The invention relates to the field of closing caps for receptacles or bottles or outer closing for receptacles or bottles previously closed by a cork, a stopper or any other closing means.
More particularly, the invention relates to the field of caps with a heat shrinkable skirt, in other words caps formed from a thermoplastic material that are shrunk onto the neck during crowning by the input of thermal energy, unlike metallic outer closing caps for which the skirt is crimped under the locking ring of the neck during crowning.
More specifically, the invention relates to a new method for the production of caps with a heat shrinkable skirt, outer closing caps and possibly closing caps with a heat shrinkable skirt.
Heat shrinkable (HS for short) caps have been known for a long time.
Thus, patent FR 805.771 describes the production of a PVC based cap formed by extrusion of a PVC based tube, and then after elongation, expansion of the tube at the exit from the extruder, cooling and cutting of cylindrical tubes into portions forming a heat shrinkable sleeve on the neck of a bottle.
Patent GB 1 105 713 also describes a method for the production of HS caps in which a tube made of a PVC or PS based material is made heat shrinkable by expansion and is flattened and heat sealed transversely at one end so as to close it, and cut off so as to form a flattened cap which, after separation, forms a cap with a welded head that can be placed and heat-shrunk onto a bottle neck.
Patent FR 1 372 805 also describes a method for the production of heat shrinkable tubular sleeves that can be used to seal bottle caps in which a tube is co-extruded in two different types of PE (one relatively meltable and one relatively non-meltable), then cross-linked by irradiation and then expanded.
Patent FR 1 424 731 also describes a method for the production of HS caps in which a portion of a heat shrinkable tube is shrunk onto a template above which a disk is mounted so as to form a heat shrinkable cap for which the head is formed by the disk.
Patent FR 1 441 623 describes a method for the production of a heat shrinkable casing by extrusion of PE, followed by cross-linking by irradiation, and then expansion of the casing.
Patent FR 2 115 137 also describes a method for the production of HS caps in which a blank is formed by cutting it out from a heat shrinkable plastic sheet, and in which a rolled HS cap is formed by welding the side edges by substantially axial overlap. A cap head can also be glued. This cap can be combined with a bottle cork.
Patent FR 2 201 957 also describes a method for the production of HS caps in which a sleeve formed from an extruded tube made of a heat shrinkable and expanded material, is shrunk onto a tapered mandrel on the head of which a stopper made of a heat-formable but non heat shrinkable material is placed.
Patent FR 2 219 080 also describes a HS cap formed on a mandrel by heat shrinkage starting from a PVC or PS tubular part, the end forming the head of the cap being obtained by compaction and compression of a portion with length equal to the length of the tubular part.
Patent U.S. Pat. No. 5 118 460 describes a method for the production of HS caps by moulding. Similarly, patent FR 2 708 513 describes a method for the production of HS caps in which a preform is formed firstly by moulding and is then expanded afterwards.
French patent FR 2 817 193 on behalf of the applicant also describes a method for the production of HS caps that uses an irradiation means.
Problems that Arise
Known caps or caps with heat shrinkable skirts, and particularly those described in French patent FR 2 817 193, have several disadvantages:
All these caps also need to be easily opened—without the cap necessarily being provided with easy opening means, either by cutting the top part of the cap with a knife or by “peeling” the cap with a knife from the bottom of the cap depending on habits in each country, being done so without any risk of injury.
According to the invention, the method for the production of caps or caps with a heat shrinkable skirt comprises:
It is advantageous to have D0>D1, in particular for reasons of productivity and to obtain a high output rate from the extruder. It is also advantageous to have a relatively low D1 to obtain a relatively high D2/D1 ratio so as to have a cap that can be heat-shrunk. However, there is no reason why D0 and D1 should not be substantially equal.
The S0/S1 ratio is a measurement of axial drawing, the material flow equal to S.V remaining constant, where V is the linear velocity, such that when S decreases the velocity V of the tube increases accordingly.
On the other hand, for a pure radial expansion, only the diameter D increases, the area S and the velocity V no longer being modified.
The instantaneous velocity V was measured at different points on a tube made of thermoplastic material, for example by projection on the extruded tube just at the exit from the extruder, with colored marks at a uniform spacing of Δ10 along the axial direction, such that the measurement of Δ11 and Δ12 using the stroboscopic device provides a means of calculating V1 and V2 knowing V0, the velocity of the material flow or the extruded tube at the exit from the extruder.
