EP3810421A1 - Film for agricultural use and relative manufacturing process - Google Patents
Film for agricultural use and relative manufacturing processInfo
- Publication number
- EP3810421A1 EP3810421A1 EP19742969.9A EP19742969A EP3810421A1 EP 3810421 A1 EP3810421 A1 EP 3810421A1 EP 19742969 A EP19742969 A EP 19742969A EP 3810421 A1 EP3810421 A1 EP 3810421A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- plastic film
- hdpe
- ethylene
- layer
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 44
- 239000002985 plastic film Substances 0.000 claims abstract description 18
- 229920006255 plastic film Polymers 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 15
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 13
- 229940099514 low-density polyethylene Drugs 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000004701 medium-density polyethylene Substances 0.000 claims abstract description 9
- 239000004698 Polyethylene Substances 0.000 claims abstract description 4
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims abstract 2
- 229940063583 high-density polyethylene Drugs 0.000 claims description 41
- 239000000654 additive Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 5
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000012963 UV stabilizer Substances 0.000 claims 1
- 238000000071 blow moulding Methods 0.000 claims 1
- 229920001903 high density polyethylene Polymers 0.000 abstract description 36
- 229920001684 low density polyethylene Polymers 0.000 abstract description 11
- 229920001179 medium density polyethylene Polymers 0.000 abstract description 7
- -1 polyethylene Polymers 0.000 abstract description 7
- 229920001038 ethylene copolymer Polymers 0.000 abstract description 4
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 10
- 239000000575 pesticide Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 230000010494 opalescence Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2410/00—Agriculture-related articles
Definitions
- This invention relates to a film for agricultural use and the relative manufacturing process.
- the invention relates to a plastic film for agricultural use containing high-density polyethylene (FIDPE).
- FIDPE high-density polyethylene
- the polymeric films currently used in agriculture are usually based on polyolefinic polymers having optical and mechanical properties which comply with the requirements of EU Regulation EN 13206:2017, which classifies the plastic covering films used in agriculture and horticulture.
- the plastic films in agriculture are mainly used for covering greenhouses in order to protect and favour the growth of the plants.
- they are used in greenhouses for forming a barrier which provides a protection for the cultivated plants against the weather conditions, for filtering solar radiation, for determining a balanced thermal effect between day and night.
- the films for agriculture are mainly produced with the following variants of polyethylene:
- LDPE low-density polyethylene
- MDPE medium-density polyethylene
- LLDPE linear low-density polyethylene
- mLLDPE metallocene-based linear low-density polyethylene a base
- EVA ethylene copolymers
- Said variants can be produces in mono-extrusion mode or in co extrusion with several layers.
- systems of this type can only be used for a limited time since they are exposed to solar radiation and to the use of chemical agents inside cultivations and the are often not able to filter the UV rays in an optimum manner.
- HDPE is, on the other hand, widely used in the production of films in the food packaging sectors (small bags, sheets for wrapping food, etc.), in the industrial sector, for example for making counter covers, large bags, etc.
- HDPE is only transformed for the production of mono filaments and raffia which are then woven and/or interlaced with frames for packaging covering netting or meshes but not into films for covering greenhouses or tunnels, either the mono-extruded or co-extruded variants.
- the solution according to the invention falls within this context, providing a film for agricultural use containing high-density polyethylene (HDPE) with a physical process of combination of the HDPE with layers of polymers and copolymers, and thus without the need for any chemical reaction during the production step and no need for the modification of the standard extrusion systems.
- HDPE high-density polyethylene
- UV stabilisers HALS, NOR HALS
- Table 1 shows the permeability values of the polyolefinic polymers and copolymers to carbon dioxide (CO2), oxygen (O2) and transmission of water vapour (WVTR), in 25 pm mono-extruded films.
- the data shows a better barrier effect of the HDPE and consequently, since the HDPE is more impermeable, a greater resistance to the absorption of the treatments with pesticides inside the greenhouse and consequently a controlled migration, because it is slower, of any anti-drop and/or anti-fog additives inserted in the structure of the co-extruded film.
