Recyclable multilayer packaging laminate with barrier coating

Abstract

The present invention relates to laminates and foldable tubes and bags, which are generally used for packaging household and personal care products, in particular toothpaste and cosmetic cream. Disclosed is a multilayer laminated film comprising a top printable layer, a bottom sealant layer, and an intermediate layer therebetween wherein the top printable layer is free of MDPE and comprises at least one of LDPE or LLDPE and HDPE; the sealant layer comprises polyethylene; and the intermediate layer is extrusion laminated to the printable layer and the sealant layer, and includes a barrier coating.

Description

Technical Field

[0001] The present invention relates to laminates and collapsible tubes generally used for packaging household and personal care products, particularly toothpaste. Background Art

[0002] Collapsible tubes are usually made of laminates, ie multilayer materials, wherein the layers are connected to each other, for example by coextrusion or adhesive lamination. As laminates are often used to package various products, certain features and properties, in particular barrier properties, have been considered important.

[0003] EVOH (ethylene vinyl alcohol) is often used to improve the oxygen barrier properties of polyethylene based laminates. EVOH enhances the gas barrier and helps to retain flavors for longer. Alternatively, aluminum foil is also widely used to improve the barrier properties, especially the barrier properties of laminated tubes (tubes made from laminated films). Laminates containing aluminum are often referred to as aluminum-based laminates (ABL). Typically, a thin layer of aluminum foil of about 5 to 12 μm is sufficient. Typically, ABL laminates are made of polyolefins, especially polyethylene, such as high-density polyethylene (HDPE). Tubes of laminates containing aluminum are called ABL tubes. However, aluminum-based laminates cannot usually be easily recycled in PE recycling streams. Therefore, plastic-based laminates (PBL) were invented.

[0004] ABL tubes have not yet been phased out. In PBL tubes, EVOH is used instead of aluminum to make them easily recyclable while still having the required barrier properties. In PBL tubes, the amount of EVOH is usually expressed as a % by weight of the multilayer laminate. Alternatively, it can be expressed as a % of the total thickness of the laminate.

[0005] Plastics are used in a wide variety of applications, such as packaging and consumer goods. Plastics are in high demand in these applications due to their relatively low production costs and good balance of properties.

[0006] Millions of tons of plastics are produced worldwide to meet the growing demand. Most of these synthetic plastics are produced from increasingly scarce fossil sources such as oil and natural gas. The production of plastics from fossil sources contributes to increasing greenhouse gas levels. As a result, the widespread use of plastics leads to the generation of millions of tons of plastic waste each year. Most of the used plastics end up in landfills, some as garbage, and some end up in water bodies.

[0007] WO 21070197 A1 (Essel) discloses a multilayer film comprising a print layer, a tie layer, a second tie layer and a sealant layer. The multilayer film comprises 80 to 95% HDPE, so it is recyclable in the HDPE stream.

[0008] WO 21070198 A1 (Essel) discloses a laminated tube made from a laminate in which the top layer comprises HDPE and MDPE. This combination is said to balance stiffness and flexibility.

[0009] US10889093 B2 (Colgate) discloses a laminate wherein the uppermost and lowermost layers have molecular orientations that result in non-zero stress values ​​for each layer. The multilayer structure has a net stress value that is less than the greater stress value of the multiple layers.

[0010] WO 20098947 A1 (Constantia) discloses a packaging laminate having a first laminate layer and a second laminate layer, the first laminate layer being a coextruded and biaxially stretched composite of a cavitated substrate layer, a tie layer and a barrier layer, the cavitated substrate layer having 5 to 30 wt. %, preferably 15 to 25 wt. % of a cavitating agent and having a PE content of at least 60 vol. %, the barrier layer being made of a barrier polymer, preferably polyamide or ethylene vinyl alcohol copolymer, with a maximum thickness of 20 % of the total thickness of the first laminate layer, wherein the tie layer is arranged between the substrate layer and the barrier layer, and the first laminate layer is connected to the second laminate layer at its barrier layer.

[0011] WO 19172932 A1 (Colgate) discloses a recyclable package comprising:

[0012] an outer layer consisting essentially of a first high density polyethylene (HDPE);

[0013] an inner layer comprising a second HDPE;

[0014] a barrier layer positioned between the outer layer and the inner layer;

[0015] a first tie layer positioned between the outer layer and the barrier layer; and a second tie layer positioned between the inner layer and the barrier layer.

