Patent Grant
10654243
The present invention relates to a honeycomb sandwich sheet or panel, based on polypropylene, with a central thermoformed film, the process and apparatus for producing said sheet.
Honeycomb or blister sandwich sheet or panel refers to a honeycomb sheet, preferably made of polypropylene, that can have a grammage, i.e. weight per square metre, typically ranging from 200 to 4000 g/m2 approximately. This product has specific characteristics such as a considerable rigidity and hardness, even in the presence of a good resilience (i.e. fracture strength). It also has a fill factor, i.e. ratio between the volume of plastic material with respect to the total volume occupied by the product, of 30÷50%.
Thanks to this particular honeycomb structure, blister sheet has a particularly interesting resistance/specific weight ratio; in particular, this feature is of particular interest and importance in the packaging field, where there is a specific tendency towards progressively reducing the weight of the packaging product, thus eliminating the overpackaging phenomenon.
The current state of the art describes and uses honeycomb or blister sheets or panels which, very schematically, consist in the hot joining of three different films, of which one (the central film) is a thermoformed film. As a result of said thermoforming, the central film acquires the characteristic honeycomb form, this guaranteeing a significant increase in the static moment of inertia in the three directions and therefore increasing the relative resistance modules.
The particular conformation of the central film gives the end product mechanical properties (rigidity, load resistance, etc.) and functional properties (lightness, malleability, etc.), that in recent years have led to the use of a blister panel or sheet in various applications, with excellent results.
The product, as briefly described above, however, has some significant critical aspects, “physiological” so to speak, which are inherent in its very structure, i.e. a considerable asymmetry, revealed in a sectional view, and great difficulty in guaranteeing the correct characteristics of levelness and resistance in the case of high grammages (typically over 2000 g/m2) of the product.
In other words, the evident and inevitable asymmetry of thermoformed sheets or films has repercussions on the end product, causing a series of well-known drawbacks, whereas the difficulty in producing so-called “heavy” sheets or panels restricts and limits their use in applications for which they are conceptually ideal.
The above asymmetry can first of all be noted in a cooling process of the two sides of the thermoformed sheet, which follow two different timeframes due to the different mass involved: the thermoformed side, or blister, in fact, due to the same thermoforming process, becomes thinner, losing mass with respect to the bottom and requiring less time for cooling.
As a result, after the subsequent welding of the thermoformed sheet with the two outer sheets, the different elastic shrinkage of the two sides of the thermoformed sheet, specifically due to the different masses involved, causes a kind of curling effect, i.e. a transversal curvature, in the end product which, in fact, makes the sheet or panel unusable.
Various procedures, methods and apparatuses have been studied and developed, which have proposed to correct this defect, but the problem of the natural asymmetry of the end product basically remains, and is also manifested in the different finish of the two outer sides of the sheet, i.e. the outer side welded to the blister side of the thermoformed sheet often has the imprint of the blisters themselves, consequently making the final panel or sheet unusable for high-quality applications.
A partial solution to this latter problem is described in patent application MI2014A001110: this describes a honeycomb sheet or panel based on thermoplastic polypropylene, comprising a structure consisting of two flat outer films, thermowelded to a central film consisting of a thermoformed blister film repeated in a regular and continuous pattern, the two flat outer films being composed of a coextruded two-layer film (AB), based on thermoplastic polypropylene, wherein the internal layer (A) faces the central thermoformed film, and the central thermoformed blister film is composed of a coextruded three-layer film (ABA), based on thermoplastic polypropylene, wherein the two outer layers (A) face the flat outer films and said structure also envisages a further layer C thermowelded to the outer layer B of the two flat outer films.
The process and apparatus that represent the state of the art closest to the present invention are described in EP1638770. The process described in EP'770 envisages the production of a blister sheet with the following passages: extrusion of an upper or bottom film, a central film and a lower or top film, starting from the corresponding granule; thermoforming of the central film; calibration and partial cooling of the bottom and top film; heating of at least one side of the bottom and top film and coupling of the two bottom and top films to the thermoformed film. This process is carried out in an apparatus that comprises at least three extrusion heads, which form the extrusion group, followed by a thermoforming group and calibration and cooling groups, the thermoforming group and calibration and cooling groups in turn being connected to a coupling group. This process, which already allows a high-quality product to be obtained, does not completely solve the problems indicated herein, as the central thermoformed sheet in any case has a basic asymmetry, which creates the necessity of using additional stabilization and tempering devices (so-called hot-air and cold-air ovens) downstream of the extrusion and forming process described above.
