ZA200610580B

ZA200610580B - Seals made of a multi-layered material for sealing means, particularly a sealing capsule

Info

Publication number: ZA200610580B
Application number: ZA200610580A
Authority: ZA
Inventors: Granger Jacques
Original assignee: Alcan Packaging Capsules
Priority date: 2004-06-11
Filing date: 2005-06-09
Publication date: 2008-06-25
Also published as: DE602005023611D1; ES2352846T3; NO338527B1; FR2871446B1; CA2570372A1; EP1765688B1; AU2005256760B2; AR050669A1; EP1765688A1; WO2006000706A8; FR2871446A1; WO2006000706A1; ATE481332T1; CA2570372C; AU2005256760A1; NO20070166L

Description

FIELD OF THE INVENTION

The invention relates to the field of seals associated with stopper means for sealing up containers, typically the field of cork, top or stopper cap seals.

STATE OF THE ART

A known multi-layer material seal is described in

EP C0 970 893 Al wherein EVCE 1s used as a Larrier material.

Seals are algo known that comprise PVDC as a barrier material.

A multi-layer material seal is thus known, for example, which has the following structure:

LPDE/EVA/PVDC/EVA/LDPE/EPE/LDPE/EVA/PVDC/EVA/LDPE

In this structure, used particularly as a stopper cap seal, the EVA acts as an adhesive layer to bond the

LDPE to the PVDC, and EPE denotes an expanded PE.

PROBLEMS POSED

The problems posed are of several types: - on the one hand, in order to be cost-effective, the seals are typically formed from strip material, typically by cutting with a punch, such that a not insubstantial part of said strip material, in practice typically about 20% in the case of round seals cut vcontiguously”, forms a skeleton or offcuts which go for waste. In fact, when the strip material intended to form these seals comprises a material including chlorine, typically PVDC, recycling the skeleton, and possible recycling the seals at the end of their life span poses problems, in particular problems of corrosion through the formation of hydrochloric acid,

- moreover the presence of PVDC does not allow a seal with a uniform structure to be preserved,

- on the other hand, the applicant has conducted stopper tests on bottles of wine for laying down using stopper caps fitted with seals, even though traditionally, bottles of wine for laying down are closed by cork stoppers, and it has noted that, in many cases, the seal used in caps sealing up wine for laying down interfered with the behaviour of the wine over time, in other words, its ageing process.

Furthermore, the applicant has found that seals comprising EVOH, although able to form a barrier that is in principle effective or adapted to the ageing of the wine, could * not be used as they were unstable in storage,

- furthermore, the invention aims to obtain seals that have, with a comparable barrier, a smaller production cost,

- finally, the applicant has noted that caps fitted with standard seals were not necessarily adapted, in terms of the level of barrier to oxygen or to steam, to the conservation of wines, since each wine requires a certain barrier level, or a barrier located in a given range of values.

Indeed, the ageing of some wines involves a controlled atmosphere exchange, and therefore a pre-set barrier level.

The seals according to the invention aim to resolve these problems, while still providing the required tightness, in other words having no liquid leaks.

DESCRIPTION OF THE INVENTION

According to the invention, the multi-layer material leakproof seal intended for use in a stopper means for a container intended to contain a food product, said container typically being a bottle intended to contain an alcoholic drink and said stopper means being typically a stopper cag, comprises a layer

C of thermoplastic material with a density of between 200 and 500 kg/m®, and a layer B forming a barrier to oxygen.

In this seal: a) said layer B forms or comprises a coating of - non-organic material, b) said seal comprises a layer S forming a support of said layer B, said support layer S being or not being in contact with said layer C, so as to give a structure that comprises either a succession of layers

Cc, B and S, a structure shown symbolically as C/B/S in the case of adjacent layers C, B and S, the layer S being intended to be in contact with said food product, or a succession of layers C, S and B, a structure represented symbolically as C/S/B in the case of adjacent layers C, S and B, the layer B being intended to be in contact with said product.

The seals according to the invention address the problems posed, while still providing the required tightness, in other words having no liquid leaks.

Indeed, these seals are formed from chlorine-free strip material, the barrier B not comprising any PVDC, such that recycling the skeleton, and possibly recycling the seals at the end of their lifespan poses no problem, in particular poses no problem of corrosion through the formation of hydrochloric acid.

Moreover, the barrier layer B is a layer which, despite its slight degree of relative thickness compared with the layer C, has a high barrier level, such that recycling the skeleton in the layer C may occur without drawbacks. The layer C is typically at least 1000 times thicker than the barrier layer B, and even sometimes 10,000 times thicker than the barrier layer B.

The applicant has conducted tests on stoppering bottles of wine for laying down, using stopper caps fitted with seals according to the invention which ensured the correct ageing of wines, without modifying the properties of these seals over time, and without furthermore encountering the problems with stoppers which can arise more or less randomly with traditional cork stoppers.

The invention furthermore makes it possible to obtain a whole series of seals with a smaller production cost, particularly through the possibility of having a more straightforward multi-layer structure for a comparable barrier level.

AMENDED SHEET DATED 19 JUNE 2008

Finally, the invention makes it possible to obtain a range of seals as a barrier to oxygen or to steam, so as to be able to adapt the barrier level to each type of wine, with a view to the ageing thereof. 5

DESCRIPTION OF THE FIGURES

All the figures relate to the invention.

Figure la is a cross-section view of a stopper cap (4) fitted with a multi-layer seal (1, 1’) according to the invention. This cap (4) comprises a threaded insert (40) and a metal shell (41). mhe structure of the rulsi-layer seal (1, 17) in figure la has been shown in figure 1b and corresponds to the symbolic representation C/B/S, corresponding to the succession of layers A, B and S, S being the layer in contact with the liquid.

