Packaging and dispensing device suitable for packaging an oxidation-sensitive composition

Abstract

A device (1) comprising: - a container having a body defining at least partly a chamber (13) intended for containing the composition, - a piston (20) that is able to move in said chamber (13), comprising: · a piston body (21) made of a first material, especially a thermoplastic material, comprising a central portion (28, 29) and at least one sealing lip (24) that bears against the interior surface of the body (11), · a part (91) made of a second material having a lower permeability to oxygen than the first material, said part extending in projection along said longitudinal axis (X) over more than the major part of the interior cross section of the body (11) of the container.

Description

[0001] Description

[0002] Title: Packaging and dispensing device suitable for packaging an oxidation-sensitive composition

[0003] Technical field

[0004] The present invention relates to devices for packaging and dispensing a fluid composition, and more particularly those suitable for receiving an oxidation-sensitive composition.

[0005] Prior art

[0006] In the cosmetics field, a certain number of active agents are sensitive to a phenomenon of degradation by a mechanism of oxidation. Non-limitative illustrations of these active agents that are sensitive to oxidation include especially ascorbic acid and derivatives thereof such as 5,6-di-O-dimethylsilyl ascorbate, 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 P-carotene, retinol palmitate or acetate; flavonoids, especially resveratrol, and polyunsaturated fatty acids.

[0007] Specific forms of packaging have therefore been developed for these compositions, especially tubes made with multilayer films comprising at least one layer forming a barrier to oxygen, made for example of ethylene-vinyl alcohol (EVOH) or of aluminium.

[0008] However, these tubes have the drawback of becoming difficult to empty when not very much composition remains in the interior, and the extraction rate is often lower than desired. In addition, this type of packaging and dispensing has been known for a long time and remains relatively unattractive to the consumer, as it does not convey the markers of luxury.

[0009] Flexible inner bag devices also exist but are relatively complex and costly in their construction.

[0010] Moreover, devices having a glass container equipped with a pipette have been proposed, but these devices are not suitable for creamy or pasty compositions.

[0011] Applications KR1024413886A1, WO2021125513A1, WO201760631 Al, KR101422069A1, KR101021611A1, KR200421315UY1 and W02009151188A1 disclose packaging devices comprising a cylindrical body at least partially defining a chamber containing the composition, the device being equipped with a pump which has an aspiration duct opening into this chamber. A piston is mounted in the body so as to define the bottom of the chamber, and may rise towards the pump as the chamber is emptied. These known devices are not intended for effective and long-lasting protection of an oxidation-sensitive composition.

[0012] Application KR 2018 0078806 describes a polyketone film having oxygen barrier and mechanical properties.

[0013] Application KR 2021 0004661 aims to propose a cosmetic container that has impact resistance and abrasion resistance and prevents the manifestation of undesirable odours that may be generated by certain materials in contact with the cosmetic contents.

[0014] US4896832 describes a dispensing device suitable for delivering a dose of insulin by the nasal route.

[0015] Disclosure of the invention

[0016] There is therefore a need to have a packaging and dispensing device which is suitable for packaging and protecting an oxidation-sensitive composition, and which provides a complete or partial remedy for the drawbacks of the devices proposed for this purpose to date.

[0017] Summary of the invention

[0018] The invention aims to meet this need, and achieves this, according to one of its aspects, by proposing a device for packaging and dispensing a fluid composition, comprising:

[0019] a container having a body which is cylindrical, with a circular or other, especially oblong, for example oval, cross section, extending along a longitudinal axis and defining at least partly a chamber intended for containing the composition,

[0020] a piston that is movable inside said body, being able to move axially therein in response to the composition being withdrawn from said chamber, this piston comprising: o a piston body made of a first material, especially a thermoplastic material, comprising a central portion and at least one sealing lip that bears against the interior surface of the cylindrical body of the container and has a flexibility allowing it to conform to the shape of the cross section of said body,

[0021] o a part forming an oxygen barrier, made of a second material having a lower permeability to oxygen than said first material, said part extending in projection along said longitudinal axis over more than the major part of the interior cross section of the cylindrical body of the container, and preferably over more than 60%, better still 70%, even better still 80%, or even 90% of said interior cross section, even better still more than 99%, or even the entirety of said cross section. The permeabilities to oxygen are compared under the same conditions, representative of the behaviour with regard to the diffusion of oxygen 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 standards ASTM D3985 or ISO 15105 can be compared.