Furthermore, in the case of sheets or panels having a high grammage and a high thickness, a physical limitation to their production is also linked to the thermoformability of the material used, which comprises not only the polymer (i.e. the polypropylene mentioned above) but also mineral fillers such as calcium carbonate, with the double objective of increasing the resistance characteristics of the end product and reducing the material cost.
On the one hand, the necessity of having materials with an extremely high elastic modulus, i.e. that require considerable force for causing a small elongation, limits the possibilities of effecting “deep” thermoformings, i.e. thermoformings necessary for the production of sheets having a high thickness and grammage.
A further aspect to be taken into consideration is the necessity of “charging” the polymer with mineral fillers in different percentages, typically from 10% to 60% by weight, which creates a further limitation, i.e. the necessity of using so-called “compounds”, i.e. compounds of mineral fillers and polymer (in this case polypropylene), previously mixed and extruded in the form of granules. This process is currently effected off-line by granulating machines.
Furthermore, in the case of the use of compound granules, the producer of sheets, i.e. of the end product, is compelled to avail of an extremely large stock of raw materials: he must in fact have at his disposal granules with various concentrations of material charged for different uses, consequently a necessity that requires the availability of numerous, different lots of compounds, each characterized by a different concentration of the filler and/or a different mineral filler. This also affects the sheet producer with respect to the suppliers of these compounds: he will generally be compelled to have a limited choice of both suppliers and compounds with different concentration percentages of mineral fillers, of the same supplier.
The present invention proposes to provide a sandwich sheet or panel made of thermoplastic material, which overcomes the drawbacks of the known art.
More specifically, the objective of the present invention is to provide a honeycomb sandwich sheet or panel, based on thermoplastic polypropylene, composed of outer films, joined to a central layer which comprises a thermoformed blister film having a cylindrical form or other forms (honeycomb structure) repeated in a regular and continuous pattern, wherein the particular conformation of the central layer gives the sheet mechanical properties, load resistance and structural and functional characteristics.
An objective of the present invention is therefore to provide a honeycomb sandwich sheet or panel, based on polypropylene, that has the specific characteristics of the sheet object of patent application MI2014A001110, at the same time eliminating the drawbacks previously described.
An objective of the present invention is therefore to provide a honeycomb sandwich sheet or panel, characterized by a much greater thermoforming depth with respect to the thermoformed sheets or panels according to the state of the art, typically a double forming depth.
A further objective of the present invention is to provide a honeycomb sandwich sheet or panel with a complete symmetry of the structure of the thermoformed blister sheet or panel.
Finally, objectives of the present invention are a process and apparatus for producing the honeycomb sandwich sheet or panel that also allow the use of mineral fillers directly in powder form.
In the drawings:
An object of the present invention relates to a honeycomb sandwich sheet or panel, based on thermoplastic polypropylene, comprising a structure consisting of two flat outer films, at the top and bottom 10, 12, welded to an inner or central film 11, blister thermoformed 13, with blisters repeated in a regular and continuous pattern, wherein said inner thermoformed film is welded on both faces or sides, said sheet being characterized in that the flat outer films (10,12) and the inner thermoformed film (11) are composed of three coextruded layers.
More specifically, the thermoforming of the inner or central film 11 is effected contemporaneously in both positive and negative on the two faces or sides of the same film 11, with blisters 13 preferably having the same shape, size and number, suitable for guaranteeing the symmetry of the thermoformed structure.
The thermoforming of the inner or central film 11 is therefore a symmetrical thermoforming with respect to the thermoforming plane, suitable for guaranteeing a thermoformed structure having a substantially constant thickness.
This characteristic substantially distinguishes the sheet according to the present invention from a sheet with a central film thermoformed only on one side or face, i.e. having a structure which is not symmetrical with respect to the thermoforming plane. This second sheet, in fact, cannot be characterized by a substantially constant thickness of the thermoformed film: the thermoformed, or blister, side in fact, due to the same thermoforming process, becomes thinner, losing mass with respect to the bottom. These differences in thickness together with different cooling times of the two sides of the film lead to an inevitable asymmetry of both the central film and the final sheet, causing a “curling” effect of the sheet, once the central thermoformed film has been welded to the flat outer films.
