include ethylene and alpha-olefins such as propene, 1-butene, isobutene, 1-hexene, 1-octene, and even an arylaliphatic compound bearing an aryl substituent on another aliphatic molecule, particularly an aryl substituent on an ethylenically unsaturated carbon atom. Examples of arylaliphatic hydrocarbons among those with ethylenic unsaturation include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropylstyrene.

[0038] Polyketone polymers consisting of copolymers of carbon monoxide and ethylene or of terpolymers of carbon monoxide and ethylene with a second hydrocarbon with ethylenic unsaturation having at least three carbon atoms, in particular an alpha-olefin such as propene, are particularly suitable for the invention.

[0039] The physical properties of the polyketone are adjustable according to the molecular weight, whether it is a copolymer or a terpolymer, and in the case of the terpolymer, the nature of the second hydrocarbon motif with ethylenic unsaturation considered.

[0040] Advantageously, when the polyketone terpolymer is used, there are at least two units containing an ethylene fraction for each unit containing a second hydrocarbon fraction in the terpolymer.

[0041] The polyketone polymer is preferably formed of monomeric units of chemical formula (I) and / or monomeric units of chemical formula (II):

[0042] -(CH2CH2-CO)- (I)

[0043] -(CH2CH(CH3)-CO)- (II)

[0044] In one embodiment, the polyketone polymer comprises at least and in particular consists of a copolymer comprising repeating motifs represented by the general formula (I).

[0045] In another embodiment, the polyketone polymer comprises at least one terpolymer comprising repeating motifs represented by the general formula (I) and repeating motifs represented by the general formula (II).

[0046] In particular, the polyketone polymer can have an average molecular weight, Mw, of 150000 to 375000, in particular of 175000 to 350000.

[0047] In particular, the polyketone polymer may have a number average molecular weight of 50,000 to 250,000, in particular 70,000 to 150,000.

[0048] These molecular weights are measured by gel permeation chromatography, GPC using hexafluoroisopropanol, HFIP, and by reference to polymethyl methacrylate, PMMA.

[0049] The polyketone polymer used in the present invention generally has a melting point of 175 °C to 300 °C, and generally of 210 °C to 270 °C.

[0050] The polyketone polymer is generally obtained by copolymerization of carbon monoxide and at least one ethylenically unsaturated compound. As stated above, examples of ethylenically unsaturated compounds copolymerizing with carbon monoxide include α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, vinylcyclohexane, etc.; aromatic alkenyl compounds such as styrene, α-methylstyrene; cyclopentene, cyclic olefins such as norbomene, 5-methylnorbornene, 5-phenylnorborene, tetracyclododecene, tricyclododecene, trichoundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetracyclododecene; vinyl halides such as vinyl chloride; acrylic esters such as ethyl acrylate, methyl acrylate, etc.

[0051] Among these, the preferred ethylenically unsaturated compounds are alpha-olefins, preferably alpha-olefins having 2 to 4 carbon atoms, more preferably at least ethylene.

[0052] The copolymerization of carbon monoxide with ethylene, optionally in the presence of an additional ethylenic unsaturation compound, and preferably propene, is carried out using a complex organometallic catalyst consisting of (a) the transition metal compound from group 9, 10, or 11, and (b) a ligand having an element from group 15, the catalyst being produced by contacting the two components. Any method can be used as a method for bringing the two components into contact. contact. It is thus possible to prepare a solution in which two components are mixed in advance in a suitable solvent, and to use the two components which can be supplied separately to the polymerization system and brought into contact with each other in the polymerization system.

[0053] As a polymerization process, a solution polymerization process using a liquid medium, a suspension polymerization process, a vapor phase polymerization process in which a small amount of a high concentration polymer is impregnated with a catalyst solution, and the like may be considered.

[0054] Polymerization can be discontinuous or continuous.

[0055] The reactor used in the polymerization can be used as is known or modified, and the reaction temperature during polymerization is from 50 °C to 100 °C, and the reaction pressure is appropriate in the range of 40 bar to 60 bar. The resulting polymer is recovered via post-polymerization filtration and purification processes, and the remaining catalytic composition is removed with a solvent such as alcohol or acetone.

