WO2022136448A1 - Utilisation de polyéthylène haute densité (pehd) comme couche de contact de films stratifiés utilisés dans l'emballage de solutions et de substances agrochimiques - Google Patents

Utilisation de polyéthylène haute densité (pehd) comme couche de contact de films stratifiés utilisés dans l'emballage de solutions et de substances agrochimiques Download PDF

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Publication number
WO2022136448A1
WO2022136448A1 PCT/EP2021/087116 EP2021087116W WO2022136448A1 WO 2022136448 A1 WO2022136448 A1 WO 2022136448A1 EP 2021087116 W EP2021087116 W EP 2021087116W WO 2022136448 A1 WO2022136448 A1 WO 2022136448A1
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layer
agrochemical
contact layer
methyl
hdpe
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PCT/EP2021/087116
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English (en)
Inventor
Peter Johansen
Torben FOGTMANN
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Danapak Flexibles A/S
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Publication of WO2022136448A1 publication Critical patent/WO2022136448A1/fr

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    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/085—Layered products comprising a layer of metal comprising metal 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 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/09—Layered products comprising a layer of metal comprising metal 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 comprising polyesters
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • 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
    • B32B2439/00—Containers; Receptacles

Definitions

  • HDPE high-density polyethylene
  • the present invention relates to the use of HDPE as a contact layer of laminate films, wherein a layer, optionally coextruded, comprising a contact layer and at least one tie layer is adhered to a base layer, as well packagings making use of the laminate films to seal often liquid formulated agrochemical substances.
  • substances including highly reactive and in some cases hazardous substances such as pesticides and chemical fertilizers, are packed as solutions, powders, granules etc. in various cans, containers, bags, pouches or dose packets, resulting in special requirements for the packaging, laminate, or film for sealing these substances in order to ensure that no adverse leaking, degradation or uptake takes place.
  • the requirements of a packaging, film or laminate are typically: Mechanically stable laminate that does not separate or deform Ensuring that the packaging is child proof to increase safety of potentially hazardous compounds
  • the enclosed agrochemical substances optionally in solution do not react with the surface with which it is in contact or migrate through or into it or cause leakage.
  • agrochemical substance is selected from the group consisting of agrochemical active substances, such as: herbicides, such as glyphosate ((N-phosphonomethyl)glycine), di- chlorprop-p ((R-2-(2,4-dichlorophenoxy)propanoic acid), MCPA (2-methyl-4- chlorophenoxyacetic acid), Dicamba (3,6-dichloro-2-methoxybenzoic acid); insecticides, such as deltamethrin ([(S)-cyano-(3-phenoxyphenyl)- methyl] (lR,3R)-3-(2,2-dibromoethenyl)-2,2-dimethyl-cyclopropane-l-car- boxylate); fungicides/insecticides such as oils, such as
  • a high density polyethylene (HDPE) polymer as contact layer of a laminate film for sealing agrochemical substances, said film comprising : i) a base layer, which is water and/or oxygen resistant; ii) a tie layer iii) and the contact layer wherein the laminate film is used, for example as a lidding film, for a container comprising a compound selected from the group of agrochemicals consisting of agrochemical active substances, such as herbicides, such as glyphosate ((N-phosphonomethyl)glycine), dichlorprop-p ((R-2-(2,4-dichloro- phenoxy)propanoic acid), MCPA (2-methyl-4-chlorophenoxyacetic acid), Dicamba (3,6-dichloro-2-methoxybenzoic acid); insecticides, such as deltame- thrin ([(S)-cyano-(3-phenoxyphenyl)-methyl] (lR,3R)
  • HDPE high
  • HDPE as a contact layer provide packagings and containers with sufficient resistance to a broad range of agrochemical substances as well as the solvent typically used therefor.
  • Experiments also show a wear resistant laminate that will meet the mechanical requirements. Still the laminated may be produced by a number of methods thereby providing a flexible cost-efficient way of producing the products for use according to the invention.
  • the contact layer is the layer which is in contact with the contents of the container, suitably the contact layer is or consists of a high density polyethylene.
  • the contact layer can be one or more layers.
  • the contact layer is a monolayer.
  • the contact layer is a monolayer consisting of one substance.
  • the contact layer has a loading of at least 5 g/m 2 , preferably at least 10 g/m 2 .