Figures 2a to 8d are similar to figure 1b and illustrate a variety of structures of multi-layer seals * (L, 1’, 1’) according to the invention. The following table shows for each figure the structure of the multi- layer seal:

EN

EN A

S/B/C’/Ad’ /M/AA/B/S

ET ct eo fwemerese - fw samme nae savory [vor or Snare RE or So

EE V or P/M/Ad’'/B/S/AA/C'/S/B/Ad’/M/V or P

In figures 2a to 8d, only the layers C, C’', B and

S have been hatched. The other layers I, Ad, ad’, M etc have not been hatched in the interests of clarity.

Figure 9 is a diagrammatic representation of the manufacture of a multi-layer strip material (2) of the type "C/B/E", with a layer C (20) formed by extrusion on a twin layer strip film B/E (23) supplied on a spool (24), and the manufacture of corresponding seals (1, 1’, 1’) by cutting out of the strip (2) of multi-layer material C/B/E formed in this manner, the skeleton (3) then being returned to the feed hopper (22) of the extrusion machine (21) and thus recycled in the layer

C.

Figure 10a is a view from above of a portion of multi-layer material strip (2; after round seals 1, 1’) have been cut out, and known as the "skeleton" (3).

Figure 10b is a vertical cross-section view of a plane seal (1, 1’) of the C/S/B type.

Figure 10c is a vertical cross-section view of a thermoformed seal (1, 1') of the C/S/B type. »

DETAILED DESCRIPTION OF THE INVENTION

According to the invention, said barrier layer B may form or comprise a non-organic layer constituted by a coating of SiO.

According to another embodiment of the invention, said barrier layer B may form or comprise a coating of aluminium oxide.

According to another embodiment, said barrier layer B may form or comprise a coating of carbon.

According to another embodiment of the invention, said barrier layer B may form or comprise a nano- particle dispersion of exfoliated platelets of a phyllosilicate clay.

Whatever embodiment is selected, said barrier layer B may be of selected thickness or of selected content of non-organic material, to give a seal with permeability to oxygen of less than 5 cm®/m?/7.

Said barrier layer B may be of selected thickness or of selected content of said non-organic material, to give a seal with permeability to oxygen of between 5 and 10 cm®/m?/j.

Said barrier layer B may be of selected thickness or of selected content of said non-organic material, to give a seal with permeability to oxygen of between 10 and 20 cm’/m?/3.

Said barrier layer B may be of selected thickness or of selected content of said non-organic material, to give a seal with permeability to oxygen of between 20 and 40 cm’/m?/73.

Said barrier layer B may be of selected thickness or of selected content of said non-organic material, to * give a seal with permeability to oxygen of over 40 cm3/m?/j and typically of up to 80 cm’/m’/j.

Indeed, it is important to have available a range of seals with different ranges of permeability to oxygen, insofar as each type of wine may require, for optimum conservation and ageing, a seal which provides a more or less significant level of gaseous exchange with the outer atmosphere.

Generally speaking, the level of gaseous exchange will be less for white wines than for red wines.

According to the invention, said barrier layer B may have a thickness of between 10 nm and 250 nm when said non-organic material is selected from a coating of

SiOx, or a coating of aluminium oxide or a coating of carbon.

Said barrier layer B may also be formed by a dispersion of exfoliated nano-particles in a resin or a plastic material with a thickness of between 1 um and 30 um.

According to the invention said layer C may have a thickness E. typically between 0.5 mm and 2.5 mm.

Said layer C may be formed of a material M constituted by or comprising a layer of expanded polyolefin typically expanded PE or EPE.

Said layer C may be constituted by or comprise a layer of thermoplastic material with density between 200 and 500 kg/m’.

Typically, said layer C may be a layer of expanded or cellular polyolefin, typically a layer of expanded

PE or EPE, with density between 350 kg/m’ and 450 kg/m’. -

Said layer C may be constituted by or comprise a layer of elastomer, typically SEBS or silicon.

According to the invention, said support layer S may be formed out of the material Ms selected from a polyolefin or a PET, typically a PP, of thickness Eg typically between 10 um and 50 pm. See figure lb.

As is shown in diagrammatic form particularly in figure 2a, an intermediate layer I may be interposed between said layer C and said layer B, said intermediate layer I being a layer of polyolefin, and typically a layer of PE, of thickness E; typically between 10 pm and 50 um, to give for said multi-layer material a structure represented symbolically as

C/1/B/S or as C/I/S/B.

Indeed, it may be useful or necessary to manufacture the multi-layer material I/B/S separately, since the layer I is able to act to protect the barrier layer B and/or provide the connection with the layer C.

Depending particularly on the nature of said layer

B, and as shown in diagrammatic form in figures 2b and 2c, a layer of adhesive Ad may be interposed between said layer B and said layer C or said layer I, said adhesive layer Ad typically having a thickness Ea of less than 5 um, to give for said multi-layer material a structure represented symbolically as C/A4d/B/S or c/I/Ad/B/S or C/Ad/S/B or C/I/Ad/S/B or C/A4d/I/B/S or

C/Ad/I/S/B.

According to another embodiment of the invention shown in figures 3a to 3f and 6a to 8d, said layer C may be a central layer C’' possibly forming a plane of y symmetry in respect of said multi-layer material, to give for said multi-layer material structures selected from: a) S/B/C'/B/S,B/S/C'/S/B,S/B/C'/B/S, as shown in figure 3a, b) structures comprising at least one intermediate layer I, in particular: s/B/I/C’/1I/B/S,B/S/1I/C’'/1I/S/B, s/B/1/C*/1/S/B,S/B/C'/1I/B/S,B/S/C’'/1/S/B,S/B/C'/1/S/B,

S/B/I/C*'/S/B, as shown in figure 3b, c) structures comprising at least one adhesive layer Ad, in particular: Ss/B/ad/C'/Ad/B/S,

B/S/Ad/C'/ad/S/B, S/B/C'/Ad/B/S,B/S/C’/Ad/S/B, as shown in figure 3c,

d) structures comprising at least one adhesive layer Ad and an intermediate layer I, in particular: s/B/Ad/I/C’'/I/Ad/B/S,B/S/ad/1/C’'/I/Ad/S/B,S/B/I/A4d/C'/A d/1/B/S,B/S/I/ad/C’'/Ad/1/S/B,S/B/1/C'/I/Ad/B/S,B/S/TI/C’ /I/Ad/S/B,S/B/I/C’'/Ad/1/B/S,B/S/I/C'/Ad/I/S/B, as shown in figures 3d to 3e.