In the following description, unless otherwise specified, the term “honeycomb sheet or panel” refers to a structure composed of flat non-thermoformed films and thermoformed films welded to each other, the term “films” refers to the single thermoformed or non-thermoformed elements that form the sheet, the term “layer” refers to the elements forming the film.
Each film consists of three coextruded layers, whereas each sheet or panel is preferably composed of at least two non-thermoformed films and one thermoformed film, extruded contemporaneously.
In particular, the honeycomb or blister sheet or panel according to the present invention preferably consists, as already indicated, of a flat upper or top outer film, a central thermoformed film and a flat lower or bottom outer film.
Each single film is preferably composed of three layers, for example according to the structures A-B-A, A-B-C, C-B-A and all combinations thereof.
It is not necessary for all the layers A, B or C, forming the different films to come from the same extruder (i.e. extruder A, or B, or C), but the presence of the same number of extruders as the layers forming the whole of the final sheet can be envisaged.
In other words, if the final sheet has a structure consisting of A-B-A+A′-B′-A′+A″-B″-A″, there can be an extruder A for the layer A, an extruder B for the layer B, an extruder A′ for the layer A′, an extruder B′ for the layer B′, and so forth.
The flat outer films preferably consist of films of polypropylene copolymer (preferably a block or random polypropylene copolymer, with ethylene and/or butane monomers inserted in the propylene chains) and homopolymer and/or relative mixtures, said films having chemical properties that make them particularly suitable for hot coupling, at the same time ensuring a high adhesion and relatively low welding temperature. This is therefore a multilayer structure produced in coextrusion with three layers, wherein the three-layer coextruded structure A-B-A is preferably composed of an internal layer B of polypropylene homopolymer and two outer layers A of polypropylene copolymer.
In the case of coextruded multilayer structures A-B-C or C-B-A or combinations thereof, the structure is the result of the coextrusion of three different polymers coming from three different extruders, the two outer layers of the film A and C can therefore be composed of different types of polypropylene, whether they be polypropylene homopolymers, copolymers, or of any other nature.
The possibility/necessity of having three different polymers in the films that form the flat outer films of the sheet or panel according to the present invention, depends on the fact that, in some applications, the outermost layer of the film can be coupled with possible further outer films: consequently, depending on the structure selected, it can be the layer A or C, and may have to meet particular physical/chemical characteristics, bearing in mind the requirement that the layer of flat outer film directly welded to the inner or central thermoformed film, must have weldability characteristics suitable for guaranteeing the perfect adhesion between said thermoformed film and non-thermoformed film.
These considerations are obviously valid for both of the flat outer films.
The inner thermoformed film preferably consists of a film of polypropylene copolymer (preferably a block or random polypropylene copolymer, with ethylene and/or butane monomers inserted in the propylene chains) and homopolymer and/or relative mixtures, having particularly high physico-mechanical properties, and therefore suitable for guaranteeing that the end product, i.e. the honeycomb or blister panel or sheet, has the desired qualities from the point of view of mechanical resistance and lightness. This is therefore a film with multilayer structure produced in coextrusion with three layers, wherein the three-layer coextruded structure A-B-A is preferably composed of an internal layer B of polypropylene homopolymer and two outer layers A of polypropylene copolymer.
The outer layers of the flat outer films 10, 12 and the inner thermoformed film 11, the same as or different to each other, are preferably made of polypropylene copolymer and the inner layers of the flat outer films 10,12 and inner thermoformed film 11 are preferably made of polypropylene homopolymer, possibly with the addition of mineral fillers.
An object of the present invention also relates to a process for the production of a honeycomb sandwich sheet or panel which comprises the following phases:
a) contemporaneous extrusion of at least three multilayer films 10,11,12, starting from a corresponding polymer or from a corresponding polymer compound and mineral filler: an outer bottom film 10, an inner or central film 11, and an outer top film 12;
b) thermoforming of said inner or central film 11;
c) coupling by means of thermowelding of said non-thermoformed flat outer films 10,12 with said inner or central thermoformed film 11,
wherein said thermoforming of the inner film 11 is effected contemporaneously in both positive and negative on the two sides or faces of the inner film 11 and the beginning of the coupling phase is contemporaneous for all the outer and inner, thermoformed and non-thermoformed films 10,11,12.
The process for the production of a honeycomb sandwich sheet or panel according to the present invention can also comprise, upstream of phase a), a mixing phase of polypropylene and mineral filler in powder form, to form the compound in granule form to be used in the subsequent phase a).