This method gives a means of solving the problems that arise. Firstly, it does not use any irradiation device, such that the disadvantage in the previous method developed by the applicant is eliminated, related particularly to the negative image of any type of irradiation with the general public.
Furthermore, it has been observed that the caps obtained with the method according to the invention, and printed, were easily heat shrinkable and were not affected by axial distortion of the printed pattern after shrinkage on the neck.
Finally, the method according to the invention was tested with a large number of different materials and combinations of different thermoplastic materials, both in the form of a single layer extruded material and in the form of dual or three layer co-extruded material, such that it was possible to obtain a wide variety of caps with a different feel, appearance, elasticity, contact sonority with a more or less dull or crystalline sound, flexibility and cuttability with a knife, etc.
Thus, in particular the method according to the invention provides a means of reproducing all types of sensorial impressions achieved with existing caps, either always or at least usually approaching these sensorial impressions, and even enriching them with new impressions, so that it becomes possible to propose “tailor made” products at the request of customers.
All Figures relate to the invention.
a to 3d relate to the production of tube portions.
a diagrammatically shows the main equipment in the production line (3) for tube portions.
b illustrates the method of production and the production line (3) in operation, in parallel to
c shows a partial view illustrating a variant of the method of production and the production line in
This Figures in which the axially drawn tube arrives from the left shows, from left to right, an entry ring with diameter D1 that can be used as a calibration ring, an expansion area provided with orifices (3410) and an inside wall with diameter D2, the assembly formed by cooperation between an internal tubular metallic part and an external chamber (348) provided with vacuum grips (349). The right part of the radial expansion device comprises an auxiliary cooling means, typically formed by spraying or circulation of cold water.
a illustrates the case in which the axial drawing step extends from the exit from the die to the entry to the radial expansion device, the changes in the thermoplastic material during the different production phases of tube portions, the equipment of the production line (3) not being reused, and with the following from left to right:
a shows the thicknesses E and the linear velocities V of the plastic material along the axial direction.
a to 7 illustrate the production of caps (1b) starting from portions of tubes made as illustrated in FIGS. 1 to 3d.
a to 4d show sectional views along the axial direction (10) that illustrate the different phases of an embodiment of the method according to the invention. In this method, the tube portion is a “long” portion including a lower part that will form the skirt and therefore corresponding substantially to the height H of the cap, and an upper part that will form the head.
a shows the initial position of the long portion with respect to the conformation mandrel and its head.
b shows the blank (26, 27) after heat shrinkage of the long portion obtained by the input of heat Q, blank that includes an upper part (270) located above the head of the mandrel.
c and 4d represent formation of the head by compression of the upper part (270) between the head of the mandrel and a matrix with relative displacement to the mandrel along the axial direction (10).
The final cap (1, 1a, 1b, 1c) is shown in
f shows the printed cap obtained as illustrated in
a to 5d illustrate another embodiment of the cap according to the invention in which the cap comprises an insert comprising a head and a skirt. As illustrated in
As illustrated in
e and 5f relate to the case in which the cap is a cap for the neck of a champagne bottle (8′) closed by a headed stopper (80′).
e shows a sectional view, while 5f shows a side view corresponding to
a to 7 illustrate various embodiments of the method and the corresponding device (4) for shaping tube portions. The device (4) typically comprises a carousel (41) with a vertical or horizontal rotation axis (410), typically including 4 to 8 mandrels, with 4 to 8 corresponding angular positions.
a shows a carousel (4) comprising 4 mandrels and 4 angular positions in solid lines:
b is a partial representation of
a to 8d corresponding to
e is a sectional view of the final cap (1b).
a to 9d are diagrammatic axial sectional views of the axially drawn tube represented between the exit from the die and the radial expansion device.
In
In
In
c shows the case in which the cooling device has been positioned at an axial distance>L0 which results in D<D1. The axially drawn tube is not forced into contact with the input ring or crown of the radial expansion device, which leads to the appearance of a radial expansion problem.
d shows the case in which the cooling device has been positioned at an axial distance<L0 which leads to D>D1. The axially drawn tube has a diameter significantly greater than the diameter of the ring of annular chamber at the input to the expansion device, and the result is a problem of a high axial force to be applied to the axially drawn tube, the ring or annular chamber then forming a bottleneck for the axially drawn tube, in particular an increase in the axial tension force possibly leading to an undesirable axial drawing during the radial expansion step b).
a to 10d are similar to
a and 12b are partial views related to the axial tension means formed by two facing driving rollers.
a is a sectional view in a vertical plane perpendicular to the axial direction.
b is a sectional view in a vertical plane containing the axial direction.
