The invention concerns the field of capping recipients, typically bottles, for containing liquids over several years, typically beverages, which are sensitive to oxidation, effervescent or otherwise, or even packaged under pressure. It concerns the field of stopper caps suitable for guaranteeing a sufficient gas tightness seal between the interior and exterior of the recipient. More particularly it concerns screw type stopper caps cooperating with a threaded neck of the recipient such that the capsules can be screwed and unscrewed.
A large number of stopper caps are already known for so-called non carbonated liquids or so-called still liquids (CO2 content less than 1.2 g/l). These is capsules often comprise an add-on seal adapted to the stopping of bottles, the liquid content of which, not sensitive to oxidation, is maintained at a pressure near atmospheric pressure.
Stopping means are also known for liquid under pressure, such as Champagne wines, comprising a cork stopper with head which is secured to the neck by means of a wire cage. In this case, it is not possible or easy to restop the neck with the cork.
Stopper caps are also known for maintaining the pressure owning to a compounded liner formed by a PVC based “compound” or mixture.
Several types of problems are posed in the field of tight capsules.
Conventional seals do not enable a liquid and gas tightness to be obtained, in particular with pressures inside the recipient ranging from 10 bar to 15 bar, i.e. from 1 MPa to 1.5 MPa, for a temperature range typically from 0° C. to 50° C., and for a period of possibly several years or even several decades.
Regarding the compounded liners, the PVC-based compound habitually used comprised at least a plasticizer such as DOP (dioctylphtalate) whose use is now prohibited by law in the European Union. Substitution plasticizers such as DEHP (di-ethylhexylphtalate) pose other problems as they require special equipment to implement them, their use thus resulting in costly investments. DEHPs are also on the point of being prohibited by law.
Furthermore, improving the seal must not result in downgrading the easiness by which the capsule is opened. In particular, when a screw type capsule is concerned, manual unscrewing must be performed with a torque within the standard range typically from 0.1 N·m (minimum for a capsule of 16 mm in diameter) to 3 N·m (maximum for a capsule of 41 mm in diameter), which corresponds to a standard manual force. Furthermore, it would be of no use to have a recipient with a hermetic seal with good pressure resistance it was then very difficult to open or if doing so would require special tools such as pliers.
According to the invention, the stopper cap, having an axial direction, comprises a shell, with a skirt and a head essentially perpendicular to said axial direction, and a seal arranged inside said shell, typically against the internal surface of said head, said stopper cap being designed to hermetically plug the neck of a recipient, typically a bottle, by axial and lateral compression of said capsule and said seal against said neck. Said capsule is characterized in that:
Said outer layer is placed in contact with the mouth of the neck of the recipient. This layer consists made of a deformable plastic material so that its surface is, during stoppering, indented by the mouth of the neck which is made of a clearly more rigid material, such as glass, and that it continues, after stoppering, to match the surface relief of said mouth under the influence of axial compression resulting from the stoppering and crimping. In order to enable easy removal of the capsule, the material of said outer layer advantageously forms with the material of the recipient, a contact with a low friction coefficient, typically a Coulomb coefficient less than 0.25, preferably less than 0.2. Typically, this material is made of a polyamide or polyethylene, is advantageously loaded with a slip additive.
This combination of means resolves the problems posed. Furthermore, the applicant was able to observe that these means enabled an excellent liquid and gas tightness to be obtained, and are particularly advantageous for the stopping means of liquids under pressure as they enable excellent resistance to pressure to be obtained.
According to a hypothesis proposed by the applicant, the form seal according to the invention would be fold free, very probably owing to the presence of the malleable support layer within the set of adjacent layers, which is difficult to obtain with a conventional form seal. This may explain the possibility to obtain an excellent seal and excellent pressure resistance.
According to the invention, the seal is a multilayer add-on seal that, when on the inside of the capsule shell, does not have a simple disk shape but that of a goblet with an axial edge, substantially cylindrical, the height of which is substantially of the same value as the thickness of the substantially flat part of the seal. This form seal can be, for example, a stamped or thermoformed disk then introduced into the bottom of the capsule shell. Advantageously, the form seal is obtained from a disk or a wafer cut in a multilayer strip with a diameter greater—approximately of two times its thickness—than the internal diameter of the shell at the level of the head, then pressed into the capsule by force, by means of a mandrel for example. Owing to the support layer, which gives its overall mechanical behavior to said set of adjacent layers, the seal is shaped without creation of folds that lead to leaks.
