Biodegradable and recyclable barrier paper laminate

Abstract

A biodegradable and recyclable barrier paper laminate including an inorganic barrier layer that prevents permeation.

Description

Technical Field

[0001] This invention relates to a biodegradable and recyclable barrier paper laminate for flexible packaging applications or product delivery systems such as pouches, bags, and sachets. The barrier paper laminate comprises a biodegradable and recyclable paper layer in combination with a biodegradable polymer layer, a biodegradable primer layer, an inorganic barrier layer, and a biodegradable polymer sealing layer. This barrier paper laminate offers several advantages over prior art paper-based flexible packaging. Background Technology

[0002] Paper packaging is gaining popularity among consumers because it is perceived as more natural, biodegradable, and recyclable. However, uncoated paper has poor barrier properties, and attempts to improve barrier properties by adding coatings often result in reduced paper biodegradability in various environments and also reduced recyclability of packaging in commercial paper recycling systems.

[0003] Uncoated paper packaging is often highly biodegradable in certain environments and very easily recycled in commercial paper recycling systems. However, paper without any coating or adhesive cannot easily form fully functional packaging. Furthermore, uncoated paper packaging can only be used to contain dry products that do not require any type of water / moisture or gas, fragrance, or grease barrier. If the product is sensitive to moisture, it will be damaged as moisture will quickly penetrate the packaging. If it is sensitive to oxygen, oxidation will occur. If the product is oily, grease will migrate through the paper and leave unsightly stains on the outside of the packaging. If the product contains fragrance, the fragrance will escape from the packaging and alter the intended odor of the product. If the product contains any moisture, it will cause the uncoated paper to soften. However, if a coating is added to the paper to improve barrier properties and / or make it sealable, it is desirable that the coating does not affect the overall biodegradability of the packaging under a range of most desirable environmental conditions in the event of improper disposal. Non-biodegradability can have adverse environmental impacts, such as the persistent presence of microplastics in seawater. Moreover, when a coating is added, great care must be taken to avoid adversely affecting the recyclability of the packaging in commercial paper recycling systems.

[0004] A common approach to addressing poor barrier properties of paper and making it sealable is to add a coating of polyethylene-based or ethylene-based copolymers or other non-biodegradable polymers to the paper surface through coating, printing, or lamination. However, if the polyethylene coating is too thick, it will adversely affect the recyclability of the paper laminate in a typical commercial paper recycling system. Numerous examples exist of polyethylene coatings causing problems in the paper recycling process, particularly when thicker coatings are used to enhance seal strength and / or barrier properties. Examples of such problems are, but are not limited to: i) coatings that clog repulping tanks and filters in the system; ii) coatings that tightly adhere to the paper fibers and prevent a high percentage of paper fibers from being released into the water of the repulping system; and iii) coatings that ultimately bind to the recycled paper and adversely affect the appearance or properties of the resulting recycled paper.

[0005] If such a polyethylene coating is made very thin, such that it can be peeled off and sent to a landfill or burned to fuel a plant, leaving the paper fibers to be collected and recycled back into paper, then the entire structure can be considered recyclable in the paper recycling stream. However, such a structure still has several drawbacks because while the paper will biodegrade if improperly disposed of in the environment, the polyethylene coating will not. Instead, the polyethylene layer will form persistent microplastics that will have an adverse impact on the environment and become a non-nutritive food source for some animals. Furthermore, many consumers notice the glossy appearance of the polyethylene layer on the inner surface of the paper composite and negatively perceive it as an unnatural material. The polyethylene coating will also negatively impact the packaging's ability to be composted via industrial or household composting unless consumers can easily and reliably remove the polyethylene coating before composting.

[0006] Conversely, if biodegradable polymers are used instead of polyethylene for the coating, it is well known that biodegradable materials have poor moisture barrier properties. Such biodegradable polymer coatings would have to be very thick, causing problems during paper recycling.

[0007] Therefore, there is an unmet need for paper laminates for flexible packaging applications that have moisture barrier and sealing layers, reduce environmental impact in environments such as soil and aquatic environments as well as in composting cases, and also improve recycling efficiency in industrial paper repulping systems. Summary of the Invention

[0008] A biodegradable and recyclable barrier paper laminate is provided that is compatible with home or industrial composting facilities, is biodegradable when improperly disposed of in the environment, and can be recycled in industrial paper recycling facilities (if collected).

[0009] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate comprising a biodegradable and recyclable paper layer having an outer surface and an inner surface; a first biodegradable polymer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable and recyclable paper layer; a first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable polymer layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable primer layer; a second biodegradable primer layer having an outer surface and an inner surface, the inner surface being disposed on the inner surface of the inorganic barrier layer; and a second biodegradable polymer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the biodegradable primer layer and acting as a heat-sealing layer.

[0010] For some applications, all of these layers will not be necessary, and therefore additional layered structures can be used instead, as described below.

[0011] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate being made of: a biodegradable and recyclable paper layer having an outer surface and an inner surface; a first biodegradable polymer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable paper layer; a first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable polymer layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable primer layer; and a second biodegradable polymer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the inorganic barrier layer. The final layer serves as a heat-sealing layer.

[0012] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate being made of: a biodegradable and recyclable paper layer having an outer surface and an inner surface; a biodegradable polymer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable and recyclable paper layer; a first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable polymer layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable primer layer; and a second biodegradable primer layer having an outer surface and an inner surface, the inner surface being disposed on the inner surface of the inorganic barrier layer. The final layer serves as a heat-sealing layer.

[0013] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate being made of: a biodegradable and recyclable paper layer having an outer surface and an inner surface; a first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable and recyclable paper layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable primer layer; a second biodegradable primer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the inorganic barrier layer; and a biodegradable polymer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the second biodegradable primer layer. The final layer serves as a heat-sealing layer.

[0014] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate being made of: a biodegradable and recyclable paper layer having an outer surface and an inner surface; a first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable and recyclable paper layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable primer layer; and a second biodegradable primer layer having an outer surface and an inner surface, the inner surface being disposed on the inner surface of the inorganic barrier layer. The final layer serves as a heat-sealing layer.

[0015] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate being made of: a biodegradable and recyclable paper layer having an outer surface and an inner surface; a first biodegradable polymer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable paper layer; a first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable polymer layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable primer layer; a second biodegradable primer layer having an outer surface and an inner surface, the inner surface being disposed on the inner surface of the inorganic barrier layer; a biodegradable adhesive layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the second biodegradable primer layer; and a second biodegradable polymer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the biodegradable adhesive layer. The final layer serves as a heat-sealing layer.

[0016] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate being made of: a biodegradable and recyclable paper layer having an outer surface and an inner surface; a first biodegradable polymer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable paper layer; a first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable polymer layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable primer layer; a biodegradable adhesive layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the inorganic barrier layer; and a second biodegradable polymer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the biodegradable adhesive layer. The final layer serves as a heat-sealing layer.

[0017] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate being made of: a biodegradable and recyclable paper layer having an outer surface and an inner surface; a first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable and recyclable paper layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable primer layer; a second biodegradable primer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the inorganic barrier layer; a biodegradable adhesive layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the second biodegradable primer layer; and a biodegradable polymer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the second biodegradable primer layer. The final layer serves as a heat-sealing layer.

[0018] A biodegradable and recyclable barrier paper laminate is provided, the barrier paper laminate being made of: a biodegradable and recyclable paper layer having an outer surface and an inner surface; a first biodegradable polymer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable paper layer; an inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the first biodegradable polymer layer; a biodegradable primer layer having an outer surface and an inner surface, the inner surface being disposed on the inner surface of the inorganic barrier layer; and a second biodegradable polymer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the second biodegradable primer layer. The final layer serves as a heat-sealing layer. Attached Figure Description

[0019] Figure 1A cross-section of the uncoated, biodegradable, and recyclable paper layer 10 is shown.

[0020] Figure 2 A cross-section of a first biodegradable polymer layer 20 coated on a biodegradable and recyclable paper layer 10 is shown.

[0021] Figure 3 A cross-section of a first biodegradable primer layer 30 coated on a first biodegradable polymer layer 20 is shown, which is coated on a biodegradable and recyclable paper layer 10.

[0022] Figure 4 A cross-section of an inorganic barrier layer 40 coated on a biodegradable primer layer 30 is shown. The biodegradable primer layer is coated on a biodegradable polymer layer 20, which is coated on a biodegradable and recyclable paper layer 10.

[0023] Figure 5 A cross-section of a second biodegradable primer layer 50 coated on an inorganic barrier layer 40 is shown. The inorganic barrier layer is coated on a first biodegradable primer layer 30, which is coated on a first biodegradable polymer layer 20, which is coated on a biodegradable and recyclable paper layer 10.

[0024] Figure 6 A cross-section of one embodiment of a complete biodegradable barrier paper laminate according to the present invention is shown, the barrier paper laminate comprising a second biodegradable polymer layer 60 coated on a second biodegradable primer layer 50, the second biodegradable primer layer being coated on an inorganic barrier layer 40, the inorganic barrier layer being coated on a first biodegradable primer layer 30, the first biodegradable primer layer being coated on a first biodegradable polymer layer 20, and the first biodegradable polymer layer being coated on a biodegradable and recyclable paper layer 10.

[0025] Figures 7A-7B Two cross-sectional images of a biodegradable and recyclable barrier paper laminate 150 obtained by scanning electron microscopy are shown. Figure 7a) shows a cross-sectional image obtained by conventional scanning electron microscopy, and Figure 7b) shows a cross-sectional image of one embodiment of the biodegradable and recyclable barrier paper laminate obtained by scanning electron microscopy combined with energy-dispersive X-ray spectroscopy.

[0026] Figure 8 A schematic diagram of a first embodiment of a method for preparing a first biodegradable and recyclable barrier paper laminate 150 is shown.

[0027] Figure 9 The layout of the interior of a vacuum chamber for laying an inorganic barrier layer for vapor deposition according to the present invention is shown.

[0028] Figures 10A-10C A schematic diagram illustrating the application of a biodegradable and recyclable barrier paper laminate is shown.

[0029] Figures 11A-11B Photographs of two different biodegradable and recyclable barrier paper composites 150 are shown. The photograph in Figure 11a) shows the front and back of a biodegradable and recyclable paper barrier composite made using a SiOx-based inorganic coating; the underlying biodegradable and recyclable paper layer (which is white) is clearly visible from both the front and back. The photograph in Figure 11b) shows the front and back of a biodegradable and recyclable paper barrier composite made using an aluminum-based inorganic coating; the underlying biodegradable and recyclable paper layer (which is white) is only visible from the back, and not from the front. These photographs demonstrate how transparent the SiOx layer is, and how highly opaque the aluminum coating is.

[0030] Figure 12 A cross-sectional image of the biodegradable and recyclable barrier paper laminate, named HPX-KOTH-IS-1, described in Example 5, is shown, obtained by scanning electron microscopy. Detailed Implementation

[0031] This invention describes a biodegradable and recyclable barrier paper laminate that offers several advantages over prior art barrier paper laminates, as well as several methods for preparing the biodegradable and recyclable barrier paper laminate.

[0032] As used herein, the term “water vapor transmission rate” or “WVTR” refers to the rate at which water vapor passes through a membrane or substrate when measured according to the water vapor transmission test method set forth in the Test Methods section.

[0033] As used herein, the term “oxygen permeability” or “OTR” refers to the rate at which water vapor permeates through a membrane or substrate when measured according to the oxygen permeability test method set forth in the Test Methods section.

[0034] As used herein, the term "dissolution time" refers to the time required for a water-soluble membrane (such as a membrane made of polyvinyl alcohol) to dissolve when measured according to the dissolution test method presented in the Test Methods section.

[0035] As used in this article, the term "water dispersibility" refers to the ability to break down into small fragments smaller than 1 millimeter in water. These fragments may, but do not need to, remain stably suspended in water.

[0036] As used herein, the term "copolymer" refers to a polymer formed from two or more repeating monomer units of different types. As used herein, the term "copolymer" also encompasses terpolymers, such as terpolymers having a distribution of vinyl alcohol monomer units, vinyl acetate monomer units, and possibly butenediol monomer units; however, if the copolymer is substantially completely hydrolyzed, the vinyl acetate monomer units may be substantially absent.

[0037] As used herein, the term “degree of hydrolysis” refers to the molar percentage of vinyl acetate units that are converted into vinyl alcohol units when polymerized vinyl alcohol is hydrolyzed.

[0038] As used herein, when the term “about” modifies a particular value, it means a range equal to the particular value plus or minus twenty percent (+ / - 20%). For any embodiment of the embodiments disclosed herein, in various alternative embodiments, any disclosure of a particular value may also be understood as approximately equal to the disclosed range of that particular value (i.e., + / - 20%).

[0039] As used herein, when the term “approximately” modifies a particular value, the term means a range equal to the particular value plus or minus fifteen percent (±15%). For any embodiment of the embodiments disclosed herein, in various alternative embodiments, any disclosure of a particular value may also be understood as approximately equal to the disclosed range of that particular value (i.e., ±15%).

[0040] As used herein, when the term “substantially” modifies a particular value, it means a range equal to the particular value plus or minus ten percent (±10%). For any of the embodiments disclosed herein, in various alternative embodiments, any disclosure of a particular value may also be understood as approximately equal to the disclosed range of that particular value (i.e., ±10%).

[0041] As used herein, when the term “almost” modifies a particular value, it means a range equal to the particular value plus or minus five percent (±5%). For any of the embodiments disclosed herein, in the various alternative embodiments, any disclosure of a particular value may also be understood as approximately equal to the disclosed range of that particular value (i.e., ±5%).

[0042] The embodiments described below are for illustrative purposes and should not be construed as limiting the scope of the invention.

[0043] Figure 1A cross-section of a biodegradable and recyclable paper layer 10 is shown. The biodegradable and recyclable paper layer 10 has a first surface 12 and a second surface 14 opposite to the first surface 12, a thickness 116 between the surfaces 12 and 14, and a basis weight obtained from the thickness 116 and the paper density. Preferably, the surface of the paper to be coated should be as substantially flat as possible in order to achieve optimal barrier properties once the remaining structural layers are added.

[0044] The biodegradable and recyclable paper layer 10 has a basis weight of approximately 20 g / m³. 2 Approximately 200g / m 2 Preferably about 40g / m 2 Approximately 120g / m 2 More preferably about 50g / m 2 Approximately 100g / m 2 And more preferably about 60g / m 2 Up to 85g / m 2 Within the range.

[0045] In some cases, it may be desirable to apply the present invention to paperboard, which is thick paper ranging from 200 g / m² to 1000 g / m². In this case, the selected biodegradable and recyclable paper layer is generally thick enough to be considered paperboard rather than paper, especially if it is thicker than 200 g / m². In other cases, a biodegradable and recyclable barrier paper laminate formed on a biodegradable and recyclable paper layer of ≤200 g / m² can be later laminated (once constructed) to a paperboard layer of ≥200 g / m² to produce a paperboard structure with high barrier resistance.

[0046] Figure 2 A cross-section of a first biodegradable polymer layer 20 is shown, the first biodegradable polymer layer having a first surface 22 and a second surface 24 opposite to the first surface 22 and a thickness 216 between the first surface 22 and the second surface 24, the first biodegradable polymer layer being applied to substantially cover at least one of the first surface 12 or the second surface 14 of the biodegradable paper layer 10.

[0047] The thickness 216 of the first biodegradable polymer layer 20 coated onto the biodegradable and recyclable paper layer can be in the range of about 1 μm to about 100 μm, preferably about 3 μm to about 50 μm, more preferably about 1 μm to about 10 μm, and even more preferably between 5 μm and about 15 μm.

[0048] The biodegradable polymer layer 20 comprises at least one biodegradable polymer. Depending on the application, the biodegradable polymer may be water-soluble or water-insoluble. If water-soluble is selected, the biodegradable polymer may be selected from available options to dissolve in water within seconds, minutes, or hours at a temperature of 23°C. Biodegradable polymers that require more than 24 hours to dissolve in water at 23°C will not be considered water-soluble.

[0049] Figure 3 A cross-section of a first biodegradable primer layer 30 is shown. The first biodegradable primer layer has a first surface 32 and a second surface 34 opposite to the first surface 32, and a thickness 316 between the first surface 32 and the second surface 34. This first biodegradable primer layer is applied to substantially cover at least one of the first surface 22 or the second surface 24 of the biodegradable polymer layer 20. The first biodegradable polymer layer 20 has a first surface 22 and a second surface 24 opposite to the first surface 22, and a thickness 216 between the first surface 22 and the second surface 24. This first biodegradable polymer layer is applied to substantially cover at least one of the first surface 12 or the second surface 14 of the biodegradable and recyclable paper layer 10.

[0050] The thickness of the biodegradable primer layer 30 is in the range of about 0.1 μm to about 30 μm, preferably from about 0.2 μm to about 15 μm, and more preferably from about 0.5 μm to about 7 μm.

[0051] The importance of a biodegradable primer layer lies in flattening the underlying structure, which consists of a biodegradable polymer layer situated on a biodegradable and recyclable paper layer, to maximize the performance of the inorganic barrier layer on top. Equally important is the ease with which the inorganic barrier layer deposits and adheres to the biodegradable primer layer. We have found that without a biodegradable primer layer and by placing the inorganic barrier layer alone directly on the polymer layer, the achieved barrier performance is up to two orders of magnitude worse than without the biodegradable primer layer. This is unrelated to the fact that the biodegradable primer layer itself has very little inherent barrier resistance when tested alone. Depending on the exact application of the structure, the biodegradable primer layer can be based on hybrid inorganic-organic chemistry; or it can be based solely on organic chemistry.

[0052] Figure 4A cross-section of an inorganic barrier layer 40 is shown, the inorganic barrier layer having a first surface 42 and a second surface 44 opposite to the first surface 42, and a thickness 416 between the first surface 42 and the second surface 44, the inorganic barrier layer substantially covering the surface 32 of a biodegradable primer layer 30. A first biodegradable primer layer 30 having a first surface 32, a second surface 34 opposite to the first surface 32, and a thickness 316 between the first surface 32 and the second surface 34 is applied to substantially cover at least one of the first surface 22 or the second surface 24 of a biodegradable polymer layer 20. A first biodegradable polymer layer 20 having a first surface 22, a second surface 24 opposite to the first surface 22, and a thickness 216 between the first surface 22 and the second surface 24 is applied to substantially cover at least one of the first surface 12 or the second surface 14 of a biodegradable and recyclable paper layer 10.

[0053] The thickness of the inorganic barrier layer 40 is in the range of about 2 nm to about 1000 nm, preferably about 10 nm to about 200 nm, and more preferably about 20 nm to about 100 nm.

[0054] The inorganic barrier layer is formed by vapor deposition.

[0055] In some embodiments, a suitable vapor-deposited inorganic coating may be formed from a metal. In other embodiments, a suitable vapor-deposited inorganic coating may be formed from metal oxides and related compounds.

[0056] In some embodiments, plasma-assisted chemical vapor deposition (PECVD) can be used to form vapor-deposited inorganic coatings. In other embodiments, atomic layer chemical vapor deposition (ALCVD) can be used instead. In still other embodiments, physical vapor deposition (PVD) can be used instead.

[0057] The inorganic barrier layer 40 according to the invention can be optically opaque, translucent, or transparent, depending on the specific chemical properties applied. Typically, a metal barrier layer such as aluminum will produce an opaque barrier layer, while a metal oxide barrier layer such as aluminum oxide or silicon dioxide will produce a transparent barrier layer.

[0058] Preferably, the inorganic barrier layer 40 is slightly flexible. When converting paper structures through production lines used for printing, pressing, cutting, rewinding, and other typical conversion operations, or when preparing articles such as bags that include biodegradable barrier paper laminates, the entire biodegradable barrier paper laminate structure is typically folded, bent, and sometimes slightly stretched. This can cause some barrier layers to break, potentially reducing their performance as barrier layers. Therefore, it is preferable that the barrier layer 40 is slightly flexible and can be stretched without breaking as the rest of the structure is stretched. Preferably, the barrier layer 40 can elongate by at least 1%, at least 2%, or at least 5% as the underlying biodegradable paper layer, biodegradable polymer layer, and biodegradable primer layer are stretched. In some cases, it may be necessary for the barrier layer to stretch up to 10% or even up to 20% without breaking. Typically, metallic barrier layers, such as aluminum, will have slightly greater flexibility than metal oxide barrier layers, such as alumina or silica. In one implementation, this is achieved by dividing the inorganic barrier layer into multiple distinct inorganic barrier sublayers separated by multiple distinct biodegradable polymer sublayers.

[0059] Figure 5 A second biodegradable primer layer 50 is shown, having a first surface 52 and a second surface 54 opposite to the first surface 52, and a thickness 516 between the first surface 52 and the second surface 54, and substantially covering the surface 42 of the inorganic barrier layer 40; the inorganic barrier layer 40 has a first surface 42 and a second surface 44 opposite to the first surface 42, and a thickness 416 between the first surface 42 and the second surface 44, and substantially covers the surface 32 of the biodegradable primer layer 30; an application having the first surface 32... A first biodegradable primer layer 30 with a second surface 34 opposite to the first surface 32 and a thickness 316 between the first surface 32 and the second surface 34 is applied to substantially cover at least one of the first surface 22 or the second surface 24 of the biodegradable polymer layer 20; a first biodegradable polymer layer 20 having a first surface 22 and a second surface 24 opposite to the first surface 22 and a thickness 216 between the first surface 22 and the second surface 24 is applied to substantially cover at least one of the first surface 12 or the second surface 14 of the biodegradable and recyclable paper layer 10.

[0060] The thickness of the second biodegradable primer layer 50 between the first surface 52 and the second surface 54 is in the range of about 0.1 μm to about 30 μm, preferably about 0.2 μm to about 15 μm, and more preferably about 0.5 μm to about 7 μm.

[0061] Figure 6A cross-section of a fully biodegradable and recyclable barrier paper composite structure 150 having multiple layers is shown. The structure includes a biodegradable paper layer 10 having a first surface 12, a second surface 14 opposite to the first surface 12, and a thickness 116 between the first surface 12 and the second surface 14. A first biodegradable polymer layer 20 is attached to the biodegradable paper layer, the first biodegradable polymer layer having a first surface 22, a second surface 24 opposite to the first surface 22, and a thickness 216 between the first surface 22 and the second surface 24, and substantially covering at least one of the first surface 12 or the second surface 14 of the paper layer 10. A biodegradable primer layer 30 is attached to the first biodegradable polymer layer, the biodegradable primer layer having a first surface 32, a second surface 34 opposite to the first surface 32, and a thickness 316 between the first surface 32 and the second surface 34, and substantially covering the second surface 24 of the biodegradable polymer layer 20. An inorganic barrier layer 40 is attached to a first biodegradable primer layer 30. This inorganic barrier layer has a first surface 42, a second surface 44 opposite to the first surface 42, and a thickness 416 between the first surface 42 and the second surface 44, and substantially covers surface 32 of the biodegradable primer layer 30. A second biodegradable primer layer 50 is attached to the inorganic barrier layer 40. This second biodegradable primer layer has a first surface 52, a second surface 54 opposite to the first surface 52, and a thickness 516 between the first surface 52 and the second surface 54, and substantially covers surface 42 of the inorganic barrier layer 40. A second biodegradable polymer layer 60 is attached to the biodegradable primer layer 50. This second biodegradable polymer layer has a first surface 62, a second surface 64 opposite to the first surface 62, and a thickness 616 between the first surface 62 and the second surface 64, and substantially covers surface 52 of the biodegradable primer layer 50. This final layer serves as a heat-sealing layer.