As shown in the portions of figures 3a and 5a between the dotted lines A and A’, said layer C’ may be formed by the layers C/Ad’'’/C, Ad’’ being another adhesive layer, the layer Ad‘’’ and said adhesive layers

Ad and Ad’ being able to be formed of one adhesive of the same type or of adnesives of different types.

As shown diagrammatically in figures 4a to 6e, said seal (1, 1’, 1’’') may comprise a metal layer M, typically in the form of a metal film My made of Sn or

Al or in the form of a metal layer Mp formed by vacuum coating of metal, typically a layer of Cr or Al.

According to one embodiment of the invention, said * metal layer M may be interposed between said barrier layer B and said layer C or said layer C’, possibly by means of an adhesive layer Ad or an adhesive layer Ad’, different or not different from said adhesive layer Ad, in such a way that a part of said seal comprises a multi-layer structure part selected from: a) ¢C or C’'/M/B/S, C or C'/M/S/B, as shown in figures 4a or 5a, b) structure parts comprising an intermediate layer I, in particular: C or C'/I/M/B/S, C or c’/I/M/S/B, as shown in figures 4b or 5b,

Cc) structure parts comprising at least one adhesive layer Ad, in particular: C or C’'/Ad/M/B/S, C or Cc’'/Ad/M/S/B, C or c'/ad’'/M/A4A/B/S, C or c’/ad’' /M/AA/S/B, as shown in figures 4c, 5c, 5e and 5f, ad) structure parts comprising at least one intermediate layer I and an adhesive layer Ad and/or an adhesive layer Ad’, in particular: C or C'/I/M/Ad/B/S,

Cc or C'/I/Ad/M/B/S, C or C'/1/ad/M/S/B, as shown in particular in figures 4d and 5d.

According to another embodiment of the invention, said barrier B may be included between said metal layer

M and said layer C or C', possibly by using an adhesive layer Ad or an adhesive layer Ad’, different or not different from said adrnesive layer Ad, in such a way that a part of said seal comprises a multi-layer structure part selected from: a) C or C’'/B/S/M, C or C'/S/B/M, as shown in figure 6a, b) structure parts comprising an intermediate layer I, in particular: CC or C'/I/B/S/M, C or y c’'/I/S/B/M, as shown in figure 6b, c) structure parts comprising an adhesive layer

Ad, in particular: C or C’/Ad/B/S/M, C or c’'/Ad/S/B/M, as shown in figure 6c, 4d) structure parts comprising at least one intermediate layer I and an adhesive layer Ad and/or

Ad’, in particular: C or C'/Ad/I/B/S/M, C or c'/1/Aad/B/S/M, C or C'/Ad/I/S/B/M, C or c'/I/Ad/S/B/M or C'/I/Ad/S/B/AQ’'/M, as shown in figures 6d and 6e.

Whatever the embodiment of the invention, said metal film My may be constituted by a film of Sn or Al, with a thickness Ey of between 5 um and 20 um, and typically a thickness of 10 um.

Said metal layer Mp formed by vacuum deposition of metal may be a vacuum metal plated layer with a thickness of between 10 nm and 1000 nm, deposited on said support S or on another support S’, as shown in figure 4d.

According to another embodiment of the invention shown in figures 7a to 7e, said layer S may be replaced by a layer M’, said layer M’ being selected from a metal film Mp of Sn or Al or a metal layer Mp formed by vacuum deposition of metal, typically a layer of Cr or of Al, on a support film S$’, to give, for said multi- layer material, structures selected from: a) M'/B/C'/B/M’',B/M'/C'/M'/B,M/B/C’'/B/M', as shown in figure 7a, b) structures comprising at least one intermediate layer I, in particular: M’/B/I/C'/I/B/M’,

B/M'/I/C'/I/M'/B,M'/B/I/C'/I/M'/B,M'/B/C'/I/B/M' ,B/M'/C +/I/M'/B,M’'/B/C'/I/M'/B,M'/B/I/C'/M'/B, as shown in * figure 7b, c) structures comprising at least one adhesive layer Ad, in particular:

M/B/Ad/C’'/Ad/B/M’' ,B/M'/Ad/C’'/Ad/M'/B,

M’'/B/C’/A4d/B/M’' ,B/M’'/C’'/Ad/M'/B, as shown in figure 7c or Te, d) structures comprising at least one adhesive layer Ad and one intermediate layer I, in particular:

M’/B/Ad/I/C'/1/Ad/B/M’',B/M/AA/I/C'/I/Ad/M’'/B,M'/B/I/Ad/ c'/Ad/I/B/M',B/M’'/I/Ad/C'/Ad/I/M'/B,M'/B/I/C'/I/AQ/B/M’ ,B/M’'/I/C'/I/Ad/M'/B,M'/B/1/C'/Ad/I/B/M',B/M'/I/C'/AG/I /M'/B, as shown in figure 7d.

However, said layer S may be replaced by a layer

M’, said layer M’' being selected from a metal film Mg of Sn or Al or a layer of metal Mp formed by vacuum deposition of metal, typically a layer of Cr or Al, on a support film S$’, in such a way that a part of said seal comprises a part of said multi-layer structure selected from: a) C or C'/M'/B/C or C’'/B/M’', as shown in figure la, b) structure parts comprising an intermediate layer I, in particular: C or C’'/I/M'/B, C or c'/1/B/M’, as shown in figure 7k, c) structure parts comprising an adhesive layer

Ad, in particular: C or C’'/Ad/M’'/B, C or C’/Ad/B/M’', as shown in figure 7c¢ or Te, d) structure parts comprising at least one adhesive layer Ad and one intermediate layer I, in - particular: C or C'/I/Ad/M’'/B, C or C’'/Ad/1I/B/M’',C,C or c'/1/Ad/B/M', C or C'/Ad/I/M'/B, C or C’/I/Ad/M'/B, as shown in figure 7d.