[0016] EP 3 785 895 A1 (Neopac, 2021) discloses a laminate for tube packaging. The laminate has at least three layers, namely an inner polyolefin layer and an outer polyolefin layer and a barrier layer sandwiched between the outer polyolefin layer and the inner polyolefin layer. The barrier layer comprises at least one polyolefin, including a barrier foil such as a monolayer foil or a coextruded foil or a laminate thereof, and wherein at least 90% of all polymers of the container are made of the same type of polyolefin. An object of the present invention is to provide a preferably airtight and liquid-tight collapsible tube made of a thermoplastic material, which can be recycled in a single material recycling stream without involving any separation steps.

[0017] WO 2021 / 079197 A1 (Braskem), US 2021 / 0308995 A1 (Nair et al.), WO 2021 / 117052 A1 (Nair), WO 2017 / 151071 A1 (Kimpai Lamitube Co., Ltd.) and WO 2018 / 070945 A1 (Kimpai Lamitube Co., Ltd.) disclose various multilayer structures. Summary of the invention

[0018] One object of the present invention is to provide a sustainable laminate for the manufacture of tubes, wherein the laminate can be made thinner but has excellent technical functionality. Another object is to provide a soft but tough laminate.

[0019] The present invention provides a sustainable laminate that enables the manufacture of opaque, translucent and transparent pipes with high OTR and WvTR. The present invention provides a laminate that is recyclable in a HDPE recycling stream.

[0020] According to a first aspect, a multilayer laminate film is disclosed, comprising a top printable layer, a bottom sealant layer and an intermediate layer between the two aforementioned layers, wherein

[0021] i) the top printable layer does not contain MDPE and comprises at least one of LDPE or LLDPE and HDPE;

[0022] ii) the sealant layer comprises polyethylene, wherein the polyethylene comprises HDPE; and iii) the intermediate layer is extrusion laminated to the printable layer and the sealant layer and comprises a barrier coating. DETAILED DESCRIPTION

[0023] The term "comprising" is not meant to limit any subsequently stated elements, but rather to include unspecified elements of primary or secondary functional importance. In other words, the steps, elements or options listed need not be exhaustive. Whenever the words "comprising" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above. Except in the operating examples and comparative examples, or where otherwise explicitly indicated, all numbers in this specification indicating the amount of material should be understood to be modified by the word "about".

[0024] It should be noted that in specifying any range of concentrations or amounts, any upper concentration can be associated with any lower concentration or amount.

[0025] As used herein, the term "flexible film" refers to a flexible polymer sheet whose thickness dimension is significantly smaller than its breadth and width, and which is primarily used to prepare packaging for storing consumer products in solid, semi-solid and / or liquid form. Flexible films can be presented as a wound roll of material. Flexible films are typically used to prepare bags, pouches, bags and other sealed packages for containing consumer products.

[0026] As used herein, the term "laminate" refers to film layers bonded together, in this case a multilayer laminate. Bonding can be achieved by extrusion, heat treatment, adhesives, or other methods known in the art for laminating two films or sheets.

[0027] As used herein, the top printable layer refers to the layer that is farthest from the product (such as toothpaste) when packaged in a package (eg, a tube) made of a multi-layer laminate film.

[0028] As used herein, the sealant layer refers to the layer that is closest to or proximal to the product when packaged in a package (eg, a tube) made of a multi-layer laminate film.

[0029] As used herein, "intermediate layer" refers to a layer located between the printable layer and the sealant layer such that one side of the intermediate layer faces the sealant layer and the other side (back side or opposite side) of the intermediate layer faces the top printable layer.

[0030] "Extrusion lamination and its grammatical variations" means gradually melting a thermoplastic resin used as a binder and fed into an extruder in the form of granules or powder until it becomes fluid. The molten resin is cast through a die between plastic films and runs on a cylinder where the extrudate cools and solidifies. Preferably, the cylinder is cooled to speed up the cooling process and avoid shrinkage, holes or melting.

[0031] The term "high density polyethylene" HDPE means a polyethylene having a density of 0.941 gm / cm 3 Up to 0.970gm / cm 3 of polyethylene.