[0062] The thickness between the first surface 62 and the second surface 64 of the second biodegradable polymer layer 60 can be in the range of about 1 μm to about 100 μm, preferably about 3 μm to about 70 μm, and more preferably about 5 μm to about 35 μm.

[0063] The second biodegradable polymer layer 60 may further comprise at least one biodegradable polymer. Depending on the application, the biodegradable polymer may be selected to be water-soluble or water-insoluble. If the application requires a water-soluble polymer, it may be selected from the available water-soluble polymer options to dissolve in water within seconds, minutes, or hours at a temperature of 30°C. Polymers that require more than 24 hours to dissolve in water at 30°C will not be considered water-soluble.

[0064] Each layer according to the invention is distinct and separate from one another. All layers are distinguished by large compositional variations over small distances, resulting in clear boundaries that are easily visible using microscopic techniques known in the art. Figure 7A Two cross-sectional images of a biodegradable and recyclable barrier paper laminate 150 obtained by scanning electron microscopy are shown. Figure 7a) shows a cross-sectional image (100PEO, 110PVOH varnish, 120bio-ORMOCER, 130PVOH, 135 sizing layer) obtained by conventional scanning electron microscopy; Figure 7b) shows a cross-sectional image of one embodiment of the biodegradable and recyclable barrier paper laminate (100PEO, 110PVOH varnish, 120bio-ORMOCER, 130PVOH, 135 sizing layer, 140 packaging paper) obtained by scanning electron microscopy combined with energy-dispersive X-ray spectroscopy.

[0065] EDX color coding helps to highlight the chemical differences between layers.

[0066] This invention describes nine different embodiments of a biodegradable and recyclable barrier paper laminate. The other eight embodiments described herein, referred to as 250, 350, 450, 550, 650, 750, 850, and 950, do not represent every layer outlined in this first embodiment.

[0067] Aqueous polymer systems can be applied in a variety of ways, as will be explained here. Without being limited by theory, the most important processability of aqueous polymer systems is believed to be: a) the solubility of the water-soluble polymer at a given temperature between 20°C and 95°C if the polymer is water-soluble; b) the ability of the polymer to form an emulsion if the polymer is not water-soluble; c) the viscosity of the aqueous polymer system containing water at a given temperature between 20°C and 95°C, where higher viscosity provides a clear distinction between layers; d) the ability to completely wet the aqueous polymer system onto a biodegradable and recyclable paper layer, or, if the application requires, onto an inorganic barrier layer or a biodegradable primer layer.

[0068] In some embodiments, it is desirable to apply the second biodegradable polymer layer 60 in a molten state to the second biodegradable primer layer 50 or the inorganic barrier layer 40. In this case, the biodegradable polymer is first melted in an extruder and then applied directly to the surface of the inorganic barrier layer 40 or the biodegradable primer layer 50 using an extrusion coating die.

[0069] In some embodiments, it is desirable to first form the second biodegradable polymer layer 60 into a self-standing film using a separate method, non-limiting examples being hot-cast extrusion, hot-blow extrusion, or solution casting. To attach the film to the surface of the inorganic barrier layer 40 or the second biodegradable primer layer 50, a biodegradable adhesive 60A is first applied to the inorganic barrier layer 40 or the second biodegradable primer layer 50. The second biodegradable polymer layer 60 is then brought into contact with the biodegradable adhesive layer 60A to form an adhesive laminate, and then a heat-sealing layer for the biodegradable barrier paper laminate is formed.

[0070] In some other embodiments, it is desirable to first form the second biodegradable polymer layer 60 into a self-standing film using a separate method, such as hot casting extrusion, hot blow extrusion, or solution casting. To attach the film to the surface of the inorganic barrier layer 40 or the biodegradable primer layer 50, the film is attached to the remainder of the substrate by thermal lamination.

[0071] In some implementations, it is desirable to lay a second biodegradable polymer layer 60 or a second biodegradable primer layer 50 on the PET film or steel strip 80 for later removal after lamination to the biodegradable and recyclable paper layer 10.

[0072] In some embodiments, it is desirable to lay a second biodegradable primer layer 50 or inorganic barrier layer 40 on the surface of a second biodegradable polymer layer 60 that has already been made (which has been made into a self-standing film by a separate method, non-limiting examples being hot casting extrusion, or hot blow extrusion or solution casting) for subsequent lamination to a biodegradable and recyclable paper layer 10.

[0073] When using water-insoluble polymer compositions, the drying process typically needs to be carried out after a short heating step to form a continuous, biodegradable polymer layer. This is also true for liquid compositions used to form a biodegradable primer layer.

[0074] When the biodegradable and recyclable barrier paper laminate according to the invention comes into contact with water, the layers will behave differently depending on their specific properties. The biodegradable and recyclable paper layers will absorb water, swell, and break down, thereby releasing cellulose fibers. The biodegradable polymer layer and primer layer on top of the biodegradable and recyclable paper layers may dissolve, swell, disintegrate, and / or separate from the surrounding layers, depending on their exact properties. Components of the various laminate layers may also be digested by bacteria in their presence. If collected and recycled, the laminate may come into contact with water during the repulping process in a typical paper recycling plant. If the laminate is flushed down drains and / or into municipal water treatment plants, or if it is added to a domestic or industrial composting system, the laminate will also come into contact with water and may come into contact with bacteria. If the laminate is improperly disposed of in municipal waterways, on land (where it experiences moist soil or other materials or sediment), on the top surface of an open landfill, or if it enters aquatic environments such as streams, rivers, lakes, or the sea, it may also come into contact with water and bacteria. In all cases, the inorganic barrier layer will decompose harmlessly as the surrounding and supporting laminate layer dissolves and / or decomposes, regardless of whether the waste was preferably treated or improperly disposed of. If littered, the inorganic barrier layer may disperse into minerals that may enrich the soil. Any surface inks and / or varnishes will also biodegrade or disperse harmlessly.

[0075] All embodiments of this invention are compatible with current paper recycling systems; that is, these embodiments should readily decompose when stirred in large quantities of warm water. For typical current industrial repulping facilities, paper packaging must be soaked in warm water under constant vigorous agitation for 5 to 20 minutes to disperse and release paper fibers for collection. Due to the existence of different types of paper recycling systems in different regions and due to different government regulations and requirements in different regions, there is currently no universally accepted standard for determining whether paper laminates are recyclable. Even within the EU, different countries have different requirements. However, generally speaking, the higher the content of natural fibers in a barrier paper laminate and the lower the content of other materials (such as barrier coatings, primer layers, and heat-sealing layers) in the barrier paper laminate, the higher its likelihood of being considered recyclable in the paper recycling stream of a particular country. Some specific examples of standards that can be used to determine whether barrier paper laminates are recyclable include the PTS method and the Western Michigan method, each of which is described in more detail later.

[0076] If improperly disposed of in the environment, the packaging must also be rapidly dispersed to expose the maximum surface area to the bacteria responsible for biodegradation, ensuring complete consumption within a reasonable timeframe. Preferably, the packaging will biodegrade within 6 to 12 months. And if the packaging is compostable, it must undergo complete consumption within the expected normal timeframe for compostable packaging. Screening tests (OECD 301B) and OECD 306 have been used to evaluate the biodegradability of various barrier paper laminates under a range of environmental conditions, and the test methods will be described in more detail later.

[0077] The biodegradable barrier paper laminate according to the present invention may include printed areas. Printing can be achieved using standard printing techniques such as flexographic printing, gravure printing, or inkjet printing. The biodegradable barrier paper laminate according to the present invention may include a surface coating for appearance protection purposes to prevent accidental water damage or for matte / gloss effects.

[0078] Paper

[0079] The biodegradable and recyclable paper used to prepare biodegradable and recyclable barrier paper laminates is biodegradable, leaving no persistent material in the environment, and preferably recyclable in typical paper recycling streams. In practice, the paper is not made solely of 100% cellulose fibers, but also contains polymer binders, mineral adhesives, brighteners, surfactants, and other additives. These other components must be appropriately selected to ensure that (a) the paper will biodegrade without causing any ecotoxicity problems if improperly disposed of in the environment, or (b) the paper will break down and release the maximum amount of cellulose fibers for use in the repulping unit at the paper recycling facility for the preparation of recycled paper.

[0080] For commercial reasons, it is also important that paper recycling facilities obtain at least 50% by weight of cellulose fibers from the incoming batch of waste paper. To this end, it is preferred that the paper layer itself contains at least between 50% and 100% by weight of cellulose fibers, more preferably between 65% and 98% by weight of cellulose fibers, and most preferably between 75% and 95% by weight of cellulose fibers.

[0081] Because biodegradable and recyclable paper is the thickest layer in a biodegradable and recyclable barrier paper laminate, any packaging made from it will contain a high percentage of bio-based cellulose by weight.

[0082] It is anticipated that the biodegradable and recyclable paper layer of this disclosure may itself contain recycled materials as natural or synthetic fibers. For example, the biodegradable barrier paper layer composite of the present invention may contain more than 10% by weight, preferably more than 20% by weight, more preferably more than 30% by weight of recycled materials, specifically listing all values ​​within these ranges and any ranges arising therefrom. The paper layer may contain between 0% and 100% virgin paper or recycled paper or mixtures thereof.

[0083] The presence of recycled materials can be determined through visual inspection of the packaging. For example, manufacturers often advertise the use of recycled materials to attempt to demonstrate their eco-friendly product approach. To further expand on this example, some manufacturers may utilize logos, such as leaves, and wording indicating the use of recycled materials in the packaging. Typically, manufacturers may also specify the percentage of recycled materials used, such as over 50%, over 70%, etc.

[0084] Visual inspection can be as simple as using the human eye to check for signs indicating the use of recycled materials on packaging. Additionally or alternatively, visual inspection may include microscopy, such as optical microscopy, scanning electron microscopy, or other suitable methods known in the art. For example, packaging materials containing recycled paper fibers may look different under a microscope because of the wider range of natural fiber types available compared to packaging materials containing 100% non-recycled paper. As another example, under a microscope (likely a scanning electron microscope), recycled fibers may exhibit more fibrillation than their virgin fiber counterparts due to their processing.

[0085] Preferably, the paper is as substantially flat as possible on at least one side, particularly the side subsequently coated with a biodegradable polymer layer or a biodegradable primer layer. During manufacturing, the paper can be flattened by “sizing,” which industrially means coating the paper with an aqueous polymer suspension containing various inorganic fillers such as clay, calcium carbonate, titanium dioxide, methylcellulose, silica, etc. The suspension is then dried, and the paper is calendered to provide a flatter surface than before sizing, as the inorganic fillers and binders dry to fill the porous, rough surface of the paper. In some cases, the dimensions of both sides of the paper are set to be the same or different. Alternatively, the paper can be mechanically varnished during the papermaking process by a mechanical ironing / pressing step, which sometimes involves heating, in which case the paper fibers are squeezed together and flattened to densify the paper surface and remove porosity. In some cases, sizing and mechanical varnishing are combined to obtain an even flatter, more perfect surface during the papermaking process, followed by coating with an aqueous biodegradable polymer layer. In other cases, kraft paper, cellophane, or tracing paper that is already naturally very flat can be used. These papers are manufactured by densifying the paper structure throughout its thickness during production and therefore do not require further sizing or varnishing. Paper layers can also be prepared using a foam-forming process, an improved papermaking process that uses water-based foam instead of water.

[0086] Examples of paper suitable for preparing biodegradable barrier paper laminates include: Leine from Sappi. Paper (basic weight = 85g / m³) 2 Glossy paper with "OK Home Compost" certification; Nikla Select V natural linen paper (99g / m²) from Brigli and Bergmeister. 2 Paper with adhesive applied only on one side; PackPro 7.0 paper (80g / m²) from Brigli and Bergmeister. 2 Paper with adhesive on both sides; obtained from Axello paper (including tough white paper from Axello, 80g / m²) 2 It is designed to be tougher than many other papers and therefore has some advantages in the distribution chain; SCG cellophane (58 g / m²) derived from SCG / Prepack 2 As shown in Table 1 below, these papers passed the paper recycling programs of Western Michigan University in the United States and the PTS Institute in Germany. These papers also passed the OECD 301B biodegradability screening test, undergoing at least 60% biodegradation within 60 days.

[0087] Table 1 :

[0088]

[0089] Other suitable papers may include those specifically prepared for subsequent decorative metallization, such as Nikkalett Spezial TD paper (60 g / m²) from Brigland Bergmeister. 2 ).

[0090] The smoothness of the paper surface on the remaining portion coated with the barrier structure can be measured using 3D LSM. Table 2 below describes some of the smoothness of the aforementioned papers. Generally, we will prefer the roughness (S) on the side where the structure is coated. q - (as measured by 3D LSM) <1.5, in order to optimize the barrier properties of all layers added on top, especially the inorganic barrier layer, as much as possible. Note that Nikkalett Spezial TD paper, specifically designed for metallization, has a roughness of approximately 0.98 on the side designed for metallization.

[0091] Table 2 :

[0092]

[0093] To withstand the harsh conditions of high-speed manufacturing processes (where products are placed within packaging made of the laminates disclosed in this invention) and the harsh conditions of transportation, the paper layers must be sufficiently strong and resilient. Numerous methods exist for specifying paper layers. The metrics discussed below are MD tensile strength in kN / m, CD tensile strength in kN / m, MD tensile strength as a percentage, CD tensile strength as a percentage, MD bursting strength in kPa, thickness in μm, MD tensile energy absorption in J / g, CD tensile energy absorption in J / g, and basis weight in grams per square meter. While all metrics can be used in combination in this invention to select suitable paper, some metrics, alone or in combination with others, may also meet the requirements.

[0094] In situations where very strong paper is required to maintain the physical integrity of the barrier layer, it is preferable to use paper derived from [source missing]. of Paper. For example, Table 3 below shows the paper obtained from... of The tough white paper grade is derived from the properties of Mondi's Advantage Smooth White Strong paper.

[0095] Table 3 :

[0096]

[0097] Cellulose fibers used in papermaking can be derived from cork, hardwood, and non-tree fibers. Non-tree fibers typically have shorter fibers and include bamboo, grass, hemp, kenaf, flax, corn husks, cotton stalks, coffee grounds, bagasse, rice straw, wheat straw, algae, abaca, sabia grass, esparto grass, milkweed fiber, pineapple leaf fiber, wood fiber, pulp fiber, etc.

[0098] Water-soluble biodegradable aqueous polymers

[0099] In some embodiments, it is preferred that at least one of the biodegradable polymer layers is made of a water-soluble polymer. Such biodegradable polymer layers are suitable for forming a laminate between a biodegradable and recyclable paper layer and a biodegradable primer layer, and / or can be used to form a heat-sealing layer for a biodegradable and recyclable barrier paper layer assembly.

[0100] Suitable copolymers or their derivatives for use as water-soluble polymer layers are selected from polyvinyl alcohol (PVOH), polyvinyl alcohol copolymers (such as butene glycol-vinyl alcohol copolymer (BVOH)), which are produced by copolymerization of butene glycol and vinyl acetate followed by hydrolysis of vinyl acetate. Suitable butene glycol monomers are selected from 3,4-diol-1-butene, 3,4-diacoxy-1-butene, 3-acyloxy-4-ol-1-butene, 4-acyloxy-3-ol-1-butene, etc.; polyepoxides, such as polyethylene oxide or polyethylene glycol (PEG); poly(methacrylic acid), polypropylene. Acids, polyacrylates, acrylate copolymers, maleic acid / acrylic acid copolymers; polyacrylamide; poly(2-acrylamido-2-methyl-1-propanesulfonic acid (polyAMPS); polyamides, poly-N-vinylacetamide (PNVA); polycarboxylic acids and salts; cellulose derivatives, such as cellulose ethers, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose; hydroxypropyl methylcellulose; natural gums, such as xanthan gum and carrageenan; sodium alginate; maltodextrin, low molecular weight dextrin; sugars; polysaccharides; certain thermoplastic starch grades (e.g., derived from Plantic / Kuraray). (Specific grades) polyamino acids or peptides; proteins, such as casein and / or caseinates (e.g., those commercialized by Lactips).

[0101] The most preferred water-soluble biodegradable polymers are polyvinyl alcohol, polyethylene oxide, methylcellulose, and sodium alginate. For applications requiring "plastic-free" products, the majority of the components of the water-soluble polymer layer can be naturally derived polymers, such as sodium alginate. Preferably, the biodegradable polymer content in the water-soluble polymer layer is at least 60%.

[0102] The average molecular weight (measured by gel permeation chromatography) of the water-soluble biodegradable polymer is from about 1,000 Da to about 1,000,000 Da, or any integer value from about 1,000 Da to about 1,000,000 Da, or any range formed by any of the foregoing values, such as about 10,000 Da to about 300,000 Da, about 20,000 Da to about 150,000 Da, etc. More specifically, the molecular weight of polyvinyl alcohol can be in the range of 30,000 Da to 150,000 Da. The molecular weight of polyethylene oxide will be in the range of 50,000 Da to 400,000 Da. The molecular weight of methylcellulose will be in the range of 10,000 Da to 100,000 Da. Methylcellulose may also be 18% to 32% substituted methoxy and 4% to 12% substituted hydroxy-propoxy. Sodium alginate can have an average molecular weight of about 10,000 Daltons to about 240,000 Daltons.

[0103] If homopolymer polyvinyl alcohol is used, the degree of hydrolysis may be 70% to 100%, or between 70% and 100%, or preferably between 84% and 92%, or even more preferably between 86% and 90%, or any range formed by any of these values, such as 80% to 100%, 85% to 100%, 90% to 100%, 95% to 100%, 98% to 100%, 99% to 100%, 85% to 99%, 90% to 99%, 95% to 99%, 98% to 99%, 80% to 98%, 85% to 98%, 90% to 98%, 95% to 98%, 80% to 95%, 85% to 95%, 90% to 95%, etc.

[0104] Certain grades of polyvinyl alcohol can claim higher moisture resistance while remaining soluble. Examples include polyvinyl alcohols from the Exceval range derived from Kuraray, including grades Exceval HR-3010 and Exceval AQ-4104.

[0105] Water-soluble polymers can be processed via thermal extrusion and solution casting. Solution casting requires the water-soluble polymer to first be formed into a polymer solution. The polymer in the solution can be considered aqueous. In some embodiments, it is preferred that the biodegradable polymer layer used as the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer is aqueous, because a thinner, flatter, and more uniform biodegradable polymer layer can typically be formed compared to extruding and coating the biodegradable polymer layer onto the surface of the biodegradable and recyclable paper layer. In some embodiments, it is preferred that the biodegradable polymer layer used as the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer is not only aqueous but also soluble, because this will increase the rate at which the two layers can be separated in a typical paper repulping unit and thus increase the likelihood of the entire structure being recyclable in a typical paper recycling stream. Therefore, in some embodiments, it is preferred that the biodegradable polymer layer used as the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer is soluble and laid with an aqueous composition, because such a biodegradable polymer layer will be very flat (to help maximize the barrier properties of the entire structure), and its soluble nature will minimize the time the paper breaks down in a typical paper repulping flow.

[0106] Water-insoluble biodegradable aqueous polymers

[0107] In some embodiments, it is preferred that at least one layer of the biodegradable polymer layer is made of a water-insoluble polymer. These materials are commonly referred to as "bioplastics" and biodegradable polymers. Such biodegradable polymer layers are suitable for forming a laminate between a biodegradable and recyclable paper layer and a biodegradable primer layer, and / or can be used to form a heat-sealing layer for a biodegradable and recyclable barrier paper layer assembly.

[0108] In one case, biodegradable aliphatic polyesters and copolyesters can be prepared through large-scale bacterial fermentation. Collectively known as polyhydroxyalkanoates, or "PHAs," these polymers can be synthesized in fermentation plants by plants or bacteria fed with specific substrates, such as glucose. In many cases, the structural or mechanical properties of PHAs can be tailored to meet the specifications of the desired end product. PHAs and their copolymers can degrade aerobically and anaerobically. This makes them particularly suitable for composting or rapid and complete degradation in the environment. Such bioplastics are typically sold in the form in which the plastic is suspended in an aqueous emulsion and can be dried into films on a variety of substrates, although they can also be sold in granular form for extrusion film formation and coating. In some cases, the emulsion can be described as aqueous, which gives it the advantage of being able to form thinner, flatter, and more uniform coatings than those applied by thermal extrusion.

[0109] PHA can be obtained as a coating for copolymer dispersions. Danimer Scientific produces poly(β-hydroxyalkanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (NODAX). TM Kaneka produces poly(3-hydroxybutyrate-co-3-hydroxyhexanoate). Non-limiting examples of PHA copolymers include those described in U.S. Patent No. 5,498,692. Other PHA copolymers can be synthesized by methods known to those skilled in the art, such as ring-opening polymerization of microorganisms, β-lactones, dehydration condensation of hydroxyalkyl acids, and dealcoholization condensation of alkyl ethers of hydroxyalkyl acids, as described in Volova, “PolyhydroxyAlkanoates Plastic Materials of the 21st Century: Production, Properties, and Application,” Nova Science Publishers, Inc., (2004), which is incorporated herein by reference.

[0110] Other possible biodegradable water-insoluble polymers may include biodegradable thermoplastic materials selected from the group consisting of: aliphatic aromatic polyesters (e.g., derived from BASF). ), specific grades of thermoplastic starch (e.g., MATER-BI from Novamont or from Plantic / Kuraray) ), polybutylene succinate (PBS), polybutylene adipate succinate (PBSA), and their copolymers (e.g., from ShoWa Highpolymer Co. (Or obtained from Mitsubishi Chemicals' PBSA) and mixtures thereof. Although these polymers are not currently typically sold in aqueous form, such forms may be developed in the future.

[0111] In some embodiments, it is preferred that the biodegradable polymer layer used as the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer is aqueous, because a thinner, flatter, and more uniform biodegradable polymer layer can be formed compared to extruding and coating the biodegradable polymer layer onto the surface of the biodegradable and recyclable paper layer. In some embodiments, it is preferred that the biodegradable polymer layer used as the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer is soluble, because this increases the rate at which the two layers can be separated in a typical paper recycling and repulping unit and thus increases the likelihood that the entire structure will be recyclable in a typical paper recycling stream.

[0112] In some implementations, water-soluble polymers are preferred for heat-sealing layers because they are less affected by high moisture content.

[0113] Optional components within the biodegradable polymer layer

[0114] The biodegradable polymer layer of the water-soluble biodegradable barrier paper composite may contain disintegrants, plasticizers, surfactants, lubricants / release agents, fillers, extenders, antiblocking agents, anti-sticking agents, defoamers, or other functional ingredients.

[0115] Some applications may require a water-soluble, biodegradable polymer layer containing a disintegrant to increase its dissolution rate in water. Suitable disintegrants are, but are not limited to, corn / potato starch, methylcellulose, mineral clay powder, cross-linked carboxymethyl cellulose (cross-linked cellulose), cross-linked polyvinyl N-pyrrolidone (PVP), and sodium carboxymethyl starch (cross-linked starch). Preferably, the water-soluble polymer layer contains between 0.1% and 15% by weight, more preferably about 1% to about 15% by weight of the disintegrant.