[0022] By virtue of the invention, the permeability of the piston to atmospheric oxygen is reduced, thereby greatly improving the storage conditions of the oxidation-sensitive composition contained in the container, the latter, moreover, being made in such a way as not to be overly permeable to oxygen.

[0023] The invention thus makes it possible to have the advantages associated with forms of packaging that use a movable piston, namely the possibility of packaging creamy or pasty compositions and dispensing them in a metered manner with a high extraction rate and a high level of comfort in use, while at the same time improving the preservation of the composition with respect to the effects of atmospheric oxygen, even with a relatively high total content of oxidation-sensitive active agent(s), for example a vitamin C or retinol content of greater than or equal to 0,1% by mass relative to the total mass of the composition.

[0024] The container is preferably made of glass, and better still of drawn glass, which makes it possible to reduce its thickness and to control the internal diameter, and especially of soda lime glass, which facilitates its recycling. The glass forms a barrier to the oxygen in the air, and the control of its interior diameter allows the piston to move easily on contact therewith.

[0025] The piston preferably comprises at least one elastomeric seal which bears against the interior surface of the body of the container; such a seal improves the impermeability to atmospheric oxygen of the piston, while further reducing the passage of air downstream of the barrier-forming part. Better still, the piston comprises two such elastomeric seals, thereby further improving the impermeability to atmospheric oxygen.

[0026] The one or more elastomeric seals are preferably attached seals, and better still O-ring seals (also known as toroidal seals).

[0027] The one or more elastomeric seals are preferably mounted on the piston body. Preferably, the latter comprises one or two annular grooves for receiving this or these elastomeric seals, especially O-ring seals.

[0028] The elastomeric seals are preferably identical, so making it easier to produce the piston.

[0029] The one or more elastomeric seals are advantageously situated axially between the sealing lip and the barrier-forming part.

[0030] The one or more elastomeric seals are preferably made of butyl.

[0031] Barrier-forming part

[0032] The barrier-forming part is preferably made of a thermoplastic material.

[0033] The barrier-forming part may comprise a peripheral lip which bears against the interior surface of the body of the container.

[0034] The barrier-forming part may cover the major part of the lower face of the body of the piston, and especially the entirety of its central region.

[0035] The barrier-forming part may have openings through which the thermoplastic material of the piston body extends. This contributes to the fastening of the barrier-forming part to the piston body, which is useful in the event of poor compatibility of the materials with one another, leading to poor adhesion of the one to the other during manufacture. Other co-operating reliefs of the recess / proj ection engaged in the recess type, especially recesses formed of blind holes, may be provided to improve the fastening of the body and of the barrier-forming part.

[0036] The openings may be made in a tubular upright of the barrier-forming part, this upright being preferably extended at the bottom by said peripheral lip. The bridges of material extending through said openings may be connected to one another by a crown inside said upright.

[0037] The thickness of the material of the body of the piston in line with said openings may be relatively high, especially more than twice that in the central part of the body, thereby limiting the diffusion of the oxygen at this level.

[0038] Said openings preferably have side faces oriented parallel to the same midplane M, thereby facilitating demoulding of the barrier-forming part.

[0039] Preferably, the barrier-forming part is made of a thermoplastic material which has a melting point higher than that of the material of the body, which makes it possible to overmould the body onto the barrier-forming part. For example, the difference in melting point for the two materials is at least 25°C, being, for example, between 160 and 210°C for an LDPE or HDPE and of the order of 235 to 255°C for the polyketone polymer Carilon® from the company Shell Chemicals.

[0040] Preferably, the packaging and dispensing device comprises a means for withdrawing the composition, and this withdrawal means is preferably a pump, the latter preferably being mounted on a neck extending said cylindrical body at the top.

[0041] The pump may comprise a central aspiration duct, descending into the chamber containing the composition.