[0056] The polyketone polymer is generally obtained by copolymerization of carbon monoxide, ethylene and optionally propene in a liquid medium in the presence of a complex organometallic catalyst comprising (a) a Group 9, 10 or 11 transition metal compound and (b) a ligand having a Group 15 element. Such a process is detailed in particular in patent KR101684889B1.

[0057] Preferably, the polyketone polymer is an aliphatic polyketone.

[0058] Preferably, the polyketone polymer is a terpolymer comprising the CO motifs, ethylene and propylene.

[0059] Preferably, the polyketone polymer has the following chemical formula:

[0060] [Chem.l]

[0061] where m and n are integers greater than or equal to 1, RI and R2, whether identical or different, independently represent an alkylene group, possibly substituted by at least one group chosen from an alkyl, an alkyne, an aryl, a hydroxyl, an amine, an amide, a halogen and / or a carboxyl, and in which the sequence or repetition of motifs is random or ordered, RI being in particular an ethylene group and R2 being in particular a propylene group, and in which the n / m ratio is less than or equal to

[0062] Preferably, the polyketone polymer being a resin obtained by polymerization and not an alloy with other polymers.

[0063] By way of representative and non-limiting example of polyketone polymers that can be used in the invention, the polymers with the designations "POKETONE" (registered trademark) (Hyosung), in particular M630A, M630F, M330A and M330V, which are particularly suited to transformation by injection molding, may be mentioned in particular.

[0064] By way of illustration of these polyketones can also be cited the commercial products “Schulaketon” (registered trademark) NV FC (Polyketone, Aliphatic LyondellBasell Industries) and Schulaketon MC FC (Polyketone, Aliphatic LyondellBasell Industries), “Carilon” (registered trademark) (Aliphatic Polyketone Shell Chemicals).

[0065] The invention also relates to the device as defined above, containing the composition. Composition

[0066] This may be a cosmetic composition dedicated to the care and / or makeup of a keratinous material and more particularly of the skin, lips and keratinous fibers, in particular hair.

[0067] This may include, in particular, a makeup composition, a skincare composition, including a sun protection composition, a perfume composition or a hair composition.

[0068] More specifically, it may be a hair cleansing or care composition such as a shampoo, a rinse-out or leave-in conditioner, a rinse-out composition to be applied before or after coloring, bleaching, perming or straightening, or between the two stages of a perm or straightening, a hair composition for maintaining the hairstyle such as a hairspray, gel, mousse or styling spray, or a hair composition such as a hair coloring composition or a permanent hair straightening composition; a makeup composition, and in particular a makeup composition for the lips, body, face or hair appendages such as a foundation, lipstick, lip gloss, blush or eyeshadow, nail polish, mascara or eyeliner;of a skincare composition, and in particular a body or face care composition, including an anti-aging serum or a makeup removal and / or cleansing composition for keratinous materials, particularly of the skin, mucous membranes such as the lips and / or eyelashes, such as a shower gel, a bath gel or a makeup remover. ;

[0069] This composition can therefore be presented in all classic galenic forms according to the applications envisaged and compatible with packaging in the device according to the invention.

[0070] The composition may be in one of the galenic forms classically used for topical applications and in particular in the form of a dispersion, a lotion, an aqueous gel or an emulsion intended for topical application.

[0071] The composition can notably be used as a skincare and / or sun protection product for the face and / or body, with a liquid to semi-liquid consistency. In particular, the composition can be more or less fluid and have the appearance of a white or colored cream, an ointment, a gel-cream, a milk, a lotion, a serum, a paste or a mousse.

[0072] These different galenic formulations can be obtained according to the preparation processes classically used in cosmetics or dermatology.