[0116] In some embodiments, the water-soluble, biodegradable polymer layer may comprise a water-soluble plasticizer. Preferably, the water-soluble plasticizer is selected from polyols, sugar alcohols, and mixtures thereof. Suitable polyols include those selected from the group consisting of: glycerol, diglycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a molecular weight of up to 400 Da, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, methyl glycol, trimethylolpropane, hexanediol, neopentyl glycol, and polyether polyols, or mixtures thereof. Suitable sugar alcohols include those selected from the group consisting of: isomaltitol, maltitol, sorbitol, xylitol, erythritol, ribitol, galactitol, pentaerythritol, and mannitol, or mixtures thereof. In some cases, plasticizers may be selected from the following list: ethanolamine, alkyl citrate, isosorbide, pentaerythritol, glucosamine, N-methylglucosamine, or sodium isopropylbenzenesulfonate. Less mobile plasticizers such as sorbitol or polyethylene oxide can promote the formation of water-soluble polymer layers with greater barrier properties compared to water-soluble polymer layers containing more mobile plasticizers such as glycerol. In some cases, when it is desirable to use as many naturally derived materials as possible, the following plasticizers may also be used: vegetable oils, polysorbate, polydimethylsiloxane, mineral oil, paraffin wax, C1-C3 alcohols, dimethyl sulfoxide, N,N-dimethylacetamide, sucrose, corn syrup, fructose, sodium dioctyl sulfosuccinate, triethyl citrate, tributyl citrate, 1,2-propanediol, monoacetates, diacetates, or triacetates of glycerol, natural gums, citrates, and mixtures thereof. More preferably, the water-soluble plasticizer is selected from glycerol, 1,2-propanediol, 2,0-dipropanediol, 2-methyl-1,3-propanediol, trimethylolpropane, triethylene glycol, polyethylene glycol, sorbitol, or mixtures thereof, most preferably from glycerol, sorbitol, trimethylolpropane, dipropanediol, and mixtures thereof. Preferably, the water-soluble polymer layer comprises between 5% and 50% by weight, preferably between 10% and 40% by weight, and even more preferably from about 12% to about 30% by weight of the plasticizer.

[0117] In some embodiments, the biodegradable polymer layer comprises a surfactant. Suitable surfactants may belong to the nonionic, cationic, anionic, or amphoteric categories. Suitable surfactants are, but are not limited to, poloxamer (polyoxyethylene polyoxypropylene glycol), alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenols and alkanolamides (nonionic), polyoxyethylene amines, quaternary ammonium salts and polyoxyethylene quaternary amines (cationic), and amine oxides, N-alkyl betaine and sulfobetaine (amphoteric). Other suitable surfactants are sodium sulfosuccinate, acylated fatty acid esters of glycerol and propylene glycol, fatty acid lactoyl esters, sodium alkyl sulfate, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, and acetylated esters of five fatty acids, and combinations thereof. Preferably, the water-soluble polymer layer comprises between 0.1% by weight and 2.5% by weight, more preferably about 1% by weight to about 2% by weight of surfactant.

[0118] In some embodiments, the biodegradable polymer layer according to the invention comprises a lubricant / stripping agent. Suitable lubricants / stripping agents are, but are not limited to, fatty acids and their salts, fatty alcohols, fatty acid esters, fatty amines, fatty amine acetates, and fatty amides. Preferred lubricants / stripping agents are fatty acids, fatty acid salts, fatty amine acetates, and mixtures thereof. Preferably, the water-soluble polymer layer comprises 0.02% to 1.5% by weight, preferably about 0.1% to about 1% by weight of the lubricant / stripping agent.

[0119] In some embodiments, the biodegradable polymer layer according to the invention comprises fillers, expanders, antiblocking agents, and anti-sticking agents. Suitable fillers, expanders, antiblocking agents, and anti-sticking agents are, but are not limited to, starch, modified starch, cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, and mica. Preferably, the biodegradable polymer layer comprises 0.1% to 25% by weight, more preferably about 1% to about 15% by weight, of fillers, expanders, antiblocking agents, and anti-sticking agents. In the absence of starch, the biodegradable polymer layer preferably comprises 1% to 5% by weight of fillers, expanders, and antiblocking agents.

[0120] In some embodiments, the water-soluble, aqueous, biodegradable polymer layer according to the invention comprises an antifoaming agent. Suitable antifoaming agents are, but are not limited to, blends of polydimethylsiloxane and hydrocarbons. Preferably, the water-soluble polymer layer comprises between 0.001 wt% and 0.5 wt%, more preferably about 0.01 wt% to about 0.1 wt% of the antifoaming agent.

[0121] At least one of the biodegradable polymer layers may be made from the water-soluble polymer according to the invention. The biodegradable barrier paper laminate may contain residual moisture in the water-soluble layer, depending on the hygroscopicity and isotherm of the laminate components as measured by Karl Fischer titration under given temperature and humidity conditions. For example, the water-soluble polyvinyl alcohol layer in the laminate may contain about 4%-8% residual moisture at 23°C and 50% RH.

[0122] Biodegradable primer layer

[0123] The role of the biodegradable primer layer is to smooth the surface of the primer-coated paper structure as much as possible before the inorganic barrier layer is deposited onto it. Generally speaking, the lower the roughness value of the substrate immediately below the inorganic barrier layer, the higher the barrier performance.

[0124] The primer also needs to adhere as well as possible to the inorganic barrier layer to form a strong interface, achieving a stable barrier layer and preventing delamination between the inorganic barrier layer and the underlying structure. In some cases, such primer layers can also be used on top of the inorganic barrier layer to prevent mechanical damage or oxidation, and in this case, they can be referred to as a protective layer. Primers can also be used to provide additional heat resistance to the thermal hysteresis often experienced during vapor deposition. In addition to being a protective layer, biodegradable primer layers are sometimes referred to as biodegradable varnishes or biodegradable varnishes. Regardless of which term is used to describe the layer, the purpose is the same.

[0125] We have found that removing the first biodegradable primer layer has a detrimental effect on the barrier properties of the entire structure. In some embodiments, it is better to use both the first and second biodegradable primer layers in the structure. In some other embodiments, we have found that the second biodegradable primer layer can be removed, which helps to maximize recyclability and reduce costs. However, in general, we have found that it is best to retain the first biodegradable primer layer to maximize the water vapor barrier properties (and other barrier properties) of the entire structure. However, in some embodiments, retaining the second biodegradable primer layer to reduce the defect density of the inorganic barrier coating laid on top of the first biodegradable primer layer may still have some advantages.

[0126] Although primers are widely used throughout the paper and plastic packaging industry, there is a particular need for biodegradable primers for this specific application to improve coatability and printability. If the primer is not biodegradable, it is preferable that it can be harmlessly dispersed without harming living organisms once the rest of the structure has been biodegraded and broken down. Therefore, suitable potential options are more limited than for other applications.

[0127] In some implementations, the primer can be an inorganic-organic hybrid polymer, such as those developed by the Fraunhofer Institute for Silicate Research in Wurzburg, Germany. or These materials are hybrids between glass and polymers, and their exact chemical properties can be customized for specific applications. and The material is synthesized via a sol-gel method and exhibits strong covalent bonds between its inorganic and organic components. The ratio of inorganic to organic components can be varied to optimize properties for specific applications. Controlled hydrolysis and condensation reactions of organic-alkoxysilanes and metal alkoxides yield hybrid polymers. The inorganic network. The organic network is formed through the subsequent polymerization of reactive organic groups, which are introduced via organo-alkoxysilanes. Typically, this involves epoxide polymerization or free radical polymerization for non-biodegradable types of acrylates or methacrylates. The formation of the organic network, and thus the curing of the material, can be induced by heat or UV light.

[0128] For this specific application In some ways superior Because it has been modified to be biodegradable. Typically, in order to prepare bio- Modified with biodegradable polymers such as deacetylated chitosan or polycaprolactone to prepare a biodegradable form, thereby forming a polymer that can interact with inorganic compounds. Network covalently coupled biodegradable functional groups. To ensure the incorporation of biodegradable components into the hybrid polymer network, some of these components are chemically modified. For example, polycaprolactone derivatives can be functionalized with triethoxy-silyl groups to allow these biodegradable components to be linked to the inorganic network subsequently through hydrolysis and condensation reactions. For the polycaprolactone type, the linking of the biodegradable precursor to the organic network of the hybrid material is achieved by functionalizing with epoxy groups. The reactive epoxy groups then participate in the polymerization reaction used to form the organic network. In contrast, deacetylated chitosan does not require modification because it can be linked to the organic network through some of its own amino groups. The deacetylated chitosan type tends to biodegrade at a faster rate. The polycaprolactone type is specifically designed with moisture-triggered antimicrobial effects.

[0129] and Non-limiting examples include those described in U.S. Patent No. 2011 / 0250441A1 and U.S. Patent No. 6709757B2, in addition to German patents DE-OS 3828098 and DE4303570.

[0130] Apply in liquid form and And once heated, it will solidify at a temperature of at least 100°C via a sol-gel method to form a very flat solid layer. The liquid must be kept cool before application to the substrate to prevent premature curing. Typically, bio- and Both of these properties result in them being only a few micrometers thick. Typically, they are applied on top of or under the inorganic barrier layer. In some embodiments, further processing is preferred. or This allows for further cross-linking, although the biodegradation rate of fully cross-linked materials will need to be balanced against any improvements in substrate performance.

[0131] In this invention, we focus on the application of single-component liquids. Typically, a wet process is used, applying the coating using roll-to-roll coating processes (such as gravure or anilox rollers) or via a trough coater. Drying is then performed using a Kronert Drytec heater maintained at 100°C, moving the coating through the dryer at 5 m / min to ensure a residence time of approximately 1 minute within the dryer. This produces a hard, glossy coating that cross-links upon exiting the dryer. Any further curing occurs on the rollers once the coating is wound up.

[0132] In some implementations, alternatives to those obtained from The Fraunhofer Institute can be used. or In addition to inorganic-organic hybrid materials. In this case, the composition used to prepare the organic-inorganic hybrid layer may contain organosilanes and metal alkoxides, as previously described. If desired, the composition may also contain additives / fillers, solvents, and polymerization catalysts.

[0133] Organosilanes may be at least one of the groups selected from compounds represented by the following chemical formula 1. When using a compound, the organosilane compound should be crosslinkable. (R')mSi X(4_i,,)(1), where X (which may be the same or different) is hydrogen, halogen, C1-12 alkoxy, acyloxy, alkyl carbonyl, alkoxy carbonyl or N(R2)2 (where R2 is H or C1-12 alkyl); R' (which may be the same or different) is C1-12 alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalenyl, alkenylaryl, arylalkynyl, alkynylaryl, halogen, substituted amino, amide, aldehyde, ketone, alkyl carbonyl, carboxyl, mercapto, cyano, hydroxyl, C1-12 alkoxy, C1-12 alkoxy carbonyl, sulfonate, phosphate, acryloyloxy, methacryloyloxy, epoxy or vinyl; oxygen or -NR2 (where R2 is H or C1-12 alkyl) may be inserted between R.sup.1 and Si to obtain X(4m) or (R'). NR2Si X(4-m); and m is an integer from 1 to 3. Organosilanes can be selected from the group consisting of: methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylethoxysilane, phenyldimethyl15methoxysilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenylethoxysilane, 3-aminopropyltriethoxysilane, 3 - Glycidoxypropyltrimethoxysilane, p-amino-2-phenylsilane, allyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-glycidoxypropyltri25methoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and mixtures thereof.

[0134] The metal alkoxide may be at least one of the groups of compounds represented by the following chemical formula 2. 35M-(R3), (2) where M is a metal selected from the group consisting of aluminum, zirconium and titanium; R3 (which may be the same or different) is a halogen, C1-12 alkyl, alkoxy, acyloxy or hydroxyl; and Z is an integer of 3 or 4.

[0135] In some cases, fillers may be added to the composition. The filler may be at least one material selected from the group consisting of metals, glass powder, diamond powder, silicon dioxide (SiO, where x is an integer from 2 to 4), and clay. Examples of fillers include metals, glass powder, diamond powder, silicon dioxide, clay (bentonite, chlorophyllite, kaolin, etc.), calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, barium hydroxide, aluminum silicate, and mixtures thereof. The solvent may be any solvent commonly used for partial hydrolysis, and distilled water is preferred. The catalyst is not particularly limited, and aluminum butoxide and zirconium propoxide are preferred.

[0136] In this composition, the amount of organosilane is preferably 20%-99.99% by weight, more preferably 50%-99% by weight, and most preferably 70%-99% by weight. The amount of metal alkoxide may be 0.01%-80% by weight, more preferably less than 70% by weight, and most preferably less than 20% by weight.

[0137] Alternative implementations for use as biodegradable primers may include, but are not limited to, biodegradable PVOH paints or biodegradable shellac paints from the Huber Group in Germany. These alternative options are also expected to be biodegradable.

[0138] Typically, any primer layer will be laid in such a manner that it produces a final cured thickness in the range of 0.1 μm–30 μm, preferably 0.2 μm–15 μm, and more preferably 0.5 μm–7 μm. It is important to keep this layer as thin as possible to maintain a good balance between protecting the barrier properties of the inorganic barrier layer and preventing problems in the recycled paper stream. If the primer layer is too thick or too difficult to break down, it may clog filters in the paper repulping unit or cause optical defects in the resulting recycled paper. Furthermore, primers can be expensive, and therefore minimizing their use will help minimize costs.

[0139] In some cases, if the primer can be safely dispersed, it can be considered safe to use a non-biodegradable primer. In such cases, it can be considered safe to use a primer based on certain chemicals, including epoxy resins, acrylic resins, methacrylates, and acrylic resins containing epoxy resin components.

[0140] Inorganic barrier layer

[0141] Adding an inorganic barrier layer is crucial for significantly reducing the overall moisture permeability of the structure. The quality of this layer and how its integrity is maintained are critical to preserving the good barrier properties of the entire structure. Its interaction with the layers beneath and above it is also very important for achieving the best possible barrier properties for the entire structure.

[0142] In some embodiments, a suitable inorganic coating can be formed by vapor deposition of a metal, including but not limited to aluminum, magnesium, titanium, tin, indium, silicon, carbon, gold, silver, chromium, zinc, copper, cerium, hafnium, tantalum, and diamond-like carbon.

[0143] In some embodiments, suitable inorganic coatings can be formed by vapor deposition of metal oxides, metal nitrides, and related compounds. As used herein, metal oxides include aluminum oxide (e.g., Al₂O₃), aluminum carbide, aluminum nitride, magnesium oxide, titanium oxide (such as titanium dioxide, titanium oxide (3), or titanium monoxide), zinc oxide, tin oxide, yttrium oxide, or zirconium oxide (e.g., zirconium monoxide), calcium oxide, boron oxide, or metal-like oxides (such as silicon oxide, silicon carbide, and silicon nitride). Silicon oxide coatings or nitride-based coatings may also be selected from SiO₂. X (where x is an integer from 1 to 4) or SiO X N Y The coating consists of groups of (where each of x and y is an integer from 1 to 3).

[0144] The barrier layer is preferably a single-component vapor-deposited layer comprising at least one of the above-mentioned groups, or comprising a layer comprising SiO2. x A bicomponent vapor-phase deposition layer consisting of at least one combination of two components from the group consisting of Al2O3, SiO / ZnO, SiO / CaO, SiO / B2O3 and CaO / Ca(OH)2.

[0145] Understandably, various processes can be used to vapor-deposit metals and metal oxides. For example, in various embodiments, chemical vapor deposition (CVD) or physical vapor deposition (PVD) processes can be used to vapor-deposit metal or metal oxide coatings. Generally, most CVD processes are likely suitable due to the stability of metals, metal oxides, and metal oxide precursors.

[0146] In some embodiments, plasma-assisted chemical vapor deposition (PCVD) processes can be used to form vapor-deposited inorganic coatings. PCVD is an improved chemical vapor deposition process in which the thermal activation energy is provided by high-energy plasma instead of direct heat. A PCVD process that can be used for the films described herein includes the steps of: vaporizing a metal or metal oxide precursor; introducing plasma to thermally modify the precursor and form an intermediate compound; and cooling the intermediate compound to form a coating on at least one surface of the structure to be coated. PCVD processes can be particularly advantageous because such processes provide the thermal energy required for vapor deposition without melting or otherwise damaging the structure to be coated.

[0147] To form metal oxide coatings, various precursor compounds can be vaporized. For example, tetramethylsilane (“TMS”) and trimethylaluminum (“TMA”) can be vaporized, respectively, to form silicon dioxide (“SiO2”) and aluminum oxide (“Al2O3”) coatings. Hexamethyldisilazane (“HMDS”), hexamethyldisiloxane (“HMDSO”), and tetraethyl orthosilicate (“TEOS”) can be similarly vaporized to form silicon oxide (“SiO2”) coatings. x ")coating.

[0148] In some implementations, atomic layer chemical vapor deposition (ALVDC) can be used alternatively. ALVDC is a chemical vapor deposition process based on sequential, self-saturating surface reactions. In such a process, a metal oxide precursor is pulsed into the chemical vapor deposition chamber and deposited layer by layer.

[0149] In some embodiments, physical vapor deposition (PVD) processes may be used alternatively. Unlike chemical vapor deposition (CVD), PVD processes use physical methods such as heating or sputtering to generate vapor from a solid precursor. The vaporized compound is adsorbed onto the substrate to be coated to form a thin layer directly. In some embodiments, suitable PVD processes for forming inorganic layers may include sputtering, such as magnetron sputtering, thermal evaporation, and electron beam (“e-beam”) evaporation.

[0150] Understandably, physical vapor deposition processes do not require the use of precursor compounds; instead, they directly vaporize the material used for the final coating. For example, an alumina coating can be formed on the surface of the structure to be coated by sputtering or electron beam evaporation of solid aluminum granules or particles.

[0151] In some implementations, the inorganic barrier coating can be applied alternatively by sputtering, ion plating, or via another sol-gel method.

[0152] The specific choice of inorganic coating will depend on the end application. Generally speaking, metal oxides are more brittle than metals, while metals can be slightly more flexible than metal oxides. In some implementations, we have found that if we use aluminum to form the inorganic barrier layer, we can obtain lower moisture permeability than if we use silicon oxide. Compared to using metals, metal oxide coatings tend to form multiple microcracks extending within the inorganic coating more easily, which can be detrimental to optimizing moisture and oxygen permeability. On the other hand, some metal oxides form very transparent inorganic barrier layers, while some metals produce very opaque inorganic barrier layers. This can be important if it is necessary to maximize the recyclability of the paper and minimize any optical defects in the recycled paper, or to construct a translucent barrier paper laminate so that the product inside the packaging is visible. Therefore, in some implementations, metal oxide barrier coatings may be preferred, even if the barrier properties are not as good as those achieved via metal barrier coatings.

[0153] According to certain embodiments, a vapor-deposited inorganic coating can be bonded directly or indirectly to a biodegradable primer layer. For example, in some embodiments, an inorganic vapor-deposited coating can be applied directly to an untreated primer layer using a chemical vapor deposition process as described above. As used herein, an untreated primer layer refers to a layer that has not undergone any treatment steps such as ablation after being formed on top of a biodegradable polymer layer. It is understood that certain vapor deposition processes can eliminate the need for treatment steps. For example, plasma-assisted chemical vapor deposition processes inherently clean the primer layer and minimize any need to prepare the primer layer prior to applying the inorganic coating.

[0154] Alternatively, in some embodiments, the vapor-deposited inorganic coating may be applied to the biodegradable primer layer after a primer layer has been prepared, for example, by cleaning. It is understood that cleaning the water-soluble layer can promote improved adhesion of the vapor-deposited inorganic coating and can minimize any defects in the inorganic coating. Generally, the primer layer can be cleaned by any suitable method. For example, in some embodiments, the water-soluble layer can be cleaned by solvent treatment or physical abrasion. In some embodiments, the primer layer can be cleaned by an ablation process. In such embodiments, one or more surfaces of the primer layer may be at least partially ablated to remove any undesirable material before the application of the vapor-deposited inorganic coating. Additionally, certain ablation processes, such as plasma ablation, can also functionalize the surface and provide functional groups to enable adhesion of the vapor-deposited inorganic coating. Generally, any suitable ablation process can be used, including, for example, plasma treatment, solvent treatment, flame treatment, photon ablation, electron beam irradiation treatment, ion bombardment treatment, ultraviolet treatment, vacuum annealing, or physical abrasion. For example, in some embodiments, prior to vapor deposition of the inorganic coating, the surface of the water-soluble layer can be ablated using helium-oxygen plasma or argon-oxygen plasma at a power of 100 W to approximately 150 W and a flow rate of 30.0 L / min. Other gases may also be used for plasma ablation, including nitrogen and ammonia. It is understood that in various embodiments, the surface of the primer layer may be partially ablated, substantially completely ablated, or completely ablated.

[0155] In some embodiments, corona treatment can be used to alter the surface energy of the first or second biodegradable primer layer and / or to clean it. This can make the inorganic barrier layer more likely to adhere to the second biodegradable polymer layer or make the second biodegradable polymer layer more easily adhered to.

[0156] In some embodiments, two or more physically separate vapor-deposited inorganic coatings may be applied to the structure. In some embodiments, the inorganic barrier coatings may be stacked on top of each other. In other embodiments, a biodegradable primer layer is used between each inorganic barrier coating to protect them. Each additional vapor-deposited inorganic coating may be applied in a manner similar to the aforementioned vapor-deposited inorganic coatings, or alternatively, they may be applied in a different manner.

[0157] A diagram is shown on page 39 of the fourth edition of the Metallization Technology Reference published by the Association of Industrial Metallizers Coaters and Laminators, illustrating a typical apparatus for applying an inorganic barrier coating to a roll of substrate.

[0158] Preferably, the thickness of the inorganic barrier coating is 2 nm to 1,000 nm, more preferably 10 nm to 200 nm, and even more preferably 20 nm to 100 nm. Alternatively, the thickness ratio of the inorganic barrier layer to the biodegradable polymer layer is about 20 to about 20,000.

[0159] Biodegradable adhesive layer

[0160] In some embodiments, a preferred biodegradable adhesive layer adheres the formed biodegradable film to the remainder of the structure of the biodegradable and recyclable barrier paper layer assembly. Such adhesives can be solution-based or solvent-based adhesive compositions. Non-limiting examples of biodegradable adhesive layers may include biodegradable polyvinyl acetate, starch, maltodextrin, natural waxes, artificial waxes, and polyester-polyurethane blends. In some embodiments, the biodegradable adhesive layer may be a commercially available grade from BASF, such as Epotal 3675, Epotal 3702, or Epotal P100ECO, all of which are biodegradable and compostable. In other embodiments, the adhesive may be from Berkshire Labels. Or Bostik 43298 Thermogrip hot melt adhesive. In some embodiments, the adhesive may be Morchem compostable bio-adhesive, such as their grades PS255+CS95 (25% solids).

[0161] In some implementations, soluble binders can have the benefit of enhancing recyclability in typical paper repulping systems because they can accelerate the barrier against paper structure breakage, which brings similar advantages to biodegradation processes.