[0042] The piston body then preferably has, at its centre, a recess which substantially matches the shape of this duct, thereby making it possible to limit the residual volume of composition present in the chamber when the piston has reached its end of travel.

[0043] The piston body is preferably made of a thermoplastic material chosen from polyolefins, especially polyethylene (PE), preferably low-density polyethylene (LDPE), polypropylene (PP), copolymers thereof and mixtures thereof.

[0044] The barrier-forming part is preferably made of a thermoplastic material, preferably a polyketone polymer (PK). Polyketone polymer (PK)

[0045] These polymers have the structural specificity of possessing a carbon backbone consisting of carbon monoxide and of alpha-olefin units.

[0046] Ethylenically unsaturated hydrocarbons, suitable for use as precursors of "polyketone" polymers, have up to 20, preferably up to 10, carbon atoms. The ethylenically unsaturated hydrocarbons are especially ethylene and alpha-olefins such as propene, 1-butene, isobutene, 1 -hexene, 1 -octene, or even an arylaliphatic bearing an aryl substituent on another aliphatic molecule, more particularly an aryl substituent on an ethylenically unsaturated carbon atom. Examples of arylaliphatic hydrocarbons among ethylenically unsaturated hydrocarbons comprise styrene, p-methylstyrene, p-ethyl styrene and m-isopropyl styrene.

[0047] Polyketone polymers consisting of copolymers of carbon monoxide and ethylene or of terpolymers of carbon monoxide and ethylene with a second ethylenically unsaturated hydrocarbon having at least three carbon atoms, more particularly an alpha-olefin such as propene, are very particularly suitable for the invention.

[0048] The physical properties of the polyketone are adjustable as a function of the molecular weight, because it is a copolymer or a terpolymer, and, in the case of the terpolymer, as a function of the nature of the second ethylenically unsaturated hydrocarbon unit under consideration.

[0049] 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.

[0050] The polyketone polymer is preferably formed of monomer units of chemical formula (I) and / or of monomer units of chemical formula (II):

[0051] -(CH2CH2-CO)- (I)

[0052] -(CH2CH(CH3)-CO)- (II)

[0053] In one embodiment, the polyketone polymer comprises at least and especially consists of a copolymer comprising repeating units represented by the general formula (I). In another embodiment, the polyketone polymer comprises at least one terpolymer comprising repeating units represented by the general formula (I) and repeating units represented by the general formula (II).

[0054] More particularly, the polyketone polymer may possess an average molecular weight, Mw, of 150000 to 375 000, more particularly of 175 000 to 350000.

[0055] More particularly, the polyketone polymer may possess a number-average molecular weight of 50000 to 250000, more particularly of 70000 to 150000.

[0056] These molecular weights are measured by gel permeation chromatography, GPC, using hexafluoroisopropanol, HFIP, and by reference to polymethyl methacrylate, PMMA.

[0057] 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.

[0058] The polyketone polymer is generally obtained by copolymerization of carbon monoxide and at least one ethylenically unsaturated compound. As specified above, examples of ethylenically unsaturated compounds that copolymerize with carbon monoxide include a-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l -pentene, 1-octene, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, vinylcyclohexane, etc.; alkenylaromatic compounds such as styrene, a-methylstyrene; cyclopentene, cyclic olefins such as norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene; tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetracyclododecene; vinyl halides such as vinyl chloride; acrylic esters such as ethyl acrylate, methyl acrylate, etc.

[0059] Among these, the preferred ethylenically unsaturated compounds are alphaolefins, preferably alpha-olefins having from 2 to 4 carbon atoms, more preferentially at least ethylene.

[0060] The copolymerization of carbon monoxide with ethylene in the presence, where appropriate, of a subsidiary ethylenically unsaturated compound, and preferably propene, takes place by means of an organometallic complex catalyst consisting of (a) the group 9, 10 or 11 transition metal compound, and (b) a ligand having a group 15 element, the catalyst being produced by contacting of the two components. Any process may be used as a contacting process. 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 contacted with one another in the polymerization system.