[0032] The term "medium density polyethylene" MDPE means a polyethylene having a density of 0.926 gm / cm 3 Up to 0.941gm / cm 3 of polyethylene.

[0033] The term "low density polyethylene" LDPE means a polyethylene having a density of 0.919 gm / cm 3 Up to 0.935gm / cm 3 The term "linear low density polyethylene" means a polyethylene having a density of 0.919 gm / cm 3 Up to 0.925gm / cm 3 of polyethylene.

[0034] The term "stiffness" refers to a material's resistance to deformation under an applied force.

[0035] The term "Young's modulus" as used herein refers to a property of a material calculated by measuring the ratio of stress induced in a material to strain. Young's modulus gives a measure of the stiffness of a material or the ease with which it can be stretched or bent. The higher the value of Young's modulus, the less the material can be stretched or elongated and the higher the stiffness. It is expressed in N / m 2 Or Pascal (Pa) measurement.

[0036] The term "melt flow index" or "MFI" as used herein refers to the grams of polymer that flow through a capillary per 10 minutes. It is a measure of the ease with which a polymer melt flows, expressed in g / 10 minutes.

[0037] As used herein, the term "polyolefin(s)" includes a class of thermoplastic polymers widely used in the consumer and petrochemical industries and refers to polymers that contain in polymerized form a large amount of an olefin monomer, such as ethylene or propylene (based on the weight of the polymer), and optionally may contain one or more comonomers. Polyolefins are generally composed of simple olefins (also known as polyolefins having the general formula (C n H 2n For example, polyethylene (PE) is prepared by polymerizing ethylene (C 2 H 4 ) is a polyolefin made from olefin propylene (C 3 H 6 ) is another common polyolefin made from

[0038] "Polyethylene" or "ethylene-based polymer" means a polymer comprising greater than 50% by weight of units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Preferably, polyethylene means low density polyethylene (LDPE); linear low density polyethylene (LLDPE); medium density polyethylene (MDPE); or high density polyethylene (HDPE). More preferably, polyethylene means at least one of the following: low density polyethylene (LDPE); medium density polyethylene (MDPE); or high density polyethylene (HDPE).

[0039] Preferably, the melt index (h) of polyethylene is 50 g / 10 minutes or less, preferably 20 g / 10 minutes or less, wherein the melt index is measured under the conditions of 190°C and a standard weight of 2.16 kg. In some embodiments, polyethylene has a melt index (h) of at most 15 g / 10 minutes. In some embodiments, polyethylene has a melt index (h) of at most 10 g / 10 minutes. In some embodiments, polyethylene has a melt index (h) of less than 5 g / 10 minutes.

[0040] Various commercially available polyethylenes include LDPE, such as DOWLEX TM Linear low-density polyethylene, such as DOWLEX TM 2038.68G. Examples of commercially available HDPE that can be used in embodiments of the present invention include DOW TM HDPE resin and DOWLEX TM Any other suitable commercially available polyethylene may be selected for use in the polymer composition based on the teachings herein.

[0041] LDPE is readily available, for example, PE 1017 (Ml = 7; d = 0.917) from Chevron, San Francisco, California, SLP 9045 (Ml = 7.5; d = 0.908) from Exxon, Houston, Texas, and ZCE 200 (Ml = 3; d = 0.918) from Mobil Chemical Corporation, Fairfax, Virginia. The term LLDPE means a copolymer of ethylene and a small amount of an olefin containing 4 to 10 carbon atoms, having a molecular weight of about 0.910 to about 0.926 g / cm 3 and a MI of 0.5 to about 10 g / 10 minutes. LLDPE is readily available, for example, from Dow Chemical Company, Midland, Michigan. 2045.03 (Ml = 1.1; d = 0.920). MDPE is readily available, for example from The Dow Chemical Company 2027A, and NOVA 74B and NOVA 14G from Nova Corporation, Sarnia, Ontario, Canada.

[0042] It is preferred that the multilayer laminate film has a water vapor transmission rate (WvTR) of 0.1 to 1 g / mm at 37.8°C and 90% RH. 2 / day, preferably 0.25 to 1 g / mm 2 / day, more preferably 0.55 to 1 g / mm 2 / day. WvTR was measured using ASTM F 1249 method.