According to a preferred solution, after compression, the geometry of the seal is such that its periphery is not abutted against the inner peripheral surface of the shell head. In other words, the curvature radius R of the fillet connecting the center part of the seal and the axial peripheral edge, typically between is 0.5 mm and 2 mm, is greater than the curvature radius R′ of said shell in the zone where said head and said skirt connect. It is only during stoppering, when the head is compressed at least axially, that the peripheral part of the seal abuts on the inner surface of the periphery of the head of the shell.
During the stoppering operation, i.e. once the recipient has been filled, the capsule is crimped around the neck, the axial edge of the seal can not only be against the inner surface of the periphery of the head of the shell but it can also be deformed by axial elongation and radial shrinkage, if the capsule undergoes deformation on the periphery of the head of the shell that it transmits to the seal. This deformation can include for example, lateral compression, in the centripetal radial direction, due to the planetary passage of rollers or the combination of a necking and an axial traction which would result from the axial depression of an ring-shaped compression head.
The applicant noted that the deformation undergone during stoppering, in particular the combination of the necking, the elongation and the abutting against the head of the shell, significantly improved the conditions of intimate contact between the seal and the mouth of the recipient, thus the liquid and gas seal over an extended period of time, provided that the seal was properly deformed—i.e. without any fold—when it was placed in the capsule.
Advantageously, the skirt comprises, in its part closest to the head, an inner radial projection, typically an ring-shaped inner rib, forming a stop for the said axial edge of the said seal. Preferably, the said inner radial projection is placed at an axial distance from said head which was chosen notably based on said axial height h, such that said edge of the seal is blocked axially by said inner radial projection. Preferably, this distance is defined in such a way that the said seal remains constrained after being placed inside the said shell.
The shell can be metalloplastic or metallic, typically made of tin, or a tin alloy, is steel or aluminum, or aluminum alloy.
Advantageously, said seal has a thickness E ranging from 1 mm to 3 mm, and preferably, from 1.2 mm to 2.5 mm.
The set of adjacent layers can be formed by a multilayer film that is assembled to the resilient layer by bonding, lamination, welding or any other conventional means. As indicated above, each of the layers of the set of adjacent layers can fulfill several of the functions described in b2.1, b2.2 and b2.3. In addition, the order b2.1, b2.2 and b2.3 in which these layers are described is not an indication as to the positioning of the layers in relation to one another. The set of adjacent layers can also be formed by a layer (or a set of layers) covered on one of its faces by a thin covering, such as a coating applied by PVD (physical vapor deposition), CVD (chemical vapor deposition) or plasma assistance.
Advantageously, the seal has a symmetrical structure: two sets of identical adjacent layers are arranged in a symmetrical manner on either side of the resilient layer. The interest of a symmetrical structure resides in greater machinability of the seals, enabling them to be manipulated in any position before being placed inside the shell.
Advantageously, said resilient layer is an expanded polyethylene (EPE) layer having a density between 0.2 to 0.5 and preferably between 0.25 and 0.48.
The malleable support layer has a thickness chosen based on the thickness and the mechanical characteristics of the other layers so as to impart overall satisfactory mechanical behavior to the set of adjacent layers, guaranteeing in particular that no folds are created when the seal is introduced into the shell.
Said support layer can be metallic or organic. The applicant has indeed found that it was preferable that the layer not comprise a layer of cellulosic material is or of “Kraft” type paper. In such cases, the periphery of the seal nearly systematically creates folds making it difficult to obtain a good seal between the capsule and the mouth of the bottle. If the set of adjacent layers comprises a metallic layer as a support, this layer can also serve as a barrier layer. If the set of adjacent layers does not comprise a metallic layer, the support layer is chosen with a thickness substantially greater than that of the adjacent organic barrier layer. In this way, said barrier layer, generally rigid and fragile, can be more easily deformed without losing its properties.