  • the tie layer has one layer and the loading of the one layer is at least 3 g/m 2 , or the tie layer has a plurality of layers and the loading of at least one layer of the plurality of layers is at least 3 g/ m 2 , or the total loading of the plurality of layers is at least 3 g/ m 2 .
  • the tie layer may be made up of 1, 2, 3, 4 or 5 layers.
  • one of or all the layers of the tie layers are coextruded with the contact layer. Coextrusion allows for lower loadings and thus when aiming for loadings of the tie layer(s) in the lower end, coextrusion of the tie layers and the contact layer is most suitable. Lower loadings with good properties is desirable from a cost perspective. Further, the co-extrusion layer is preferably co-extrusion coated to the base layer.
  • the contact layer should comprise at least 30% (w/w) HDPE, preferably at least 35% (w/w) HDPE in relation to the total weight of the contact layer.
  • the contact layer is HDPE.
  • the contact layer may comprise about 100% (w/w) HDPE, or the contact layer consists essentially of, or consists of HDPE.
  • Laminate films according to the invention may further comprise a first outer layer laminated to the base layer side of the laminate film. Thus, such further layers may provide further mechanical strength to the film.
  • the films according to the invention may be used as sheet lids either sealed to a container, held within the lid for a container or both.
  • the invention also provides a laminated sheet for a container holding an agrochemical substance and an optional solvent, said sheet comprising:
  • a base layer which is water and/or oxygen resistant
  • coextrusion layer comprises at least one tie layer and a contact layer, wherein the contact layer comprises a high density polyethylene (HDPE), the at least one tie layer being disposed between the base layer and the contact layer
  • HDPE high density polyethylene
  • the invention provides a container comprising an agrochemical substance and an optional solvent, and a container lid and a sheet lid, wherein the sheet lid comprises a sheet corresponding to a laminate film according to the invention; the sheet lid is arranged with the contact layer facing a welding surface of the container, said welding surface surrounding an opening of the container, and a bottom welding surface of the contact layer is welded to the welding surface of the container
  • the container comprises an agrochemical composition preferably selected from the group of agrochemicals consisting of agrochemicals, such as herbicides, such as glyphosate ((N-phosphonomethyl)glycine), dichlorprop-p ((R-2-(2,4-dichlorophenoxy)propanoic acid), MCPA (2-methyl-4-chlorophe- noxyacetic acid), Dicamba (3,6-dichloro-2-methoxybenzoic acid); insecticides, such as deltamethrin ([(S)-cyano-(3-phenoxyphenyl)-methyl] (lR,3R)-3-(2,2- dibromoethenyl)-2,2-dimethyl-cyclopropane-l-carboxylate); fungicides/insec- ticides such as oils, such as essential oils, such as peppermint oil; chemical fertilizers such as tripotassium orthophosphate and carbamide; agrochemical emulsifiers
  • the base layer is aluminum and the sheet lid is induction welded to the welding surface of the container.
  • the sheet lid is preferably integrated with the lid. According to the invention it was found that proper sealing could be obtained with laminates according to the invention this is unexpected since high density is typically associated with lower seal strength.
  • herbicides such as glyphosate ((N-phosphonomethyl)glycine), Dicamba (3,6-dichloro-2-methoxybenzoic acid), and phenoxy herbicides such as dichlorprop-p ((R-2-(2,4-dichlorophenoxy)propanoic acid) and MCPA (2- methyl-4-chlorophenoxyacetic acid) ; insecticides, such as deltamethrin ([(S)- cyano-(3-phenoxyphenyl)-methyl] (lR,3R)-3-(2,2-dibromoethenyl)-2,2-di- methyl-cyclopropane-l-carboxylate); fungicides/insecticides such as oils, such as essential oils, such as peppermint oil; or chemical fertilizers such as tripotassium orthophosphate and
  • embodiments and variations to embodiments are usable in shielding solvents used for the formulation of agrochemicals, for example cyclohexanone, N-methyl-2-pyrrolidone, l-methoxy-2-propanol, propane-1, 2- diol, and saline solution; as well as agrochemical emulsifiers/wetting agents, such as ethoxylated castor oil and calcium dodecylbenzene sulfonate.
  • agrochemicals for example cyclohexanone, N-methyl-2-pyrrolidone, l-methoxy-2-propanol, propane-1, 2- diol, and saline solution
  • agrochemical emulsifiers/wetting agents such as ethoxylated castor oil and calcium dodecylbenzene sulfonate.