[0073] The volume of composition initially contained in the container ranges, for example, from 1mL to 300mL. Brief description of the drawings

[0074] The invention will be better understood upon reading the detailed description that follows, the non-limiting examples of its implementation, and upon examination of the accompanying drawing, in which:

[0075] [Fig. 1] [Fig. 1] schematically represents in perspective an example of a conditioning and distribution device according to the invention,

[0076] [Fig.2] [Fig.2] represents an enlarged detail of [Fig.1], without the O-rings,

[0077] [Fig.3] [Fig.3] is a partial, schematic, longitudinal section of the piston,

[0078] [Fig.4] [Fig.4] is an elevation view of the piston,

[0079] [Fig.5] [Fig.5] is a cross-section along VV of [Fig.4],

[0080] [Fig.6] [Fig.6] is an exploded view of a variant of the device,

[0081] [Fig.7] [Fig.7] is an elevational view, with transparency of the container, of the device of the [Fig.6],

[0082] [Fig.8] [Fig.8] is a longitudinal section of the device of [Fig.7],

[0083] [Fig.9] [Fig.9] represents detail IX of [Fig.8],

[0084] [Fig. 10] [Fig. 10] illustrates comparative results. Description of the implementation methods

[0085] Figure 1 illustrates a conditioning and distribution device 1 conforming to an example of implementation of the invention, comprising a container 10 having a cylindrical body 11 of revolution, with longitudinal axis X, in which a piston 20 is received.

[0086] The container 10 has a neck 14 of which only the shoulder at its base is partially apparent on the [Fig.1], on which is mounted a pump 30 without air intake, the latter being known in itself and comprising for example, as illustrated, an actuation button 32, movable relative to a body 31 fixed to the container.

[0087] A chamber 13 is formed inside the container 10 between the piston 20 and the pump 30, to contain a composition C to be dispensed. This latter is advantageously an oxidation-sensitive composition. This composition may in particular contain one or more of the aforementioned active ingredients, namely ascorbic acid and its derivatives such as 5,6-di-O-dimethylsilylascorbate, the potassium salt of dl-alpha-tocopheryl-21-ascorbyl phosphate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, phloroglucinol, enzymes, ferulic acid, retinol, retinol derivatives such as 3-carotene, retinyl palmitate or retinyl acetate; flavonoids in particular resveratrol and polyunsaturated fatty acids.

[0088] The pump 30 includes a suction conduit 33, which opens into the chamber 13.

[0089] The mounting of the pump 30 on the container can be carried out in such a way as to guarantee the required airtightness against oxygen, by any known means, in particular by means of one or more seals made of a suitable material.

[0090] The body 11 of the container can be provided at its lower end with a base 40, which comprises, for example, as illustrated, two concentric outer and inner skirts 41 and 42 connected at their base by a transverse wall 43 extending perpendicularly to the axis X and enabling the device to stand vertically when placed by its base 40 on a horizontal flat surface.

[0091] The cylindrical wall of the body 11 is inserted between the skirts 41 and 42.

[0092] The outer skirt 41 may have axial ribs 44 on its inner surface, so as to obtain the necessary clamping on the wall of the body 11 of the container.

[0093] The base 40 may also include, as illustrated, a central tubular shaft 45, which connects at its base to the wall 43, and which may be provided on its inner surface with axial ribs 47.

[0094] If we refer more particularly to figures 2 to 5, we see that the piston 20 comprises a body 21 molded in one piece from thermoplastic material, for example a polyolefin such as LDPE or PP.

[0095] The body 21 comprises a tubular upright 22 with axis X which connects superiorly, via an outwardly radially oriented expansion 23, to a flexible sealing lip 25 directed upwards and outwards, and arranged to apply a fluid-tight seal to the inner surface of the container body 11. The largest outer diameter of the lip 25 is greater than the inner diameter of the body 11, so as to obtain a mechanical interference between the two, guaranteeing the seal.

[0096] The body 21 has below a tubular skirt 26 of larger diameter than the upright 22 and which connects to the latter by forming an annular shoulder 26a.

[0097] The body 21 also includes a central portion 28 in the shape of a bowl, which connects to the base of the upright 22 by means of an intermediate flared portion 29.

[0098] The thickness ei of the intermediate portion 29 is, for example, between 0.6 and 1.4 mm, and is approximately 1 mm. The thickness of the cup-shaped portion 28 can be within the same range of values, or even be the same.