Said outer layer is a flexible organic layer facilitating an intimate and impermeable contact with the material of the recipient. Advantageously, this outer layer has a low friction coefficient, typically below 0.25, preferably below 0.2, with the material of the bottle. Among the possible materials, rather a polyolefine, for example, a polyethylene (PE), possibly loaded with a slip additive, a polyvinylidene chloride (PVDC), a polyethylene terephtalate (PET) or even, preferably, a polyamide (PA) would be chosen. The applicant has indeed noted that a good tightness on a capped neck depended as much, if not more, on the ability of the seal to intimately match the shape of the mouth than the intrinsic properties of permeability of the component layers of the seal: it is of no use that a layer, such as a metallic layer, offers an excellent barrier to diffusion if the latter is not sufficiently malleable to match as close a possible the relief imposed by the micro-asperities of the material of the mouth so as to have an intimate contact with same. Plastic materials, and particularly polyamides, exhibit excellent behavior in this respect.
In certain embodiments of the invention, said layer of barrier material comprises a metallic layer, typically aluminum or tin or their respective alloys.
Other embodiments of the invention present seals more easy to recycle, made entirely or nearly entirely of plastic materials. In this case, said barrier layer can be a mineral such as silicium oxide SiOx deposited on one of the component is plastic layers of the seal. The barrier layer can also be an organic barrier material such as an ethylene vinyl alcohol copolymer (EVOH), a polyvinylidene chloride (PVDC), in particular a Saran, or even a polyamide (PA).
The seals can have several possible structures. The preferred structures comprise a core of said resilient layer, having a thickness typically between 1 and 3 mm, generally 2 mm, and, adjacent to at least one face of said core, a set of adjacent layers that is:
a) either a metalloplastic complex set, of P/Adh/M/Adh/P′ type or even of M/Adh/P/Adh/M′/Adh/P′ type, where P and P′ symbolize plastic materials, possibly different, M and M′ symbolize metals, possibly different, and Adh designates an adhesive layer suitable for the assembly of metallic layers and polymeric layers, typically made of polyurethane (PUR) or EAA (ethylene-acrylic acid copolymer), for example, PE/EAA/Sn/EAA/PVDC or PE/EAA/Al/EAA/PA for the first case and Al/EAA/PE/EAA/Al/EAA/PA for the second case;
b) or an entirely plastic set, for example a coextruded or bonded multilayer film of PE/EVOH/PE type or, preferably, a layer of polyamide (PA) covered by a think layer of silicium oxide SiOx (x near 2, typically between 1.5 and 1.8), having a thickness typically between 50 and 80 nm. In this last case, and particularly if the bottle is glass, the thin layer of silica is advantageously placed toward the resilient layer, typically of EPE, so as to leave the polyamide layer in contact with the mouth of the neck.
In another embodiment, said capsule comprises a metallic outer shell and an inner plastic insert, said insert being integral with said metallic shell, its bottom abutting against the head of the shell, in such a way that said form seal is no longer connected by force to said head but to the bottom of said insert.
Regardless of the embodiments considered, said shell can comprise a means to detect initial opening typically including a guarantee band attached by a plurality of bridges to an upper part of said shell, said guarantee band is remaining integral with said neck during initial opening causing said bridges to break. The skirt of the shell can also comprise at least one ring forming an ring-shaped radial projection, said ring being placed below said guarantee band or a line of weakening, so as to protect said guarantee band or said line of weakening when the skirt is crimped to the neck by the formation of a lower necking part. Said skirt can also externally comprise a plurality of axial splines to make it easier to grip the capsule manually when it is opened for the first time.
Another subject according to the invention is a method for manufacturing a stopper cap in which:
Advantageously, the seal is formed by the passage of the peripheral edge of the disk between said punch and said die, then it is forced into the bottom of the shell by axial displacement of the punch in the shell and the edge of the seal is held in tension by a sliding contact between the outer surface of the axial edge and the inner well of the shell. Advantageously, the disk is transformed into a seal which is forced into the bottom of the shell in one single is axial movement of the punch, the die and the shell being kept stationary.