Furthermore, the process that envisages said further mixing phase, can be carried out in continuous, introducing one or more twin-screw extruders prior to the extrusion head(s), so as to feed the process directly with pure polypropylene granules and powder of mineral fillers, such as for example, calcium carbonate, fiberglass or the like.
Thanks to the thermoforming of the inner or central film on both sides or faces, a honeycomb sheet or panel is finally obtained, composed of three films, of which one is a central thermoformed film, absolutely and completely symmetrical.
An essential aspect of the process according to the present invention is that the production of this type of sheet or panel takes place in contemporaneous regime conditions: this means that all the elements (i.e. all the films, thermoformed and non-thermoformed) must be produced at the same moment, in order to guarantee the necessary symmetry, not only geometrical (relatively simple to obtain), but also and above all a thermal symmetry.
These elements, in fact, must not only be produced at the same moment, but they must also reach the couplings under substantially similar thermal conditions, specifically to guarantee the thermal symmetry.
The film run (i.e. the path followed by all of the films) is extremely important and has been specifically conceived so that the films reach the coupling phase with substantially similar characteristics.
The term substantially similar characteristics means that each film reaches the coupling phase at a temperature ranging from −10° C. to +10° C. with respect to the welding temperature of the material used, or that the differences in temperature between the films reaching the coupling phase are lower than 10° C. approximately.
In particular, the coupling phase by means of thermoforming can take place either by mechanical thermoforming or vacuum thermoforming and can be effected according to the embodiments of the process for the production of the panel or sheet according to the present invention, described in the enclosed
the thermoforming of the inner or central film 11 is effected by means of a shaping cylinder 16, including both grooves 14 and ridges 15, preferably having the same shape, size and number in order to guarantee the symmetry of the thermoformed structure, wherein the thermoforming given by the grooves 14 is obtained by suction and the thermoforming given by the ridges 15 is guaranteed by a jet of external air, hot or cold, depending on the material used and grammage, welding, in a single step, the two smooth outer films 10 and 12, onto the inner or central thermoformed film 11, until the end product is obtained, i.e. the honeycomb sheet or panel 10-11-12 (
the thermoforming of the inner or central film 11 is effected by means of the contemporaneous mechanical action of two cylinders 16, 16′ opposite and identical, whose grooves 14 and ridges 15 intersect each other, thus effecting the thermoforming of the film 11, subsequently welding, in a single step, the two smooth outer films 10 and 12, onto the inner or central thermoformed film 11, until the end product is obtained, i.e. the honeycomb sheet or panel 10-11-12 (
The coupling phase by means of thermowelding c) is carried out by welding the films (10,11,12) to each other, each film (10,11,12) reaching said coupling phase at a temperature ranging from −10° C. to +10° C. with respect to the welding temperature of the outer layer of the same film (10,11,12), or the films (10,11,12) reach the coupling phase at temperatures which differ from each other by a value lower than 10° C.
A fundamental advantage, however, of the honeycomb sheet or panel according to the present invention is the perfectly symmetrical structure and a thermoforming depth which is at least double with respect to a solution with a single thermoformed film, obviously with the same raw material used (and therefore thermoformability characteristics).
Furthermore, the versatility of the process according to the present invention also allows sheets or panels that are intentionally asymmetrical to be obtained, by simply using two flat outer films which are not the same in terms of thickness and/or envisaging further films welded onto said outer films.
A further object of the present invention also relates to an apparatus for the production of a honeycomb or blister sheet or panel, said apparatus comprising an extrusion group consisting of at least three extrusion heads, downstream of said extrusion group there being a thermoforming group and a calibration and cooling group, the thermoforming groups and the calibration and cooling groups being connected, in turn, to a coupling group, wherein the thermoforming group comprises a shaping cylinder, suitable for thermoforming a film on both sides or faces in positive and negative.
Said apparatus can also comprise one or more twin-screw extruders upstream of the extrusion group.
A further object of the present invention relates to the use of the honeycomb blister sheet or panel according to the present invention, as a protection element or packaging element.
As already observed, a fundamental advantage of the honeycomb sheet or panel according to the present invention is the perfectly symmetrical structure and a thermoforming depth which is at least double with respect to a solution with a single thermoformed film.