[0043] Preferably, the multi-layer laminated film has an oxygen transmission rate (OTR) of 0.1 to 1 cm at 37.8°C and 90% RH. 3 / m 2 / day 1atm, preferably 0.25 to 1cm 3 / m 2 / day / 1atm, still more preferably 0.25 to 0.8cm 3 / m 2 / day / 1atm, more preferably 0.25 to 0.6cm 3 / m 2 / day / 1atm. OTR is measured using ASTM D 3985 method.

[0044] Printable polyethylene layer

[0045] Preferably, the top printable layer comprises at least one of LDPE or LLDPE and HDPE. The top printable layer is free of MDPE, meaning that the top printable layer comprises less than 3% MDPE. Preferably, the top printable layer comprises at least one of LDPE or LLDPE and HDPE, wherein the HDPE content in the layer is 10 to 60% by weight. It is particularly preferred that the top printable layer comprises LDPE and LLDPE. In this case, it is preferred that the top layer comprises 40 to 80% by weight LDPE and 10 to 30% by weight LLDPE. Processing aids and masterbatches may also be added and are typically contained in the top printable layer.

[0046] It is further preferred that the thickness of the top printable layer accounts for 10 to 35 weight % of the total thickness of the laminate.

[0047] It is still further preferred that the top printable layer in turn comprises a sublayer of at least one of LDPE or LLDPE and HDPE.It is further preferred that the top printable layer comprises a sublayer of HDPE, a sublayer of LDPE and a sublayer of LLDPE.

[0048] Alternatively, it is preferred that the top printable layer has a structure preferably comprising at least 3 sublayers. Preferably, the top sublayer comprises HDPE, still preferably, the top sublayer comprises at least one of LLDPE and LDPE and HDPE, preferably, the top sublayer comprises HDPE and LLDPE. Also preferably, the top sublayer comprises LLDPE or LDPE, preferably LLDPE. When comprising at least 3 layers, the top printable layer may include an intermediate sublayer comprising HDPE, preferably at least one of LLDPE or LDPE (preferably LLDPE), and HDPE. Preferably, the inner sublayer comprises LLDPE or LDPE, preferably LLDPE.

[0049] Preferably, the top printable layer has a thickness ranging from 5 μm to 105 μm, preferably from 7 μm to 100 μm. Preferably, the thickness is at least 15 μm, still preferably at least 17 μm, further preferably at least 25 μm, still more preferably at least 30 μm, but preferably the thickness does not exceed 95 μm, still preferably does not exceed 80 μm, still more preferably does not exceed 70 μm.

[0050] Sealant layer

[0051] Preferably, the sealant layer at the bottom of the laminate comprises HDPE, preferably the sealant layer comprises at least one of MDPE, LDPE or both and HDPE. Preferably, the sealant layer comprises at least one of MDPE and LDPE and HDPE. Preferably, the sealant layer comprises a HDPE sublayer, wherein the sublayer comprises at least one of MDPE and LDPE and HDPE.

[0052] Preferably, the sealant layer comprises at least one of MDPE, LDPE or LLDPE and HDPE. Preferably, the sealant layer comprises at least one of MDPE and LLDPE and HDPE. More preferably, the LLDPE is a metallocene LLDPE.

[0053] Preferably, the thickness of the sealant layer accounts for 10 wt % to 35 wt % of the total thickness of the laminate.

[0054] Preferably, the sealant layer is a 3-layer structure. Preferably, the sealant layer has a structure including a first sublayer comprising MDPE. Preferably, the middle sublayer comprises HDPE, preferably HDPE and MDPE, and the innermost sublayer comprises LLDPE and MDPE. The term innermost refers to the sealant layer as the sublayer of the sealant layer closest to the product when packaged with a package (e.g., a tube) made of a multilayer laminated film.

[0055] Preferably, the sealant layer has a thickness ranging from 5 μm to 105 μm, preferably from 7 μm to 100 μm, preferably at least 15 μm, still preferably at least 17 μm, further preferably at least 25 μm, still more preferably at least 30 μm, but preferably the thickness does not exceed 95 μm, still preferably does not exceed 80 μm, still more preferably does not exceed 70 μm.