As shown in figures 8a to 8d, when said layer B or said layer M or M' is an outer layer intended to be in contact with the food product, said layer B or said layer M or M' may be coated with a layer of varnish V, typically a food varnish, in such a way that said seal has a structure comprising externally "“/B/V”" or “/M(M')/V".

According to another embodiment of the invention, and as shown in figures 8a to 8d, when said layer B or said layer M or M’' is an outer layer intended to be in contact with said food product, said layer B or said layer M or M’' may be coated with a protective layer P, typically of polyolefin, possibly anchored by an adhesive layer Ad'’’, in such a way that said seal has a structure ending in “/B/P” or in “/M(M’')/P", or in

B/Ad'’'’'/P'’' or in “/M(M')/Ad’'’''/P’'’.

Typically, said thickness Ec of said layer C or of said layer C’' may represent from 70% to 99% of the total thickness Ej; of said seal. See figure 1b.

As shown particularly in figure 10b, said seal (1) may form a plane seal (1’) typically obtained by cutting said multi-layer material in a strip or typically two-dimensional format.

However, as shown in figure 10c, said seal (1) may form a shaped seal (177) typically obtained by thermoforming said multi-layer material in a strip or two-dimensional format.

Another purpose of the invention is constituted by container stopper means comprising a seal (1, 1’, 1'") * according to the invention.

This stopper means may comprise a stopper cap (4) fitted with a seal (1, 1’, 1‘’) according to the invention, said container typically being a bottle intended to contain, as a food product, an alcoholic drink, typically wine.

As shown in figure la, said stopper cap (4) may comprise a typically threaded plastic material insert (40), said seal (1, 1’, 1’'’) being anchored to said insert (40), and an outer shell (41) of metal, typically of Al or Sn, or metallised plastic, or plastic.

Another purpose of the invention is constituted by the use of a seal (1, 1’, 1'') according to the invention in a container stopper means, and more especially by this use in the event of said container being a bottle intended to contain an alcoholic drink, typically wine.

Another purpose of the invention is constituted by the method for manufacturing a seal according to the invention.

In this method, and as shown diagrammatically in figure 9: a) a mu_ti-layer component B/S or I/B/S or

I1/Ad/B/S or B/M' may be supplied or formed depending on circumstances, in the form of a strip material Bs, b) said layer C or C’ may be formed, typically by extrusion of said material Mc, forming a strip Be, c) a strip By of said multi-layer material may be formed by laminating said strip Bz onto at least one * surface of said strip Bc, d) said seals may be cut from said strip By of said multi-layer material, forming a skeleton (3) or waste which are recycled in said material Mc intended to form said layer C or CC’, so as to give a low material cost for said seal.

A portion of a skeleton (3) of this kind has been shown in figure 10a.

EMBODIMENT EXAMPLES

20 pum OPP trade films were supplied coated with a layer of SiOx of between 20 nm and 150 nn.

12 um PET trade films were also supplied coated with a layer of SiOx of between 20 nm and 150 nm.

These films are films in spools 690 mm in width or breadth.

Thus, for all tests, the layer B corresponds to a layer of SiOx, and the layer S is either 12 um PET, or 20 pm OPP.

A - Manufacturing multi-layer structures or films

Al. Manufacturing the structure I or C/B/S

The layers C or C' were formed by extruding 690 mm wide layers of expanded PE or EPZ, to form directly the multi-layer film or material EPE/SiOx/PET or OPP, i.e. symbolically C/B/S, the B/S film bonding directly onto the layer C at the exit of the extruder prior to being cooled. See figure 1b.

To form the structure C/B/S in a strip (2), the device shown diagrammatically in figure 6 was used. * The layer C of EPE had a density of 0.380 (density of 380 kg/m’) and a thickness of 1.8 mm.

A2. Manufacturing the structures 2a to 2c

Structure 2a = C/I/B/S (see figure 2a),

Structure 2b = C/Ad/B/S (see figure 2b),

Structure 2c = C/I/Ad/B/S (see figure 2c),

Structure 2d = C/I/A4d/S/B (see figure 2d),

For the layer I, a 20 um thick layer of LDPE was taken, in these tests and generally in all tests including a layer I.

The layer Ad is a layer of adhesive for 2 um thick trade PE.

To manufacture the structure 2a, the layer I was extruded between the layer C and the film B/S.

To manufacture the structure 2b, the surface B of the film B/S was coated with a coating of adhesive layer Ad before being overlaid onto the layer C.

To manufacture the structure 2c, the structure

I/Ad/B/S was formed first by using as the layer I a film of LDPE of the same thickness (20 um), then this structure was assembled with the layer C at the exit of the extruder.

To manufacture the structure 2d, the surface S of the film B/S was ccated with a coating cf adhesive layer Ad before being overlaid onto the layer C.

A3. Manufacturing the structures 3a to 3f

Structure 3a = S/B/C’'/B/S (see figure 3a),

Structure 3b = S/B/I/C’'/I/B/S (see figure 3b),

Structure 3c = S/B/C’'/I/B/S, * Structure 3d = S/B/A4/I/C'/I/Ad/B/S (see figure 3d),

Structure 3e = S/B/Ad/I/C’'/I/B/S (see figure 3e),

Structure 3f = S/B/C’'/I/Ad/B/S (see figure 3f), structure 3a was formed like structure 1, by placing B/S on either side of the layer C, becoming C'.

Structure 3b was formed like structure 2a by placing I/B/S on either side of the layer C, becoming

Cc’.

Structure 3c is a mixed structure which was formed by assembling on one surface of the central layer C, the structural component I/B/S as in structure 2b and by assembling on the other surface S/B as in structure 1, the layer C then becoming the layer C’.

Structure 3d was formed like structure 2c, by placing I/Ad/B/S on either side of the layer C, becoming C’'.