[0061] As a polymerization process, a solution polymerization process using a liquid medium, a suspension polymerization process, a vapour-phase polymerization process in which a small amount of a high-concentration polymer is impregnated with a catalyst solution, and the like can be considered.

[0062] The polymerization may be batchwise or continuous.

[0063] The reactor used in the polymerization may be used as it is known or treated, and the reaction temperature during the polymerization is from 50°C to 100°C and the reaction pressure is taken in the range from 40 bar to 60 bar. The resulting polymer is recovered via post-polymerization filtration and purification processes and the catalyst composition remaining is removed with a solvent such as alcohol or acetone.

[0064] The polyketone polymer is generally obtained by copolymerization of carbon monoxide, ethylene and, where appropriate, propene in a liquid medium in the presence of an organometallic complex catalyst comprising (a) a group 9, 10 or 11 transition metal compound and (b) a ligand having a group 15 element. A process of this kind is especially detailed in patent KR10168489.

[0065] Preferably, the polyketone polymer is an aliphatic polyketone.

[0066] Preferably, the polyketone polymer is a terpolymer comprising CO, ethylene and propylene units.

[0067] Preferably, the polyketone polymer has the chemical formula:

[0068] [Chem 1]

[0069]

[0070] where m and n are integers greater than or equal to 1, R1 and R2, which are identical or different, independently of one another represent an alkylene group optionally 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 the units is random or ordered,

[0071] R1 being more particularly an ethylene group and R2 being more particularly a propylene group,

[0072] and in which the ratio n / m is less than or equal to A.

[0073] Preferably, the polyketone polymer is a resin obtained by polymerization and not an alloy with other polymers.

[0074] As non-limitative representatives of polyketone polymers that may be used in the invention, mention may be made especially of the polymers having the Poketone name (Hyosung), especially M630A, M630F, M330A and M330V, which most particularly lend themselves to transformation by injection moulding.

[0075] As illustrations of these polyketones, mention may also be made of the commercial products Schulaketon NV FC (Polyketone, Aliphatic, LyondellBasell Industries) and Schulaketon MC FC (Polyketone, Aliphatic, LyondellBasell Industries) and Carilon (Aliphatic Polyketone, Shell Chemicals).

[0076] A further subject of the invention is the device as defined above, containing the composition.

[0077] Composition

[0078] The composition may be a cosmetic composition for caring for and / or making up a keratin material and more especially the skin, the lips and keratin fibres, more particularly the hair.

[0079] It may especially be a make-up composition, a care composition, especially a sun protection composition, a perfume composition or a hair composition.

[0080] More specifically, it may be a composition for cleansing or caring for the hair, such as a shampoo, a rinse-out or leave-in conditioner, a rinse-out composition to be applied before or after dyeing, bleaching, permanent-waving or relaxing, or else between the two steps of a permanent-waving or relaxing procedure, or a hair composition for maintaining the hairstyle, such as a hair styling lacquer, gel, mousse or spray, or a hair composition such as a hair dyeing composition or a permanent hair reshaping composition; a make-up composition, and especially a make-up composition for the lips, the body, the face or epidermal derivatives, such as a foundation, a lipstick, a lip gloss, a face powder, an eyeshadow, a nail varnish, a mascara or an eyeliner; a care composition, and especially a body or face care composition, especially an anti-ageing serum or a composition for removing make-up from and / or cleansing keratin materials, especially the skin, mucous membranes such as the lips and / or the eyelashes, such as a shower gel, a bath gel or a makeup remover.

[0081] This composition may thus take any conventional presentation form according to the applications envisaged that is compatible with packaging in the device according to the invention.

[0082] The compositions may take any presentation form conventionally used for topical application, and especially the form of a dispersion, a lotion, an aqueous gel or an emulsion intended for topical application.

[0083] The composition may especially be used as a care product and / or sun protection product for the face and / or the body, with a liquid to semi-liquid consistency. More particularly, the composition may be more or less fluid and may have the appearance of a white or coloured cream, an ointment, a cream-gel, a milk, a lotion, a serum, a paste or a foam or mousse.

[0084] These various presentation formulations may be obtained by the preparation processes conventionally used in cosmetics or dermatology.