[0162] In some embodiments, in order to minimize the thickness of the adhesive layer, it is preferable to deposit the adhesive from the solution.

[0163] In some embodiments, the adhesive is preferably laid in continuous layers to achieve maximum bond strength between layers. However, in other embodiments, the adhesive is preferably laid in discontinuous layers to maximize the rate at which the entire structure can break down during paper recycling or biodegradation.

[0164] In some cases, if the adhesive is very thin, can be safely dispersed, and if it is based on specific chemical properties that do not cause ecotoxicity issues, then the use of non-biodegradable adhesives can be considered safe. Possible options include polyurethane-based adhesives or ionomer-based adhesives.

[0165] Non-aqueous biodegradable polymers

[0166] For the use of biodegradable and recyclable barrier paper laminates in many packaging applications (e.g., single-use or limited-use pouches) or other forms of packaging, at least one outer layer is required to be suitable for heat sealing. In some embodiments, in addition to serving as a laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer, a described aqueous biodegradable polymer layer (water-soluble or water-insoluble) may also be used as the heat-sealing layer. Such layers have been previously described. However, in some other embodiments, a non-aqueous biodegradable polymer layer may be preferred to form the heat-sealing layer of this structure.

[0167] Many biodegradable polymer compositions are not readily available in aqueous form at present (although they may be in the future), but offer significant advantages when used as heat-sealing layers, such as resistance to high humidity conditions, enabling them to form stable heat-sealing layers in many different environments while remaining biodegradable. Non-aqueous compositions must be applied using methods different from those used for applying aqueous biodegradable polymer layers.

[0168] Examples of polymers suitable for heat sealing but not typically available in aqueous form (although they may be available in slurries) include biodegradable thermoplastics selected from the group consisting of: aliphatic aromatic polyesters (e.g., those from BASF). ), certain thermoplastic starches (e.g., MATER-BI from Novamont or from Plantic / Kuraray) ), polybutylene succinate and its copolymers (e.g., from ShoWa High polymer Co. Or from Mitsubishi Chemicals PBSA), polycaprolactone, poly(adipate-co-butylene terephthalate), polylactic acid and mixtures / blends thereof.

[0169] Other biodegradable polymers, sometimes available in aqueous form but sometimes only in thermoplastic form, include previously described PHAs and PHA copolymers, such as poly(β-hydroxyalkanoates), and NODAX, derived from Danimer, a poly(3-hydroxybutyrate-copolymer-3-hydroxyhexanoate). TMAnd poly(3-hydroxybutyrate-copolymer-3-hydroxyhexanoate) derived from Kaneka. Non-limiting examples of PHA copolymers include those described in U.S. Patent No. 5,498,692. Other PHA copolymers can be synthesized by methods known to those skilled in the art, such as ring-opening polymerization of microorganisms, β-lactones, dehydration condensation of hydroxyalkyl acids, and dealcoholization condensation of alkyl ethers of hydroxyalkyl acids, as described in Volova, “Polyhydroxy Alkanoates Plastic Materials of the 21st Century: Production, Properties and Applications,” Nova Science Publishers, Inc., (2004), which is incorporated herein by reference.

[0170] In some cases where biodegradation is only possible in industrial composting conditions, there may be preferred embodiments in which the heat-sealing layer is made of a biodegradable polymer based on polylactic acid (PLA) or other polymers that are only biodegradable in industrial composting conditions. However, in some cases, when a polymer that is only compostable in industrial composting facilities (e.g., PLA) is blended with a polymer that is more prone to biodegradation (e.g., PHA), resulting in a very small PLA region within the blend, the PLA blend may indeed undergo biodegradation in home composting conditions, not just in industrial composting facilities.

[0171] Selection of biodegradable polymers for laminates and / or heat-sealing layers

[0172] When the biodegradable polymer coating used for the heat-sealing layer is not water-based, it can be applied via hot extrusion coating, hot lamination, or adhesive lamination processes. If adhesive lamination is used, the biodegradable adhesive layer needs to be applied directly to the second biodegradable primer layer or directly to the inorganic barrier layer. A preform is then applied to the biodegradable adhesive layer. The biodegradable polymer composition can be formed into a preform using various methods, including solution casting, hot-cast film extrusion, and hot-blown film extrusion. Alternatively, if hot extrusion coating is used, the biodegradable polymer composition is melted within an extruder; the molten biodegradable polymer composition is hot-extruded onto the surface of the second biodegradable primer layer or directly onto the inorganic barrier coating; subsequently, the second biodegradable polymer composition is cooled to form the second biodegradable polymer layer.

[0173] In some embodiments, the biodegradable polymer layer used as the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer is preferably aqueous rather than non-aqueous. This is because a thinner, flatter, and more uniform biodegradable polymer layer can typically be formed compared to if the biodegradable polymer layer were extruded and coated onto the surface of the biodegradable and recyclable paper layer. In some embodiments, it is preferred that the biodegradable polymer layer used as the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer is soluble, as this increases the rate at which the two layers can be separated in a typical paper repulping unit and thus increases the likelihood of the entire structure being recyclable in a typical paper recycling stream. In some embodiments, it is preferred that the biodegradable polymer layer used as the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer is soluble and laid with an aqueous composition, because such a biodegradable polymer layer would be very flat (to help maximize the barrier properties of the entire structure), and its soluble nature would minimize the time the paper breaks down in a typical paper repulping stream.

[0174] In some embodiments, the laminate between the biodegradable and recyclable paper layer and the biodegradable primer layer may need to be laid with a non-aqueous composition. This embodiment is generally less preferred because it cannot utilize the thinner, flatter, and more uniform layer that can typically be formed when coated with an aqueous composition. However, there may be certain situations where this option still needs to be chosen.

[0175] If hot extrusion coating is used to apply a non-aqueous composition, the biodegradable polymer composition is melted in an extruder; the molten biodegradable polymer composition is hot-extruded onto the surface of a biodegradable and recyclable paper layer, and then cooled to form a first biodegradable polymer layer.

[0176] An alternative option is to apply the layer via adhesive lamination, although this would be less preferred as it would increase the overall thickness and the total number of layers in the structure. If this arrangement is used, the biodegradable adhesive layer needs to be applied directly to the biodegradable and recyclable paper layer. The preform is then applied to the biodegradable adhesive layer. The biodegradable polymer composition can be formed into a preform using various methods, including solution casting, hot-cast film extrusion, and hot-blown film extrusion. A biodegradable primer layer is then coated onto it.

[0177] In some cases, thermal lamination can be used to adhere a biodegradable and recyclable paper layer to a biodegradable polymer layer.

[0178] Regardless of the application method, in some implementations, it may be advantageous to optimize the sealing of the heat-sealing layer using commercial equipment by using a biodegradable polymer layer with a lower melt temperature rating compared to the rating of the lamination between the biodegradable and recyclable paper layer and the biodegradable primer layer.

[0179] Method for preparing biodegradable and recyclable barrier paper laminates

[0180] There are many non-limiting embodiments of the method for preparing the biodegradable and recyclable barrier paper laminate described herein. For example... Figure 8 As illustrated, a biodegradable and recyclable barrier paper laminate 150 with an inorganic barrier layer can be prepared in multiple steps under specific conditions by coating a biodegradable polymer layer, a biodegradable primer layer, and an inorganic barrier layer on top of a biodegradable and recyclable barrier paper layer. Different embodiments will involve different combinations of methods for completing the biodegradable barrier paper laminate and may include coating and drying of aqueous polymer compositions (some of which are solutions of water-soluble polymers and some of which are emulsions of water-insoluble polymers), a heating step for cases using water-insoluble biodegradable polymer emulsions instead of water-soluble biodegradable polymer solutions, vapor deposition of the inorganic barrier layer, thermal extrusion coating of the biodegradable polymer composition, and adhesive coating of a biodegradable adhesive to adhesively laminate the pre-formed biodegradable polymer layer to the remainder of the structure. Not all embodiments will involve... Figure 8 All the steps shown, Figure 8 Only one example of a specific process that can be used to obtain a particular structure is shown.

[0181] In one embodiment, a method for preparing a first biodegradable and recyclable barrier paper laminate 150 includes the following steps:

[0182] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0183] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0184] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0185] d) Remove any liquid from the first system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0186] e) Apply the vapor-deposited continuous layer 40 of the inorganic barrier layer to the inner surface of the first biodegradable primer layer 30;

[0187] f) Apply the second liquid system of the biodegradable primer composition to the inner surface of the vapor-deposited inorganic barrier layer 40;

[0188] g) Remove liquid from the second aqueous system of the biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0189] h) Apply the second aqueous system of the waterborne biodegradable polymer composition to the inner surface of the second biodegradable primer layer 50;

[0190] i) Remove water from a second aqueous system of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 60.

[0191] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0192] In the second embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 150 includes the following steps:

[0193] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0194] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0195] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0196] d) Remove liquid from the first system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0197] e) Apply the vapor-deposited continuous inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer;

[0198] f) Apply the second liquid system of the biodegradable primer composition to the inner surface of the vapor-deposited inorganic barrier layer 40;

[0199] g) Remove liquid from the second system of the biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0200] h) Melt the second biodegradable polymer composition in an extruder; thermally extrude the molten second biodegradable polymer composition onto the surface of the second biodegradable primer layer 50;

[0201] i) Cool the second biodegradable polymer composition to form a second biodegradable polymer layer 60.

[0202] When the water-based biodegradable polymer composition or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0203] In the third embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 150 includes the following steps:

[0204] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0205] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0206] c) Applying a first aqueous system of the liquid biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0207] d) Remove liquid from the first system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0208] e) Apply a vapor-deposited continuous inorganic barrier layer to the inner surface of the first biodegradable primer layer 30;

[0209] f) Apply the second liquid system of the biodegradable primer composition to the inner surface of the inorganic barrier layer 40;

[0210] g) Remove water from the second system of the biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0211] h) Films made from biodegradable polymer compositions can be obtained individually through a variety of methods, including solution casting, hot casting film extrusion, and hot blown film extrusion.

[0212] i) The film made of the biodegradable polymer composition is applied to the surface of the biodegradable primer layer and thermally bonded together to form a second biodegradable polymer layer 60.

[0213] When the water-based biodegradable polymer composition or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0214] In the fourth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 650 includes the following steps:

[0215] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0216] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0217] c) Applying a first aqueous system of the liquid biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0218] d) Remove liquid from the first system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0219] e) Apply a vapor-deposited continuous inorganic barrier layer to the inner surface of the first biodegradable primer layer 30;

[0220] f) Apply the second liquid system of the biodegradable primer composition to the inner surface of the inorganic barrier layer 40;

[0221] g) Remove water from the second system of the biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0222] h) Apply the biodegradable adhesive 60 to the inner surface of the second biodegradable primer layer 50;

[0223] i) Films made from biodegradable polymer compositions can be obtained individually through a variety of methods, including solution casting, hot casting film extrusion, and hot blown film extrusion.

[0224] j) The membrane made of the biodegradable polymer composition is applied to the surface of the biodegradable adhesive to form a second biodegradable polymer layer 60.

[0225] When the water-based biodegradable polymer composition or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0226] In the fifth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 250 includes the following steps:

[0227] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0228] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0229] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 10;

[0230] d) Remove any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0231] e) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0232] f) Applying a second aqueous system of the aqueous biodegradable polymer composition to the inner surface of the inorganic barrier layer;

[0233] g) Remove water from the second aqueous system of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 60.

[0234] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0235] In the sixth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 250 includes the following steps:

[0236] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0237] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0238] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0239] d) Remove any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0240] e) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0241] f) Melting the second biodegradable polymer composition in an extruder;

[0242] g) The molten second biodegradable polymer composition is thermally extruded onto the surface of the inorganic barrier layer 40;

[0243] h) Cool the second biodegradable polymer composition to form a second biodegradable polymer layer 60.

[0244] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0245] In the seventh embodiment, the method for preparing the biodegradable barrier paper laminate 250 includes the following steps:

[0246] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0247] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0248] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0249] d) Remove any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0250] e) Apply the vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer;

[0251] f) Films made from biodegradable polymer compositions can be obtained individually by a variety of methods, including solution casting, hot casting film extrusion, and hot blown film extrusion.

[0252] g) The membrane made of the biodegradable polymer composition is applied to the surface of the inorganic barrier layer 40 and thermally bonded together to form a second biodegradable polymer layer 60.

[0253] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0254] In the eighth embodiment, the method for preparing the biodegradable barrier paper laminate 750 includes the following steps:

[0255] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0256] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0257] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0258] d) Remove any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0259] e) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0260] f) Apply the biodegradable adhesive 60 to the inner surface of the inorganic barrier layer 40;

[0261] g) A film 60 made of a biodegradable polymer composition can be obtained individually by a variety of methods, including solution casting, hot casting film extrusion and hot blown film extrusion.

[0262] h) The membrane made of the biodegradable polymer composition is applied to the surface of the biodegradable adhesive to form a second biodegradable polymer layer 60.

[0263] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0264] In the ninth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 450 includes the following steps:

[0265] a) Applying a first liquid system of a biodegradable primer composition to the inner surface of a biodegradable and recyclable paper layer, preferably mechanically varnished and / or sizing, or kraft paper or cellophane to avoid moisture swelling; removing any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer;

[0266] b) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0267] c) Applying a second liquid system of the biodegradable primer composition to the inner surface of the vapor-deposited inorganic barrier layer 40;

[0268] d) Remove liquid from the second aqueous system of the biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0269] e) Apply the aqueous system of the waterborne biodegradable polymer composition to the inner surface of the biodegradable primer layer 50;

[0270] f) Remove water from the aqueous system of the aqueous biodegradable polymer composition to obtain a biodegradable polymer layer 60.

[0271] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0272] In the tenth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 450 includes the following steps:

[0273] a) Applying a first liquid system of a biodegradable primer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling.

[0274] b) Remove any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0275] c) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0276] d) Apply a second liquid system of the biodegradable primer composition to the inner surface of the vapor-deposited inorganic barrier layer 40;

[0277] e) Remove liquid from the second aqueous system of the biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0278] f) Melt the second biodegradable polymer composition in an extruder; thermally extrude the molten second biodegradable polymer composition onto the surface of the second biodegradable primer layer 50;

[0279] g) Cool the second biodegradable polymer composition to form a second biodegradable polymer layer 60.

[0280] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0281] In the eleventh embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 450 includes the following steps:

[0282] a) Applying a first liquid system of a biodegradable primer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling.

[0283] b) Remove any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0284] c) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0285] d) Apply a second liquid system of the biodegradable primer composition to the inner surface of the vapor-deposited inorganic barrier layer 40; remove the liquid from the second aqueous system of the biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0286] e) Films made from biodegradable polymer compositions can be obtained individually through a variety of methods, including solution casting, hot-cast film extrusion, and hot-blown film extrusion.

[0287] f) The membrane made of the biodegradable polymer composition is applied to the surface of the biodegradable primer layer and thermally bonded together to form a second biodegradable polymer layer 60.

[0288] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0289] In the twelfth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 850 includes the following steps:

[0290] g) Apply a first liquid system of the biodegradable primer composition to the inner surface of a biodegradable and recyclable paper layer 10, which is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling.

[0291] h) Remove any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0292] i) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30.

[0293] j) Apply a second liquid system of the biodegradable primer composition to the inner surface of the vapor-deposited inorganic barrier layer 40; remove the liquid from the second aqueous system of the biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0294] k) Apply the biodegradable adhesive layer 60 to the inner surface of the second biodegradable primer layer 50;

[0295] l) Films made from biodegradable polymer compositions can be obtained individually through a variety of methods, including solution casting, hot casting film extrusion, and hot blown film extrusion.

[0296] m) The membrane made of the biodegradable polymer composition is applied to the surface of the biodegradable adhesive to form a second biodegradable polymer layer 60.

[0297] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0298] In the thirteenth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 350 includes the following steps:

[0299] a) Applying an aqueous system of an aqueous biodegradable polymer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling.

[0300] b) Remove water from the aqueous system of the aqueous biodegradable polymer composition to obtain the biodegradable polymer layer 20;

[0301] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0302] d) Remove any liquid from the first system of the aqueous biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0303] e) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0304] f) Apply the second liquid system of the biodegradable primer composition to the inner surface of the vapor-deposited inorganic barrier layer 40;

[0305] g) Remove liquid from the second aqueous system of the biodegradable primer composition to obtain a second biodegradable primer layer 50.

[0306] When the water-based biodegradable polymer or primer composition is not water-soluble, an additional step is usually required to heat the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer. This heating step is usually unnecessary when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0307] In the fourteenth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 550 includes the following steps:

[0308] a) Applying a liquid system of the first biodegradable primer composition to the inner surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling.

[0309] b) Remove liquid from the system of the first biodegradable primer composition to obtain the first biodegradable primer layer 30;

[0310] c) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0311] d) Apply a second liquid system of the biodegradable primer composition to the inner surface of the vapor-deposited inorganic barrier layer 40;

[0312] e) Remove liquid from the second aqueous system of the biodegradable primer composition to obtain a second biodegradable primer layer 50.

[0313] In some cases, it may be necessary to apply a corona treatment to the layer on which a biodegradable polymer layer or primer layer has been added, in order to increase the surface energy of the layer, which in turn will enhance the adhesion between the two layers.

[0314] In the fifteenth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 150 includes the following steps:

[0315] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the surface of a removable flat carrier 80, such as a PET film or a steel strip;

[0316] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0317] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0318] d) Remove water from the first liquid system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0319] e) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0320] f) Apply the second liquid system of the biodegradable primer composition to the inner surface of the inorganic barrier layer 40;

[0321] g) Remove liquid from the second system of the aqueous biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0322] h) Applying a second aqueous system of the aqueous biodegradable polymer composition to the surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0323] i) Combining the outer surface of the second biodegradable primer layer 50 with a second aqueous system of the aqueous biodegradable polymer composition coated on the biodegradable and recyclable paper 10;

[0324] j) Remove water from a second aqueous solution of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 60;

[0325] k) Remove the flat carrier 80 from the resulting biodegradable barrier paper laminate.

[0326] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0327] In the sixteenth embodiment, the method for preparing the second biodegradable and recyclable barrier paper laminate 250 includes the following steps:

[0328] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the surface of a removable flat carrier 80, such as a PET film or a steel strip;

[0329] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0330] c) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0331] d) Apply the liquid system of the biodegradable primer composition to the inner surface of the inorganic barrier layer 40;

[0332] e) Remove liquid from the second system of the aqueous biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0333] f) Applying a second aqueous system of the aqueous biodegradable polymer composition to the surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0334] g) Combining the outer surface of the second biodegradable primer layer 50 with the second aqueous system of the aqueous biodegradable polymer composition coated on the biodegradable and recyclable paper 10;

[0335] h) Remove water from the second aqueous solution of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 60;

[0336] i) Remove the flat carrier 80 from the resulting biodegradable barrier paper laminate.

[0337] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0338] In the seventeenth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 350 includes the following steps:

[0339] a) Applying a first liquid system of a biodegradable primer composition to the surface of a removable flat carrier 80, such as a PET film or steel strip;

[0340] b) Remove water from a first liquid system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0341] c) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0342] d) Apply the second liquid system of the biodegradable primer composition to the inner surface of the inorganic barrier layer 40;

[0343] e) Remove liquid from the second system of the aqueous biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0344] f) Applying a second aqueous system of the aqueous biodegradable polymer composition to the surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0345] g) Combining the outer surface of the second biodegradable primer layer 50 with the second aqueous system of the aqueous biodegradable polymer composition coated on the biodegradable and recyclable paper 10;

[0346] h) Remove water from the second aqueous solution of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 60;

[0347] i) Remove the flat carrier 80 from the resulting biodegradable barrier paper laminate.

[0348] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0349] In the eighteenth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 450 includes the following steps:

[0350] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the surface of a removable flat carrier 80, such as a PET film or a steel strip;

[0351] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0352] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0353] d) Remove water from the first liquid system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0354] e) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0355] f) Applying a second liquid system of the biodegradable primer composition to the surface of a biodegradable and recyclable paper layer 10, which is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling.

[0356] g) Combine the outer surface of the inorganic barrier layer 40 with a second system of a water-based biodegradable primer (still wet) coated on biodegradable and recyclable paper 10;

[0357] h) Remove liquid from the second system of the aqueous biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0358] i) Remove the flat carrier 80 from the resulting biodegradable barrier paper laminate.

[0359] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0360] In the nineteenth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 550 includes the following steps:

[0361] a) Applying a first liquid system of a biodegradable primer composition to the surface of a removable flat carrier 80, such as a PET film or steel strip;

[0362] b) Remove water from a first liquid system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0363] c) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0364] d) Apply a second liquid system of the biodegradable primer composition to the surface of a biodegradable and recyclable paper layer 10, which is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0365] e) Combine the outer surface of the inorganic barrier layer 40 with a second system of an aqueous biodegradable primer (still wet) coated on biodegradable and recyclable paper 10;

[0366] f) Remove liquid from the second system of the aqueous biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0367] g) Remove the flat carrier 80 from the resulting biodegradable barrier paper laminate.

[0368] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0369] In the twentieth embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 950 includes the following steps:

[0370] a) Applying a first aqueous system of an aqueous biodegradable polymer composition to the surface of a removable flat carrier 80, such as a PET film or a steel strip;

[0371] b) Remove water from a first aqueous system of the aqueous biodegradable polymer composition to obtain a first biodegradable polymer layer 20;

[0372] c) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 20;

[0373] d) Remove water from the first liquid system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0374] e) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0375] f) Applying a second aqueous system of the aqueous biodegradable polymer composition to the surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0376] g) Combining the outer surface of the inorganic barrier layer 40 with a second aqueous system of an aqueous biodegradable polymer composition coated on biodegradable and recyclable paper 10;

[0377] h) Remove water from the second aqueous solution of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 60;

[0378] i) Remove the flat carrier 80 from the resulting biodegradable barrier paper laminate.

[0379] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0380] According to the twenty-first embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 150 includes the following steps:

[0381] a) A film 60 made of a biodegradable polymer composition can be obtained individually by a variety of methods, including solution casting, hot casting film extrusion and hot blown film extrusion, the film being as rigid as possible to support the coating to be added;

[0382] b) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer;

[0383] c) Remove water from the first liquid system of the biodegradable primer composition to obtain a first biodegradable primer layer 30;

[0384] d) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 30;

[0385] e) Apply the second liquid system of the biodegradable primer composition to the inner surface of the inorganic barrier layer 40;

[0386] f) Remove liquid from the second system of the aqueous biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0387] g) Applying a second aqueous system of the aqueous biodegradable polymer composition to the surface of a biodegradable and recyclable paper layer, which is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0388] h) The outer surface of the second biodegradable primer layer 50 is combined with a second aqueous system of an aqueous biodegradable polymer composition (still wet) coated on biodegradable and recyclable paper;

[0389] i) Remove water from a second aqueous solution of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 20.