In order to axially block the seal in the head of the shell, the skirt can comprise, in its part closest to the head, referred to as the “upper part”, an inner radial projection, typically an ring-shaped groove, which forms a stop for the axial edge of said seal. Said seal is placed beyond said inner radial projection by force, between the head and the inner radial projection, the extremity of the axial edge abutting against said inner radial projection, the distance between the inner wall of the head and said inner radial projection being preferably defined such that said seal can be restrained.
If the capsule comprises an insert, this method also includes a step in which an insert forming a molded plastic part comprising a head and a skirt is procured, said disk is assembled with said insert instead of assembling it to said shell, so as to obtain said seal typically under stress assembled to said insert. Said insert can either be assembled to said shell before said seal is formed in said insert, or first assemble said seal to said insert, said insert thus equipped with said seal typically under stress, then being secured to said shell.
Another object of the invention is a method for stoppering the neck of a bottle, said neck comprising at least a mouth, an upper axial part adjoining said mouth of the neck and of outside diameter D1 and a counter-ring of outside diameter D3 forming a crimping shoulder with a lower part of diameter D3′<D3, the method in which:
a) a stoppering device is used comprising notably an axial compression end cap comprising two coaxial parts, one central part, referred to as the “axial compression head”, the other peripheral part, referred to as the “ring-shaped end cap” or “necking ring”, these two parts may be integral or mobile in relation to one another and a crimping means, typically a roller;
b) a stopper cap according to the invention is used,
c) said capsule is placed on said neck, said capsule, typically cylindrical, having an internal diameter adapted to the dimensions of said neck, such that said head of said capsule can axially abut against said mouth, said form seal being interposed between said head and said mouth,
d) said axial compression ram with its center part and its peripheral part are displaced together in the direction of the capsule, so as to compress the head of the shell and the form seal by flattening the latter against said mouth;
e) an additional axial displacement is made of the sole peripheral part of the compression end cap in such a way that the part of said capsule opposite said upper axial part of the neck undergoes necking by passing from an external diameter Do to an external diameter D′o<Do, said necking leading to the radial compression of said axial edge of the seal against at least a fraction of the upper axial part of the neck;
f) said crimping means is applied radially against said skirt so as to push the metal of said skirt under said shoulder.
This method applies mainly to screw type capsules. In this case, the neck of the recipient equally comprises, between the upper axial part and the counter-ring, a threaded part comprising at least a screw thread groove, of external diameter D2>D1 and of diameter D′2<D2 in the grove bottom, and the stoppering device also has a thread forming tool, such that between step e) and step f), said thread forming tool is applied radially against the skirt of the capsule so as push the metal of said skirt into said groove on the threaded part of the neck, so as to thus form a metal skirt with a thread.
Advantageously, the necking rate D′o/Do is between 0.91 and 0.96, preferably between 0.92 and 0.95, and is typically 0.94.
Another object of the invention is a capped bottle obtained by the previous method.
Another object of the invention is the use of stopper caps according to the invention or obtained by the method according to the invention, to stop bottles containing a liquid under pressure.
All the figures relate to the invention.
a, 4b and 4c are left-hand axial half-sectional views which represent the first steps of the stoppering operation by which the capsule (1) is secured to the neck (40) of a bottle (4).
The seal 3 is a form seal pressed inside the shell 2′ by force. It has a center part 30 typically plane and perpendicular to the axial direction 10 and an axial peripheral edge 31 connected to said center part 30. Its axial height h, measured from the level of the surface of the center part of the seal, is essentially equal to the thickness of the center part 30, between 0.5 and 2 mm.
Said seal 3 is a multilayer form seal made from a disk 3′ cut from a multilayer strip, a few structures of which are given in the example below. It is blocked axially by an inner radial projection: the ring-shaped groove 22.
The following examples describe various band structures produced to obtain the disks used to make the seals according to the invention.