- Table 2 shows comparative values of diffused transmittance (haze) of the light, measured according to ISO 14782, between a mono-extruded film made of LDPE and one made of HDPE, both with thicknesses of 70 pm, which can be further modified by adding mineral additives of spheres of various kinds.
- Table 3 shows the values of the resistance to UV radiation of the film, expressed in kLangley (kly), for various mono-extruded films with a thickness of 50 pm, measured in Florida, hie is an exposure zone characterised by a solar radiation of approximately 140 kly/year. The measurements have been carried out on polymers without the addition of any UV stabilising additive, upon reaching 50% of their initial mechanical characteristics
- the film according to the invention contains in co-extrusion:
- the HDPE leaving the possibility of using the traditional polyolefinic polymers or/with copolymers inside in order to have all the advantages described above (high mechanical strength, better resistance to UV degradation, better impermeability to any passage of treatments with pesticides);
- the HDPE in combination in the remaining layers with traditional polyolefinic polymers and/or copolymers (LDPE, LLDPE, mLLDPE, EVA, EBA, etc.) to mainly enhance just the mechanical characteristics of the latter, with the consequent possibility of reducing the thicknesses (if the HDPE is present in the outer layer(s) the performance levels are those described above). Any addition of HDPE in the inner layer(s) would drastically improve the mechanical characteristics of the film as indicated in Table 4).
- traditional polyolefinic polymers and/or copolymers LDPE, LLDPE, mLLDPE, EVA, EBA, etc.
- the layer or layers of HDPE can have a minimum thickness of 1 .5 pm and a maximum thickness which can correspond to 90%, preferably 60%, of all the structure (for example, a co extruded film consisting of 5 layers and with a thickness of 150 pm, preferably not more than 90 pm which can be made of HDPE, distributed in one or more layers, inside and/or outside).
- the maximum thickness of total HDPE in the film can be approximately 200 pm, above which the film would have a rigidity and optical characteristics, such as opalescence, which would not be suitable for agriculture.
- the film according to the invention is made by means of co-extrusion processes known for making film for agricultural covers of greenhouses or tunnels, both with blow technology and by casting.
- the film according to the invention is obtained by means of the coex blow process, feeding the various hoppers of the extruder with the polymeric matrices described above, in which the HDPE is placed in one or more inner and/or outer layers of the film.
- the mixture of polymers is heated by the extruder to a temperature which can vary between 180 °C and 230 °C in order to obtain a homogeneous mixture.
- UV stabilisers for example HALS, NOR HALS, UV absorber, Nickel Quencher
- pesticides for example, methylated HALS, NOR HALS
- any mineral additives for example, kaolin, silicon, nepheline, etc.
- spheres of various chemical nature such as glass, PMMA, ceramic, etc.
- any refreshing additives for example, modified mica
- NIR near infrared
- any anti-drop additives for example, fatty acid esters
- anti fog additives for example, modified silicones
- any anti-blocking additives in the co-extrusion process for example, synthetic and natural silica
- gliding agents erucamides, polyammidic waxes, etc.
- the aim of the invention is therefore to make a plastic film for agricultural use containing high-density polyethylene (HDPE), with thicknesses which can vary according to the desired performance levels for the requested application, in order to increase the resistance to UV radiation, diffuse the light and substantially improve the mechanical characteristics, as well as the resistance to any aggression of plant protection products/pesticides.
- HDPE high-density polyethylene
- a further aim of the invention is that said device can be manufactured with substantially reduced costs, with regard to both the productions costs and the management costs.
- Yet another aim of the invention is to provide a process and device which is substantially simple, safe and reliable.
- a first specific object of the invention is therefore a plastic film for agricultural use comprising at least one layer of high-density polyethylene (HDPE) and at least one layer of a second polyolefinic material selected between low-density polyethylene (LDPE), medium-density polyethylene (MDPE), linear polyethylene, linear low-density polyethylene (LLDPE) based on metallocenes (mLLDPE), ethylene copolymers (such as, for example, EVA and EBA), which can be obtained by means of a physical process for combination of said high-density polyethylene with said polyolefinic material.