A4. Manufacturing the structures 4a to 4d

Structure 4a = C/M/B/S (see figure 4a)

Structure 4b = C/I/M/B/S (see figure 4D)

Structure 4c = C/Ad/M/Ad’/B/S (see figure 4c)

Structure 4d = C/I/M/Ad/B/S (see figure 4d)

Structure 4e = C/M/Ad4/B/S

Structure 4f = C/S’'/M/Ad/B/S (see figure 4d)

Structure 4g = C/I/X/S/B

For layer M was used: - a layer of metal plated by vacuum deposition of 500 nm thick aluminium, in the case of tests 4a, 4f and 4g the metal layer M being a vacuum deposition layer Mp formed on the film B/S in the case of test 4a and 4b, on the support S’ (15 um of PE) in the case of test 4f, * and on the layer I in the case of test 4g, - a layer of tin or aluminium from 6 to 10 um thick forming a film My for the other tests.

The structure 4a was formed by vacuum metal plating the film B/S to obtain the structure M/B/S, then by assembling it with the layer C before it is cooled.

In the case of structure 4b, the structure M/B/S was assembled with the layer C with a 2 pm adhesive layer Ad’.

The structure 4c was formed by assembling a layer of Sn (M) with the film B/S and with the layer C using two layers of adhesive Ad and Ad’, typically identical.

The structure 4d was formed by assembling a layer of Sn (M) with the film B/S using a layer of adhesive

Ad, the structure M/Ad/B/S then being assembled with the layer C before it is cooled.

The structure 4e was formed by poly-laminating the metal strip M between the layer C and the film B/S, : using an adhesive layer Ad.

The structure 4f was formed by forming the film

S’'/M by vacuum deposition of metal, and by poly- laminating it between the layer C and the film B/S, using an adhesive layer.

The structure 4g was formed py forming the film

I/M by vacuum deposition of metal and by directly poly- laminating the film I/M between the layer C and the film S/B.

A5. Manufacturing the structures 5a to 5i

Structure 5a = S/B/M/C'/M/B/S (see figure 5a) * Structure 5b = S/B/C’'/I/M/B/S (see figure 5b)

Structure 5¢ = S/B/Ad/M/C’'/M/Ad/B/S (see figure 5c) structure 5d = S/B/Ad/M/C’'/I/B/S (see figure 5d)

Structure 5e = S/B/C’/M/Ad/B/S (see figure 5e)

Structure 5f = S/B/C’/Ad’'/M/Ad/B/S (see figure 5f)

Structure 5g = S/B/C’'/M/S/B 25% Structure 5h = B/S/C'/M/S/B

Structure 5i = B/S/M/C'/M/S/B

This series of structures 1s similar to the one denoted 3a to 3f.

The structure 5a was formed by forming the film

S/B/M by vacuum deposition of metal on the layer B of the film B/S, then by placing it on either side of the layer C’, by hot polylaminating.

The structure 5b is asymmetrical and was formed by co-extruding the component C’/I and by assembling by polylaminating the film M/B/S of the structure 5a, and the film B/S.

The structure 5c is symmetrical and was formed by polylaminating on either side of the layer C', a metal layer My (6 um Al or Sn metal film) and the film B/S using an adhesive layer Ad. The component M/Ad/B/S may be formed first.

The structure 5& is asymmetrical and was ZIormed, by co-extruding the component CcC’'/I and by polylaminating on one surface the film B/S, and the metal layer My, another film S/B being assembled to the metal layer My using an adhesive layer Ad.

The component S/B/Ad/M (identical to M/Ad/B/S) which was then laminated onto the co-extruded component " C/I, was also formed first.

The structure 5e was formed from the film S/B and from the structure M/Ad/B/S (see structure 5c and 5d), and by extruding the layer C’ between the film S/B and the structure M/A4/B/S.

The structure 5f differs from the structure 5e through the presence of an adhesive layer Ad’ between the layer C’' and the component M/Ad/B/S.

The structure 5g is formed from the film S/B and from the component M/S/B formed by vacuum deposition of a metal layer M, onto the surface S of the film S/B, by polylaminating the extruded layer C' between the film s/B and the film M/S/B.

The structure 5h was formed by polylaminating the extruded layer C’ between the film B/S (=film S/B) and the film M/S/B.

The structure 5i was formed by polylaminating the extruded layer C’ between the films M/S/B.

A6. Manufacturing the structures 6a to 6f

Structure 6a = S/B/C’'/B/S/M

Structure 6b = S/B/I/C’'/I/B/S/M

Structure 6c = S/B/C’'/Ad/B/S/M

Structure 6d = S/B/Ad/I/C'/Ad’'/I/B/S/M

Structure 6e = M/S/3/AG/I/C'/I/B/S/X

Structure 6f = B/S/C’'/Ad/M

To manufacture the structures 6a to 6e, first of all the component B/S/M was formed by metal plating the surface S of the film B/S, and a process was then used similar to the one used for previous similar - structures.

To manufacture the structure 6f, the film B/S was laminated onto one surface of the extruded layer C’ and a metal film M was bonded onto the other surface using a layer of adhesive Ad.

In the same way, the structure 6g was also formed similar to the structure 6f: B/S/A4/C’'/Ad/M.

A7. Manufacturing the structures 7a to 7e

Structure 7a = M'/B/C’'/B/M' or S

Structure 7b = M’'/B/I/C’'/I/B/M’' or S

Structure 7c = M’'/B/Aad/C’'/Ad/M’ or S

Structure 7d = M’'/B/Ad’'/I/C/I/A4d/B/M’' or S

Structure 7e = S’'/M’/B/Ad/C’/Ad/B/M'/S'

To manufacture these structures, the component

M'/B is formed. To do this, a metal layer M’ was used as a support for the barrier layer B, this metal layer

M' replacing the support layer S. This metal layer M’ is a metal layer of Sn or Al with a thickness of between 6 and 10 um.

The structures 7a to 7d comprise on either side of the layer C’', either the same component M'/B, or the component M’'/B on one side of the layer C’ and the component B/S on the other side of the layer C'.

In the case of the structure 7e, the metal layer ¥' is formed by a layer cof metal plating Mp, formed on a support S’ (15 um film of PE or PET).