According to the invention, the axial drawing step may be delimited on the output side by a cooling zone in which a cooling means lowers the temperature of the axially drawn tube to a temperature T1, the temperature T1 being chosen:
The temperature T1 may be such that ΔT, equal to T0—T1, varies from 30° C. to 150° C. and typically from 45° C. to 100° C.
As illustrated in
As illustrated in
In this case, the ring may include a part with diameter D1 so as to form a calibration ring from which a tube with diameter D1 projects, typically axially drawn and cooled to temperature T1.
According to another variant cooling means (not shown in any figure) the cooling means may include air or water projection inside the axially drawn tube, typically through a pipe passing through the die.
The temperature drop ΔT obtained in the cooling area, like axial drawing, increases the mechanical properties of the drawn tube which is advantageous in a method in which tension is applied on the tube at the end of the production line. However, since the radial expansion step that follows the axial drawing step creates a large tube deformation, which assumes a low stiffness of the drawn tube at the entry to the radial expansion device, this temperature drop ΔT must be controlled and limited.
Regardless of the cooling method, the cooling means that is applied after the axial drawing step at the exit from the extruder over the length L0, tends to fix the diameter of the axially drawn tube as illustrated in
The length L0 corresponding to the axial drawing may typically be between 0.2 m and 2 m. It can be noted that a large number of physical parameters vary along this length L0 and therefore have a gradient, including the diameter D, the thickness E, or the velocity V of the tube.
As illustrated in
As illustrated in
As illustrated in
This annular chamber can firstly regulate the diameter of the axially drawn tube, by controlling the pressure Pa that tends to increase in the presence of a plating defect, the outside air then being able to pass through the orifices; it can be used firstly to heat the tube if necessary before it enters the expansion area due to a means of heating the annular chamber symbolized by an electrical resistance (T′1) in
Thus, the temperature of the axially drawn tube can be finely adjusted so as to facilitate its expansion in the expansion area.
The radial expansion can be obtained either by keeping the inside of the tube (21, 22, 23) under pressure, or by keeping the outside of the tube under negative pressure.
The radial expansion can preferably be obtained by keeping the tube under a vacuum, the radial expansion device including a suction inside wall using vacuum creation holes such that the tube with diameter D1 is forced into contact with the inside wall of the expansion area and/or into contact with the inside wall, with inside diameter D2, the temperature T1 being chosen to be as low as possible so as to obtain high heat shrinkage, but high enough to enable the radial expansion.
The inside wall with diameter D2 may be a tubular metallic part, typically a steel, aluminum, copper alloy part, for example such as a bronze or cupro-nickel alloy, the part possibly being a sintered part capable of allowing air to pass through.
This inside wall may be surface treated, either to minimize friction forces between the inside wall and the tube, the inside wall possibly being coated at least partly with PTFE, or to give a particular surface appearance to the tube, typically a satin or “glass polished” appearance, the inside wall comprising a relief or surface roughness capable of creating the appearance.
Typically, the radial expansion step in the expansion area, can result in an increase of the diameter from D1 to D2 or ΔD=D2−D1 to at least 10 mm, over a distance L1 less than 250 mm and typically less than 100 mm, such that the ΔD/L1 ratio is as high as possible and typically more than 1/25, and thus the radial expansion includes a low or negligible axial expansion component. The upper limit of the ΔD/L1 ratio varies with the thermoplastic material from which the tube is made; it is typically of the order of 3.
Caps according to the invention can be shrunk onto a neck in the radial direction only, with no substantial modification of the axial component depending on the height of the caps due to this separation between prior axial drawing and subsequent radial expansion, such that the axial position of these caps remains unchanged after heat shrinkage and that any image printed on these caps also remains intact depending on the axial direction.
According to the invention and as shown in
The tubular metallic part and the inner wall may thus have a temperature gradient, with a relatively hot entry diameter D1 and a relatively cold exit diameter D2.