  • the laminate film or final laminate film encloses an agrochemical composition or solution and the laminate film is sealed/welded into a pouch, sachet or is used as a lidding film to a container.
  • film designates a product comprising a base layer laminated, for example by adhesive lamination, extrusion lamination, co-extrusion or co-extrusion coating to a contact layer. Further outer layers may be added such as polyethylene terephthalate (PET) and paper.
  • PET polyethylene terephthalate
  • a "packaging” is in the context of the invention intended to mean a final laminate film, a composition or compound and a container sealed with or by the films according to the invention.
  • oxygen and water resistant contemplates material for which the oxygen transfer rate (OTR) and/or water vapor transfer rate (WVTR) is no more than 1 preferably no more than 0.1 as further detailed below.
  • OTR oxygen transfer rate
  • WVTR water vapor transfer rate
  • MVTR moisture vapor transfer rate
  • the term "mechanically wear resistant layer” as used to describe the outer layer should be understood as a material which is suitable for the manufacture of a flexible packaging.
  • the mechanically wear resistant layer may be chosen from but are not limited to materials such as polyethylene or polyamide based sheets, ortho-phthalaldehyde based sheets, or polyester based sheets or combinations.
  • the mechanically wear resistant material i.e. the first outer layer, can be provided as a film that is biaxially oriented to give the packaging a higher mechanical strength, such as tear strength.
  • the term "biaxially oriented” should be understood such that the provided polymer film has been stretched in both a longitudinal and a transverse direction during manufacturing.
  • exterior side should be understood in its broadest sense.
  • exterior is used for defining the direction opposite of the side that is facing the composition or compound to be sealed by the laminate film of the present invention. This means that the terms exterior, exterior side or exterior environment are independent on whether additional layers are coated, laminated or otherwise attached to the film. Thus, the word is used for specifying in which direction a side of a layer is facing relative to the substance to be packaged.
  • the base layer may be selected from but not limited to a metal foil, preferably aluminum foil, a polymer selected from polyamide, polyvinylidene chloride, silicon or aluminium oxide coated polyesters, and/or fluro polymers, such as commercial Alu foil from e.g. Hydro, or AIOx coated PET films obtainable from e.g. Toray Films Europe, or SiOx coated PET films obtainable from e.g. Celplast under the tradename Ceramis®.
  • a metal foil preferably aluminum foil
  • a polymer selected from polyamide, polyvinylidene chloride, silicon or aluminium oxide coated polyesters and/or fluro polymers, such as commercial Alu foil from e.g. Hydro, or AIOx coated PET films obtainable from e.g. Toray Films Europe, or SiOx coated PET films obtainable from e.g. Celplast under the tradename Ceramis®.
  • water and/or oxygen resistance suitably encompasses materials having an oxygen transfer rate (OTR) equal to or below 1 cm 3 /m 2 /24hr/bar according to ASTM standard D3985 at 23°C and 0% RH and/or water (or moisture) vapor transfer rate (WVTR) equal to or below 1 g/m 2 /24hr according to ASTM standard F1249 at 38°C and 90%RH, preferably both the WVTR and the OTR are below 0.01 g/m 2 /24hr or 0.01 cm 3 /m 2 /24hr/bar respectively.
  • OTR oxygen transfer rate
  • WVTR water (or moisture) vapor transfer rate
  • the base layer of the film is selected to provide a number of properties to a laminate film and packaging comprising the laminate film.
  • the base layer may give desired barrier and support properties to the final laminate/packaging.
  • the base layer may be a gas and water impermeable base layer, more preferably a water and/or oxygen resistant base layer.
  • the base layer comprises a metal foil, such as aluminum.
  • a metal foil such as aluminum.
  • Aluminum is price competitive, a superior barrier to all gases and moisture. Furthermore, similar to other metal-like materials, aluminum has good dead-fold properties, i.e. it does not unfold once folded, it reflects radiant heat, and gives a decorative appeal to laminates and packages.
  • the thickness of the base layer is 5 - 15 pm, preferably 7 - 12 pm, more preferred 8 - 10 pm, such as 9 pm, particularly when the base layer comprises or consists of aluminium.
  • the thickness may be higher, for example in the range of 1 - 50 pm.