To manufacture the structures 7a to 7e, a process was used similar to the one used for previous similar structures.

A8. Manufacturing the structures 8a to 8d - Structure 8a = M’'/B/Ad/C’/A4d/B/M'/V or P

Structure 8b = V or P/M’'/B/Ad/C’'/Ad/B/M'/V or P

Structure 8c = V or P/B/S/Ad/C’'/Ad/S/B/V or P

Structure 84 = V or P/M/Ad’'/B/S/Ad/C’'/S/B/Ad’/M/V or P

These structures 8a to 8d were manufactured either by applying a layer of varnish V, typically at 3 g/m?, to the relevant structures, or by applying a protective film P, typically by calendering.

B - Manufacturing seals

Plane seals (1, 1') were obtained by cutting with a punch from the multi-layer strip material (2) obtained previously.

In the case of round seals (1, 1’) a skeleton (3) is left as shown in figure 10a, a skeleton which is typically recycled, as shown diagrammatically in figure 9.

In the case of a multi-layer structure not comprising a layer of tin, the skeleton (3) obtained after cutting out the seals was recycled in the layer C or C'.

C - Results obtained

These plane seals (1, 1’) had a great variety of levels of permeability to gases and typically to oxygen and a great variety of thickness, so as to give seals belonging to different categories as follows: category I: < 5 cm’/m?/] category II: 5-10 cm’/m*/j

Category ITI: 10-20 cm’/m?/j

Category IV: 20-40 cm’/m?/j g Category V: 40-80 cm’/m?/j

These seals were placed into stopper caps (4) of the same type as the one shown in figure la.

These caps (4) typically comprise an outer metal shell (41) able to be inserted under the finish of the bottle to be sealed, and an inner insert (40) of plastic material, an insert (40) which is typically threaded so as to engage with the threading of the finish.

The seal (1, 1’) is placed inside the insert (40) and is typically held in place by a radial groove or radial projections (42) formed inside the insert (40).

ADVANTAGES OF THE INVENTION

The invention allows a great variety of seals adapted to each type of wine for packaging to be obtained in a cost-effective way.

The invention thus allows screw capping to be developed to replace the use of corks as the traditional means for stoppering wine bottles.

KEY TO REFERENCE NUMBERS

SEAL i

SEAL plane 1° ' SEAT, snaped (heat formed) Lr

MULTI-LAYER MATERIAL 2

MULTI-LAYER MATERIAL STRIP 2

EXTRUDED LAYER “C” 20

EXTRUDER 21

FEEDER FOR 20 22

STRIP OF “B/S” or B/M’ 23 * SPOOL OF “B/S” or B/M’ 24

SKELETON of 2 recycled at 22 3

STOPPER CAP 4

THREADED INSERT 40

OUTER SHELL 41

MEANS of anchoring 1 to 40 42

Claims

1. Leakproof seal made of a multi-layer material intended to be used in a stopper means for a container intended to contain a food product, including a layer C able to withstand resilient axial compression, and a layer B forming a barrier to oxygen, wherein: a) said layer B forms or comprises a coating of non-organic material, b) said seal comprises a layer S forming a support of said layer B, said support layer S being or not being in contact with said layer C, to give a structure that comprises either a succession of layers C, B and S, a structure represented symbolically as C/B/S in the case of adjacent layers C, B and S, the layer S being intended to be in contact with said food product, or a succession of layers C, S and B, a structure represented symbolically as C/S/B in the case of adjacent layers C, S and B, the layer B being intended to be in contact with said food product, c) said layer C is formed of a material Mc constituted by or comprising a layer of expanded polyolefin.

2. Seal according to claim 1 wherein said coating of said barrier layer B forms or comprises a non- organic coating constituted by a coating of SiOx.

3. Seal according to any one of claims 1 to 2 wherein said ccating of said barrier layer B forms or comprises a coating of aluminium oxide. AMENDED SHEET DATED 19 JUNE 2008

4, Seal according to any one of claims 1 to 3 wherein said coating of said barrier layer B forms or comprises a coating of carbon.

5. Seal according to any one of claims 1 to 4 wherein said barrier layer B forms or comprises a nano- dispersion of exfoliated platelets of phyllosilicate clay.

6. Seal according to any one of claims 1 to 5 wherein said barrier layer B is of selected thickness or of selected content of said non-organic material, to give a seal with permeability to oxygen of less than 5 c’/m?/5.

: 7. Seal according to any one of claims 1 to 5 wherein said barrier layer B 1s of selected thickness or of selected content of said non-organic material, to give a seal with permeability to oxygen of between 5 and 10 cm®/m?/5.

8. Seal according to any one of claims 1 to 5 wherein said barrier layer B is of selected thickness or of selected content of said non-organic material, to give a seal with permeability to oxygen of between 10 and 20 cm’/m?/5.

9. Seal according to any one of claims 1 to 5 wherein said barrier layer B is of selected thickness or of selected content of said non-organic material, to give a seal with permeability to oxygen of between 20 and 40 cm’/m®/7.

1C. Scal according to any one of claims 1 to 5 wherein said barrier layer B 1s of selected thickness or of selected content of said non-organic material, to AMENDED SHEET DATED 19 JUNE 2008 give a seal with permeability to oxygen of over 40 cm®/m?/3 and of up to 80 cm’/m%/j.

11. Seal according to any one of claims 1 to 10 wherein said barrier layer B has a thickness of between nm and 250 nm when said non-organic material is selected from a coating of SiOx, or a coating of aluminium oxide or a coating of carbon.

12. Seal according to any one of claims 1 to 10 wherein said barrier layer B is formed by a dispersion 10 of exfoliated nano-particles in a layer of resin or plastic material with a thickness of between 1 pm and 30 pm.

13. Seal according to any one of claims 1 to 12 wherein said layer C has a thickness E. between 0.5 mm and 2.5 mm.

14. Seal according to any one of claims 1 to 13 wherein said layer C is constituted by or comprises a layer of thermoplastic material with a density between 200 and 500 kg/m’.