[0085] The volume of composition initially contained in the container ranges for example from 1 mL to 300 mL.

[0086] Brief description of the drawings

[0087] The invention may be understood better from reading the following detailed description of non-limiting exemplary embodiments thereof, and from studying the appended drawing, in which: [Fig. 1] Figure 1 shows schematically and in perspective an example of a packaging and dispensing device according to the invention,

[0088] [Fig. 2] Figure 2 shows on an enlarged scale a detail from Figure 1, without the O-ring seals,

[0089] [Fig 3] Figure 3 is a partial and schematic longitudinal section of the piston, [Fig 4] Figure 4 is an elevation view of the piston,

[0090] [Fig 5] Figure 5 is a cross section through V-V in Figure 4,

[0091] [Fig 6] Figure 6 is an exploded view of a device variant,

[0092] [Fig 7] Figure 7 is an elevation view, with the container transparent, of the device of Figure 6,

[0093] [Fig 8] Figure 8 is a longitudinal section through the device of Figure 7, [Fig 9] Figure 9 shows the detail IX of Figure 8, and

[0094] [Fig 10] Figure 10 illustrates comparative results.

[0095] Detailed description

[0096] Figure 1 illustrates a packaging and dispensing device 1 compliant with one working example of the invention, comprising a container 10 having a body 11 which is cylindrical in revolution, with a longitudinal axis X, and which accommodates a piston 20.

[0097] The container 10 comprises a neck 14 of which only the shoulder at its base is partially visible in Figure 1, on which a pump 30 is mounted without intake of air, the pump being known per se and comprising for example, as illustrated, an actuation button 32, which is movable relative to a body 31 secured to the container.

[0098] A chamber 13 is formed inside the container 10, between the piston 20 and the pump 30, for containing a composition C to be dispensed. This composition is advantageously a composition that is sensitive to oxidation. This composition may especially contain one or more of the abovementioned active agents, namely ascorbic acid and derivatives thereof such as 5,6-di-O-dimethylsilyl ascorbate, 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, retinol palmitate or acetate; flavonoids, especially resveratrol, and polyunsaturated fatty acids.

[0099] The pump 30 comprises an aspiration duct 33, which opens into the chamber 13. The pump 30 can be mounted on the container in a manner such as to ensure the desired sealing with respect to atmospheric oxygen, by any known means, in particular using one or more seals made of a suitable material.

[0100] The body 11 of the container may be equipped at its lower end with a plinth 40, which comprises for example, as illustrated, two concentric exterior and interior skirts 41 and 42 connected at their base by a transverse wall 43 extending perpendicularly to the axis X and allowing the device to stand vertically when placed on a horizontal planar surface by its plinth 40.

[0101] The cylindrical wall of the body 11 is inserted between the skirts 41 and 42. The exterior skirt 41 may comprise axial ribs 44 on its interior surface, so as to obtain the necessary purchase on the wall of the body 11 of the container.

[0102] The plinth 40 may also comprise, as illustrated, a central tubular barrel 45 which is connected at its base to the wall 43 and which may be provided on its interior surface with axial ribs 47.

[0103] Referring more especially to Figures 2 to 5, it is apparent that the piston 20 comprises a body 21 moulded as a single piece from thermoplastic material, for example a polyolefin such as LDPE or PP.

[0104] The body 21 comprises a tubular upright 22 with axis X which is connected at the top, via a widening 23 oriented radially towards the outside, to a flexible sealing lip 25 directed upwards and towards the outside, and designed to bear in a fluid-tight manner against the interior surface of the container body 11. The largest outside diameter of the lip 25 is greater than the inside diameter of the body 11, so as to obtain mechanical interference between the two, which ensures sealing.

[0105] The body 21 comprises, at the bottom, a tubular skirt 26 whose diameter is greater than that of the upright 22 and which is connected to the latter, forming an annular shoulder 26a.

[0106] The body 21 also comprises a dish-shaped central portion 28, which is connected to the base of the upright 22 by a flared intermediate portion 29.