[0390] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0391] According to the twenty-second embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 250 includes the following steps:

[0392] a) A film 60 made of a biodegradable polymer composition can be obtained individually by a variety of methods, including solution casting, hot casting film extrusion and hot blown film extrusion, the film being as rigid as possible to support the coating to be added;

[0393] b) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the polymer film layer 60;

[0394] c) Applying a liquid system of the biodegradable primer composition to the inner surface of the inorganic barrier layer 40;

[0395] d) Remove liquid from the second system of the aqueous biodegradable primer composition to obtain a second biodegradable primer layer 50;

[0396] e) Applying a second aqueous system of the aqueous biodegradable polymer composition to the surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0397] f) Combining the outer surface of the biodegradable primer layer 30 with a second aqueous system of an aqueous biodegradable polymer composition (still wet) coated on biodegradable and recyclable paper;

[0398] g) Remove water from a second aqueous solution of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 20.

[0399] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0400] According to the twenty-third embodiment, the method for preparing the biodegradable and recyclable barrier paper laminate 450 includes the following steps:

[0401] a) A film 60 made of a biodegradable polymer composition can be obtained individually by a variety of methods, including solution casting, hot casting film extrusion and hot blown film extrusion, the film being as rigid as possible to support the coating to be added;

[0402] b) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer 60;

[0403] c) Remove water from a first liquid system of the biodegradable primer composition to obtain a first biodegradable primer layer 50;

[0404] d) Apply a vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer 50;

[0405] e) Apply a second liquid system of the biodegradable primer composition to the surface of a biodegradable and recyclable paper layer 10, which is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling.

[0406] f) The outer surface of the inorganic barrier layer 40 is combined with a second liquid system of a biodegradable primer composition (still wet) coated on biodegradable and recyclable paper;

[0407] g) Remove liquid from the second system of the aqueous biodegradable primer composition to obtain a second biodegradable primer layer 20.

[0408] In some cases, it is preferable to apply the second liquid system of the biodegradable primer composition directly to the inorganic barrier layer, and then apply the biodegradable and recyclable paper directly to the inorganic barrier layer while the inorganic barrier layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0409] According to the twenty-fourth embodiment, the method for preparing the ninth biodegradable and recyclable barrier paper laminate 950 includes the following steps:

[0410] a) A film 60 made of a biodegradable polymer composition can be obtained individually by a variety of methods, including solution casting, hot casting film extrusion and hot blown film extrusion, the film being as rigid as possible to support the coating to be added;

[0411] b) Applying a first liquid system of the biodegradable primer composition to the inner surface of the first biodegradable polymer layer;

[0412] c) Remove water from a first liquid system of the biodegradable primer composition to obtain a first biodegradable primer layer 50;

[0413] d) Apply the vapor-deposited continuous layer of the inorganic barrier layer 40 to the inner surface of the first biodegradable primer layer;

[0414] e) Applying a second aqueous system of the aqueous biodegradable polymer composition to the surface of a biodegradable and recyclable paper layer 10, wherein the paper layer is preferably mechanically varnished and / or sizing, or is kraft paper or cellophane to avoid moisture swelling;

[0415] f) Combining the outer surface of the inorganic barrier layer 40 with a second aqueous system of an aqueous biodegradable polymer composition (still wet) coated on biodegradable and recyclable paper 10;

[0416] g) Remove water from a second aqueous solution of the aqueous biodegradable polymer composition to obtain a second biodegradable polymer layer 20.

[0417] In some cases, it is preferable to apply the second aqueous solution of the water-based biodegradable polymer composition directly onto the second biodegradable primer layer, and then apply biodegradable and recyclable paper directly onto the primer layer while the primer layer is still wet. In other cases, it is preferable to first dry the second aqueous solution of the water-based biodegradable polymer composition on any substrate to which it is placed, and then thermally laminate it to the remainder of the structure. For cases where the water-based biodegradable polymer composition is not water-soluble, an additional step of heating the biodegradable polymer composition to melt it and form a continuous biodegradable polymer layer is usually required; this heating step is generally not required when the biodegradable polymer composition is water-soluble. In some cases, it may be necessary to apply a corona treatment to the layer on which the biodegradable polymer layer or primer layer is added to increase the surface energy of the layer, which in turn enhances the adhesion between the two layers.

[0418] A biodegradable polymer layer is formed from an aqueous solution (for water-soluble polymers).

[0419] To prepare an aqueous biodegradable polymer layer 20 or 60 from a water-soluble aqueous polymer composition, an aqueous polymer solution is typically formed by dissolving a water-soluble polymer in water using a solid form and first applying moderate stirring. The solution is typically 20% by weight of the water-soluble polymer to 80% by weight of water. The aqueous polymer solution is then further combined with other additives, such as plasticizers, under moderate stirring and at high temperature to form an aqueous polymer system. The aqueous polymer system is then coated onto the substrate to be coated. Once coated, the water is removed by convection or diffusion drying methods.

[0420] Unrestricted by theory, the most important material properties of an aqueous polymer system believed to be water-soluble are: a) the solubility of the polymer in water at a given temperature between 20°C and 95°C; b) the viscosity of the aqueous polymer system at that temperature, with higher viscosity being better for maximum differentiation / separation between layers; and c) the wetting of the aqueous polymer system on a range of substrates, with higher wetting being better.

[0421] A biodegradable polymer layer is formed from an aqueous emulsion (for water-insoluble polymers).

[0422] To prepare an aqueous biodegradable polymer layer 20 or 60 from an aqueous polymer composition in which the polymer is water-insoluble, a pre-formed dispersion / emulsion of the biodegradable polymer is obtained from the manufacturer, or, if a pre-formed dispersion / emulsion is not available, it must be formed. The aqueous polymer system is then coated onto the substrate to be coated, and water is removed by convection or diffusion drying. Sufficient heat is then applied to form a continuous polymer layer.

[0423] Unrestricted by theory, the most important material properties of aqueous polymer systems are believed to be: a) the ability of biodegradable polymers to form emulsions in water; b) the viscosity of the aqueous polymer system at that temperature, with higher viscosity being better for maximum differentiation / separation between layers; and c) the wetting of the aqueous polymer system on the substrate to be coated, with higher wetting being better.

[0424] A biodegradable primer layer formed from liquid.

[0425] Some inorganic-organic hybrid primers, such as It will be made from a single liquid, and some versions may be supplied in two liquids held in two different containers, which are then mixed before application. Inorganic-organic blended primers generally must be kept cool before use to prevent premature curing. Other primers, such as PVOH varnishes and shellac, are supplied as a single liquid only. After being applied to the surface, the primer is then heated to remove any water and / or solvents. For some primers, such as inorganic-organic blended polymers, this heating step will also initiate the curing process to harden the primer layer. In some cases, a UV step or electron beam radiation may be used instead of a heating step (or in addition to a heating step) to initiate the curing process, depending on the exact chemistry chosen.

[0426] Aqueous biodegradable polymer solutions, aqueous biodegradable polymer dispersions / emulsions, and liquid biodegradable polymer solutions Application methods of degradable primers

[0427] Several methods are suitable for applying waterborne polymer layers and liquid primer layers, including wire bar coating, comma bar / Mayer bar coating, anilox roller coating, reverse roller coating, slot die extrusion coating, roll-to-roll coating, rotary gravure printing, and spraying. Flexographic printing / anilox rollers, smooth rollers (for thin layers), and slot die coating (primarily for thicker layers) are also available.

[0428] Layers can be applied in a single application or through multiple applications. Multiple layers can be used within a structure and can be adjacent to or separated from other layers.

[0429] In a structure, the various polymer layers or primer layers can have essentially the same chemical composition or different chemical compositions, depending on the desired properties of the overall structure.

[0430] The adhesion between sublayers is provided solely by molecular interactions between biodegradable polymers.

[0431] Especially for biodegradable primers, rotary gravure printing is preferred to obtain very thin layers of 1μm-5μm. Generally, low-viscosity primers are preferred to help produce a very smooth surface.

[0432] Dry aqueous biodegradable polymer solutions, aqueous biodegradable polymer dispersions / emulsions and liquids Biodegradable primer

[0433] The drying process for water-soluble or water-insoluble water-based biodegradable polymer layers or biodegradable primer layers is typically carried out using belt dryers, such as those made by... Those marketed under the trademark Drytec, by Coatema under the trademark ModulDry, and / or by FMP Technologies under the trademarks SenDry or PureDry.

[0434] In some implementations, the substrate is guided through a hot air tunnel by a belt (belt dryer), multiple idlers (roller dryer), or multiple hot air nozzles (non-contact hot air dryer). Without being theoretically limited, the most important parameters of the drying process are believed to be: a) the residence time of the substrate in the hot air tunnel, typically about 50 s for a 60 μm thick aqueous polymer system (where the polymer is water-soluble and contains 25% solids); and b) the temperature of the hot air, typically in the range of 95°C to 120°C; and the flow velocity of the hot air above the substrate, typically about 25 m / s. The heating system can be electric, hot oil, steam, or gas.

[0435] Additional heating step when using water-insoluble polymers

[0436] For aqueous polymer systems where the polymer is water-insoluble, an additional heating step may be required after drying to form a continuous polymer layer, thereby fusing the particles together via melting to facilitate the dispersion / emulsion. In one example of the water-insoluble polymer PHA, after coating the PHA dispersion onto a substrate, the layer is dried at approximately 105°C to remove water, and then the substrate is heated to a higher temperature of 170°C to form a no longer porous, continuous PHA layer. When first dried, the coating is white, porous, and powdery, and then melts into a transparent film within approximately 30 seconds at the higher temperature of 170°C. Both steps can be completed in one step at the higher temperature of 170°C, provided the coating is not too thick.

[0437] Additional information regarding the application of water-based or liquid coatings.

[0438] In some embodiments, it may be preferred that the polymer system is not solely water-based, but rather that the aqueous polymer system also contains 0 to 100% alcohol or another solvent. In this case, a special drying and ventilation system may be required to safely remove the alcohol or solvent.

[0439] Application of thermally extruded biodegradable polymer layers

[0440] In some embodiments, the biodegradable polymer composition must be applied to the remainder of the structure via a lamination method. In one embodiment, lamination involves laying a molten curtain of sealant polymer (which, if desired, becomes a heat-sealing layer of the structure, or can be used as another layer) onto specific layers of a partially formed biodegradable and recyclable barrier paper laminate, moving at high speeds (typically from about 100 ft / min to about 1000 ft / min, preferably from about 300 ft / min to about 800 ft / min) as they come into contact with cold (chilled) rolls. The molten curtain is formed by extruding the sealant polymer through a slit die.

[0441] Applications of thermally extruded biodegradable polymer films

[0442] In some implementations, lamination is achieved by thermally laminating the already produced polymer film to the remainder of the substrate.

[0443] Adhesive layer of biodegradable polymer layer

[0444] In some embodiments, lamination is achieved by coating a solution-based adhesive composition onto a substrate and then applying the resulting film onto the surface of the adhesive. Non-limiting examples have been listed.

[0445] Application of inorganic barrier layers

[0446] As mentioned earlier, there are various ways to apply inorganic barrier layers. For the samples produced, we used a vacuum mesh system manufactured by Leybold of The Fraunhofer Institute for Process Engineering and Packaging IVV in Freising, Germany, to perform physical vapor deposition on the structure using electron beam evaporation. Figure 9The layout inside the vacuum chamber is shown. A substrate roll is placed into the system, and a vacuum is drawn – a process that takes several hours due to the porosity of the paper layers within the substrate. Typically, the system is evacuated to a vacuum of 1.5 × 10⁻⁵ mbar (approximately 0.01 Torr). The maximum roll width that can be placed into the system is 280 mm. The system also cools the substrate roll prior to deposition, causing any residual water to freeze in situ – this is achieved by cooling the roll with liquid nitrogen to a temperature range of -5°C to -10°C. Using a web tension of approximately 50 N, the system unfolds the substrate, which is moving at a web speed in the range of 0.9 m / min to 1.2 m / min. Electron beam evaporation using a metal or metal oxide source is used to generate vapor, which is then deposited onto the substrate as it unfolds. When aluminum is used as the target, the aluminum target used has a purity of 99.999%. To evaporate the aluminum target, a current of 450 mA–500 mA is applied to form an electron beam focused on the target. The coating rate of aluminum is... / Second- Within the range of / second, and thus the net moves at a suitable rate to achieve the desired thickness. Note that these specific machine settings can be changed if different inorganic barrier layer chemistry compositions are used. Once the inorganic coating is applied, the substrate is rolled up again. If necessary, the surface can be cleaned with microwave plasma treatment before coating. Since the layer thickness we apply is in the range of 60nm-120nm, approximately 25m of roll material can be metallized within a day if roll changes are not required, which will require reopening the chamber and several more hours for vacuuming.

[0447] Corona treatment

[0448] In some implementations, it is necessary to increase the surface energy of a particular material layer in order to enhance the adhesion of another material layer to it. This is typically done by applying a corona treatment to the surface, although other methods (such as plasma treatment) can also achieve this. Corona treatment involves generating a discharge from an electrode at the surface of a film or substrate, which then causes an increase in the surface energy of that film or substrate. On an industrial scale, there are many suppliers of roll-to-roll corona treatment equipment, such as Enercon… https: / / www.enerconind.com / web-treating / corona-treatment.aspx For smaller-scale experiments, a handheld corona processor can be purchased.

[0449] Inks, trademarks and decorations

[0450] The biodegradable and recyclable barrier paper laminate according to the invention will be opaque in most cases, but may be translucent in some cases with proper material selection. The biodegradable and recyclable barrier paper laminate according to the invention may include printed areas. Printing can be achieved using standard printing techniques such as flexographic printing, gravure printing, or inkjet printing.

[0451] The biodegradable and recyclable barrier paper laminate according to the present invention can be configured and arranged in numerous ways as packaging. For example, the packaging may include multiple sheets that encapsulate multiple articles. Each of these sheets includes an inner surface and an outer surface. The outer surface and / or inner surface of one or more sheets may include inks or dyes that form trademarks, packaging information, and / or background colors, etc., on the packaging. Trademarks and / or other packaging information associated with the product within the packaging are disposed on the outer surface of at least one sheet. Trademarks may include logos, trade names, trademarks, icons, etc., associated with the product within the packaging. Trademarks are used to inform consumers about the product within the packaging. Packaging information may include the size of the product associated with the product within the packaging, the quantity of the product within the packaging, exemplary images of the product contained in the packaging, recyclability logos, etc.

[0452] In all aspects of this invention, the deposited ink may be solvent-based or water-based, and the pigments within the ink may be organic or inorganic, or a combination of both. In some embodiments, the ink is highly abrasion-resistant. For example, highly abrasion-resistant inks may comprise coatings cured by ultraviolet radiation (UV) or electron beam (EB). In some embodiments, any organic pigments within the ink are derived from petroleum sources. In some embodiments, any organic pigments within the ink are derived from renewable resources such as soybeans or other plants. In some embodiments, if the pigments are organic and designed to be biodegradable, any organic pigments within the ink will also be biodegradable. In other embodiments, any inorganic pigments within the ink will be made from inorganic metal oxides that are safe, dispersible, and environmentally harmless at the levels used, even if they are themselves non-biodegradable.

[0453] Non-limiting examples of inks that are non-biodegradable but do not inhibit biodegradation and can be safely dispersed during biodegradation include ECO-SUREITM from Gans Ink and Supply Co.; and solvent-based inks from EFI. And BioVu™ inks, which are entirely derived from renewable resources (e.g., corn). Others include SunVisto AquaGreen and Aquathene from SunChemicals; and INXhrc from Sakata Inx. TM and GENESIS TM GS.

[0454] Biodegradable inks are not particularly limited and can be, for example, recycled vegetable oil inks, soybean oil inks, etc. Soybean oil inks are obtained by replacing all or part of the petroleum-based solvents and drying oils in conventional inks, and this is advantageous because it allows the ink to easily separate from paper and degrade in soil. Soybean oil inks are commercially available, for example, from TOYO INK MFG.CO.,LTD. or TOPPAN PRINTING CO.,LTD. Another potential biodegradable ink is Blue Iris from Sun Chemicals.

[0455] The ink is present with a thickness of about 0.5 μm to about 20 μm, preferably about 1 μm to about 10 μm, and more preferably about 2.5 μm to about 3.5 μm.

[0456] The biodegradable barrier paper laminate of this disclosure may contain inks and / or dyes to provide a background color to the packaging of this disclosure. To further clarify the background color, it is worth noting that the paper layer includes a base color. The base color of the paper layer is the color of the packaging without inks or dyes. For example, bleached paper is white, unbleached paper is brown, paper derived from grass is green, and paper containing recyclable contents is gray. The background color is any color other than a base color, such as blue, red, green, yellow, purple, orange, black, or combinations thereof. However, if the color is obtained through inks and / or dyes, the background color may also include white, brown, or gray.

[0457] To reduce ink / dye usage and facilitate the recycling process, the natural colors of the paper layers can be utilized. For example, ink / dye can be used to define the background color of panels that are only for consumer use, while the natural colors of the paper layers can be used as the background color for other panels of flexible packaging.

[0458] Surface coating for ink protection

[0459] In some embodiments, the printed surface of the biodegradable barrier paper laminate is surface-coated to protect the ink layer from its physical and chemical environment, thereby enhancing the durability of the paper layer and providing a high-gloss or matte finish. This optional surface coating may be referred to as a varnish, lacquer, or anti-splatter layer. In some embodiments, the surface coating is made of nitrocellulose varnish, acrylic varnish, water-based varnish, or reactive two-component polyurethane varnish. A biodegradable option is preferred. In some preferred embodiments, the surface coating is made of a natural wax that has passed the OECD 301B biodegradability screening test, such as beeswax, rapeseed wax, castor oil, candelilla wax, soybean wax, palm oil wax, or another natural wax, provided that the exposure temperature does not exceed the wax's melting point. In some cases, some paraffin oil-based waxes may also pass OECD 301B. Because the thickness of the surface coating affects the recyclability and biodegradability of packaging made from the recyclable barrier paper laminate of the present invention, a thinner surface coating is preferred. The thickness of the surface coating is preferably between 0.1 μm and 25 μm, more preferably less than 10 μm, and even more preferably less than 5 μm.

[0460] Methods for preparing biodegradable and recyclable paper packaging

[0461] The biodegradable and recyclable barrier paper laminates described herein can be used to form articles, including but not limited to articles in which a typical film or sealable paper will be used as a packaging material. Such articles include, but are not limited to, bags, pouches, sachets, flow wraps, pillowcases, and other containers. Bags, pouches, sachets, flow wraps, pillowcases, and other such containers incorporating the biodegradable and recyclable barrier paper laminates described herein can be prepared in any suitable manner known in the art.

[0462] The biodegradable and recyclable barrier paper laminate prepared according to the present invention can be converted into packaging and articles using a form-fill-seal (FFS) method. Conventional FFS methods typically involve three consecutive steps in which packaging or articles are formed from the paper laminate, filled, and then sealed or closed, as described in U.S. Patent No. 6,293,402, which is incorporated herein by reference. In heat-sealing methods, there exists a temperature range above which the seal will burn out, and below which the seal will not be sufficiently robust. The seal is provided in any sealing manner known to those skilled in the art. Sealing may include applying a continuously heated element to the paper laminate and then removing the element after sealing. The heating element may be a hot bar comprising rotating jaws or heating wheels. Different types of seals include finned seals and overlapping seals.

[0463] Single-channel method

[0464] U.S. Patent No. 4,521,437 describes a well-known sealing single-channel method using a vertical forming and filling machine, which is incorporated herein by reference. In this method, a flat web of material is unwound from a roller and formed into a continuous tube by sealing the longitudinal edges of the film together to form an lap seal (i.e., a fin seal). The resulting tube is pulled vertically downwards to a filling station and collapses at a cross-section located at a sealing device below the filling station. A transverse heat seal is formed by the sealing device at the collapsed portion of the tube, thereby forming an airtight seal across the tube. After the transverse seal is formed, a predetermined volume of material to be packaged (e.g., a flowable material) enters the tube at the filling station and fills the tube upwards from the aforementioned transverse seal. The tube then falls a predetermined distance under the influence of the weight of the material in the tube and the weight of the film propulsion mechanism on the machine. The grippers of the sealing device close, causing the tube to collapse at a second cross-section located above the air / material interface in the tube. The sealing device seals laterally at the second cross-section and cuts the tube. The material-filled portion of the tube is now in the form of a pillow-shaped pouch. In this way, the sealing device seals the top of the filled bag, seals the bottom of the next bag to be formed, and separates the filled bag from the next bag to be formed in one operation.

[0465] Multichannel method

[0466] The packaging of the present invention can also be processed using a multi-channel pouch packaging machine, such as the VEGAPACK300S manufactured by QuadroPack. A high-speed multi-channel pouch processing machine is also described in U.S. Patent No. 6,966,166, which is incorporated herein by reference. The machine used in this method includes two rollers for dispensing sheets of equal-sized web film, multiple sealing devices suitable for such substrates and devices, and pump stations, such as those described below, for inserting contents (e.g., liquids, viscous materials, powders, and other substances) into the film package. Multiple packages can be produced using one or more movable reciprocating carriages that travel with the film flow through the machine, supporting each of the sealing and cutting stations. The sealing devices are applied to all edges except one, thereby forming a bag with a cavity and an opening. The desired contents of the package are inserted into the cavity through the opening. The opening is then sealed and separated from the substrate. A pair of substrate rollers are provided at the substrate roller station. Alternatively, a cutter may be positioned in the middle of a single clamping roller to divide the substrate width into two equal portions. The sheets of paper laminate are propelled through the equipment by a traction wheel station and used to form the front and back sheets of the package. The paper laminates from each roller are guided such that as the two sheets advance through the machine, they are very close to each other and in a parallel relationship. The sealing and cutting equipment includes: longitudinal sealing strips for sealing the vertical edges of the package; unidirectional rollers for holding the paper laminate in place and preventing it from sliding backward; a vertical cutter for cutting the torn slit into the package in the vertical direction; and transverse sealing strips for sealing the package in the horizontal direction. The pump station includes multiple fill dispensers communicating with a storage structure that houses the consumer product in the package. These dispensers are capable of drawing a predetermined amount of consumer product from the reservoir and depositing it into the cavity of the machine-formed paper laminate package. In a preferred embodiment, the pump station and dispensers may be driven by one or more motion-controlled servo motors communicating with a cam system. The amount of consumer product can be varied by exchanging dispensers (different dispensers with more or fewer capacities), changing the stroke of the pump cycle, changing the timing of the pump cycle, etc. Therefore, depending on the size and capacity of the packaging the machine is to form, different quantities of consumer products can be allocated.

[0467] The sealing mechanism can be a heat seal, water seal, moisture seal, ultrasonic seal, infrared seal, or any other type of seal deemed suitable.

[0468] Products

[0469] Plastic film has historically been used as a primary packaging material (store shelf packaging) for many different types of articles, but the recyclable barrier paper laminate of this disclosure can also be used. The material of this invention meets the need for flexible and resilient natural packaging materials. The recyclable barrier paper laminate of this invention meets the need for natural packaging materials that can withstand the harsh conditions of various types of packaging processes. Furthermore, it meets the need for natural packaging materials that exhibit barrier properties and can be easily recycled by consumers. Even further, the recyclable barrier paper laminate of this disclosure meets the need for natural barrier packaging materials that are considered non-plastic by consumers and are technically proven to be non-plastic.