  • the contact layer comprising HDPE must be chemically resista nt/inert to the active substance(s) of the agrochemical to be packaged and the solvent if present in this context inert means that the interior of a packaging should not leak from interior.
  • the contact layer comprising HDPE must provide low to no leaking of agrochemical substances.
  • One reference test frequently used (and tested in the below) to fulfil this no leak criteria is the following: a solution comprising Aromatic hydrocarbon mixture (Solvesso 150); Cyclohexanone, N-Methyl-2-pyrrolidone, l-Methoxy-2- propanol, 1,2-Propane diol, ethoxylated castor oil, iso-Dodecylbenzene sulpho- nate-Calcium salt and water.
  • the seal strength of a laminate should be > 2 N/15mm 180°, 100 mm/min, after 4 weeks at 55°celsius. It is believed that packagings that can withhold the above mixture will be suitable for most agrochemical substances and their solvents, if present.
  • the parameter, by which the tie and contact layer thicknesses are reflected depends on the method by which the laminate is formed, as is customary in the field.
  • the parameter used to reflect the contact layer thickness is pm.
  • the parameter used to define the contact layer and tie layer is the loading, which has the unit g/m 2 .
  • the skilled person will be able to determine the thickness of each layer from the loading and the density of the material used, if necessary.
  • the loading/thickness is given with reference to co-extruded products.
  • the loading can also be determined after production, for example by comparing the weight of coated and non-coated samples of known, equal surface area.
  • the sample to which the coating is applied could be treated to remove the substrate.
  • the coating would remain (provided it does not dissolve in acetic acid) and the loading can be determined after weighing and measuring surface area.
  • the contact layer comprises or consists essentially of a high density polyethylene (HDPE), for example in the form of the commercial products CG9620 or CG8410 sold by Borealis AG.
  • HDPE high density polyethylene
  • pure HDPE polymers with a density within the range of 0.9 to 1.1 g/cm 3 , such as 0.93 to 0.97 g/cm 3 ' such as around 0.94 and 0.96 are suitable.
  • the contact layer has a loading of at least 5 g/m 2 , preferably at least 10 g/m 2 . It was found that when the contact layer loading is higher that the loading of at least one or the plurality of tie layers better sealing was seen.
  • the loading of the contact layer is in the range of 5 to 50 g/m 2 , such as 5 to 40 g/m 2 , such as 8 to 25 g/m 2 , such as 8, 15, 20 and/or 25 g/m 2 .
  • the tie layer may be selected from : ethylene methacrylic acid (EMAA), ethylene acrylic acid (EAA), preferably an ethylene acrylic acid having an acrylic acid content of minimum 10 % (W/W) based on the total weight of the ethylene acrylic acid layer (EEA-high acid), a terpolymer of ethylene, methacrylic acid and glycidyl methacrylate, terpolymer of ethylene, acrylic ester and maleic anhydride, preferably ethylene, butyl acrylate, and maleic anhydride (t-EBAMA), acrylic ester and maleic anhydride, preferably ethylene butyl acrylate, maleic anhydride (t-EBAMA), ethylene methyl acrylate (EMA), ethylene butyl acrylate (EBA), ethylene ethyl acrylate (EEA), low density polyethylene (LDPE), poly(methyl methacrylate) (PMMA), a metallocene compound or, a combination thereof.
  • EAA ethylene methacrylic acid
  • the tie layer is constituted of one layer and the layer is a copolymer made of a material selected from a copolymer of ethylene and acrylic acid, ethylene and methacrylic acid and a terpolymer comprising ethylene, acrylic ester and a third polymer, which third polymer is preferably a glycidyl methacrylate, and more preferably a maleic anhydride.
  • the tie layer comprises at least two or consists of two layers, wherein the first layer comprises a copolymer according to the above and the at least second or more layer(s) comprises a material selected from EEA, PE, EMA, EAA or a combination.
  • the tie layer or at least one layer of a plurality of tie layers may comprise or consist of PMMA.
  • An example of a suitable PMMA is Plexiglas® HFI7.
  • the PMMA is pure.
  • the tie layer is made up of two layers, wherein the first layer consists of an ethylene methacrylic acid and the second layer consists of a low density polyethylene or a first tie layer consists of a low density polyethylene, and a second tie layer consists of an ethylene methacrylic acid.
  • the tie layer has one layer and the loading of the one layer is at least 3 g/m 2 , or the tie layer has a plurality of layers and the loading of at least one layer of the plurality of layers is at least 3 g/m 2 , or the total loading of the plurality of layers is at least 3 g/m 2 .