One of the advantages of the process for the production of the honeycomb or blister sheet or panel according to the present invention consists in the production of the panel by means of a single production step, wherein single production step means that the final sheet or panel is produced in a single plant starting from the raw material (i.e. the granule or also powder when mineral fillers are used, in one or more twin-screw extruders), without the production of semifinished products, with a consequent lower energy consumption and, indirectly, with a lesser environmental impact, above all thanks to the drastic reduction in waste products.
A further advantage is represented by the absence of delamination thanks to the absolute adhesion specifically guaranteed by the fact that each single film forming the sheet or panel according to the present invention is composed of three layers contemporaneously extruded by means of a coextrusion process.
In this way, another problem present in the products and processes according to the state of the art can also be limited, if not completely eliminated, i.e. the necessity of finding a mixture of materials that has good physico-mechanical characteristics and at the same time allows a coupling at relatively low temperatures, without the risk of detachment of the films forming the honeycomb blister panel or sheet.
A mixture of materials that satisfies these requirements is inevitably the result of a compromise between the requirements of the production process and the desired characteristics for the end product, i.e. the honeycomb sheet or panel, but both of these needs cannot clearly be 100% satisfied, as this is a compromise, as already mentioned.
In particular, as previously described, a honeycomb blister panel or sheet according to the present invention is preferably composed of a flat outer upper or top film, an inner or central film thermoformed on both faces or sides and a flat outer lower or bottom film.
For higher grammages, as already indicated, the presence of mineral fillers is necessary, which are suitable for guaranteeing the correct mechanical resistance properties of the honeycomb blister panel or sheet, at the same time reducing the material cost of the end product.
Furthermore, the process for the production of the panel or sheet according to the present invention also allows the concentration of mineral fillers to be varied, without having to stock the corresponding compound, and above all it allows said fillers to be used in powder form, i.e. in their natural configuration state. This solution is enabled by the choice of a so-called twin-screw extruder for the extrusion of the layer(s) of coextruded films that comprise said mineral fillers.
In the apparatus according to the present invention, a twin-screw extruder can also be envisaged for the extrusion of the layer(s) that require mineral fillers. A single twin-screw extruder can be present, that can feed all the extrusion heads necessary for the production of the panel or sheet according to the present invention (typically not less than three, but there can be four, five, or six, etc.) with the use of the same number of gear pumps, or as many twin-screw extruders can be present as the layers of film forming the end product of the panel or sheet according to the present invention that also require the presence of mineral fillers, coupling each extrusion head with a gear pump to guarantee the correct flow-rate of material also in the presence of high counter-pressures of the extrusion head, typical of these applications.
Further advantages of the process for the production of the honeycomb or blister panel or sheet according to the present invention are the following: first of all, this is a continuous process that starts from the granule and/or even from the polymer and powders of mineral fillers and directly produces the end product, i.e. the honeycomb sheet or panel, without intermediate passages. A stock of film reels is therefore not necessary, with relative economical advantages with respect to both the logistics and transportation.
It is also possible to directly produce any required grammage (obviously within a defined variation range) and with any colouring, practically “just in time”, with a minimum product waste for obtaining the variation in thickness.
The process according to the present invention also allows a considerable energy saving deriving from the fact that all of the films involved in the process itself require little heating, thanks to the sufficiently high caloric content they maintain in close proximity of the various couplings.
The process according to the present invention also has the further advantage of envisaging the use of materials having high mechanical properties, as central layer of the three-layer coextruded product, which forms both the flat outer films and also the inner thermoformed film, without influencing the weldability of the single films.
Materials having high weldability characteristics can also be used as outer layers of the three-layer coextruded product, which forms both the flat outer films and also the inner thermoformed films, without influencing the mechanical properties of the end product.
Furthermore, the process according to the present invention has the definite advantage of minimizing waste products during the starting operations, as this is a continuous process, and also and above all at regime, thanks to the possibility of recycling the cut edges for preferably feeding the extruders of the central layers of the three-layer coextruded products, that form all of the films, without significant variations in the characteristics of the end product.
The honeycomb or blister panel or sheet according to the present invention is also characterized by the complete absence of residual internal stress, above all in the case of films having a completely symmetrical structure (i.e. where the thicknesses of the flat outer films are substantially equal).
Furthermore, the honeycomb or blister panel or sheet has a high levelness, also thanks to the coupling of the films, which is obtained at temperatures close to the vicat temperature and thanks to the use of specific materials for the outer layers, which allow a strong adhesion also in the presence of relatively limited contact pressures, in addition of course to the fact that the couplings of the flat outer films are preferably effected with the outer layers of the inner or central thermoformed film.