[0470] like Figures 10A-10C As shown, the present invention also includes an article comprising a product composition 400 and a biodegradable and recyclable barrier paper laminate 150 (as previously described), which can be formed into a container 350, such as a bag, pouch, capsule, or bag, to contain the product composition. For simplicity, the article of interest herein will be described in the manner of a biodegradable and recyclable barrier paper bag, but it should be understood that the discussion herein also applies to other types of containers.

[0471] The bag 350 formed by the aforementioned method can be of any form and shape suitable for retaining the composition 400 contained therein until it is desired to release the composition 400 from the biodegradable and recyclable barrier paper laminate bag 350, such as by tearing it open. The bag 350 may include one compartment or two or more compartments (i.e., the bag may be a multi-compartment bag). In one embodiment, the biodegradable and recyclable barrier paper laminate bag 350 may have two or more compartments.

[0472] In one embodiment, a biodegradable and recyclable barrier paper laminate can be sealed onto different biodegradable and recyclable barrier paper laminates that have been prepared in different ways. For example, a translucent biodegradable and recyclable barrier paper laminate can be sealed onto an opaque biodegradable and recyclable barrier paper laminate. This allows consumers to see the product inside the packaging without altering the recyclability of the packaging or reducing the overall barrier properties of the packaging.

[0473] In one embodiment, a biodegradable and recyclable barrier paper laminate can be sealed to a water-soluble barrier film without attached paper. This creates a window into the packaging, allowing consumers to see the product without altering the packaging's recyclability.

[0474] A bag or other container 350 may contain a unit dose of one or more compositions 400 from a series of products, which may include (but is not limited to) containers for consumer products. As used herein, "consumer products" means, for example, materials used in hair care, beauty care, oral care, health care, personal hygiene, and household cleaning. Non-restrictive examples of consumer products include shampoos, conditioning agents, mousses, facial soaps, hand soaps, body soaps, liquid soaps, bar soaps, moisturizers, lotions, shaving liquids, toothpastes, mouthwashes, hair gels, hand sanitizers, laundry detergent compositions, dishwashing liquids, dishwasher detergent compositions, hard surface cleaners, stain removers, fabric strengtheners and / or fabric softeners, cosmetics and over-the-counter medicines, electronic products, pharmaceuticals, confectionery, pet health products, medical cannabis-derived products, industrial hemp-derived products, CBD-based products, other products derived from non-cannabis drugs, vitamins, non-pharmaceutical natural / herbal "health" products, razors, absorbent products, wipes, hair gels, food and beverages, animal-derived foods, menstrual cups, peeling pads, electronic and electrical consumer devices, brushes, applicators, earplugs, eye masks, eye patches, face masks, agricultural products, plant-based foods, plant seeds, pesticides, anticides, alcoholic beverages, animal-derived foods, and new product forms.

[0475] The biodegradable and recyclable barrier paper laminate of this disclosure can be used as a primary packaging material for absorbent articles. As used herein, the term "absorbent article" refers to a device for absorbing and containing excretions, and more specifically, a device placed close to or adjacent to the wearer's body to absorb and contain various excretions from the body. Absorbent articles of this disclosure include, but are not limited to, diapers, adult incontinence briefs, training pants, diaper fasteners, menstrual pads, feminine hygiene pads, incontinence pads, padding, absorbent inserts, sanitary liners, tampons, menstrual pants, sponges, tissues, paper towels, wipes, flannel, etc.

[0476] The composition 400 within bag 350 can be in any suitable form, including but not limited to: powder, solid foam, fiber, solid, granules, liquid, gel, paste, cream, capsule, pill, sugar-coated pill, solid foam, fiber, absorbent article, nonwoven fabric, etc. The bag is particularly suitable for dry products, except for some pastes, gels, and liquid products containing less than 30% water, more preferably less than 20% water. The packaging and articles of the present invention are resistant to consumer products. As used herein, "resistant" means the ability of packaging and articles to maintain their mechanical properties and appearance on their surface without degradation of the packaging and articles through diffusion via consumer products through the packaging material.

[0477] Other product forms (articles) that can be packaged in such packaging and / or alternatively manufactured from biodegradable and recyclable paper barrier linings themselves include disposable aprons, laundry bags and covers, disposable medical bedding, skin patches, face masks, disposable gloves, disposable medical gowns, medical devices, skin wraps, agricultural mulches, shopping bags, refill bags, reloadable components in durable systems, interlayer bags, garbage bags, emergency blankets and clothing, building / building structure wraps and moisture-proof linings, primary packaging for transport such as envelopes and mailbags, automotive wrapping paper (for transporting vehicles), non-absorbent textiles and clothing, and articles that can be used to package clothing such as skirts, shirts, suits and shoes.

[0478] For packaging applications, the different compartments of the multi-compartment bag 350 can be used to separate incompatible ingredients. For example, it may be necessary to separate dry shampoo and dry conditioner or laundry detergent and laundry additives into separate compartments.

[0479] Due to improvements in water vapor and oxygen barrier properties, dyes and fragrances commonly used in some products should exhibit greater stability inside bags made of biodegradable paper barrier laminates compared to bags made of unbarrier paper laminates. Furthermore, the barrier against the migration of oils, surfactants, and other chemicals contained within the packaging may be improved compared to packaging made of unbarrier paper laminates.

[0480] At the end of its lifespan, the packaging can be recycled by consumers using a conventional paper recycling system. The structure will be broken down in a repulping system, allowing the paper's cellulose fibers to be recycled. Any soluble polymers will dissolve and be filtered out, eventually biodegrading, or can be recovered from the wastewater of the recycling plant for reuse. Any insoluble polymers will be captured on the filtration equipment of the paper recycling plant. Any barrier materials are inert, harmless, and naturally occurring, and will be safely dispersed in wastewater. However, if discarded, the packaging will biodegrade within 6 to 12 months.

[0481] To facilitate and promote the recyclability of packaging, packaging made from the structures of this disclosure may contain less than 50% by weight of inks, dyes, barrier layers, polymer layers, adhesives, and / or synthetic fibers. The weight percentage of inks, dyes, barrier layers, polymer layers, adhesives, and / or synthetic fibers in the packaging may be less than 50% by weight, more preferably less than 30% by weight, or most preferably less than 10% by weight, specifically listing all values ​​within these ranges and any ranges arising therefrom. For example, the weight percentage of inks, dyes, barrier layers, polymer layers, adhesives, and / or synthetic fibers in the packaging material may be between 0.1% by weight and 50% by weight, more preferably between 0.1% by weight and 30% by weight, or most preferably between 0.1% by weight and 10% by weight, specifically listing all values ​​within these ranges and any ranges arising therefrom. In a specific example, the amount of inks, dyes, barrier layers, polymer layers, adhesives, and / or synthetic fibers is 5% by weight or less, or between 0.1% by weight and 5% by weight, specifically listing all values ​​within these ranges and any ranges arising therefrom.

[0482] Preferably, the resulting integral package made from the biodegradable and recyclable barrier paper laminate described in this disclosure contains at least 50% by weight of natural cellulose fibers, at least 70% by weight of natural cellulose fibers, or at least 80% by weight of natural cellulose fibers, specifically listing all values ​​within these ranges and any ranges arising therefrom.

[0483] The effectiveness of the recycling process for the packaging materials of this disclosure can be determined by the percentage of recyclability. The packaging materials of this disclosure may exhibit a recyclability percentage of 50% or greater, more preferably 70% or greater, or most preferably 80% or greater, specifically listing all values ​​within these ranges and any ranges arising therefrom. The packaging materials of this disclosure may have a recyclability percentage of 50% to about 99%, more preferably about 85% to about 99%, or most preferably about 90% to about 99%. The recyclability percentage of the packaging materials of this disclosure is determined by test PTS-RH:021 / 97 (draft October 2019) under Category II, as conducted by PapiertechnischeStiftung located at Pirnaer Strasse 37, 01809 Heidenau, Germany.

[0484] Along with the recyclability percentage, the total nonconforming percentage can be determined by Category II of PTS-RH:021 / 97 (October 2019 draft). The total nonconforming percentage of the packaging materials of this disclosure can be less than about 50%, more preferably less than about 30%, or most preferably less than about 10%, specifically including all values ​​within these ranges and any ranges arising therefrom. For example, the total nonconforming percentage of the packaging materials of this disclosure can be from 0.5% to 50%, more preferably from 0.5% to 30%, or most preferably from 0.5% to 10%, specifically listing all values ​​within these ranges and any ranges arising therefrom.

[0485] It is worth noting that the test method PTS-RH:021 / 97 (October 2019 draft) includes a hand-made paper test. Trained screening personnel test one or more sheets of recycled packaging material hand-made paper for visual defects and stickiness. If the number of visual defects is too high or if the hand-made paper is too sticky, the packaging material is rejected. According to the PTS-RH:021 / 97 (October 2019 draft) method, if the number of visual defects is acceptable and the hand-made paper is not too sticky, the packaging material is approved for further processing. When using certain combinations, the packaging materials of this disclosure may produce an acceptable level of appearance defects during this step of the method. For some combinations, if the packaging has passed the repulping test but failed the visual test, additional tests are conducted to understand the packaging's usage in specific countries globally, which may have different quality requirements for incoming recyclable materials.

[0486] Some of the packaging materials in this disclosure can produce the previously mentioned recyclable percentage and pass the paper hand test. Therefore, in those cases, the packaging materials of this disclosure can obtain a "pass" overall score or final result when subjected to the PTS-RH:021 / 97 (October 2019 draft) recycling test method.

[0487] It is also worth noting that alternative methods exist for determining the recyclable percentage of the packaging materials of this disclosure. If the PTS-RH:021 / 97 (October 2019 draft) method is unavailable, a test conducted by the University of Western Michigan can be used. The test conducted by the University of Western Michigan is a repulpability test. The results of the repulpability test provide the percentage yield of the sample material. According to the repulpability test, the packaging materials of this disclosure can achieve a yield percentage greater than about 50%, more preferably greater than about 70%, or most preferably greater than about 80%, specifically listing all values ​​within these ranges and any ranges arising therefrom. The packaging materials of this disclosure can have a pulp yield percentage of 50% to about 99%, more preferably about 85% to about 99%, or most preferably about 90% to about 99%.

[0488] It should also be noted that, generally speaking, the PTS-RH:021 / 97 (October 2019 draft) methodology tends to be more indicative of performance in European paper recycling systems. Furthermore, the expected percentage of recyclability targets vary across different European countries to account for recyclable barrier paper laminates. Typically, targets range from at least 50% recyclability expected in some countries (e.g., France) to at least 80% recyclability expected in others (e.g., Germany). However, the testing methodology conducted by the University of Western Michigan tends to be more indicative of performance in North American paper recycling systems, and typically an 80% yield percentage will be considered recyclable barrier paper laminates in North America. In Asia, no specific recyclability targets or regulations have been established, and therefore we assume that Asian countries will expect at least a 50% recyclability percentage target (as determined by the PTS-RH:021 / 97 (October 2019 draft) method) and / or at least a 50% minimum yield percentage (as determined by the University of Western Michigan testing method) to be considered recyclable in Asia.

[0489] Test methods

[0490] When testing and / or measuring materials, if the relevant test method does not specify a particular temperature, the test and / or measurement shall be performed on the specimens at a temperature of 23°C (±3°C), wherein such specimens have been pre-conditioned to this temperature. When testing and / or measuring materials, if the relevant test method does not specify a particular humidity, the test and / or measurement shall be performed on the specimens at a humidity of 35% (±5%), wherein such specimens have been pre-conditioned to this humidity. Testing and / or measurement shall be performed by trained, skilled, and experienced personnel in accordance with good laboratory practices using appropriately calibrated equipment and / or instruments.

[0491] 1) Biodegradation screening tests OECD 301B and OECD 306

[0492] Ideally, the major components (paper, laminates, primer, barrier layers, sealant) should be tested individually, and then the final packaging should be tested for biodegradability according to OECD 301B. The final packaging includes all major and minor (inks, varnishes) components and is open at one end to simulate disposal after being opened by a consumer. The final packaging should also be tested in seawater according to OECD 306. The pass / fail success criteria are shown in Table 4 below:

[0493] Table 4: OECD Biodegradation Test Methods and Acceptance Standards

[0494]

[0495] The sample should be biodegraded by at least 60% within 60 days, preferably by at least 60% within 30 days.

[0496] Aerobic biodegradability is measured by the amount of carbon dioxide (CO2) produced by the test material, according to the standard test methods defined in OECD Methods 301B and 306. This test is performed according to the specified OECD test protocol, but over a period of 60 days. Preferred polymers should achieve at least 60% biodegradability, as measured by CO2 production over 60 days in standard methods 301B and 306. These OECD test method guidelines are well known in the art and are cited herein as references {OECD (1992) Test No. 306: Biodegradability in Seawater, OECD Guidelines for the Testing of Chemicals, Section 3, OECD Publishing, Paris,} https: / / doi.org / 10.1787 / 9789264070486-en.and OECD (1992), Test No.301: ReadyBiodegradability, OECD Guidelines for the Testing of Chemicals, Section 3, OECD Publishing, Paris, https: / / doi.org / 10.1787 / 9789264070349-en .}

[0497] 2) Dissolution test method

[0498] When tested according to the slide dissolution test, this test method measures the total time for a specific film sample to completely dissolve. This slide dissolution test is test method 205 (MSTM 205) as described in paragraphs 116-131 of U.S. Patent Application Publication US20150093526A1 entitled "Water-soluble film having improved dissolution and stress properties, and packets made therefrom". The entire disclosure is incorporated herein by reference. The dissolution test method used herein is the same as that described in US20150093526A1, except that the temperature of the distilled water is 23°C and the test duration is limited to 24 hours. The results are individual and average disintegration times (time to membrane rupture) and individual and average dissolution times (time to no visible solid residue). Unless explicitly stated otherwise, the dissolution test method uses distilled water maintained at 30°C. The dissolution test method is not applicable to materials other than membranes with a total thickness equal to or less than 3 mm. If the average dissolution time measured according to the dissolution test method is less than 24 hours, the membrane according to the invention is considered to be water-soluble.

[0499] 3) Water vapor transmission rate (WVTR)

[0500] This test method is primarily based on ASTM F1249-13 and is conducted under the following test conditions: the test gas temperature is 38°C (±0.56°C) and its relative humidity is 50% (±3%), or, if tropical conditions are required, the test gas temperature is set to 38°C (±0.56°C) and its relative humidity to 90% (±3%). The carrier gas is 100% N2 (dry). The equipment used to run the test is a Permatran-W water vapor permeability instrument conforming to written specification QMS 702-004. This water vapor permeability test method is not applicable to materials outside the scope of ASTM F-1249-13 (§1.1).

[0501] If the barrier properties of a particular substrate are too poor, especially if the coating on the paper substrate is very thin and the equipment is not properly sealed, it is impossible to measure WVTR by ASTM F1249-13. In these cases, a different test method is used, namely the ASTM E96 cup test method. However, it is still possible to compare the results from the two different test methods. For ASTM E96, if tropical conditions are required, the temperature is 38°C and the humidity is 90% relative humidity, or if tropical conditions are not required, the humidity is sometimes 50% relative humidity.

[0502] For any test method, water vapor transmission rate is expressed in g / m 2 / Daily report. If normalized by barrier thickness, water vapor permeability is expressed in g.μm / m 2 Daily report.

[0503] Unless otherwise specified, all WVTR tests were conducted at the Mocon laboratory in Minneapolis.

[0504] 4) Oxygen permeability (OTR)

[0505] This test method is primarily performed according to ASTM F1927 under the following test conditions: unless otherwise specified, the temperature of the test gas is 23°C (±0.56°C) and its relative humidity is 80% (±3%), and the concentration of the test gas is 100% O2. The carrier gas is 98% N2 and 2% H2, and the carrier gas humidity is 0%. The test gas pressure is 760 mmHg. The equipment used for this test is an Oxtran 2 / 21 oxygen permeability analyzer conforming to test procedure QMS 702-002.

[0506] If the barrier properties of a particular substrate are too poor, especially if the coating on the paper substrate is very thin and the equipment is not properly sealed, it is impossible to measure WVTR by ASTM F1927. In these cases, a different test method, F3136, is used. However, it is still possible to roughly compare the results from the two different test methods. For F3136, the temperature of the test gas is 23°C (±0.56°C) and its relative humidity is 39%, and the concentration of the test gas is 20.9% O2 (indoor air). The equipment used to perform this test is a Mocon OpTech-O2 model P instrument conforming to test procedure QMS 702-002.

[0507] For any test method, oxygen permeability is expressed in cc / m 2 / Daily report. If normalized by barrier thickness, water vapor transmission rate is expressed in cc.μm / m 2 Daily report.

[0508] Unless otherwise specified, all OTR tests were conducted at Mocon's Laboratory in Minneapolis, USA.

[0509] 5) Oil and grease resistance test (box test)

[0510] Grease resistance was measured using the TAPPI T 559cm-12 Grease Resistance Test for Paper and Paperboard. Unless otherwise specified, grease tests were performed at the SGS Integrated Paper Service in Appleton, Wisconsin, USA.

[0511] The samples were tested and conditioned under the TAPPI standard conditions shown in Table 5 below. No pretreatment was performed on the samples.

[0512] Table 5: Tappi Standard Conditions

[0513] indoor conditions

[0514]

[0515] The TAPPI T 559cm-12 grease resistance test report for paper and paperboard samples and samples passing through box 12 is greater than or equal to 12.

[0516] 6) Individual layer thickness

[0517] A 20 μm thick cross-section of the film sample was cut using a sliding slicer (e.g., Leica SM2010 R), placed under a light transmission mode optical microscope (e.g., Leica Diaplan), and imaging analysis software was applied to measure the thickness of individual layers. The layer was also measured using a scanning electron microscope, sometimes supplemented with energy-dispersive X-ray spectroscopy for further comparison of different layers.

[0518] 7) thickness

[0519] The thickness (caliper / thickness) of the monolayer test samples was measured under static load using a micrometer according to the pharmacopoeia method ISO 534, with modifications mentioned herein. All measurements were performed in a laboratory maintained at 23°C ± 2°C and 50% ± 2% relative humidity, with the test samples conditioned in this environment for at least 2 hours prior to testing.

[0520] Thickness is measured using a micrometer equipped with a pressure foot capable of applying a stable pressure of 70 kPa ± 0.05 kPa to the test sample. The micrometer is a static-heavy instrument with readings accurate to 0.1 micrometers. A suitable instrument is the TMI digital micrometer model 49-56, available from Testing Machines Inc., New Castle, DE, or an equivalent. The pressure foot is a flat, circular, movable surface with a diameter smaller than the sample, capable of applying the required pressure. A suitable pressure foot diameter is 16.0 mm. The test sample is supported by a horizontal, flat reference platform that is larger than and parallel to the surface of the pressure foot. Calibrate and operate the system according to the manufacturer's instructions.

[0521] Measurements are performed on single-layer test samples taken from raw material rolls or sheets, or from finished product packaging. When removing test samples from finished packaging, care is taken to avoid contaminating or deforming the sample during the process. The removed sample should be free of residual adhesive and obtained from an area of ​​the packaging free of seams or creases. Ideally, the test sample should be 200 mm in diameter. 2 And it must be larger than the pressure foot.

[0522] To measure thickness, first zero the micrometer relative to a horizontal, flat reference platform. Place the test sample on the platform, with the test position centered below the pressure foot. Gently lower the pressure foot at a rate of 3.0 mm per second until full pressure is applied to the test sample. Wait 5 seconds, then record the thickness of the test sample, accurate to 0.1 micrometers. Repeat this process for a total of ten replicate test samples. Calculate the arithmetic mean of all thickness measurements and report the value as "Thickness," accurate to 0.1 micrometers.

[0523] 8) Basis weight

[0524] The basis weight of the test sample is the mass (in grams) per unit area (in square meters) of a single material layer, and is measured according to the pharmacopoeia method ISO 536. The mass of the test sample is cut into known areas, and the mass of the test sample is determined using an analytical balance accurate to 0.0001 g. All measurements are performed in a laboratory maintained at 23°C ± 2°C and 50% ± 2% relative humidity, and the test samples are conditioned in this environment for at least 2 hours prior to testing.

[0525] Measurements are performed on test samples taken from raw material rolls or sheets, or from finished product packaging. When removing test samples from finished product packaging, care is taken to avoid contaminating or deforming the sample during the process. The removed sample should be free of residual adhesive and taken from an area of ​​the packaging free of any seams or creases. Test samples must be as large as possible to account for any inherent material variability.

[0526] Measure the dimensions of the monolayer test samples using a calibrated steel ruler or equivalent from NIST. Calculate and record the area of ​​the test samples, accurate to 0.0001 square meters. Obtain the mass of the test samples using an analytical balance and record it, accurate to 0.0001 grams. Calculate and record the basis weight by dividing the mass (in grams) by the area (in square meters), accurate to 0.01 grams per square meter (gsm). Repeat this process for a total of ten replicate test samples. Calculate and report the arithmetic mean of the basis weights, accurate to 0.01 grams per square meter.

[0527] 9) Roughness measurement of substrate / individual layer (S) q )

[0528] The root mean square roughness (Sq) was measured using a 3D laser scanning confocal microscope, such as the Keyence VK-X200 series microscope purchased from the Keyence Corporation of America. This microscope includes a VK-X200K controller and a K-X210 30 measurement unit. The manufacturer's software, VK Viewer version 2.4.1.0, was used for data collection, and the manufacturer's software, Multifile Analyzer version 1.1.14.62 and VK Analyzer version 3.4.0.1, were used for data analysis. If desired, the manufacturer's image stitching software, VK Image Stitching version 2.1.0.0, was used. The manufacturer's analysis software, 15377P 22, conforms to ISO 25178. The light source used was a semiconductor laser with a wavelength of 408 nm and a power of approximately 0.95 mW. The sample to be analyzed was obtained by cutting a piece of the article from the article including the area to be analyzed, the size of which was suitable for appropriate analysis under the microscope. To measure the Sq of the etched portion of an article, a sample including the etched area should be obtained, and the analysis should be performed only above the etched portion of the sample. If the sample is not flat but flexible, it can be held downwards on the microscope stage using tape or other means. If measurements would be more accurate when the sample is not flattened due to its shape, flexibility, or other characteristics, a correction can be used, as explained below. Measurement data from the sample are obtained using a 20X objective suitable for non-contact profilometry, such as the 20X Nikon CF IC Epi Plan DI interferometric objective with a numerical aperture of 0.40. Data are acquired using the "Expert Mode" of the acquisition software, where the following parameters are set as described herein: 1) the height scan range is set to cover the height range of the sample (this may vary from sample to sample depending on the surface morphology); 2) the Z-axis step size is set to 0.50 μm; 3) the actual peak detection mode is set to "On"; and 4) the laser intensity and detector gain for each sample are optimized using the automatic gain feature of the instrument control software. Prior to analysis, the data were corrected using the manufacturer's 20Multifile Analyzer software as follows: 1) 3x3 median smoothing, where the center pixel of a 3x3 pixel array is replaced by the median of the array; 2) noise removal using weak height cutting (following the built-in algorithm in the analysis software); and 3) shape correction using waveform removal (0.5mm cutoff). A reference plane was specified using the area setting method, selecting the same area as used for shape removal. Areas including foreign impurities, traces of human intervention during sample collection, or any other obvious anomalies should be excluded from the analysis, and substitute samples should be used for any samples that cannot be accurately measured.The obtained value is the root mean square roughness Sq of the measured portion of the sample. Unless otherwise specified, all percentages are weight percentages based on the weight of the composition. Unless otherwise specifically stated, all ratios are weight ratios. All numerical ranges are narrower ranges including endpoints; the upper and lower limits of the described ranges are interchangeable to further form ranges not explicitly described. The number of significant digits does not limit the quantity indicated or the precision of the measurement. All measurements are understood to be performed at approximately 25°C and ambient conditions, where “ambient conditions” refers to conditions at approximately one atmosphere and approximately 50% relative humidity.