[0056] Middle Layer

[0057] Preferably, the water vapor transmission rate (WvTR) of the intermediate layer at 37.8°C and 90% RH is 0.1 to 1 g / mm 2 / day, preferably 0.1 to 0.8 g / mm 2 / day, more preferably 0.1 to 0.55 g / mm 2 / day. WvTR was measured using ASTM F 1249. WvTR was measured using ASTM F 1249.

[0058] Preferably, the oxygen transmission rate (OTR) of the intermediate layer at 37.8°C and 90% RH is 0.1 to 1 cm 3 / m 2 / day 1atm, preferably 0.25 to 1cm 3 / m 2 / day / 1atm, still more preferably 0.1 to 0.8cm 3 / m 2 / day / 1atm, more preferably 0.1 to 0.5cm 3 / m 2 / day / 1atm. OTR is measured using ASTM D 3985 method.

[0059] Preferably, the thickness of the intermediate layer accounts for 20 to 60 weight % of the total thickness of the laminate.

[0060] Preferably, the intermediate layer comprises HDPE. More preferably, the intermediate layer comprises at least one of MDPE and LDPE and HDPE, more preferably HDPE and at least MDPE, further preferably both MDPE and LDPE and HDPE. Preferably, the intermediate layer does not contain LLDPE. Preferably, the intermediate layer comprises 50 wt% to 100 wt% HDPE and at most 50 wt% of at least one of MDPE and LDPE or both MDPE and LDPE.

[0061] Preferably, the intermediate layer comprises at least 3 sublayers, more preferably, the intermediate layer comprises 3, 5 or 7 sublayers. Preferably, in the intermediate layer, the barrier coating is sandwiched between sublayers, preferably between at least two sublayers. Preferably, the intermediate layer comprises at least two sublayers comprising HDPE and a barrier coating sublayer, wherein the barrier coating sublayer is sandwiched between two sublayers comprising HDPE. More preferably, the barrier coating is sandwiched between sublayers comprising at least one of MDPE and LDPE, more preferably at least MDPE, and preferably both MDPE and LDPE, and HDPE. More preferably, the barrier coating is sandwiched between two sublayers comprising HDPE and two further sublayers comprising at least one of MDPE and LDPE, more preferably at least MDPE, and preferably both MDPE and LDPE, wherein the further sublayers are on both sides of the HDPE sublayer.

[0062] Preferably, the intermediate layer does not contain LLDPE.

[0063] Preferably, when the intermediate layer comprises 3 sub-layers, it comprises a primary laminate layer, an intermediate layer having barrier properties and a secondary laminate layer.Preferably, the laminate layer comprises HDPE or MDPE.

[0064] Preferably, when the multi-layer laminate film is a metallized structure, the main laminate layers are metallized.

[0065] It is further preferred that the intermediate layer is a 3-7 layer structure. Preferably, the intermediate layer has sublayers, and the sublayers include a main lamination sublayer, a first bonding sublayer, an intermediate sublayer with barrier properties, a second bonding sublayer and a secondary lamination layer.

[0066] Preferably, when the multilayer laminated film is a metallized structure, the intermediate layer is preferably a 5-layer structure, which is composed of a main layer with barrier properties, a first bonding sublayer, an intermediate sublayer, a second bonding sublayer and a secondary lamination sublayer in sequence. The main lamination sublayer may be metallized.

[0067] Preferably, when the intermediate layer is a 7-layer structure, it is composed of a main laminate sublayer, a first sublayer, a first bonding sublayer, an intermediate barrier coating sublayer, a second bonding sublayer, a second sublayer, and a secondary laminate layer in sequence. Preferably, when the intermediate layer is metallized, preferably, the main laminate layer is metallized. Preferably, the thickness of the metallization is less than 7 μm, still preferably less than 5 μm.

[0068] Preferably, the barrier coating or sub-film accounts for 0.0001% to 30% of the total thickness of the intermediate layer. Preferably, the barrier coating comprises ethylene-vinyl alcohol copolymer, or aluminum foil, or a combination of vinyl alcohol copolymer and aluminum foil. Preferably, the barrier coating comprises ethylene-vinyl alcohol copolymer. When present, aluminum foil is preferably present as a metallization on the main laminate layer. Further preferably, the thickness of the barrier coating accounts for 1% to 5%, still preferably 1% to 3% of the total thickness of the laminate. Before applying any coating, the surface of the polyolefin film can be treated to increase its surface energy. This can be done by any of several known conventional techniques.