According to the invention, the diameter D0 of the die forming the extruded tube may typically vary from 20 mm to 50 mm, and its slit width or thickness E0 may typically vary from 0.5 mm to 3 mm, so as to have a flow of plastic material from the extruder typically varying from 10 kg to 100 kg of plastic material/hour.
Similarly, the diameter D1 of the axially drawn tube may typically vary from 5 to 20 mm, and its thickness E1 can typically vary from 0.2 mm to 0.6 mm, with a D1/D0 ratio equal to not more than 0.6, and with an E1/E0 ratio equal to not more than 0.6.
The diameter D2 of the radially expanded tube may typically vary from 20 mm to 50 mm and its thickness E2 from 0.05 mm to 0.35 mm, and typically 0.075 mm to 0.15 mm, with a D2/D1 ratio equal to not more than 2 and with an E2/E1 ratio equal to not more than 0.6.
As illustrated in
The relative axial mobility of the radial expansion device with respect to the die has been represented by the double arrow “”.
Similarly, the cooling means may be placed at a distance L0<L from the die, the distance L0 being chosen particularly as a function of the plastic material so as to obtain sufficient axial drawing, the cooling means typically being free to move along the axial direction so as to obtain a regulation of the diameter D1 at the input to the radial expansion device by a displacement ΔL0 of the cooling means around the distance L0.
The relative axial mobility of the cooling means with respect to the die has been represented by the double arrow “” in
With the method according to the invention and as illustrated in
Furthermore, the displacement ΔL0 may be controlled in particular by the axial tension force Ft applied by the tension means, any increase or positive difference ΔFt in the force Ft typically implying a positive difference ΔD1 in the diameter of the axially drawn tube (with respect to the diameter D1 of the input ring (340, 340′), the axially drawn tube then having a larger diameter than the entry diameter into the radial expansion device, the positive difference ΔFt possibly being corrected by a positive displacement ΔL0 so as to reduce the diameter of the axially drawn tube by ΔD1.
Thus, this embodiment of the manufacturing method according to the invention is very advantageous because it comprises a permanent regulation means leading to excellent production uniformity, but this regulation also means considerably reducing the start-up time of the method and also the adjustment time during a change of plastic material.
According to the invention, the thermoplastic material may also be composed of or may comprise at least one first thermoplastic material with a glass transition temperature Tg equal to at least 40° C., and typically chosen from among PET, PVC, PS, PMMA, or a mix of these materials, or copolymers of PET, PVC, PS, PMMA, so as to obtain thin caps with good mechanical strength alone and that can be used on the crowning line.
However, the thermoplastic material may include or may be composed of at least one second thermoplastic material with a glass transition temperature Tg less than 50° C. and typically less than 10° C., and typically chosen from among polyolefins such as PE, PP, PB or from among ethylene copolymers such as EVA, EMA, EAA, ethylene and propylene copolymers or from among thermoplastic elastomers such as SIS, SEBS, or a mix of these elastomers. If the second plastic material would be used alone, a greater thickness might be necessary to give a good mechanical strength to the cap.
Advantageously, the thermoplastic material may include a mix of the first thermoplastic material and the second thermoplastic material, the mix including at least 50% by volume of the first thermoplastic material, and 10 to 50% by volume of the second thermoplastic material, so as to obtain caps with a range of textures and flexibility depending on the relative content of the first and second thermoplastic materials.
Thus, the invention can be used with a large number of thermoplastic materials, provided that their mechanical characteristics are compatible with the formation of caps. The invention may potentially be applied to any thermoplastic material that can be drawn in the axial direction and can be expanded radially according to the invention.
According to one embodiment of the invention, the thermoplastic material may form or comprise a multi-layer material, the multi-layer material comprising a first layer composed of the first thermoplastic material and a second layer composed of the second thermoplastic material, the multi-layer material possibly including an internal adhesive layer.
Furthermore, all or some of the thermoplastic material may contain a micronised filler typically chosen from among talc, calcium carbonate, barium sulphate, titanium oxide, organic or mineral pigments, nanoparticle clays, so as to color the thermoplastic material.
Thus, due to a wide variety of plastics and fillers, and particularly mineral fillers, the invention offers a virtually infinite number of possibilities concerning sensorial properties of manufactured caps, particularly feel, appearance, “sonority” properties, cuttability with a knife, etc.