[0107] The thickness ei of the intermediate portion 29 is for example between 0.6 and 1.4 mm, having a value for example of about 1 mm. The thickness of the dish-shaped part 28 may be within the same range of values, or may even be the same. The profiles of the dish-shaped part 28 and that of the flared intermediate portion 29 are such that they substantially conform to the shape of the duct 33 and that of the lower surface of the pump body surrounding it, such that the volume of the residual space remaining between the piston 20 and the pump 30 at the end of the piston travel is small, for example less than 3 mL, so as to maximize the extraction rate.

[0108] The body 21 may be manufactured by injection moulding with a point of injection located in the bottom of the dish-shaped part 28, on the pump side 30.

[0109] The upright 22, substantially half-way between the shoulder 23a defined by the widening 23 and the shoulder 26a, bears a radial annular rib 27, the free end of which has substantially the same outside diameter as the widening 23 and the skirt 26.

[0110] The rib 27, with the shoulders 23a and 26a, defines two respective annular grooves 71 and 72 that are intended to receive O-ring seals 81 and 82, shown schematically in Figure 3. Preferably, the inside diameter of these seals, before mounting, is less than that of the bottom of the grooves 71 and 72, such that the seals 71 and 72 are stretched during mounting. The seals have an outside diameter, when mounted on the body 21, greater than the inside diameter of the body 11, so as to obtain the desired mechanical interference, making it possible to obtain sealing with respect to dynamic air, i.e. when the piston 20 moves.

[0111] The piston 20 comprises a barrier-forming part 91, produced here by moulding thermoplastic material, preferably made of polyketone polymer (PK) or any other material having at least the same oxygen barrier effectiveness.

[0112] This part 91 comprises a dish-shaped central portion 92 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 is for example from 0.6 mm to 1.4 mm, being for example around 1 mm.

[0113] The central portion 92 is extended downwards, beyond the bottom wall 96, by a hollow spike 97 designed to engage in the central barrel 47 of the plinth 40, so making it possible to ensure mechanical coupling of the piston 20 and of the plinth 40 before the first dispensing of composition by the pump 30. The spike 97 may have a draft angle a of a few degrees, for example 2°. This may serve as a bottom stop and support for the piston 20 during the assembly of the glass, piston and plinth subassembly.

[0114] The flared portion 99 is connected at its periphery to a tubular upright 93, which is extended downwards, forming a shoulder 94, by a peripheral lip 95 that extends obliquely downwards and towards the outside and whose thickness decreases in the direction of its free end, this lip 95 being intended to bear against the interior surface of the body 11 of the container 10. The largest outside diameter of the lip 95 is greater than the inside diameter of the body 11, so as to obtain the desired mechanical interference.

[0115] The upright 93 is traversed by openings 93a, for example substantially half-way up, as illustrated. These openings 93a, as can be seen in Figure 5, have side faces parallel to the longitudinal axis X and contained in respective planes Pi to Pio, all parallel to the same median plane M, which is a plane of symmetry for the piston 20.

[0116] These openings 93a are traversed, as can be seen in Figure 3, by bridges 26b of material which connect the skirt 26 to an interior crown 26c that extends in contact with the radially interior face.

[0117] The body 21, on the upright 26, at the same level as the openings 26b, has two diametrically opposite grooves 26d, of shallow depth, which are separated by portions 26f of the same outside diameter as the upright 26. The grooves 26d make it possible to close the carriages of the mould over a smaller diameter and not to "scratch" the bottom zone without a parting line during demoulding.

[0118] In order to manufacture the piston 20, it is possible to start by moulding the barrier-forming part 91, in a multi-shell mould, with demoulding of the openings 93a by moving two opposite half-shells away parallel to the median plane M. The material can be injected from a central injection point situated in the bottom of the spike 97. The lip 95 may be moulded within a part of the mould without a parting line situated on the circumference of the lip, thereby reducing the risks of creating a relief that is detrimental to the desired sealing.

[0119] Next, the body 21 may be overmoulded onto the part 91, by injection, for example, of the thermoplastic material from the bottom of the dish-shaped part 28, the injected material passing through the openings 93a to the interior crown 26c. As for the lip 93, the lip 24 may be moulded within a part of the mould without a parting line situated on the circumference of the lip, thereby reducing the risks of creating a relief that is detrimental to the sealing.