[0099] The profiles of the bowl-shaped part 28 and that of the flared intermediate portion 29 are such that they substantially follow the shape of the conduit 33 and that of the lower surface of the pump body which surrounds it, so that the volume of the residual space remaining between the piston 20 and the pump 30 at the end of the piston stroke is small, for example less than 3mL, so as to maximize the recovery rate.

[0100] The body 21 can be manufactured by injection molding with an injection point located in the bottom of the bowl-shaped part 28, on the pump 30 side.

[0101] The upright 22 carries, substantially midway between the shoulder 23a defined by the widening 23 and the shoulder 26a, a radial annular rib 27, the free end of which has substantially the same outside diameter as the widening 23 and the skirt 26.

[0102] The rib 27, together with the shoulders 23a and 26a, defines two respective annular grooves 71 and 72, intended to receive O-rings 81 and 82, shown schematically in [Fig. 3]. Preferably, the inner diameter of these O-rings, before assembly, is smaller than that of the bottom of the grooves 71 and 72, so that the O-rings 71 and 72 are stretched during assembly. The O-rings have an outer diameter, when mounted on the body 21, greater than the inner diameter of the body 11, so as to obtain the desired mechanical interference, enabling dynamic airtightness, i.e., during the movement of the piston 20.

[0103] The piston 20 includes a barrier part 91, made here by molding thermoplastic material, preferably polyketone polymer (PK) or any other material having at least the same oxygen barrier efficiency.

[0104] This part 91 comprises a central portion 92 in the shape of a bowl and a flared portion 99, which follow the contour of the parts 28 and 29 of the body 21. The thickness e2 of the portion 99 goes for example from 0.6mm to 1.4mm, being for example on the order of 1mm.

[0105] The central portion 92 is extended below, beyond the bottom wall 96, by a hollow stud 97 arranged to engage in the central shaft 47 of the base 40, which This ensures mechanical coupling of the piston 20 and the base 40 before the first distribution of the composition by the pump 30. The pin 97 may have a draft angle of a few degrees, for example 2°. This can serve as a lower stop and support for the piston 20 during the assembly of the glass, piston and base sub-assembly.

[0106] The flared portion 99 connects at its periphery to a tubular upright 93, which is extended below, forming a shoulder 94, by a peripheral lip 95 extending obliquely downwards and outwards, the thickness of which decreases towards its free end, this lip 95 being intended to apply itself to the inner surface of the body 11 of the container 10. The largest outer diameter of the lip 95 is greater than the inner diameter of the body 11, so as to obtain the desired mechanical interference.

[0107] The upright 93 is traversed by openings 93a, for example substantially at mid-height, as illustrated. These openings 93a have, as can be seen in [Fig. 5], lateral faces parallel to the longitudinal axis X and contained in respective planes Pi to P10, all parallel to the same median plane M, which is a plane of symmetry for the piston 20.

[0108] These openings 93a are crossed, as can be seen in [Fig.3], by material bridges 26b which connect the skirt 26 to an inner ring 26c extending into contact with the radially inner face.

[0109] The body 21 has on the upright 26, at the same level as the openings 26b, two diametrically opposed, shallow grooves 26d, separated by portions 26f of the same outside diameter as the upright 26. The grooves 26d allow the mold carriages to be closed on a smaller diameter and prevent the lower area from being "scratched" without a parting line during demolding.

[0110] To manufacture the piston 20, one can start by molding the barrier part 91 in a multi-shell mold, with demolding of the openings 93a by separating two opposing half-shells parallel to the median plane M. The material can be injected from a central injection point located in the bottom of the pin 97. The lip 95 can be molded within a part of the mold without a parting line located on the circumference of the lip, which reduces the risks of creating a relief detrimental to the desired seal.

[0111] Next, the body 21 can be overmolded onto the part 91, for example by injecting the thermoplastic material from the bottom of the bowl-shaped part 28, the injected material passing through the openings 93a to the inner ring 26c. As with the lip 93, the molding of the lip 24 can be carried out within a part of the mold without a parting line located on the circumference of the lip, which reduces the risk of creating a relief that is detrimental to sealing.