  • the loading of one, at least one or a plurality of tie layers is in the range of 3 to 25 g/m 2 , such as 3 to 15 g/m 2 , such as 5-10 g/m 2 .
  • each of the tie layers have a loading of at least 3 g/m2. In some embodiments it is preferred than the tie layer or plurality of tie layers are thinner than the contact layer.
  • the laminates according to the invention may further comprise a first outer layer laminated to the base layer side of the laminate film.
  • the first outer layer may be made from a material selected from but not limited to paper, polyethylene or polyamide based sheets, ortho-phthalaldehyde based sheets, or polyester based sheets, or combinations, such as the commercial product F- PAP sold by Flexpet. It is preferred that the first outer layer is a combination of materials, when polyester based sheets are used.
  • PET polyethylene terephthalate
  • the first outer layer and the laminate film are laminated to provide a packaging.
  • Laminating the first outer layer to the laminate film provides a strong laminate when tested on several parameters, while the packaging is easy to wrap and seal/weld.
  • the laminate film may further comprise a second outer layer facing the exterior side of the first outer layer.
  • the second outer layer is a paper layer.
  • the paper layer is typically printed with the name, color and/or logo of the product and manufacturer of the product. It is also or alternatively contemplated that the first outer layer can be printed.
  • the laminate film further comprises a second outer layer.
  • the laminate may constitute the sheet lid of a lid for a container.
  • the laminate films according to the invention may be prepared by adhesive lamination, extrusion lamination or coextrusion coating.
  • one solution for producing the laminate film involves adhesive lamination.
  • Adhesive lamination enables production at high speed as well as the ability to use a wide variety of films and also allows for thin skins.
  • adhesives lamination is less specialized than e.g. extrusion coating. This at the cost of higher capital costs.
  • adhesive lamination provides for higher lamination strength, and adhesive lamination provides for a good alternative to extrusion coating in providing new laminate films in other manners.
  • the adhesive lamination can be performed either by solvent free or solvent based lamination, preferably the lamination is solvent based.
  • the solvent is ethyl acetate or methyl ethyl ketone, while other suitable solvents are contemplated and within the scope.
  • the adhesive is a two-component adhesive, preferably based on polyurethane and aromatic or aliphatic amines. Such two-component adhesives are well known in the art. Solvent based adhesive lamination is preferred as it allows for longer chains and this will result in a stronger bonding of the laminate.
  • the base layer and the contact layer are directly adhesive laminated meaning that no further layers are in between but the adhesive layer/tie layer.
  • extrusion lamination is used.
  • the extrusion lamination may use a copolymer made of high density polyethylene and a material selected from a copolymer of ethylene and acrylic acid, ethylene and methacrylic acid and a terpolymer comprising ethylene, acrylic ester and a third polymer, which third polymer is preferably a glycidyl methacrylate, and more preferably a maleic anhydride, or alternatively the extrusion lamination may use PMMA.
  • the laminate film may be co-extruded or co-extrusion coated.
  • the laminates are provided by a method comprising the steps of: i) providing a base layer, which is water and/or oxygen resistant; ii) providing a contact layer; iii) coating the base layer with a coextrusion layer, said coextrusion layer comprising the contact layer and a tie layer; and iv) allowing the coextrusion layer and the base layer to adhere.
  • an adhesive and/or polymer agent may be applied between the various layers.
  • the adhesive and/or polymer agent used between the first outer layer and the base layer or the second outer layer may be made of the same or a different material as the adhesive used for the adhesive lamination of the base layer and the contact layer.
  • the agent applied between these layers may be a two-component adhesive, or may be extrusion laminated using a polymer selected from the group of materials used as tie layer according to the invention or a water based glue, the latter in particular when using a paper layer.
  • suitable adhesives are adhesives approved for use in packing products and are well known to the skilled person.
  • a suitable adhesive may be selected from but is not limited to polyurethane based adhesives, epoxy-based adhesives, or acryl-based adhesives, well known to the skilled person.
  • the adhesive used for the adhesive lamination is a two component adhesive commonly known in the art. Thus, it is based on polyurethane and epoxy, such as polyurethane and aromatic or aliphatic amines.