[0120] Where PK is used to mould the part 91 and LDPE to mould the body 21, sandwiching the upright 93 between the skirt 26 and the crown 26c, and passing the bridges 26b of material through the openings 93 a, ensure good mechanical strength of the two parts, despite the chemical incompatibility of the materials which leads to the absence of adhesion of one part to the other. Next, the seals 81 and 82 can be mounted in their respective grooves 71 and 72.

[0121] In order to assemble the device 1, it is possible to insert the piston 20 borne by the plinth 40, with the spike 97 engaging in the barrel 45, until the plinth 40 has been inserted completely on the body 11.

[0122] The composition C may then be introduced into the inside of the container 10 before the pump 30 is fitted.

[0123] To use the device 1, the user actuates the pump 30.

[0124] The departure of composition C from the chamber 13 located above the piston 20, and the absence of intake of air, are accompanied by a negative pressure that causes the piston 20 to rise in the direction of the pump 30.

[0125] During this rise, the lip 24 ensures fluid sealing by bearing against the interior surface of the body 11 of the container. The force exerted on the piston 20 is enough to cause the hollow spike 97 to disengage from the barrel 45.

[0126] The part 91 limits the diffusion of oxygen through it, because of its low permeability. In the example illustrated, the part 91, in projection along the axis X, occupies substantially the whole interior cross section of the body 11.

[0127] The air which can, despite everything, pass over the lip 95 on account of the imperfect contact that may exist between the latter and the interior surface of the body 11 strikes the O-ring seals 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.

[0128] A low level of diffusion of oxygen over time through the piston 20 is thus obtained, while at the same time having a piston 20 capable of sliding sufficiently easily along the container to be able to rise therein when a negative pressure is generated by the departure of composition C from the chamber 13.

[0129] The uptake of oxygen by the composition during storage is, for example, less than 0.005 mg / L / day at 23°C.

[0130] The variant illustrated in Figures 6 to 9 differs from the one just described with reference to Figures 1 to 5 in the absence of a plinth 40 and in the shape of the lower end of the container 10.

[0131] In this example, the lower end of the container 10 has a slight widening 15. Figure 9 illustrates the fact that the nominal diameter d of the O-ring seals 81 and 82 is greater than the distance w separating the bottom of the grooves 71 and 72 from the interior surface of the body 11, with preferably the relationship 0.85t / <vi’<0.92t / .

[0132] The interference ii or i2 between the lips 24 and 95 and the interior 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 -0.15 mm.

[0133] Comparative results

[0134] The change in the content of oxygen inside a container according to the invention as described in the figures, comprising two butyl seals (A), an LDPE body and a Poketone (Hyosung) barrier-forming part, was measured relative to that of a container (B) according to the invention differing from (A) in the presence of a single butyl seal instead of two, and of a container (C) differing from (A) in the absence of a butyl seal.

[0135] The test / storage conditions are: 1 atm / 21°C / 50% rh

[0136] For each of the groups of results A, B or C, the left bar represents the minimum value, the middle bar the average and the right bar the maximum value.

[0137] It is seen that with two butyl elastomer seals, the uptake of O2 in the container is very markedly less. However, even without a butyl seal, performance is already good relative to certain known devices.

[0138] Of course, the invention is not limited to the examples that have just been described.

[0139] For example, the piston 20 may be given only a single O-ring seal, or even none, depending on the sensitivity of the composition to oxygen.

[0140] The pump 30 may be replaced with a valve, and a pressure may be exerted on the piston 20 from the side opposite the valve, for example by a spring, in order to tend to reduce the volume of the chamber containing the composition when the valve is opened by the user.

[0141] The container 10 may be made of a material other than glass, for example of metal or of metallized PP.

[0142] The body 21 may be made of a material other than LDPE or PP.

[0143] The container, when it is made of glass, may receive an anti-UV coating.

[0144] The housings 93a may not be open right through.