15. Seal according to any one of claims 1 to 14 wherein said layer C is constituted by or comprises a layer of elastomer.

16. Seal according to any one of claims 1 to 15 wherein said support layer S is formed out of a material Ms selected from a polyolefin, of thickness Es between 10 pm and 50 um.

17. Seal according to any one of claims 1 to 16 wherein an intermediate layer I 1s interposed between said layer CC and said Dbarrier layer B, said intermediate layer I being a layer of polyolefin, of thickness E- typically between 10 pm and 50 pm, to give AMENDED SHEET DATED 19 JUNE 2008 for said multi-layer material a structure represented symbolically as C/I/B/S or as C/I/S/B.

18. Seal according to any one of claims 1 to 17 wherein a layer of adhesive Ad is interposed between said layer B and said layer C or said layer I, said adhesive layer having a thickness Ej of less than 5 um, to give for said multi-layer material a structure represented symbolically as C/Ad/B/S or C/I/Ad/B/S or C/Ad/S/B or C/I/Ad/S/B or C/Ad/I/B/S or C/Ad/I/S/B.

19. Seal according to any one of claims 1 to 18 wherein said layer C is a central layer C’ forming a plane of symmetry in respect of said multi-layer material, to give for said multi-layer material structures selected from: a) s/B/cC’/B/S,B/S/C’'/S/B,S/B/C’'/B/S, b) structures comprising at least one intermediate layer I, c) structures comprising at least one adhesive layer Ad, d) structures comprising at least one adhesive layer Ad and an intermediate layer I,.

20. Seal according to any one of claims 1 to 19 wherein said layer C’ is formed by the layers C/Ad’’/C, Ad’’ being another adhesive layer, said adhesive layer Ad’’ and said adhesive layers Ad and Ad’ being able to be formed of one adhesive of the same type or of adhesives of different types.

21. Seal according to any one of claims 1 to 20 comprising a metal layer M, in the form of a metal film

M:. of Sn or Al or in the form of a metal layer Mg formed by vacuum deposition of metal. AMENDED SHEET DATED 19 JUNE 2008

22. Seal according to claim 21 wherein said metal layer M is interposed between said barrier layer B and said layer C or said layer C’, possibly by means of an adhesive layer Ad or an adhesive layer Ad’, different or not different from said adhesive layer Ad, in such a way that a part of said seal comprises a multi-layer structure part selected from: a) C or C'/M/B/S, C or C’'/M/S/B, b) structure parts comprising an intermediate layer I, c) structure parts comprising at least one adhesive layer Ad, d) structure parts comprising at least one intermediate layer I and an adhesive layer Ad and/or an adhesive layer Ad’.

23. Seal according to claim 21 wherein said barrier B is included between said metal layer M and said layer C or C’, possibly by using an adhesive layer Ad or an adhesive layer Ad’, different or not different from said adhesive layer Ad, in such a way that a part of said seal comprises a multi-layer structure part selected from: a) C or C'/B/S/M, C or C'/S/B/M, b) structure parts comprising an intermediate layer I, c) structure parts comprising an adhesive layer Ad, d) structure parts comprising at least one intermediate layer I and an adhesive layer Ad and/or

Ad’. AMENDED SHEET DATED 19 JUNE 2008

24. Seal according to any one of claims 20 to 23 wherein said metal film My is constituted by a film of Sn or Al, with a thickness Ey of between 5 um and 20 pm.

25. Seal according to any one of claims 20 to 23 wherein said metal layer Mp formed by vacuum deposition of metal is a vacuum metal plated layer with a thickness of between 10 nm and 1000 nm, deposited on said support S or on another support S’.

26. Seal according to any one of claims 1 to 20 wherein said layer S is replaced by a layer M’, said layer M’ being selected from a metal fi'm My of Sn or Al or a metal layer Mp formed by vacuum deposition of metal on a support film S’, to give, for said multi- layer material, structures selected from: a) M’/B/C'/B/M', B/M’/C’/M'/B, M'/B/C’"/B/M’, b) structures comprising at least one intermediate layer I, c) structures comprising at least one adhesive layer Ad, in particular: M/B/Ad/C’ /Ad/B/M’, B/M’ /Ad/C’ /nd/M’' /B, M’/B/C’/Ad/B/M', B/M’/C’/Ad/M’/B, d) structures comprising at least one adhesive layer Ad and one intermediate layer I.

27. Seal according to any one of claims 1 to 20 wherein said layer S is replaced by a layer M’, said layer M’ being selected from a metal film My of Sn or Al or a metal layer Mp formed by vacuum deposition of metal on a support film S$’, in such a way that a part of said seal comprises a part of said multi-layer structure selected from: a) C or C'"/M’/B, C or C’'/B/M’, AMENDED SHEET DATED 19 JUNE 2008 b) structure parts comprising an intermediate layer I, c) structure parts comprising an adhesive layer Ad, d) structure parts comprising at least one adhesive layer Ad and one intermediate layer I.

28. Seal according to any one of claims 1 to 27 wherein, when said layer B or said layer M or M’ is an outer layer intended to be in contact with said food product, said layer B or said layer M or M’ is coated with a layer of a varnish V in such a way that said seal has a structure comprising exterrally “/B/V” or N/MM) VT.

29. Seal according to any one of claims 1 to 27 wherein, when said layer B or said layer M or M’ is an outer layer intended to be in contact with said food product, said layer B or said layer M or M’ is coated with a protective layer P anchored by an adhesive layer Ad’’’, in such a way that said seal has a structure ending in “/B/P” or in “/M(M’)/P”, or in B/Ad’'’’/P’'’ or in “/M(M")/Ad'"""/P"".

30. Seal according to any one of claims 1 to 29 wherein said thickness E: of said layer C or of said layer C’ represents from 70% to 99% of the total thickness Ej; of said seal.

31. Seal according to any one of claims 1 to 30 forming a plane seal (1’) obtained by cutting said multi-layer material in a strip or in a two-dimensional format.