  • An exemplary commercial polyurethane adhesive usable according to the invention is LOCTITE LIOFOL LA 3644-21 MHS/LA 6055 obtainable from Loctite® or AdcoteTM 811A EA/MOR-FREETM 200C co-reactant obtainable from Dow.
  • a solvent is suitably selected from: ethyl acetate, acetone and methyl ethyl ketone or other solvents well known to the skilled person.
  • the solvent and the two-component adhesive are mixed in a specific ratio in a usual manner as specified by the manufacturer.
  • the base and hardener is mixed in a ratio recommended by the adhesive supplier - typically 8: 1 to 15: 1 calculated on solid content, but other ratios are contemplated.
  • the solvent is added to provide a viscosity in the range of 15 to 22 sec, such as around 17 - 18 sec as measured by DIN CUP 4 a method well known to the skilled person under the DIN 53211 standard.
  • the order in which the different layers of the packaging according to the invention are applied to the base layer is flexible.
  • the first outer layer may be applied before the adhesive lamination and the other way around. The order depends on which production line is suitable in a specific situation.
  • the obtained laminate film is heat sealable or weldable, preferably induction weldable.
  • Induction welding is an unusual method used for HDPE seal layers and it is unexpected that strong laminates were obtained.
  • a heat sealable laminate film is capable of sealing to itself during heat sealing without creating any deformation. Deformation is undesirable in relation to quality assurance, and in some producer's place restrictions on the extent to which films and/or laminates with any deformation are allowed for packing. Therefore, the mechanical properties are very important from a production cost efficiency perspective. Similarly, it is important that the laminates are tight and do not allow actives and solvent to leak.
  • the laminate film obtained in the present invention should preferably fulfil the test described above or texts towards specific substances.
  • Laminate for use according to the invention meet both the reference test and the specific tests for a broad range of substances.
  • Laminate films of the invention may suitably enclose or seal a container comprising a composition or compound comprising an active ingredient selected from the group consisting of glyphosate ((N-phosphonomethyl)gly- cine), Dicamba (3,6-dichloro-2-methoxybenzoic acid), dichloro-p ((R-2-(2,4- dichlorophenoxy)propanoic acid), MCPA (2-methyl-4-chlorophenoxyacetic acid), deltamethrin ([(S)-cyano-(3-phenoxyphenyl)-methyl] (lR,3R)-3-(2,2- dibromoethenyl)-2,2-dimethyl-cyclopropane-l-carboxylate), peppermint oil, tripotassium orthophosphate and carbamide.
  • glyphosate ((N-phosphonomethyl)gly- cine)
  • Dicamba (3,6-dichloro-2-methoxybenzoic acid)
  • a laminate film should preferably comply with International standards such as 16 CFR ⁇ 1700.20 (for USA) and ISO 8317 (2003) corresponding to DIN EN ISO 8317 (2004) (for Europe) for child resistant packagings.
  • the sealing of the packaging is achieved in such a way that the contact layer of the laminate film is facing the compound, composition or solution so that the remaining part of the laminate film is not in contact herewith.
  • the compound or composition is held within the interior of the packaging and will therefore only have direct contact with the contact layer of the layer of the laminate film or also the container in which it is held.
  • the laminate film may also be used as a lidding sheet of a container.
  • a packaging comprising an agrochemical substance, optionally in a solution, and a container with a lid and a sheet lid, wherein the sheet lid comprises a sheet comprising a base layer, which is water and/or oxygen resistant, and a layer, optionally coextruded, wherein the layer comprises at least one tie layer and a contact layer, wherein the contact layer comprises a high density polyethylene (HDPE), and the at least one tie layer being disposed between the base layer and the contact layer, the sheet lid is arranged with the contact layer facing a welding surface of the container, said welding surface surrounding an opening of the container, and a bottom welding surface of the contact layer of the sheet lid is welded to the welding surface of the container,
  • HDPE high density polyethylene
  • the container comprises an agrochemical substance, preferably selected from the group of agrochemicals consisting of agrochemical active substances, such as herbicides, such as glyphosate ((N-phosphonomethyl)gly- cine), dichloroprop-p ((R-2-(2,4-dichlorophenoxy)propanoic acid), MCPA (2- methyl-4-chlorophenoxyacetic acid), Dicamba (3,6-dichloro-2-methoxyben- zoic acid); insecticides, such as deltamethrin ([(S)-cyano-(3-phenoxyphenyl)- methyl] (lR,3R)-3-(2,2-dibromoethenyl)-2,2-dimethyl-cyclopropane-l-car- boxylate); fungicides/insecticides such as oils, such as essential oils, such as peppermint oil; chemical fertilizers such as tripotassium orthophosphate and carbamide; as well as herb
  • the base layer is aluminium, and/or the sheet lid is induction welded to the welding surface of the container.