Claims

AS FILED Claims1. Device (1) for packaging and dispensing a fluid composition (C), comprising:a container (10) having a body (11) which is cylindrical, with a circular or other cross section, extending along a longitudinal axis (X), and defining at least partly a chamber (13) intended for containing the composition, a piston (20) that is movable inside said body (11), being able to move axially therein in response to the composition (C) being withdrawn from said chamber (13), this piston (20) comprising:o a piston body (21) made of a first material, especially a thermoplastic material, comprising a central portion (28, 29) and at least one sealing lip (24) that bears against the interior surface of the container body (11) and has a flexibility allowing it to conform to the shape of the cross section of said body,o a part (91) forming an oxygen barrier, made of a second material having a lower permeability to oxygen than the first material, said part extending in projection along said longitudinal axis (X) over more than the major part of the interior cross section of the body (11) of the container.

2. Device according to Claim 1, wherein the barrier-forming part (91) extends in projection along said longitudinal axis (X) over more than 95% of said interior cross section, better still more than 99%, even better still the entirety of said cross section.

3. Device according to one of Claims 1 and 2, wherein the piston (20) comprises at least one elastomeric seal (81, 82), preferably made of butyl, that bears against the interior surface of the body (11) of the container.

4. Device according to Claim 3, wherein the piston (20) comprises two elastomeric seals (81, 82), preferably made of butyl, that bear against the interior surface of the body (11) of the container.

5. Device according to one of Claims 3 and 4, wherein the one or more seals (81, 82) are attached O-ring seals, preferably identical when there are two of them.AS FILED 6. Device according to any one of the preceding claims, wherein the barrierforming part (91) is made of a thermoplastic material.

7. Device according to Claim 6, wherein said material is a polyketone (PK) polymer.

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

9. Device according to Claim 7 or 8, wherein the polyketone polymer is a terpolymer comprising CO, ethylene and propylene units.

10. Device according to any one of Claims 7 to 9, wherein the polyketone"polymer has the chemical formulawhere m and n are integers greater than or equal to 1, R1 and R2, which are identical or different, independently of one another represent an alkylene group optionally 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 the units is random or ordered, R1 being preferably an ethylene group and R2 preferably a propylene group, and in which the ratio n / m is less than or equal to *4.

11. Device according to any one of Claims 7 to 10, wherein the poly ketone polymer is a resin obtained by polymerization and not an alloy with other polymers.

12. Device according to any one of Claims 1 to 11, wherein the barrier-forming part (91) comprises a peripheral lip (95) that bears against the interior surface of the body of the container.

13. Device according to any one of Claims 1 to 12, wherein the barrier-forming part (91) covers the major part of the lower face of the body (21) of the piston, and especially the entirety of its central region (28, 29).

14. Device according to any one of Claims 1 to 13, wherein the barrier-forming part (91) has openings (93 a) through which the first material of the body (21) of the piston (20) extends.AS FILED 15. Device according to Claims 12 and 14, wherein the openings (93a) are made in a tubular upright (93) of the barrier-forming part, this upright (93) being preferably extended at the bottom by said peripheral lip (95).

16. Device according to one of Claims 14 and 15, wherein said openings (93a) have side faces oriented parallel to the same midplane (M).

17. Device according to any one of Claims 1 to 17, wherein the barrier-forming part (91) is made of a thermoplastic material that has a melting point higher than that of the first material of the body (21), the body (21) being overmoulded onto the barrier-forming part (91).

18. Device according to any one of the preceding claims, wherein the container (10) is made of glass, better still of drawn glass, especially of soda lime glass.

19. Device according to any one of the preceding claims, wherein the body (21) of the piston (20) is made of a thermoplastic material chosen from polyolefins, especially polyethylene (PE), preferably low-density polyethylene (LDPE), polypropylene (PP), copolymers thereof and mixtures thereof.

20. Device according to any one of the preceding claims, containing the composition (C), the latter containing at least one oxidation-sensitive active agent, chosen from ascorbic acid and derivatives thereof such as 5,6-di-O-dimethylsilyl ascorbate, 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 P-carotene, retinol palmitate or acetate; flavonoids, especially resveratrol, and polyunsaturated fatty acids.

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