In particular, these caps may be very soft to the touch, very different from the normal feel of plastic materials, or their feel may be similar to the feel of tin-based caps. The applicant assumed that this could be due to the undoubtedly heterogeneous mix of two materials with different Tg values.
According to one embodiment of the invention and as illustrated for example in
The disc may be obtained by cutting a sheet material, possibly transparent, made of a material chosen from among plastics, metal strips or sheets, paper or cardboard or multi-layer assemblies of these materials. This embodiment is advantageous to obtain composite caps for which the nature of the head is different from the skirt.
The disc may possibly be composed of an excise disc. This disc may comprise any type of system particularly to identify the cap, to monitor and assure traceability of packaged products, and to form an anti-fraud and anti-theft means.
According to another embodiment of the invention illustrated in
The insert may comprise a thread and be provided with a sealing means so as to form a closing cap (1b). See
According to another embodiment of the method according to the invention, and as illustrated in
In this embodiment, the upper part has a length calculated to provide a sufficient quantity of plastic material to form the head without there being any unnecessary over thickness or under thickness that would make the cap unusable.
However, as illustrated in
Furthermore, as illustrated in
It is advantageous to take advantage of the presence of a cavity that can be heated, to fix a complementary element onto the head of the cap without requiring an additional step in the method.
As is normally the case, the caps are usually decorated or printed. According to the invention, the printing may be formed on the tube portion, and/or on the skirt, and/or on the head, and/or on the heat-shrunk skirt blank, either before or after assembling or forming the head of the cap.
The invention makes it possible to print tube portions to the extent that it can avoid subsequent axial deformation, the radial deformation during heat shrinkage on the neck itself being limited by the geometry of the neck, as for example as illustrated in
To form the printing, inks that can be cross-linked by radiation can be used, typically UV inks such that the printing is typically formed at a temperature below the temperature at which the cap shrinks.
As shown in
If there are several lines (73) of printing nozzles in parallel, identical or different patterns can be printed in parallel which makes the method particularly flexible and advantageous because printing may be done directly starting from a pattern transmitted by the customer purchasing the caps as soon as the pattern is received.
According to the invention, all or some of the thermoplastic material (20, 200, 201) can be colored in-depth. In this case, the objective is to form either a background color on which the printout is formed, or possibly to form a colored but unprinted cap.
Advantageously, the multi-layer material may include an outside layer made of a plastic material, typically polar or with a high surface energy, so that it can be printed and that leads to an illustration bonding to the outside layer. It may include an inside layer composed of an activatable adhesive so that the cap can be glued locally on the neck, typically by local heating.
As illustrated in
Traditionally, the outer closing caps (1c) used on wine bottles closed by a cork stopper, are cut with a knife and do not include any easy opening means. However, the invention includes all types of caps with an easy opening means.
As illustrated in
The applicant has observed that it was possible to apply tension on the radially expanded tube using a pair of rollers, the tube being flattened at the exit from the radial expansion device without deteriorating the appearance of the final cap (1, 1a, 1b, 1c). This tension means is advantageous particularly due to its ease of use and its small size.
Another purpose of the invention consists of heat shrinkable outer closing caps (1c) obtained using the method according to the invention and typically intended for outer closing of previously closed bottle necks, with a height H of between 20 and 100 mm and with a skirt thickness between 0.05 mm and 0.5 mm.
Another purpose of the invention consists of heat shrinkable outer closing caps (1c) obtained according to the invention, with height H between 20 and 60 mm and with a skirt thickness between 0.05 mm and 0.5 mm.
Another purpose of the invention consists of heat shrinkable closing caps (1b) obtained according to the invention. These caps that include an insert as illustrated in
Another purpose of the invention consists of heat shrinkable caps for sparkling wines or pressurized fizzy drinks obtained according to the invention, with a height H of between 60 and 200 mm and with a skirt thickness of between 0.1 mm and 1.0 mm. Such caps are illustrated in
Another purpose consists of caps with skirts made of a heat shrinkable thermoplastic material, the head possibly being made of the heat shrinkable thermoplastic material, in which the thermoplastic material may include a mix of:
The mix may include at least 50% by volume of the first thermoplastic material and from 10 to 50% by volume of the second thermoplastic material.
Regardless of the type of cap, the caps according to the invention may comprise a layer of reactivatable thermoadhesive coating on the inside, typically a “hot-melt” layer so as to fix all or part of the caps on the necks.