  • the sheet lid may also be integrated with the lid.
  • Tie layer 2 Nucrel® 0609HSA (an ethylene methacrylic acid)
  • Tie layer 1 PE MU5 (a PE, e.g. Borealis® CA9150)
  • Contact layer Borealis® CG9620 (an HDPE)
  • Table 1 Loading of coextrusion layer samples As can be seen, there was a discrepancy between the target loading and the actual loading. It is thought that in practice the discrepancies lie in the tie layer loadings being lower than the target values.
  • Puncture resistance - according to ASTM F1306 with the following modifications: sample diameter 48mm instead of 34.9mm and puncture tool tip diameter 3.0 mm instead of 3.2 mm).
  • the sealing strength test was made under the following conditions: 160°C, 500N pressure, 0.5 seconds.
  • the exploration strength test was made as follows: a four-sided sealed bag was sealed with parameters 160°C, 0.5 seconds and 500 N pressure, with a size of 80mmx90mm including a 5mm wide sealing area. The bag was held and penetrated with a syringe connected to a pressure device. The bag was then inflated to a pressure of 0.2 bar in one test (Exploration test 1) and 0.25 bar in another test (Exploration test 2). The success criteria for a given laminate is to withhold the pressure for 30 seconds without bursting.
  • Tear strength levels range from 1.5 to 6.1 N. The results indicate that the main influence on tear strength is the thickness of the contact layer, rather than the thickness of the tie layers or total thickness of the coextrusion layer.
  • samples 1 to 9 show puncture resistance from 36.7N to 46.4N (front side). This is only an increase of approximately 22 percent even though the coating weight increases as much as 4 times from the lowest loading to the highest. This indicates that the main influence on puncture resistances is the base material.
  • Sample 1 has a contact layer loading of 7.4 g/m 2 which is almost the same as sample 2, but sample 2 has a significantly higher seal strength.
  • Sample 5 has a contact layer loading of 14 g/m 2 but has a sealing strength lower than sample 4 which has a contact layer loading of 12 g/m 2 . It is noted that the measured total loading of sample 5 was 17 g/m 2 , even though the target of the layer distribution was 20 g/m 2 , which indicates that the loading of the tie layers is, in reality, lower than 3 g/m 2 which may explain the difference.
  • the packaged sachets were weighed and stored in a heating cabinet at 40 °C. After 5 and 10 weeks the sachets were weighed to establish the weight loss resulting from migration of the respective compounds/composition through the respective laminate films. The test was performed in triplicate for each substance.
  • the tested agrochemical compounds/compositions were the following:
  • Table 3 Weight loss of sachets of films identified in Table 1, packed with selected compounds/compo- sitions
  • the tested laminate films prove capable of retaining the tested chemicals at a desired level.
  • the exception is Compound 6., acetic acid 15% (v/v), which is highly corrosive against aluminium, meaning that the barrier function of the base layer ceases to exist if just a small quantity of acid succeeds in migrating through the co-extruded layer.
  • the base layer should preferably not be aluminum.
  • Comparative sample 1) - coextrusion/polyamide contact Pap40/PET23/PE/AI9/Coex(Nucrel 0609 3g / Escor 5110 3g / Grivory G16 PA 20g) i.e. an outer layer of paper/polyethylene terephthalate/polyethylene, an aluminium base layer and two tie layers with coextruded polyamide contact layer.
  • Comparative sample 2 Comparative sample 2 - coextrusion/EVOH contact Papir40/PET23/PE/AI9/Coex( Nucrel 0609 4g / Escor 5110 4g / EVAL C109B (EVOH) 20g) i.e. an outer layer of paper/polyethylene terephthalate/polyethylene, an aluminium base layer and two tie layers with coextruded EVOH contact layer. Comparative sample 3) - coextrusion/COC contact
  • Papir40/PET23/AI9/Coex( Nucrel 0609 4g / Lotader 3410 4g / Topas 8007F- 600 COC 22g) i.e. an outer layer of paper/polyethylene terephthalate/polyethylene, an aluminium base layer and two tie layers with coextruded COC contact layer.