[0112] In the case of using PK to mold part 91 and LDPE to mold body 21, the sandwiching of the upright 93 between the skirt 26 and the crown 26c, and the passage of the material bridges 26b through the openings 93a, ensures the mechanical stability of the two parts, despite the chemical incompatibility of the materials which leads to a lack of adhesion between them. Subsequently, the seals 81 and 82 can be mounted in their respective grooves 71 and 72.

[0113] To assemble the device 1, the piston 20 carried by the base 40 can be inserted, with the pin 97 engaged in the barrel 45, until the base 40 is fully inserted onto the body 11.

[0114] Composition C can then be introduced inside container 10 before mounting pump 30.

[0115] To use device 1, the user operates pump 30.

[0116] The departure of composition C from chamber 13 located above piston 20, and the absence of air intake, is accompanied by a depression which causes piston 20 to move upwards towards pump 30.

[0117] During this upward movement, the lip 24 ensures a fluid seal by pressing against the inner surface of the container body 11. The force created on the piston 20 is sufficient to disengage the hollow pin 97 from the barrel 45.

[0118] Part 91 limits the diffusion of oxygen through it, due to its low permeability. In the illustrated example, part 91 occupies, in projection along the X-axis, substantially the entire internal cross-section of body 11.

[0119] The air which can nevertheless pass through the lip 95 due to the imperfect contact which may exist between the latter and the inner surface of the body 11 is struck by the O-rings 81 and 82, which oppose the rise of the air between the piston 20 and the wall of the container 10, above the lip 95.

[0120] This gives us a low diffusion of oxygen over time through the piston 20, while having a piston 20 capable of sliding easily enough along the container to be able to move back up into it when a depression is generated by the departure of composition C from chamber 13.

[0121] Oxygen uptake by the composition during storage is, for example, less than 0.005 mg / L / day at 23°C

[0122] The variant illustrated in figures 6 to 9 differs from that which has just been described with reference to figures 1 to 5 by the absence of a base 40 and by the shape of the lower end of the container 10.

[0123] In this example, the lower end of the container 10 has a slight enlargement 15.

[0124] Figure 9 illustrates that the nominal diameter d of the O-rings 81 and 82 is greater than the distance w separating the bottom of the grooves 71 and 72 from the inner surface of the body 11, with preferably the relation 0.85d <iK0,92d.

[0125] The interference ii or i2 between the lips 24 and 95 and the inner surface of the body 11 is for example between -0.1 and -0.2 mm at the radius, being for example of the order of -0.15mm. Comparative results

[0126] The evolution of the oxygen level inside a container according to the invention as described in the figures, comprising two butyl seals (A), a body made of LDPE and a barrier part made of Poketone (Hyosung), was measured, as was a container (B) according to the invention differing from (A) by the presence of a single butyl seal instead of two, and a container (C) differing from (A) by the absence of a butyl seal.

[0127] The test / storage conditions are: latm / 21°C / 50%RH

[0128] For each of the result groups A, B or C, the left bar represents the minimum value, middle value the average and rightmost value the maximum value.

[0129] It can be seen that with two butyl elastomer seals, the O2 reabsorption in the container is significantly reduced. However, even without a butyl seal, the performance is already good compared to some known devices.

[0130] Of course, the invention is not limited to the examples just described.

[0131] For example, the piston 20 may receive only one O-ring, or even none, depending on the sensitivity of the composition to oxygen.

[0132] The pump 30 can be replaced by a valve, and pressure can be exerted on the piston 20 on the side opposite the valve, for example by a spring, to tend to reduce the volume of the chamber containing the composition when the valve is opened by the user.

[0133] The container 10 can be made of a material other than glass, for example of metal or metallized PP.

[0134] The body 21 can be made of a material other than LDPE or PP.

[0135] The container, when made of glass, can receive an anti-UV lacquer.

[0136] The 93a dwellings may not have an opening.