[0529] 10) Heat sealing strength

[0530] Unless otherwise stated, test method ASTM F88-06 is used to measure the heat seal strength of heat seals formed from various barrier paper laminates.

[0531] Example

[0532] The following two compositions used to prepare the soluble layer are used in almost all of the examples listed in this section, therefore the methods for preparing these two compositions are listed here and need not be repeated:

[0533] Preparation of an aqueous laminate composition (named FROZEN 3A)

[0534] Heat 650 g of deionized water to 50 °C in a Thermomix™ 5. Add 400 g of solid PVOH powder (Selvol 205, from Sekisui Chemicals) at a stirring level of 2.5 to 3.0 and set the temperature to 85 °C. When the temperature of 85 °C is reached (within approximately 5 minutes), reduce the stirring level to 1.0 to 1.5 to avoid extreme foaming. After stirring continuously at 85 °C for 30 minutes, the polymer is dissolved. In parallel, mix 100 g of glycerol with 100 g of deionized water at 85 °C. Then, mix the polymer and plasticizer solution together at 85 °C at a stirring level of 1.0–1.5 for approximately 5 minutes. Store the solution at room temperature overnight to eliminate any residual foam.

[0535] Preparation of an aqueous sealing layer composition (named FROZEN 3B)

[0536] Heat 1070 g of deionized water to 50 °C in a Thermomix™ 5. Add 400 g of solid PVOH powder (Selvol 205, from Sekisui Chemicals) at a stirring level of 2.5 to 3.0 and set the temperature to 85 °C. When the temperature of 85 °C is reached (within approximately 5 minutes), reduce the stirring level to 1.0 to 1.5 to avoid extreme foaming. After stirring continuously at 85 °C for 30 minutes, the polymer is dissolved. In parallel, mix 50 g of sorbitol and 50 g of glycerol with 100 g of deionized water at 85 °C. Then, mix the polymer and plasticizer solution together at 85 °C at a stirring level of 1.0–1.5 for approximately 5 minutes. Store the solution at room temperature overnight to eliminate any residual foam.

[0537] Example 1: Biodegradable paper based on a polyvinyl alcohol heat-sealed layer but without a primer or barrier layer Degradable and recyclable barrier paper laminate :

[0538] Under tropical conditions (38°C / 90% RH), PVOH-coated paper exhibits a g / m³ of approximately 1271 g / m³. 2 MVTR per day. Most dry consumer products require much better barrier properties than those, and typically need to be as low as <5 g / m² at 38°C / 90% RH. 2 The moisture barrier permeability is 0.5 days or even lower. Therefore, we generally cannot use PVOH-coated paper alone to manufacture functional packaging; we must add a barrier layer. Furthermore, whatever barrier layer is added to the structure needs to be biodegradable (or safely dispersed once the rest of the structure has biodegraded and decomposed) and recyclable in a conventional paper recycling system. Below, we describe how such an example is prepared so that it can be compared with a later example in which a barrier layer has been added:

[0539] Example 1 was prepared at The Fraunhofer Institute IVV, Freiburg, Germany. :

[0540] In one non-limiting embodiment (HPX-RAW), a 62 μm thick biodegradable and recyclable paper grade, sold in PackPro 7.0 by Brigli and Bergmeister (B&B), is used. The paper has two sides; one side is sized by Brigli and Bergmeister using a mineral coating to prepare for subsequent coating, while the other side is unsized. The sized side of the paper is then coated with a PVOH-based aqueous heat-sealing composition, FROZEN 3B (formulation shown earlier), maintained at 85°C, using an anilox roller. A wet layer of approximately 55 μm thickness is laid. A convection dryer / heater (from...) is used. The solution was dried at 90°C using Drytec (a brand of sorbitol), producing a heat-sealing layer approximately 18 μm thick upon drying. The resulting dry heat-sealing layer consisted of 80% Selvol 205 (obtained from Sekisui Chemicals), 10% glycerol, and 10% sorbitol. The structural layers are summarized in Table 6 below:

[0541] Table 6: Structure of HPX-RAW :

[0542]

[0543] Example 2: Biodegradable based on paper, polyvinyl alcohol laminate, aluminum barrier layer and polyvinyl alcohol heat seal layer And recyclable barrier paper laminate :

[0544] We first constructed a structure without any primer layer designed to maximize the quality and stability of the aluminum layer to understand whether a primer was truly necessary to provide the required range of barrier properties. The structure, made of paper, PVOH, and aluminum, was prepared as described below. If we do not need to use a primer, we can have a simpler structure, reducing manufacturing steps and also minimizing the use of expensive materials, both of which will likely reduce the overall cost of the structure.

[0545] Example 2 was prepared at The Fraunhofer Institute IVV, Freiburg, Germany. :

[0546] In one non-limiting embodiment (HPX-A100-3B), a 62 μm thick biodegradable and recyclable paper grade, sold in PackPro 7.0, from Brigli and Bergmeister (B&B), is used. The paper has two sides; one side is sized by Brigli and Bergmeister using a mineral coating to prepare for subsequent coating, while the other side is unsized. The sized side of the paper is then coated with a PVOH-based aqueous laminate composition, FROZEN 3A (see previously common formulation), maintained at 85°C, using an anilox roller. Moisture from the solution is partially absorbed into the paper, but also removed using a convection dryer / heater (from...). The PVOH layer (from Drytec brand) was dried at 90°C to produce a PVOH layer approximately 9 μm thick upon drying. The resulting dried laminate consisted of 80% Selvol 205PVOH (from Sekisui Chemicals) and 20% glycerol (from Cremer). The prepared roll was then placed in the vacuum system of an electron beam evaporation unit (manufactured by Leybold) and evacuated to create a vacuum – a process that takes several hours due to the porosity of the paper layers within the substrate. Typically, the system is evacuated to 1.5 × 10⁻⁶. - 5A vacuum of mbar (approximately 0.01 Torr) is applied. Once inside the system, the substrate is cooled to a temperature range of -5°C to -10°C with liquid nitrogen before deposition, causing any residual water to freeze in situ. The system then unfolds the substrate, moving at a web speed in the range of 0.9 m / min to 1.2 m / min, using a web tension of approximately 50 N. Electron beam evaporation using an aluminum source is used to generate vapor, which is then deposited onto the substrate as it unfolds. The aluminum target used has a purity of 99.999%. To evaporate the aluminum target, a current of 450 mA–500 mA is applied to the electron source to form an electron beam focused onto the aluminum target. The coating rate of aluminum on the substrate is... / Second- Within the range of / second, and thus the mesh moves at a suitable rate to obtain the desired film thickness. Once the inorganic coating is applied, the substrate is rolled up again. Overall, 100nm of aluminum is applied to the top surface of the substrate to prepare this particular sample. The aluminum source needs to be cooled to prevent oxidation before the vacuum chamber can be opened, so approximately 30 minutes must be waited. After this time, air is allowed into the chamber and the substrate roll can be removed. As the next step, the structure is coated with the water-based heat-sealing layer composition FROZEN 3B, maintained at 85°C, using an anilox roller. A wet layer of approximately 55μm thickness is laid. A convection dryer / heater (from...) is used. The solution was dried at 90°C using Drytec (a brand of dry heat sealant) to produce a heat-sealing layer approximately 18 μm thick when dry. The resulting dry heat-sealing layer consisted of 80% Selvol 205 (obtained from Sekisui Chemicals), 10% glycerol, and 10% sorbitol.

[0547] The details of each layer and their purpose within the resulting structure are summarized in Table 7 below:

[0548] Table 7: Structure of HPX-A100-3B

[0549]

[0550]

[0551] The resulting structure was then subjected to a series of physical tests to assess its suitability for the application. These tests included moisture permeability testing, oxygen permeability testing, grease resistance testing, heat seal strength testing, recyclability testing, and biodegradability testing. The results of these samples are summarized in Table 8 below:

[0552] Table 8: Structure of HPX-A100-3B :

[0553]

[0554] As shown in Table 8, the moisture permeability at 38°C / 90% RH is approximately 264 g / m²·day, which is only 20% of the permeability measured for paper coated with PVOH, but is still quite high and higher than the permeability required for most packaging products. As mentioned earlier, some dry laundry products require a moisture barrier of <5 g / m²·day at 38°C / 90% RH or even lower. However, oxygen permeability and grease resistance are good, and the recycling score for repulped fibers is excellent, at 99.6%. The results confirm the need to explore whether a biodegradable primer, or one that is harmless once the rest of the structure is biodegraded, can further reduce moisture permeability while still allowing the structure to pass repulping tests at a typical paper recycling plant.

[0555] The actual product was prepared at The Procter and Gamble Company, USA, and Mueller Corporation, USA. Example 2 :

[0556] To further explore these primerless structures, we also conducted similar tests at another external laboratory in the United States (Mueller Corporation) to test a wider range of aluminum thicknesses. PackPro 7.0 was first coated with PVOH at The Procter and Gamble Company in West Chester, Ohio, USA, and samples were then sent to Mueller Corporation for aluminum deposition. The samples were then returned to The Procter and Gamble Company, where a top layer of PVOH was coated onto the aluminum before testing the moisture barrier layer. The resulting structures and the obtained results are shown in Table 9 below, which shows samples prepared in a very similar manner to those described above, except for the use of a wider range of aluminum thicknesses.

[0557] Table 9 - Details of Mueller's samples:

[0558]

[0559] The resulting structure was then subjected to a series of physical tests to assess its suitability for the application. These tests included moisture permeability testing, oxygen permeability testing, grease resistance testing, heat seal strength testing, recyclability testing, and biodegradability testing. The results of these samples are summarized in Table 10 below:

[0560] Table 10 - Results from Mueller samples :

[0561]

[0562] As can be seen from Table 10, even when we increased the aluminum layer from 100 nm to 1000 nm, the moisture transmittance of these new structures remained quite high at 38°C / 90% RH. Typically, the moisture transmittance values ​​are much higher than those required for packaging most products. One sample – Mueller-A500-3B – showed an average MVTR of approximately 20 g / m².day, which is better than other metallized samples manufactured at Mueller. However, this is still not good enough for our primary product target of <5 g / m².day MVTR at 38°C / 90% RH. Furthermore, most industrial-scale metallizers do not apply aluminum in the form of a 500 nm thick layer because this would be very expensive; most industrial metallizers apply aluminum layers in the 5 nm–100 nm range for cost-effectiveness and speed. The results further confirm the need to explore whether the primer is biodegradable or harmless once the rest of the structure is biodegraded, while still allowing the structure to pass repulping tests in a typical paper recycling plant.

[0563] Example 3: Based on paper, polyvinyl alcohol laminate, Primer, aluminum barrier layer and polyethylene Biodegradable and recyclable barrier paper laminate for alcohol-based heat-sealing layers :

[0564] Following the results observed in Example 1, we explored biodegradable... The use of a primer. The preparation structure is described below.

[0565] Example 3 was prepared at The Fraunhofer Institute IVV, Freiburg, Germany. :

[0566] In one non-limiting embodiment (HPX-O-A100-3B:KOTH1), a 62 μm thick biodegradable and recyclable paper grade, sold in PackPro 7.0 by Brigli and Bergmeister (B&B), is used. The paper has two sides; one side is sized by Brigli and Bergmeister using a mineral coating to prepare for subsequent coating, while the other side is unsized. The sized side of the paper is then coated with a PVOH-based aqueous laminate composition, FROZEN 3A (see previously known formulations), maintained at 85°C, using an anilox roller. Moisture from the solution is partially absorbed into the paper, but also removed using a convection dryer / heater (from...). The PVOH (Drytec brand) was dried at 90°C to produce a PVOH layer approximately 9 μm thick upon drying. The resulting dried laminate consisted of 80% Selvol 205PVOH (from Sekisui Chemicals) and 20% glycerol (from Cremer). As a next step, liquid was also added to the top using an anilox roller. Primer layer. Then use the same convection dryer / heater maintained at 100°C (from...). Drytec brand) cured The substrate is moved through the dryer at a speed of 5 meters per minute to ensure that the coating remains in the dryer for approximately 1 minute. This curing process forms... The primer layer has a very flat surface, and once dried, it is approximately 3.5 μm thick. To prepare an even more perfect and harder support layer for metallization, we then repeat... The primer layer is applied and cured to create a layer that, once cured, is approximately 9 μm thick in total. During the second curing... After the first layer, an extremely flat and stable surface is formed to receive the subsequent aluminum coating. The prepared roll is then placed in the vacuum system of an electron beam evaporation unit (manufactured by Leybold) and evacuated to create a vacuum—a process that takes several hours due to the porosity of the paper layers within the substrate. Typically, the system is evacuated to 1.5 × 10⁻⁶. -5 A vacuum of mbar (approximately 0.01 Torr) is applied. Once inside the system, the substrate is cooled to a temperature range of -5°C to -10°C with liquid nitrogen before deposition, causing any residual water to freeze in situ. The system then unfolds the substrate, moving at a web speed in the range of 0.9 m / min to 1.2 m / min, using a web tension of approximately 50 N. Electron beam evaporation using an aluminum source is used to generate vapor, which is then deposited onto the substrate as it unfolds. The aluminum target used has a purity of 99.999%. To evaporate the aluminum target, a current of 450 mA–500 mA is applied to the electron source to form an electron beam focused onto the aluminum target. The coating rate of aluminum on the substrate is... Second Within the range of / second, and thus the mesh moves at a suitable rate to obtain the desired film thickness. Once the inorganic coating is applied, the substrate is rolled up again. Overall, 100nm of aluminum is applied to the top surface of the substrate to prepare this particular sample. The aluminum source needs to be cooled to prevent oxidation before the vacuum chamber can be opened, so approximately 30 minutes must be waited. After this time, air is allowed into the chamber and the substrate roll can be removed. As the next step, liquid is also applied using an anilox roller. The third protective layer of primer is added directly on top of the aluminum layer. The same convection dryer / heater (obtained from [source missing]) is used, maintained at 120°C. The coating is cured using Drytec brand products, while the substrate is moved through the dryer at a speed of 5 m / min to ensure the coating remains in the dryer for approximately 1 minute. This curing process results in a layer approximately 3.5 μm thick after drying. Primer layer. Finally, using an anilox roller, coat the structure with the water-based heat-sealing composition FROZEN 3B, maintained at 85°C. Lay a wet layer approximately 55 μm thick. Use a convection dryer / heater (from...) The solution was dried at 90°C using Drytec (a brand of dry heat sealant) to produce a heat-sealing layer approximately 18 μm thick when dry. The resulting dry heat-sealing layer consisted of 80% Selvol 205 (obtained from Sekisui Chemicals), 10% glycerol, and 10% sorbitol.

[0567] Details of each layer and their purpose within the HPX-O-A100-3B:KOTH1 structure, as well as two other structures HPX-O-A120-3B and HPX-O-A60-3B, are summarized in Table 11 below. The other two structures are identical to HPX-O-A100-3B:KOTH1, except that HPX-O-A120-3B has a 120 nm thick aluminum layer (laid out by applying two 60 nm thick aluminum layers) and HPX-O-A60-3B has a 60 nm thick aluminum layer.

[0568] Table 11: Structural Details :

[0569]

[0570]

[0571] The resulting structure was then subjected to a series of physical tests to assess its suitability for the application. These tests included moisture permeability testing, oxygen permeability testing, grease resistance testing, heat seal strength testing, recyclability testing, and biodegradability testing. The results of these samples are summarized in Table 12 below:

[0572] Table 12: Results of physical tests on the structure :

[0573]

[0574] As can be seen from Table 12, the moisture transmittance of the two samples described in this section meets even the WVTR target of our primary product objective at 38°C / 90%RH, which requires a MVTR < 5 g / m²·day (dry laundry detergent) at 38°C / 90%RH. Even samples with an aluminum layer thickness of 60 nm, in addition to the sample with a 100 nm aluminum layer, still meet this WVTR requirement. However, the sample with 100 nm aluminum performs better for oxygen transmittance and is therefore likely preferred overall. The sample with 120 nm aluminum does not perform as well as the sample with a thinner aluminum layer – this is likely because it has been reported that as the layer becomes thicker, in addition to higher application costs, the sample may be more prone to breakage, so it may be best to target with an aluminum layer of 100 nm or less.

[0575] We also evaluated the substrate's ability to transform into a complete package under more stressful high humidity / temperature conditions, such as those found in many parts of the world where the natural moisture level in the air can be very high, even inside air-conditioned buildings. To evaluate this, we placed the HPX-O-A100-3B:KOTH1 substrate in rooms with varying humidity levels. Samples were evaluated every 30 minutes for the first three hours, and then daily for the following week. In particular, we found that a room set at 40°C / 75% RH caused the specific PVOH heat-sealing layer tested to become opaque, swollen, and wrinkled within the first three hours after being placed in that room. This made it difficult to form a good heat seal to create a well-sealed package. (Note: Other PVOH layers used for lamination onto the paper layer did not experience these problems.) Therefore, we concluded that the HPX-O-A100-3B:KOTH1 structure would be best suited for use in areas of the plant with very well controlled humidity levels to prevent humidity from rising too high until the package has fully formed and sealed. For areas where this was not feasible, we decided to explore other options for the polymer used for the innermost layer (i.e., the heat-sealing layer). Some of the examples below are results of this study.

[0576] Example 4: Based on paper, polyvinyl alcohol laminate, Primer, aluminum barrier layer and several alternatives A biodegradable and recyclable barrier paper laminate with a soluble heat-sealing layer. :

[0577] To overcome some of the problems with the soluble PVOH heat-sealing layer explained in Example 3, we prepared some new structures with alternative soluble heat-sealing layers. If entirely possible, we wanted to retain the soluble heat-sealing layer because it makes it easier to pass paper recyclability testing schemes, as it dissolves and breaks down so rapidly in the paper repulping unit. Therefore, we experimented with the PVOH used in Example 3 with the addition of fillers to reduce its moisture sensitivity. We also experimented with different soluble polymers such as PEO and PEO blended with methylcellulose. While attempting to reduce moisture sensitivity, we also needed to ensure that the heat-sealing strength of the soluble heat-sealing layer remained strong. PVOH provided us with a strong seal (Table 12), but we did not know how strong the heat seal would be with other soluble polymers. The rest of the structure remained the same as in Example 3 (HPX-O-A100-3B:KOTH1), while the heat-sealing polymer was changed. The resulting structure is summarized below.

[0578] Additional compositions for soluble heat-sealing layers (other than FROZEN 3A and FROZEN 3B) need to be prepared as follows:

[0579] Preparation of an aqueous PVOH-based sealing layer composition containing microtalc filler (named FROZEN3C)

[0580] Heat 1070 g of deionized water to 50 °C in a Thermomix™ 5. Add 400 g of solid PVOH powder (Selvol 205, from Sekisui Chemicals) at a stirring level of 2.5 to 3.0 and set the temperature to 85 °C. When the temperature of 85 °C is reached (within approximately 5 minutes), reduce the stirring level to 1.0 to 1.5 to avoid extreme foaming. After stirring continuously at 85 °C for 30 minutes, the polymer is dissolved. In parallel, mix 50 g of sorbitol and 50 g of glycerol with 100 g of deionized water at 85 °C. Then, mix the polymer and plasticizer solution together at 85 °C at a stirring level of 1.0–1.5 for approximately 5 minutes. Store the solution at room temperature overnight to eliminate any residual foam. Microtalc (Finntalc M05SL from Mondo Minerals) was added in small steps to a heated (85°C) viscous solution in Thermomix to a level of 40% by weight before use, thereby forming a highly viscous gray dispersion in order to test and reduce the moisture sensitivity of the heat seal to moisture in the air.

[0581] Preparation of an aqueous PEO-based sealing layer composition (named FROZEN 4A)

[0582] 1000 g of deionized water was heated to 60 °C in a Thermomix™ 5. 240 g of solid PEO powder (WSR N-80, from Dow Chemicals) was carefully added gradually at a stirring level of 2.5 to 3.0, and the temperature was set to 85 °C. The polymer was dissolved after stirring continuously at 60 °C for 1 hour. In parallel, 120 g of a 50% glycerol / sorbitol solution was added at 60 °C. Finally, the polymer and plasticizer solutions were mixed together at 60 °C at a stirring level of 2.5 to 3.0 for approximately 5 to 10 minutes. The solution was then stored overnight at room temperature.

[0583] Preparation of an aqueous PEO-based sealing layer composition containing microtalc fillers (named FROZEN 4B)

[0584] 1000 g of deionized water was heated to 60 °C in a Thermomix™ 5. 240 g of solid PEO powder (WSR N-80, from Dow Chemicals) was carefully added step-by-step at 60 °C with a stirring level of 2.5 to 3.0. After stirring continuously at 60 °C for 1 hour, the polymer was completely dissolved. In parallel, a solution of 120 g of 50% glycerol and 50% sorbitol was added at 60 °C. The polymer and plasticizer solutions were mixed together at 60 °C with a stirring level of 2.5 to 3.0 for approximately 5 to 10 minutes. The solution was then stored overnight at room temperature. Microtalc (Finntalc M05SL) was added in small steps with moderate stirring to a level of 40 wt% of the heated (60 °C) solution prior to use to form a highly viscous gray dispersion, in order to test and reduce the moisture sensitivity of the heat-sealed layer to airborne moisture.

[0585] Preparation of an aqueous PEO and methylcellulose-based sealing layer composition (named FROZEN 5)

[0586] First, heat 1000g of deionized water to 60°C in a Thermomix™ 5. Carefully and gradually add 240g of solid PEO powder (WSR N-80, from Dow Chemicals) at 60°C with a stirring level of 2.5 to 3.0. After stirring continuously at 60°C for 1 hour, the polymer is completely dissolved. In parallel, add 120g of a solution of 50% glycerol and 50% sorbitol at 60°C. Mix the polymer and plasticizer solutions together at 60°C with a stirring level of 2.5 to 3.0 for approximately 5 to 10 minutes. Then store the solution at room temperature overnight. Microtalc (Finn talc M05SL) is added in small steps with moderate stirring to 40% by weight of the heated (60°C) solution before use to form a highly viscous gray dispersion, in order to test and reduce the moisture sensitivity of the heat-sealed layer to airborne moisture.

[0587] Second, 1070g of deionized water was heated to 50°C in a Thermomix™ 5. 200g of methylcellulose was carefully added gradually at a stirring level of 2.5 to 3.0, and the temperature was set to 60°C. After stirring continuously at 60°C for 2 hours, the polymer was dissolved. In parallel, 100g of a 50% glycerol + 50% sorbitol solution was added.

[0588] Finally, mix the two polymer solutions at a selected ratio of 50:50 at 60°C with a stirring level of 2.5 to 3.0 for approximately 5 to 10 minutes. The solution is then ready for use.