[0069] Particularly preferably, the film comprises a first lamination layer between the top printable polyethylene layer and the intermediate layer, and a second lamination layer between the sealant polyethylene layer and the intermediate layer. When present, it is preferred that the thickness of each lamination layer is in the range of 10 μm to 30 μm. Preferably, the thickness of the printable polyethylene layer and the sealant polyethylene layer is 80 μm to 150 μm. Preferably, the first lamination layer comprises 50 wt % to 100 wt % LDPE, more preferably 80 wt % to 100 wt % LDPE, still preferably 100 wt % LDPE. Preferably, the first lamination layer comprises LDPE and ethylene acrylate (EAA). Preferably, the second lamination layer comprises 50 wt % to 100 wt % LDPE, more preferably 80 wt % to 100 wt % LDPE, still preferably 100 wt % LDPE. Preferably, the top printable layer, the sealant layer at the bottom and the intermediate layer present in the multilayer laminated film are extrusion laminated.

[0070] Preferably, the total thickness of the laminate ranges from 50 μm to 350 μm, more preferably from 175 μm to 350 μm, and further preferably the total thickness of the laminate ranges from 50 μm to 300 μm. More preferably, it is from 60 μm to 250 μm, further preferably from 70 to 150 μm. The range of 50 μm to 300 μm is generally suitable for laminates that can be used to manufacture foldable tubes.

[0071] Preferably, the bonding sublayer comprises a modified polyolefin. Preferably, the modified polyolefin is based on an ethylene polymer or a propylene polymer. Preferably, the bonding sublayer comprises a modified polyolefin selected from the group consisting of maleated polyethylene, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, anhydride-grafted ethylene / 1-butene copolymers, anhydride-grafted ethylene / 1-hexene copolymers, polyethylene vinyl acetate copolymers, ethylene methyl acrylate copolymers, anhydride-grafted ethylene / 1-octene copolymers, maleated polyethylene, and maleic anhydride-grafted polyethylene. Preferably, the sublayer comprises those selected from maleated polyethylene and polyethylene-grafted maleic anhydride, still preferably polyethylene-grafted maleic anhydride.

[0072] Preferably, the multilayer laminated film according to the first aspect of the present invention is a plastic-based laminate (PBL) and does not contain an aluminum layer. An aluminum layer means that the plastic-based multilayer laminated film according to the present invention does not have an aluminum layer with a thickness of 7 microns or more, more preferably 7 to 12 microns.

[0073] The multilayer laminate film may contain suitable additives, such as stabilizers, neutralizers, lubricants or antioxidants. In principle, additives for polyolefins such as polyethylene or polypropylene are also suitable for cycloolefin polymer films. Examples of UV stabilizers that can be used are absorbers, such as hydroxyphenylbenzotriazole, hydroxybenzophenone, formamidine or benzylidene camphor; quenchers, such as cinnamate or nickel chelate; free radical scavengers, such as sterically hindered phenols, hydroperoxide scavengers, such as nickel or zinc complexes of sulfur-containing compounds, or light stabilizers and mixtures thereof. Examples of suitable lubricants include fatty acids and their esters, amides and salts; silicones or waxes, such as polypropylene or polyethylene waxes. Examples of antioxidants that can be added are free radical scavengers, such as substituted phenols and aromatic amines, and / or peroxide scavengers, such as phosphites, phosphates and thio compounds.

[0074] According to a second aspect of the present invention, there is provided a method for preparing a multilayer laminate film, the method comprising the following steps:

[0075] i. providing a top printable layer, the top printable layer being free of MDPE and comprising at least one of LDPE or LLDPE and HDPE;

[0076] ii. providing a sealant layer comprising polyethylene, wherein the polyethylene comprises HDPE;

[0077] iii. providing an intermediate layer comprising a barrier coating;

[0078] iv. Extrusion laminating the intermediate layer to the top printable layer and the sealant layer by extrusion lamination.