Claims

Demands

1. Device (1) for conditioning and dispensing a fluid composition (C), comprising: - A container (10) having a cylindrical body (11), of circular or other cross-section, extending along a longitudinal axis (X), and defining at least partially a chamber (13) for containing the composition, - a piston (20) movable within said body (11), capable of moving axially therein in response to the withdrawal of the composition (C) from said chamber (13), this piston (20) comprising: • A piston body (21) made of a first material, in particular thermoplastic, comprising a central portion (28, 29) and at least one sealing lip (24) applying to the inner surface of the container body (11) and having flexibility enabling it to conform to the shape of the cross-section of said body, • a portion (91) forming an oxygen barrier,made of a second material having less permeability to oxygen than the first material, extending in projection along said longitudinal axis (X) over more than the major part of the internal section of the body (11) of the container.

2. Device according to claim 1, the barrier part (91) extending in projection along said longitudinal axis (X) over more than 95% of said inner section, better more than 99%, even better the whole of said section.

3. Device according to any one of claims 1 and 2, the piston (20) comprising at least one elastomer seal (81; 82), preferably butyl, applying to the inner surface of the body (11) of the container.

4. Device according to claim 3, the piston (20) comprising two elastomer seals (81; 82), preferably butyl, applying to the inner surface of the body (11) of the container.

5. Device according to any one of claims 3 and 4, the seal(s) (81; 82) being added O-rings, preferably identical when there are two of them.

6. Device according to any one of the preceding claims, the barrier part (91) being made of a thermoplastic material.

7. Device according to claim 6, said material being a polyketone polymer (PK).

8. Device according to the preceding claim, the polyketone polymer being an aliphatic polyketone.

9. Device according to claim 7 or 8, the polyketone polymer being a terpolymer comprising the CO, ethylene and propylene motifs.

10. A device according to any one of claims 7 to 9, the polyketone polymer having the chemical formula ----------- where m and n are integers greater than or equal to 1, RI and R2, identical or different, independently represent an alkylene group, optionally substituted by at least one group selected from an alkyl, an alkyne, an aryl, a hydroxyl, an amine, an amide, a halogen and / or a carboxyl, and wherein the sequence or repetition of motifs is random or ordered, RI being preferably an ethylene group and R2 preferably a propylene group, and wherein the ratio n / m is less than or equal to %.

11. Device according to any one of claims 7 to 10, the polyketone polymer being a resin obtained by polymerization and not an alloy with other polymers.

12. Device according to any one of claims 1 to 11, the barrier part (91) having a peripheral lip (95) applying to the inner surface of the container body.

13. Device according to any one of claims 1 to 12, the barrier part (91) covering most of the lower face of the piston body (21), and in particular all of its central region (28, 29).

14. Device according to any one of claims 1 to 13, the barrier part (91) having openings (93a) through which the first material of the body (21) of the piston (20) extends.

15. Device according to claims 12 and 14, the openings (93a) being made in a tubular upright (93) of the barrier part, this upright (93) preferably being extended below by said peripheral lip (95).

16. Device according to any one of claims 14 and 15, said openings (93a) having lateral faces oriented parallel to the same median plane (M).

17. Device according to any one of claims 1 to 16, the barrier part (91) being made of a thermoplastic material which has a higher melting temperature than the first material of the body (21), the body (21) being overmolded onto the barrier part (91).

18. Device according to any one of the preceding claims, the container (10) being made of glass, better of drawn glass, in particular of soda-lime glass.

19. Device according to any one of the preceding claims, the body (21) of the piston (20) being made of a thermoplastic material selected from polyolefins, in particular polyethylene (PE), preferably low density polyethylene (LDPE), polypropylene (PP), their copolymers and mixtures thereof.

20. Device according to any one of the preceding claims, containing composition (C), the latter containing at least one oxidation-sensitive active ingredient selected from ascorbic acid and its derivatives such as 5,6-di-O-dimethylsilylascorbate, potassium salt of dl-alpha-tocopheryl-21-ascorbyl-phosphate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, phloroglucinol, enzymes, ferulic acid, retinol, retinol derivatives such as [3-carotene, palmitate or retinyl acetate; flavonoids in particular resveratrol and polyunsaturated fatty acids.

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