This means further reinforces the tamperproof nature of the caps according to the invention, making separation of the cap from the neck impossible without at least partial and visible destruction of it.
Another purpose of the invention consists of stacks of caps according to the invention, the stacks comprising a stack of caps or tapered caps, typically printed on their outside surface.
A) Manufacturing of Tube Portions
Most tests on manufacturing of tube portions were carried out with the device (3) shown in
In these tests, an extruder with a maximum flow of 50 kg/h of a thermoplastic material was used, for which the “length/diameter” ratio of the screw was equal to 30.
An annular die or extrusion head with a diameter D0 equal to 27 mm was used, the formed extruded tube having a thickness E0 of 0.7 mm and a temperature T typically varying from 190° to 240° C.
The radial expansion step was carried out over the axial distance L0 that typically varies from 0.3 m to 0.6 m, at the exit from the annular die. The axial drawing step was then blocked using blown air as the means of cooling the axially drawn tube, such that the axially drawn tube is at a temperature varying from 140° C. to 160° C. and its diameter is equal to the diameter D1 of the entry ring (340, 340′) to the radial expansion device. This cooling means was axially mobile so that the diameter of the axially drawn tube can be adjusted to the diameter D1 of the entry ring (340, 340′).
The thickness E1 of this drawn tube at the entry of the radial expansion device was 0.35 mm, which corresponds to an S0/S1 ratio of 3.86, which results in a relatively high axial drawing ratio.
A radial expansion device with a length of 500 mm was used, free to move axially, and separated from the die by a distance L typically varying from 0.5 m to 1 m and provided with an entry ring with diameter D1 equal to 14 mm and an inner wall with an inside diameter D2 equal to 35 mm.
The radial expansion device shown in
Tests were also carried out with a nearby device with the inside profile shown in dashed lines in
For the tests, a vacuum of 0.35 bars was maintained using the vacuum connector (349).
The device was cooled with water, such that the radially expanded tube exits from the device at ambient temperature, typically at approximately 25° C., which corresponds to a temperature drop of the tube of about 120° C. between the inlet and the outlet of the radial expansion device.
The thickness E2 of this radially expanded tube was 0.14 mm.
The axial tension means used is a system with two rollers or possibly with two belt type pullers that rotate in opposite directions and when they move towards each other, they push the expanded tube over a sufficient axial length to apply a minimum pressure on the surface of the expanded tube so as to not mark the tube surface.
This axial tension system, like the chopping means (36) that follows it, are devices known in themselves.
Typical procedure for a test on the laboratory device used:
Tests were also carried out on an industrial line with an extruder flow D and a tension velocity V 5 times greater.
60 mm “long” portions of tubes (24, 241) were cut in order to manufacture outer closing caps with a heat shrinkable skirt (1c) according to the method illustrated in
B) Nature of the Thermoplastic Material Used in the Tests
A large number of tests were carried out. The compositions are usually mixed:
These compositions (by % weight) may also include mineral fillers CM or various fillers or additives.
The following products were used for these non-limitative tests:
I=titanium oxide white pigment
C) Manufacturing of Caps from Tube Portions
A divice (4) for forming tube portions was used consisting of a carousel (41) rotating about its axis (410) and provided with four conformation mandrels typically arranged at 90° from each other, as shown in
The method was used as illustrated diagrammatically in
Starting from a tube portion with the same dimension, caps of various dimensions were manufactured simply by varying the dimensions of the conformation mandrel and the cavity for formation of the head.
A first variant of this first embodiment illustrated in
A second variant of this first embodiment illustrated in
According to this variant, whenever a compression cavity is used, it is possible to incorporate another element into the head of the cap that can be fixed hot and/or by axial compression.
Once formed and typically printed, the outer closing caps (1c) were used as such.
The method according to the invention was also used to also form caps according to
The method according to the invention was also used to form screw closing caps (1b).
According to a first variant of the method illustrated in
According to a second variant of the method illustrated in
D) Results Obtained
Regardless of the type of cap (1b, 1c), the results obtained relate to:
d) cuttability with a knife, particularly in the case of outer closing caps (1c).
Results for tests 2 to 14 should be considered in relation to test 1.
The invention has important advantages:
Number | Date | Country | Kind |
---|---|---|---|
0313193 | Nov 2003 | FR | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/FR04/02862 | 11/8/2004 | WO | 5/10/2006 |