[0079] Preferably, the method comprises the steps of providing a first lamination layer between the top printable layer and the intermediate layer, and preferably providing a second lamination layer between the intermediate layer and the sealant layer, and then laminating the intermediate layer to the top printable layer and the sealant layer by extrusion lamination.

[0080] Preferably, the top printable layer comprises at least 2 sublayers, still preferably at least 3 sublayers, wherein the top printable layer is formed by a blown film extrusion process. Preferably, the middle layer is formed by a blown film extrusion process, preferably, the middle layer comprises at least 3 sublayers, still preferably at least 5 sublayers, still more preferably at least 7 sublayers. Preferably, the sealant layer is formed by a blown film extrusion process. Next, the top printable layer, the middle layer and the sealant layer are extrusion laminated to form a multilayer laminate film.

[0081] Packaging and use

[0082] According to yet another aspect of the present invention, there is provided an article comprising the multilayer laminated film according to the first aspect or the multilayer laminated film obtainable by the method of the second aspect.

[0083] The present invention also relates to a laminated tube comprising a cylindrical body, a shoulder and a cap, wherein the body is made of the multilayer laminated film of the first aspect of the present invention. Preferably, the ovality of the body is preferably in the range of 1 to 10%. The cap may also be optional, as it is a separate article that can be made by standard industrial methods.

[0084] The film can be used as such for any suitable packaging application, preferably a laminated tube. However, it is preferred that the film is used to make a laminate which in turn is used to make a preferably squeezable tube. Several methods of making laminated tubes are known in the art.

[0085] When the intended application is the manufacture of a collapsible tube, the outer and inner films should be capable of lap sealing, also called side seams, preferably by applying a heat lap seal, so that the sides can be sealed after the product has been filled. In this case, the innermost film should also bond to itself so that the bottom of the tube can be closed after the product has been filled.

[0086] The laminate tube comprises a body for storing the packaged product, and a shoulder comprising an outlet for dispensing the packaged product, and a cap for closing the tube.

[0087] The body may be provided externally with a print which is largely previously applied.

[0088] In conventional methods for making tubes, the body and shoulder are made separately or may be made in-line and subsequently welded together. The cap for the tube is usually made separately.

[0089] When manufacturing the tube body, the multilayer laminate is introduced into a device provided with a preform having the shape of the body and provided with an expansion hub for expanding the film to the required size. The guidance ensures that the edges of the multilayer laminate overlap. The edges are welded together with the help of a fully continuous thermal welding system.

[0090] The laminate is cut to size with the aid of a rotating knife so as to obtain a tube of the desired length. The tube obtained is placed on a compression mandrel.

[0091] The top of the tube, or the tube shoulder, is pressed into the correct shape and required size in a separate press and is provided with a small amount of molten multilayer packaging film. A compression mandrel provided with the tube body is introduced into the press, in which the shoulder is compressed and welded to the shoulder. The press is cooled, the tube is taken out of the press, and transferred to another device, in which each tube is provided with a cap. The device for making this tube can be obtained from various suppliers (e.g., AISA). The tube is sent to a filling device and filled with the required cosmetic product through the bottom that is subsequently heat-sealed.

[0092] According to another aspect of the present invention, there is provided the use of a multilayer laminated film for the manufacture of a laminated tube for providing a recyclable packaging material.

[0093] According to yet another aspect of the present invention, there is provided a use of a multilayer laminated film for providing an environmentally friendly packaging material.

[0094] Preferably, the multilayer laminated film according to the present invention is at least 16% lighter than conventional packaging materials, and preferably, the multilayer laminated film allows for less use of plastic.

[0095] The invention will now be described with the aid of non-limiting exemplary embodiments.

[0096] Example

[0097] The structures of some multi-layer laminated films of the present invention are described below.

[0098] Embodiment 1:

[0099] Top printing layer (LDPE / HDPE / LLDPE) 70μm / first lamination layer 20μm LDPE / middle layer 60μm EVOH-PE / second lamination layer 20μm / sealant PE (MDPE / HDPE / LDPE) 50μm.

[0100] Embodiment 2:

[0101] Multi-layer (1-5 layers) top printing layer (LDPE / HDPE / LLDPE) 40μm / first lamination layer 20μm LDPE / middle multi-layer (1-7 layers) 50μm EVOH-PE / second lamination layer 20μm / multi-layer (1-5 layers) sealant PE (MDPE / HDPE / LDPE) 50μm.