  • PET50/PE/AI9/ EVAL EF-E film - 30 mic EVOH Film i.e. an outer layer of polyethylene terephthalate/polyethylene with an aluminium base layer and EVOH contact layer
  • the "PE FILM 70" is a 70 pm thick film, with 6p of PA in the middle layer.
  • Example 4 Comparative permeability test against active agrochemical substances and solvents The permeability of the comparative samples was also tested. As for Example 2, samples of approximately 2 ml were packaged into sachets. The packaged sachets were weighed and stored in a heating cabinet at 40 °C. After 1 and 5 weeks the sachets were weighed to establish the weight loss resulting from migration of the respective compounds/composition through the respective laminate films. The test was performed in triplicate for each substance.
  • the tested agrochemical compounds/compositions were the following:
  • Table 5 Weight loss of sachets of films of comparative samples, packed with selected compounds/com- positions
  • the samples of the present invention perform at least as well as the conventional samples in these tests, with many of the weight loss results for HDPE samples at 5 weeks being superior to the comparative products tested.

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Abstract

La présente invention concerne l'utilisation de PEHD comme couche de contact de films stratifiés, une couche, éventuellement coextrudée, comprenant une couche de contact et au moins une couche de liaison étant collée à une couche de base, ainsi que des emballages utilisant les films stratifiés pour envelopper des substances agrochimiques formulées souvent liquides.
PCT/EP2021/087116 2020-12-22 2021-12-21 Utilisation de polyéthylène haute densité (pehd) comme couche de contact de films stratifiés utilisés dans l'emballage de solutions et de substances agrochimiques WO2022136448A1 (fr)

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EP20216663.3 2020-12-22
EP20216663 2020-12-22

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WO2022136448A1 true WO2022136448A1 (fr) 2022-06-30

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225256A (en) * 1990-04-04 1993-07-06 International Paper Company Non-metallic bag or liner for hazardous chemical containment
JPH0999528A (ja) * 1995-10-04 1997-04-15 Chisso Corp 農業用ポリオレフィン系多層フィルム
KR20040055235A (ko) * 2002-12-20 2004-06-26 에스케이 주식회사 다층 구조를 갖는 성형품
EP2303570A1 (fr) * 2008-06-24 2011-04-06 Cryovac, Inc. Film barrière evoh à choc d'autoclavage réduit
BR202012032138U2 (pt) * 2012-12-17 2017-01-03 Constructive provision introduced in cover for agrochemical packaging
WO2017100182A1 (fr) * 2015-12-07 2017-06-15 Bemis Company, Inc. Films piégeant l'oxygène, emballages et procédés associés
WO2019075001A1 (fr) * 2017-10-10 2019-04-18 A. Schulman, Inc. Produits polymères ayant une morphologie de type couche formés à partir de mélanges maîtres
WO2021004595A1 (fr) * 2019-07-11 2021-01-14 Danapak Flexibles A/S Procédés de stratification et produits stratifiés

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225256A (en) * 1990-04-04 1993-07-06 International Paper Company Non-metallic bag or liner for hazardous chemical containment
JPH0999528A (ja) * 1995-10-04 1997-04-15 Chisso Corp 農業用ポリオレフィン系多層フィルム
KR20040055235A (ko) * 2002-12-20 2004-06-26 에스케이 주식회사 다층 구조를 갖는 성형품
EP2303570A1 (fr) * 2008-06-24 2011-04-06 Cryovac, Inc. Film barrière evoh à choc d'autoclavage réduit
BR202012032138U2 (pt) * 2012-12-17 2017-01-03 Constructive provision introduced in cover for agrochemical packaging
WO2017100182A1 (fr) * 2015-12-07 2017-06-15 Bemis Company, Inc. Films piégeant l'oxygène, emballages et procédés associés
WO2019075001A1 (fr) * 2017-10-10 2019-04-18 A. Schulman, Inc. Produits polymères ayant une morphologie de type couche formés à partir de mélanges maîtres
WO2021004595A1 (fr) * 2019-07-11 2021-01-14 Danapak Flexibles A/S Procédés de stratification et produits stratifiés
WO2021004594A1 (fr) * 2019-07-11 2021-01-14 Danapak Flexibles A/S Procédés de stratification et produits stratifiés

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