32. Seal according to any one of claims 1 to 30 forming a shaped seal (1’’) obtained by thermoforming AMENDED SHEET DATED 19 JUNE 2008 said multi-layer material in a strip or two-dimensional format (2).

33. Container stopper means comprising a seal (1, 17, 1'") according to any one of claims 1 to 32.

34. Stopper means comprising a stopper cap (4) fitted with a seal (1, 1’, 1’’) according to any one of claims 1 to 32, said container typically being a bottle intended to contain, as a food product, an alcoholic drink.

35. Stopper means according to claim 34 wherein said stopper cap (4) comprises a typically threaded plastic material insert (40), said seal (I, 1’, 1'") being anchored to said insert (40), and an outer shell (41) of metal or metallised plastic, or plastic.

36. Use of a seal according to any one of claims 1 to 32 in a container stopper means.

37. Use according to «claim 36 wherein said container is a bottle intended to contain an alcohclic drink.

38. Method for manufacturing a seal according to any one of claims 1 to 32 wherein: a) a multi-layer component B/S or I/B/S or I/Ad/B/S or B/M’ is supplied or formed depending on circumstances, in the form of a strip material Bg, b) said layer C or C’' is formed, by extrusion of said material Mc, forming a strip Be, c) a strip B; of said multi-layer material is formed by laminating said strip Bz to at least one surface of said strip Bc, d) said seals are cut from said strip By; of said multi-layer material, forming a skeleton or offcuts AMENDED SHEET DATED 19 JUNE 2008 which are recycled in said material M: intended to form said layer C or C’, so as to give a low material cost for said seal.

39. Seal according to claim 19 wherein said layer CC is a central layer C’ forming a plane of symmetry in respect of said multi-layer material, to give for said multi-layer material structures selected from: a) s/B/1/C'/1/B/S,B/S/1/C'/1/S/B, S/B/I/C'/1/S/ B,S/B/C’/1/B/S,B/S/C"/1/S/B,S/B/C'/1/S/B, S/B/I/C’'/S/B, b) S/B/ARd/C’/Ad/B/S,B/S/Ad/C’/ARd/S/B,S/B/C’/Ad/B/ S,B/s/C’ /Ad/S/B, c, S/B/Ad/I/C'/I/A4/B/S,3/S/RARd4d/I/C’'/I/Ad/S/3B,5/3/1I /Ad/C’ /Ad/1/B/S,B/S/1/Rd/C’ /Rd/1/S/B,S/B/1/C'/1/Ad/B/S, B/S/1/Cc’/1/Ad/S/B,S/B/1/C’'/Ad/1/B/S,B/S/1/C'/Ad/I/S/B.

40. Seal according to claim 22 wherein said metal layer M is interposed between said barrier layer B and said layer C or said layer C', possibly by means of an adhesive layer Ad or an adhesive layer Ad’, different or not different from said adhesive layer Ad, in such a way that a part of said seal comprises a multi-layer structure part selected from: a) C or C'/I/M/B/S, C or C'/I/M/S/B, b) C or C’/Ad/M/B/S, C or C’'/Ad/M/S/B,C or C'/Ad'/ M/Ad/B/S, C or C’'/Ad’'/M/Ad/S/B, c) C or C'/I/M/Ad/B/S,C or C’/I/Ad/M/B/S,C or C'/ I1/Ad/M/S/B.

41. Seal according to «claim 23 wherein said barrier B is included between said metal layer M and said layer C or C’, possibly by using an adhesive layer Ad or an adhesive layer Ad’, different or not different from said adhesive layer Ad, in such a way that a part AMENDED SHEET DATED 19 JUNE 2008 of said seal comprises a multi-layer structure part selected from: a) C or C'/I/B/S/M, C or C'"/I/S/B/M, b) C or C’/Ad/B/S/M, C or C’/Ad/S/B/M, c) C or C'/Ad/I/B/S/M, C or C’'/I/Ad4d/B/S/M, C or C’/Ad/1/s/B/M, C or C’'/I/Ad/S/B/M or C’/I/Ad/S/B/AQ’ /M.

42. Seal according to claim 26 wherein said layer S 1s replaced with layer M’, said layer M’ being selected from a metal film My of Sn or Al or a metal layer Mp formed by vacuum deposition of metal, on a support film S’, to give, for said multi-layer materia’, structures selected from: a) M’/B/1/C’'/1/B/M' ,B/M'/I/C'"/I/M'/B,M"/B/I/C'/I /M'/B, M’/B/C'/I/B/M', B/M'/C’'/I/M’'/B, M’'/B/C'/I/M'/B, M’/B/I/C’'/M'/B, b) M/B/Ad/C’/Ad/B/M’,B/M’/Ad/C’'/Ad/M'/B,M’ /B/C’/Ad /B/M', B/M'/C'/Ad/M’'/B, c) M’/B/Ad/I/C’/I/A4/B/M’,B/M/Ad/I/C’'/I/Ad/M’'/B,M’ /B/1/Ad/C’/Ad/I/B/M',B/M’ /1/AR4/C' /Ad/I/M’" /B,M' /B/I/C’'/I /Ad/B/M’,B/M’/1/C’/I/Rd/M’'/B,M’'/B/I/C’'/Ad4/I/B/M',B/M'/I /C’ /ARd/1I/M’ /B.

43. Seal according to claim 27 wherein said layer S is replaced by a layer M’, said layer M’ being selected from a metal film Myr of Sn or Al or a metal layer Mp formed by vacuum deposition of metal, typically a layer of Cr or Al, on a support film 8S’, in such a way that a part of said seal comprises a part of said multi-layer structure selected from: a) C or C"/I/M"/B, C or C'/I/B/M’, b) C or C’'/Ad/M'/B, C or C’'/Ad/B/M', AMENDED SHEET DATED 19 JUNE 2008

. LS cy) C or C’'/1I/Ad/M*/B, C or C'/Ad/I/B/M', C or c’'/1/ad/B/M’, C or C’'/Ad/I/M’'/B,C or C’'/I/Ad/M'/B.

AMENDED SHEET DATED 19 JUNE 2008