- HDPE high-density polyethylene
- MDPE medium-density polyethylene
- LLDPE linear low-density polyethylene
- LLDPE linear low-density polyethylene
- mLLDPE metallocenes
- ethylene copolymers such as, for example, EVA and EBA
- said layer of HDPE can have a minimum thickness of 1 .5 pm and a maximum thickness of 200 pm, and the sum of the thicknesses of all the layers of HDPE cannot correspond to more than 90% of the total thickness of the film.
- said film can comprise at least three layer in which, preferably, at least one of the outer layers is made of HDPE.
- said plastic film can comprise at least one UV stabiliser, in particular HALS o NOR-HALS, UV absorber, Nickel Quencher and/or at least any ultraviolet rays absorber, and can also comprises at leat one anti-drop and/or anti-fog refreshing additive (for example, modified mica).
- at least one UV stabiliser in particular HALS o NOR-HALS, UV absorber, Nickel Quencher and/or at least any ultraviolet rays absorber
- at leat one anti-drop and/or anti-fog refreshing additive for example, modified mica.
- Another object of the invention is a process for manufacturing a plastic film as defined above, comprising a co-extrusion step, which can preferably be performed by blowing, of said at least one layer of high-density polyethylene (HDPE) and said at least one layer of at least a second polyolefinic material.
- a co-extrusion step which can preferably be performed by blowing, of said at least one layer of high-density polyethylene (HDPE) and said at least one layer of at least a second polyolefinic material.
- HDPE high-density polyethylene
- At least one anti-blocking additive can be added, for example synthetic or natural silica and/or at least one gliding agent, for example erucamides or polyammidic waxes.
- a film was made having five layers and a total thickness of 150 pm, with each layer of equal thickness, co-extruded with HDPE in just the two outer layers and LDPE in the remaining three inner layers and it was compared with a traditional film, having five layers and a total thickness of 150 pm, with each layer of equal thickness, co-extruded in all the five layers with LDPE.
- Table 4 indicates the comparative values (according to ASTM D882) of ultimate load (%) and ultimate elongation(%) in a longitudinal (MD) and transversal (TD) direction between the two co-extruded films (respectively, coex film with HDPE and traditional coex film) of equal thickness.
Landscapes
- Protection Of Plants (AREA)
- Laminated Bodies (AREA)
- Greenhouses (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT102018000006500A IT201800006500A1 (en) | 2018-06-20 | 2018-06-20 | Film for agricultural use and its production method. |
PCT/IT2019/050142 WO2019244185A1 (en) | 2018-06-20 | 2019-06-18 | Film for agricultural use and relative manufacturing process |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3810421A1 true EP3810421A1 (en) | 2021-04-28 |
Family
ID=63762669
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19742969.9A Withdrawn EP3810421A1 (en) | 2018-06-20 | 2019-06-18 | Film for agricultural use and relative manufacturing process |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3810421A1 (en) |
IT (1) | IT201800006500A1 (en) |
WO (1) | WO2019244185A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114013143A (en) * | 2021-12-03 | 2022-02-08 | 山东华致林医药科技有限公司 | High-temperature-resistant PE film |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5221570A (en) * | 1991-09-03 | 1993-06-22 | Cem Gokcen | Multilayered coextruded geomembrane |
JPH09154413A (en) * | 1995-12-01 | 1997-06-17 | Chisso Corp | Film for agriculture |
JPH09183193A (en) * | 1995-12-28 | 1997-07-15 | Chisso Corp | Multilayred film for agriculture |
JP3686237B2 (en) * | 1997-10-08 | 2005-08-24 | 株式会社クラレ | Agricultural coating |
US8034461B2 (en) * | 2005-02-09 | 2011-10-11 | Equistar Chemicals, Lp | Preparation of multilayer polyethylene thin films |
-
2018
- 2018-06-20 IT IT102018000006500A patent/IT201800006500A1/en unknown
-
2019
- 2019-06-18 EP EP19742969.9A patent/EP3810421A1/en not_active Withdrawn
- 2019-06-18 WO PCT/IT2019/050142 patent/WO2019244185A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
WO2019244185A1 (en) | 2019-12-26 |
IT201800006500A1 (en) | 2019-12-20 |
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