Four steps, a), b), c) and d) of the evolution of the seal disk 3′ in the assembly device 6 cooperating with a shell (2) have been illustrated:
The capsule chosen to illustrate the various steps of the stoppering operation in
a) represents the capsule 1 being placed on the neck 40 opposite the stoppering device 7, the capsule 1 having an internal diameter essentially equal, although slightly greater, to the largest external diameter of said neck 40. The neck 40 is threaded.
b represents the first axial compression phase of the capsule 1 on the neck 40 owing to the axial pressure exerted by the compression end cap 70 of the stoppering device 7, the axial compression head 71 and the ring-shaped end cap 72 being maintained integral during this phase. Typically, during this is phase, the axial force exerted by the end cap 70 is roughly 50 daN for a capsule measuring 30 mm in diameter. The seal 3 is flattened and indented at the mouth 41, its axial edge 31 is pressed against the inner surface of the head 20 of the shell 2.
c) represents the second axial compression phase of the capsule 1 on the neck 40 owing to the axial pressure exerted by the ring-shaped end cap 72 alone, resulting in the necking of the upper part of the skirt 21 and the edge of the head 20 against the upper axial part 42 of the neck 40. This has the effect to essentially extend the skirt 2, the lower end 219 of which reaches the lower necking part 45 of the neck for crimping of the capsule. Typically, during this phase, the axial force exerted by the ring-shaped end cap 72 is roughly 160 daN for a capsule of 30 mm in diameter.
d represents the capsule 1 crimped on the neck 40. The thread rolling tool 73 was used to push the typically metallic skirt into the threads 430 on the threaded part 43 of the neck 40, and the subsequent action of the crimping roller 74 which folded the lower end 219 of the skirt 21 under the counter-ring 44, so as to crimp the capsule to the neck. The capsule has a ring 27 forming an ring-shaped radial projection, placed below a line of weakening 24, in such a way that said line of weakening was protected when the skirt 21 was crimped to the neck 40 by the formation of the lower necking part 28.
The tightness of a capsule is expressed not only according to the intrinsic barrier properties of the seals used: the contact of the seal on the mouth of the neck plays a primordial role and it is imperative to design a test that is representative of the actual tightness conditions of the necks capped. For this reason, the applicant has developed the following tightness test:
a) the body of a capped bottle is cut to remove its lower part. The cut must be clean and as plane as possible so as to be able to place the upper part of the bottle 8 equipped with its capsule 1 on a plane plate 500, typically made of stainless steel, in a zone where it is perforated to allow two tubes 501 and 502 to pass through it. The connection between the lower end of the bottle and the stainless steel plate 8 is rendered perfectly hermetic by a thick bead 503 of epoxy resin (typically 20 mm). A gas of controlled purity, typically pure argon or pure nitrogen, is introduced inside the bottle via the tube 501. This gas is exhausted by the tube 502 which is connected to a means 504 to measure the quantity of foreign atoms (typically oxygen atoms) which have entered the bottle (Oxtran type machines). The assembly is placed in a chamber 510, which is then filled with oxygen. In order to correctly evaluate the tightness of the stoppering, several days are required before measuring the quantity of oxygen that has infiltrated into the bottle.
Tests were conducted on various STELVIN (registered trademark of the applicant) 30H60 capsules equipped with seals of 28.5 mm in diameter and 2 mm thick.
In particular:
The capsules were crimped onto the necks of bordelaise bottles. The bottles were placed in a chamber containing oxygen for 40 days.
The analyses were conducted with a dry gas (Argon) and at ambient temperature.
Certain results for seal A are very good but overall the results are rather dispersed. With this type of seal, a capsule permeability value in the order of 10−4 cc O2/day can be defined.
Seal B has the most homogenous results. With this type of seal, a capsule permeability value in the order of 1.3−10 cc O2/day can be defined.
These values, related to the surface of the seal, correspond to a permeability value in the order of 1.5 cc O2/m2/d/atmosphere. They are near but higher than the intrinsic values of oxygen permeability of plastic “barrier” films containing EVOH or PVDC, for example. This clearly shows that capsule tightness essentially depends on the nature of the contact of the seal on the mouth of the bottle neck: it is of no use to have organic seal with excellent is barrier properties if its mechanical behavior does not enable it to establish intimate contact with the glass of the recipient.
Number | Date | Country | Kind |
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0609289 | Oct 2006 | FR | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/FR07/01759 | 10/24/2007 | WO | 00 | 4/15/2009 |