Finally, the process according to the present invention allows honeycomb sheets or panels with a high grammage and high thickness, typically over 2000 g/m2, to be produced without any problems, thanks to the presence of a central thermoformed film that has a thermoforming on both faces or sides, therefore allowing a considerable increase in the total depth of the thermoforming, also in the presence of materials having a poor thermoformability, such as those used in the process in question, but which are necessary for guaranteeing the correct mechanical properties of the end product.
The sheet or panel according to the present invention has a weight ranging from 300 g/m2 to 5000 g/m2, preferably from 1000 g/m2 to 4000 g/m2.
The sheet or panel according to the present invention has a thickness ranging from 4.00 to 40.0 mm, preferably ranging from 10.00 to 30.00 mm.
The blisters present in the central thermoformed layer have a diameter ranging from 3.00 to 20.00 mm, preferably ranging from 4 to 15 mm and the height of the protrusions/blisters varies and depends on the diameter of the same, for example the height being 3.00 mm for a diameter of 3.5 mm and 10.00 mm for a diameter of 15.00 mm.
The layers A, B and C can have the same or different thickness and said thickness preferably ranges from 100 microns to 2 mm.
A sheet or panel according to the present invention is preferably composed of three films, of which two films (A-B-A and A″-B″-A″) are outer films and flat, welded to a film (A′-B′-A′) thermoformed on both faces or sides.
The sheet or panel represented in
More specifically, both the two flat outer coextruded films A-B-A and A″-B″-A″, and also the central thermoformed film A′-B′-A′, have the following characteristics:
the outer layers A, A′, A″ have a thickness, the same as or different from each other, ranging from 5 to 10% with respect to the total thickness of the corresponding coextruded film, whereas the central layers B, B′, B″ have a thickness, the same as or different from each other, ranging from 80 to 90% with respect to the total thickness of the corresponding coextruded film.
Furthermore, in the sheet or panel according to the present invention, in the embodiment according to
The flat outer films preferably have the same weight.
A specific example of a sheet or panel according to the present invention has the following features:
Sheet with a weight of 3000 g/m2;
Diameter of the blister: 14 mm;
Composition of the outer films (upper/flat A-B-A and lower/flat A″-B″-A″):
Layer A, A″:
PP copolymer (fluidity index=3 g/10′);
Layer B, B″:
PP homopolymer (fluidity index=3 g/10′) and mineral fillers (in this case talc) in a quantity equal to 20% by weight.
The central thermoformed film A′-B′-A′ envisages layers A′ with the same composition as the layers A and A″ and a layer B′ with the same composition as the layers B and B″ of the outer films indicated above.
The sheet was produced by coupling, by means of thermowelding, the flat outer non-thermoformed films with said internal or central thermoformed film on both sides in a single step, with the relative three films that reach the thermowelding point with the same thermal properties in order to guarantee perfect symmetry and compatibility with each other.
In particular, for this example, the central film is thermoformed by means of a shaping cylinder 16, including both grooves 14 and ridges 15, having the same shape, dimension and number, wherein the thermoforming given by the grooves 14 is obtained by means of suction and the thermoforming given by the ridges 15 is guaranteed by a jet of hot external air.
Weight distribution of the films with respect to the total weight of the sheet:
Upper film A-B-A/central film A′-B′-A′/lower film A″-B″-A″=35%-30%-35%.
The panel obtained has a total weight equal to 3000 g/m2.
| Number | Date | Country | Kind |
|---|---|---|---|
| UB2015A1160 | Jun 2015 | IT | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/062786 | 6/6/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2016/198354 | 12/15/2016 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6004651 | von Montgelas | Dec 1999 | A |
| 20120063706 | Fraser | Mar 2012 | A1 |
| 20170087797 | Aledi | Mar 2017 | A1 |
| Number | Date | Country |
|---|---|---|
| 10055190 | May 2002 | DE |
| 1491327 | Dec 2004 | EP |
| 1638770 | Apr 2007 | EP |
| 2025505 | Feb 2009 | EP |
| 1382436 | Jan 1975 | GB |
| 9405489 | Mar 1994 | WO |
| 2004043688 | May 2004 | WO |
| 2004113073 | Dec 2004 | WO |
| 2005105436 | Nov 2005 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20180147809 A1 | May 2018 | US |