[0102] Embodiment 3:

[0103] Multilayer (1-5 layers) Top printed PE (LDPE / HDPE / LLDPE) 60μm / First lamination layer 20μm LDPE / Heat sealable barrier layer (1-11 layers) 100μm EVOH-PE

[0104] Example details of the top print layer are as follows:

[0105] Layer-1 20μm LLDPE / Layer-2 20μm HDPE / Layer-3 Barrier layer 20μm HDPE / Layer-4 20μm HDPE / Layer-5 20μm LLDPE

[0106] Alternative exemplary details of the printable polyethylene layer are as follows:

[0107] Layer-1 17μm(LDPE-LLDPE-HDPE) / Layer-2 36μm(HDPE-LLDPE) / Layer-3 17μm(LLDPE-HDPE)

[0108] Exemplary details of the sealant polyethylene layer are:

[0109] Layer-1 12μm(LDPE-MDPE) / Layer-2 26μm(HDPE-MDPE) / Layer-3 12μm(LDPE-MDPE)

Claims

1. A multilayer laminate film comprising a top printable layer, a sealant layer at the bottom and an intermediate layer between the two layers, wherein i) the top printable layer does not contain MDPE and comprises at least one of LDPE or LLDPE and HDPE; ii) the sealant layer comprises polyethylene, wherein the polyethylene comprises HDPE; and iii) The intermediate layer is extrusion laminated to the printable layer and sealant layer and comprises a barrier coating.

2. The multilayer laminate film according to claim 1, wherein the top printable layer comprises at least one of LDPE or LLDPE and HDPE, wherein the HDPE content in the layer is 10 to 60 wt%.

3. The multilayer laminate film according to claim 1 or 2, wherein the top printable layer comprises LDPE and LLDPE.

4. The multilayer laminate film according to claim 3, wherein the top layer comprises 40 to 80 wt% LDPE and 10 to 30 wt% LLDPE.

5. The multilayer laminate film according to any one of claims 1 to 4, wherein the thickness of the top printable layer accounts for 10 wt% to 35 wt% of the total thickness of the laminate. 6 . The multilayer laminate film according to claim 1 , wherein the thickness of the sealant layer accounts for 10 to 35 wt % of the total thickness of the laminate. 7 . The multilayer laminate film according to claim 1 , wherein the thickness of the intermediate layer accounts for 20 to 60 wt % of the total thickness of the laminate.

8. The multilayer film according to any of the preceding claims, wherein the sealant layer comprises at least one of LDPE, LLDPE or MDPE and HDPE, more preferably the sealant layer comprises HDPE, LLDPE and MDPE, or HDPE, LDPE and MDPE.

9. The multilayer film according to any of the preceding claims, wherein the intermediate layer comprises at least one of MDPE or LDPE and HDPE, more preferably HDPE and MDPE, still preferably HDPE, MDPE and LDPE.

10. The multilayer film of claim 9, wherein the intermediate layer is a multilayer structure comprising at least two sublayers comprising HDPE and a barrier coating sublayer, wherein the barrier coating sublayer is sandwiched between the two sublayers comprising HDPE.

11. The multilayer laminated film according to any one of claims 1 to 11, wherein the WvTR of the intermediate layer at 37.8°C and 90%RH is 0.1 to 1 g / mm 2 / day, preferably 0.25 to 1 g / mm 2 / day, still preferably 0.55 to 1 g / mm 2 / sky.

12. The multilayer laminated film according to any one of claims 1 to 11, wherein the intermediate layer has an OTR of 0.1 to 1 cm at 37.8°C and 90% RH. 3 / m 2 / day / 1atm, preferably 0.25 to 1cm 3 / m 2 / day / 1atm, still preferably 0.25 to 0.8cm 3 / m 2 / day / 1atm.

13. The multilayer film according to any one of claims 1 to 12, wherein the total thickness of the laminate is from 175 to 350 μm.

14. A laminate tube comprising a cylindrical body, a shoulder and a cap, wherein the body is made of the multilayer laminate film according to any one of claims 1 to 13.