[0589] The structure of Example 4 was prepared at The Fraunhofer Institute IVV, Freiburg, Germany. :

[0590] In a non-limiting embodiment using an alternative soluble heat-sealing layer, a 62 μm thick biodegradable and recyclable paper grade, sold in PackPro 7.0 from Brigli and Bergmeister (B&B), is employed. This paper has two sides; one side is sized by Brigli and Bergmeister using a mineral coating to prepare for subsequent coatings, while the other side is unsized. The sized side of the paper is then coated with a PVOH-based aqueous laminate composition, FROZEN 3A (see formulation above), maintained at 85°C, using an anilox roller. Moisture from the solution is partially absorbed into the paper, but also removed using a convection dryer / heater (from...). The liquid (Drytec brand) was dried at 90°C to produce a PVOH layer approximately 9 μm thick upon drying. The resulting dried laminate consisted of 80% Selvol 205PVOH (from Sekisui Chemicals) and 20% glycerol (from Cremer). As a next step, an anilox roller was also used to dry the liquid... A primer layer is added on top of the first layer. Then, the same convection dryer / heater (obtained from [source]) is used, maintained at 100°C. Drytec brand) cured The substrate is moved through the dryer at a speed of 5 meters per minute to ensure that the coating remains in the dryer for approximately 1 minute. This curing process forms... The primer layer has a very flat surface, and once dried, it is approximately 4.5 μm thick. To prepare an even more perfect and harder support layer for metallization, we then repeated the bio-... The primer layer is applied and cured to create a layer that, once cured, is approximately 9 μm thick in total. The second layer is cured at 120°C. After the first layer, an extremely flat and stable surface is formed, which is excellent for receiving subsequent aluminum coatings. The prepared roll is then placed in the vacuum system of the electron beam evaporation unit (manufactured by Leybold) and evacuated to create a vacuum—a process that takes several hours due to the porosity of the paper layers within the substrate. Typically, the system is evacuated to 1.5 × 10⁻⁶. -5 A vacuum of mbar (approximately 0.01 Torr) is applied. Once inside the system, the substrate is cooled to a temperature range of -5°C to -10°C with liquid nitrogen before deposition, causing any residual water to freeze in situ. The system then unfolds the substrate, moving at a web speed in the range of 0.9 m / min to 1.2 m / min, using a web tension of approximately 50 N. Electron beam evaporation using an aluminum source is used to generate vapor, which is then deposited onto the substrate as it unfolds. The aluminum target used has a purity of 99.999%. To evaporate the aluminum target, a current of 450 mA–500 mA is applied to the electron source to form an electron beam focused onto the aluminum target. The coating rate of aluminum on the substrate is... / Second- Within the range of / second, and thus the mesh moves at a suitable rate to obtain the desired film thickness. Once the inorganic coating is applied, the substrate is rolled up again. Overall, 100nm of aluminum is applied to the top surface of the substrate to prepare this particular sample. The aluminum source needs to be cooled to prevent oxidation before the vacuum chamber can be opened, so approximately 30 minutes must be waited. After this time, air is allowed into the chamber and the substrate roll can be removed. As the next step, liquid is also applied using an anilox roller. Another protective layer of primer is added directly on top of the aluminum layer. The same convection dryer / heater (obtained from [source missing]) is used, maintained at 120°C. The coating is cured using Drytec brand products, while the substrate is moved through the dryer at a speed of 5 m / min to ensure the coating remains in the dryer for approximately 1 minute. This curing process forms a layer of approximately 3.5 μm after drying. Primer layer. Finally, the structure was coated with an aqueous heat-sealing composition maintained at 85°C using a laboratory coater with wire bars for controlling coating thickness and an oven with a convection dryer. Four different compositions (FROZEN 3C, FROZEN 4A, FROZEN 4B, and FROZEN 5) were used as heat-sealing layers to produce four different new structures: HPX-O-A100-3C, HPX-O-A100-4A, HPX-A100-4B, and HPX-A100-5. For each structure, a wet layer of approximately 55 μm thick from one of the different compositions was laid to prepare each different structure. The water from these solutions was dried at 90°C for 5 minutes using a steady-state convection dryer / heater to produce heat-sealing layers with a thickness in the range of 15 μm–20 μm at the time of drying.

[0591] The details of each layer and their purpose within the resulting structure are summarized in Table 13 below:

[0592] Table 13: Structural details of Example 4 :

[0593]

[0594] Then assess the effect of the resulting structure's heat seal layer itself on... The adhesion of the primer layer. This is important for maintaining the integrity of the packaging. Under high humidity conditions, we found that in addition to wrinkling, it was so poor that it may further cause the heat seal layer to peel off. Beyond the layer peeling, the HPX-O-A100-3B:KOTH1 sample showed improvement in its internal structure. The primer layer has poor adhesion.

[0595] Following this test, we also evaluated the substrate's ability to transform into a complete package under more stressful high humidity / high temperature conditions, such as those found in many parts of the world, where the natural moisture levels in the air can be very high, even inside air-conditioned buildings. To evaluate this, we placed the new substrate in rooms with varying humidity levels. Samples were evaluated every 30 minutes for the first three hours, and then daily for the following week. In particular, we found that a room set at 40°C / 75% RH caused the PVOH heat seal layer to become opaque, swollen, and wrinkled within the first three hours after being placed in that room. This made it difficult to form a good heat seal to create a well-sealed package. The results are summarized in Table 14 below, and for comparison, the results for structures HPX-A100-3B (described in the section of Example 2) and HPX-O-A100-3B:KOTH1 (described in the section of Example 3) are included in Table 14.

[0596] Table 14: Results of the Alternative Heat Sealing Layer :

[0597]

[0598] As shown in Table 14, compared to HPX-O-A100-3B:KOTH1, we observed good results in reducing moisture sensitivity by adding micro-talc as a filler. However, the addition of talc also appeared to reduce the material's ability to be heat-sealed. Furthermore, the addition of talc provided almost no improvement to the internal structure. The adhesion strength between the layer and the heat-sealing layer was assessed. Therefore, we decided to next experiment with adding an insoluble polymer as the heat-sealing layer, which is described in the next embodiment section.

[0599] Example 5: Based on paper, polyvinyl alcohol laminate, Primer, aluminum barrier layer and PBSA heat treatment Biodegradable and recyclable barrier paper laminate for sealing layer:

[0600] In further exploration of a heat-sealing layer that offers lower moisture resistance yet remains heat-sealed, is biodegradable, and does not hinder paper recycling, we decided to experiment with PBSA as the heat-sealing layer. PBSA was chosen because it has passed the OECD 301B biodegradability test, is available in industrial quantities, and companies that have tried using PBSA as a lining for paper coffee cups have reported that it performs better than PE during recycling. PBSA has been reported to swell more than PE in the paper recycling repulping tank and release paper fibers more easily. The rest of the structure remains unchanged, even the PVOH laminate. We know that because PBSA is insoluble, we will need to keep it as thin as possible, or we will be unable to recycle the paper. Therefore, we must experiment with PBSA of different thicknesses to find the correct PBSA thickness that will pass the paper recyclability test.

[0601] At The Fraunhofer Institute IVV, Freiburg, Germany and The Procter&Gamble Structure prepared at Company, West Chester, Ohio, USA. Example 5. :

[0602] In three non-limiting embodiments (HPX-O-A100-PB15:KOTH2, HPX-O-A100-PB-11:KOTH3, and HPX-O-A100-PB-7), a 62 μm thick biodegradable and recyclable paper grade, sold in PackPro 7.0 from Brigli and Bergmeister (B&B), was used. The paper had two sides; one side was sized by Brigli and Bergmeister using a mineral coating to prepare for subsequent coatings, while the other side was unsized. The sized side of the paper was then coated with a PVOH-based aqueous laminate composition, FROZEN 3A (see formulation above), maintained at 85°C, using an anilox roller. Moisture from the solution was partially absorbed into the paper, but also used in a convection dryer / heater (from...). The liquid (Drytec brand) was dried at 90°C to produce a PVOH layer approximately 9 μm thick upon drying. The resulting dried laminate consisted of 80% Selvol205PVOH (obtained from Sekisui Chemicals) and 20% glycerol (obtained from Cremer). As a next step, an anilox roller was also used to remove the liquid. A primer layer is added on top of the first layer. Then, the same convection dryer / heater (obtained from [source]) is used, maintained at 100°C. Drytec brand) cured The substrate is moved through the dryer at a speed of 5 meters per minute to ensure that the coating remains in the dryer for approximately 1 minute. This curing process forms... The primer layer has a very flat surface, and once dried, it is approximately 4.5 μm thick. To prepare an even more perfect and harder support layer for metallization, we then repeat the process. The primer layer is applied and cured to create a layer that, once cured, is approximately 9 μm thick in total. During the second curing... After the first layer, an extremely flat and stable surface is formed, which is excellent for receiving subsequent aluminum coatings. The prepared roll is then placed in the vacuum system of the electron beam evaporation unit (manufactured by Leybold) and evacuated to create a vacuum—a process that takes several hours due to the porosity of the paper layers within the substrate. Typically, the system is evacuated to 1.5 × 10⁻⁶. -5 A vacuum of mbar (approximately 0.01 Torr) is applied. Once inside the system, the substrate is cooled to a temperature range of -5°C to -10°C with liquid nitrogen before deposition, causing any residual water to freeze in situ. The system then unfolds the substrate, moving at a web speed in the range of 0.9 m / min to 1.2 m / min, using a web tension of approximately 50 N. Electron beam evaporation using an aluminum source is used to generate vapor, which is then deposited onto the substrate as it unfolds. The aluminum target used has a purity of 99.999%. To evaporate the aluminum target, a current of 450 mA–500 mA is applied to the electron source to form an electron beam focused onto the aluminum target. The coating rate of aluminum on the substrate is... / Second- Within the range of / second, and thus the mesh moves at a suitable rate to obtain the desired film thickness. Once the inorganic coating is applied, the substrate is rolled up again. Overall, 100nm of aluminum is applied to the top surface of the substrate to prepare this particular sample. The aluminum source needs to be cooled to prevent oxidation before the vacuum chamber can be opened, so approximately 30 minutes must be waited. After this time, air is allowed into the chamber and the substrate roll can be removed. As the next step, liquid is also applied using an anilox roller. The third protective layer of primer is added directly on top of the aluminum layer. The same convection dryer / heater (obtained from [source missing]) is used, maintained at 120°C. The coating is cured using Drytec brand products, while the substrate is moved through the dryer at a speed of 5 m / min to ensure the coating remains in the dryer for approximately 1 minute. This curing process forms a layer of approximately 3.5 μm after drying. Primer layer. Finally, this structure is thermally bonded to PBSA films of various thicknesses—first 15 μm, then 11 μm, and then 7 μm. The PBSA films are first manufactured on the Collins film production line at The Procter and Gamble Company in West Chester, Ohio, USA. Three different film thicknesses are prepared using the hot-cast film extrusion section of the Collins film production line to minimize thickness variation relative to hot-blown film extrusion—although some film manufacturers may be able to achieve low thickness variation even when using blown film units. The bio-PBSA granules are sourced from Mitsubishi, and the grade used is PD92PM, as it is known to have the best biodegradation kinetics for the PBSA / PBS grades sold by Mitsubishi. To cast the film on the Collins film production line, multiple extruder zones of the molten PBSA granules are set to start at 130°C, gradually increasing to 160°C, and then the feed casting die and the casting die itself are set to 160°C. Once formed into a membrane, the membrane is cut and then thermally laminated to the remainder of the structure using a Sky 480R6 lamination unit at The Procter and Gamble Company in West Chester, Ohio, USA, with a lamination roller temperature of 140°C. HPX-O-A100-PB15:KOTH2 was formed using a 15μm PBSA membrane, HPX-O-A100-PB-11:KOTH3 using an 11μm PBSA membrane, and HPX-O-A100-PB-7 using a 7μm PBSA membrane.

[0603] Using multiple laboratory-scale and small-scale supplier groups, the details of each layer and their purpose within the resulting structure are summarized in Table 15 below:

[0604] Table 15: Example 5 at The Fraunhofer Institute IVV, Freiburg, Germany and The Structural details of the composite structure constructed at the assembly point of Procter & Gamble Company, West Chester, Ohio, USA :

[0605]

[0606] In some implementations, we perform [further steps] before thermally or adhesively laminating the PBSA onto it. The layers were subjected to corona treatment. In some cases, we found that before thermally laminating PBS (15 μm), PBS (11 μm), or PBS (7 μm) into the structure, The outer corona treatment improves The lamination strength between the fiber and the corresponding PBSA layer. When corona treatment is performed before any thermal lamination, the fibers tear or rip into other layers of the structure, rather than easily separating the PBSA from the fiber. Peel off.

[0607] At Jura-Plast GmbH / Jura-Tech GmbH (Bavaria, Germany) and ROWO Coatings GmbH The structure of Example 5 was prepared at (Baden-Württemberg, Germany). :

[0608] After constructing the initial material sets outlined in Table 15 using multiple lab-scale and small-scale production line supplier groups, we moved on to constructing large rolls of material for production line trials using different industrial-scale supplier groups. For this larger roll, details of each layer and their purpose within the resulting structure are outlined in Table 16 below. We used a film converter from Jura-Plast GmbH / Jura-Tech GmbH (Bavaria, Germany) to prepare one-meter-wide rolls of complete laminated material. This converter has the capability to coat solutions onto paper and other substrates, blow-extrude films, and bond different layers together. Layer 2 (PVOH FROZEN 3A layer) and layer 3 (…) were bonded together at Jura-Plast GmbH / Jura-Tech GmbH. A layer is coated onto the paper layer. The substrate roll is then sent to a third-party metallizing equipment manufacturer, ROWOCoatings GmbH (Baden-Württemberg, Germany), to apply an aluminum vapor deposition layer, followed by corona treatment. The substrate roll is then returned to Jura-Plast GmbH / Jura-Tech GmbH to apply layer 5 (bioadhesive layer) and layer 6 (PBSA film). In this structure, the second layer is omitted. Layer, because we found that maintaining good barrier properties is not necessary - only the first layer. Layers are required.

[0609] Table 16: Example 5 in Jura-Plast GmbH / Jura-Tech GmbH and ROWO Coatings GmbH Group Structural details of the laminated structure at the junction

[0610]

[0611]

[0612] The details of the method used at Jura-Plast GmbH / Jura-Tech GmbH to construct this laminate are listed below:

[0613] 1. Coating with PVOH solution

[0614] Frozen 3.25% solids, prepared by HPX, diluted to approximately 15% to adjust viscosity and coating basis weight, applied to the glossy surface of Packpro 7.0, coating width: 1.000 mm.

[0615] 1.1 Industrial Partner: Jura-tech GmbH

[0616] 1.1.1 Machine

[0617] Printing press - gravure roller coating unit + dryer

[0618] 1.2.1 Settings: Speed: 30 m / min (limited by the foaming effect of PVOH solution), Dryer temperature: 80℃

[0619] 1.3.1 Results:

[0620] Two PVOH coatings, volume: 6700 linear meters

[0621] Weight: 3g / m2-3.5g / m2 (dry)

[0622] Total thickness: 0.5μm-1μm on the top surface of the paper (measured by SEM).

[0623] 2. Coating with PVOH paint

[0624] 15% solids, prepared by Hubergroup, diluted to approximately 10% to adjust viscosity, coated onto the dual-coating surface of Packpro 7.0, coating width: 1.000 mm.

[0625] 2.1 Industrial Partner: Jura-tech GmbH

[0626] 2.1.1 Machine

[0627] Printing press - gravure roller coating unit + dryer

[0628] 2.2.1 Settings: Speed: 50 m / min, Dryer temperature: 90℃

[0629] 2.3.1 Results:

[0630] Two PVOH paint coatings, volume: 900 linear meters

[0631] Weight: 2g / m² - 2.5g / m² (dry)

[0632] 3. Application of Ormocer paint

[0633] 44% solids, diluted to approximately 25% to adjust viscosity and coating basis weight, coating width:

[0634] 1.000mm

[0635] 3.1 Industrial Partner: Jura-tech GmbH

[0636] 3.1.1 Machine

[0637] Printing press - gravure roller coating unit + dryer

[0638] 3.2.1 Settings: Speed ​​20m / min-50m / min, Dryer temperature: 105℃ + 2 x IR heaters (maximum dryer setting)

[0639] 3.3.1 Results:

[0640] Two Ormocer coatings, volume: 6370 linear meters in three rollers (coated at different speeds).

[0641] Weight: 1.2g / m² - 1.5g / m² (dry)

[0642] Total thickness: 2.2 μm–2.5 μm on top of the PVOH layer (measured by SEM)

[0643] 4. Lamination of PBSA biofilm on aluminized and coated paper

[0644] A 19 μm PBSA membrane produced by jura-plast was laminated using Morchem bio-adhesive (PS 255eco+CS 95, 25% solids). The bio-adhesive was coated onto the PBSA membrane, dried, and then laminated onto an aluminized and varnished paperboard obtained from ROWO.

[0645] Lamination width: 1.000mm

[0646] 4.1 Industrial Partner: Jura-tech GmbH

[0647] 4.1.1 Machine

[0648] Laminating machine - Gravure roller coating unit + dryer

[0649] 4.2.1 Settings: Linear velocity 60 m / min, dryer: 80℃ + IR heater

[0650] (20%), Corona treatment membrane pretreatment: 1500W

[0651] 4.3.1 Results: Biofilm laminated barrier paper, volume: 650 linear meters (good WVTR)

[0652] Adhesive basis weight: 2.5g / m2-3g / m2 (dry)

[0653] Summary of combined results

[0654] The structures produced and shown in Tables 15 and 16 were then subjected to a series of physical tests to assess their suitability for the application. These tests included moisture permeability testing, oxygen permeability testing, grease resistance testing, heat seal strength testing, recyclability testing, and biodegradability testing. The results for these samples are summarized in Table 17 below, and HPX-O-A100-3B:KOTH1 is also shown for reference:

[0655] Physical test results of the structures shown in Tables 17, 15, and 16 :

[0656]

[0657] In addition, the moisture sensitivity of all these options was tested to assess whether the wrinkling problem had been resolved, and the results are summarized in Table 18 below:

[0658] Table 18: Results of Moisture Sensitivity, Heat Seal Strength, and Adhesion Strength :

[0659]

[0660]

[0661] As can be seen from Table 18, as expected, none of the PBSA heat-sealing layers experienced any moisture sensitivity issues. It can also be seen that the heat-sealing strength of the 15μm and 11μm PBSA layers is sufficiently strong, i.e., they meet the requirement limit of at least 3N. We did find that, under normal heat-sealing conditions, the 7μm PBSA layer gave a lower heat-sealing strength of 2.5N, which is below the target if the heat-sealing methods and heat-sealing strips used to date are employed – this value can be increased to meet the target in the future by adjusting the heat-sealing method. Furthermore, replacing the heat-sealing layer with a PBSA layer had almost no effect on moisture permeability at 38°C / 90% RH, and they remained below <5 g / m²·day.

[0662] In addition to the tests already described, some HPX-O-A100-PB11:KOTH3 substrate was formed into pouches. A second product (a beauty care product in dry solid form) was placed inside the pouch, and the last side of the pouch was sealed. The product is known to contain a high percentage of moisturizing oils, and therefore good oil barrier properties are important. The pouches containing the product were subjected to a rapid stability test, which involved placing weights on top of the pouches and exposing them to a high temperature and humidity environment (38°C / 75% RH) for an extended period. After aging, the packaging was observed to understand the product's retention within the packaging. The results showed no oil residue transferred to the outside of the packaging, and therefore the substrate was considered a good barrier layer for the product.

[0663] Example 6: Based on paper, polyvinyl alcohol laminate, alternative biodegradable primer, aluminum barrier layer and polyethylene Biodegradable and recyclable barrier paper laminate for alcohol-based heat-sealing layers :

[0664] We also explored In addition to primers, we offered other supply options. Specifically, we tested a PVOH-based primer from Huber to see if it could provide the same performance as... Same effect. We tested the primer alone and with... A mixed primer was also tested. We also tested removing the top primer and instead placing the PVOH heat-sealing layer directly on top of the aluminum layer. A total of five different new structures were prepared. In two cases, the possibility of using the primer as a heat-sealing layer for the structure was tested, which would simplify the structure as a separate heat-sealing polymer would not be needed, reducing manufacturing costs. In two other cases, a soluble heat-sealing layer was placed on top of the primer layer, so that the soluble polymer, instead of the primer, would act as the heat-sealing layer. In the fifth case, as mentioned earlier, we did not use a primer for the aluminum topcoat at all; instead, we used only the PVOH layer.

[0665] The structure of Example 6 was prepared at The Fraunhofer Institute IVV, Freiburg, Germany. :

[0666] In one non-limiting embodiment (HPX-O-A100-P1, HPX-O-A100-P2, HPX-O-A100-P1-4A, HPX-O-A100-P1-3C, and HPX-O-A100-3B), a 62 μm thick biodegradable and recyclable paper grade, sold in PackPro 7.0 from Brigl and Bergmeister (B&B), was used. The paper had two sides; one side was sized by Brigland Bergmeister using a mineral coating to prepare for subsequent coatings, while the other side was unsized. The sized side of the paper was then coated with a PVOH-based aqueous laminate composition, FROZEN 3A (see formulation above), maintained at 85°C, using an anilox roller. Moisture from the solution was partially absorbed into the paper, but also used in a convection dryer / heater (from...). The liquid (Drytec brand) was dried at 90°C to produce a PVOH layer approximately 9 μm thick upon drying. The resulting dried laminate consisted of 80% Selvol 205PVOH (from Sekisui Chemicals) and 20% glycerol (from Cremer). As a next step, an anilox roller was also used to dry the liquid... A primer layer is added on top of the first layer. Then, the same convection dryer / heater (obtained from [source]) is used, maintained at 100°C. Drytec brand) cured The substrate is moved through the dryer at a speed of 5 meters per minute to ensure that the coating remains in the dryer for approximately 1 minute. This curing process forms... The primer layer has a very flat surface, and once dried, it is approximately 4.5 μm thick. To prepare an even more perfect and harder support layer for metallization, we then repeat the process. The primer layer is applied and cured to create a layer that, once cured, is approximately 9 μm thick in total. During the second curing... After the first layer, an extremely flat and stable surface is formed, which is excellent for receiving subsequent aluminum coatings. The prepared roll is then placed in the vacuum system of the electron beam evaporation unit (manufactured by Leybold) and evacuated to create a vacuum—a process that takes several hours due to the porosity of the paper layers within the substrate. Typically, the system is evacuated to 1.5 × 10⁻⁶. -5 A vacuum of mbar (approximately 0.01 Torr) is applied. Once inside the system, the substrate is cooled to a temperature range of -5°C to -10°C with liquid nitrogen before deposition, causing any residual water to freeze in situ. The system then unfolds the substrate, moving at a web speed in the range of 0.9 m / min to 1.2 m / min, using a web tension of approximately 50 N. Electron beam evaporation using an aluminum source is used to generate vapor, which is then deposited onto the substrate as it unfolds. The aluminum target used has a purity of 99.999%. To evaporate the aluminum target, a current of 450 mA–500 mA is applied to the electron source to form an electron beam focused onto the aluminum target. The coating rate of aluminum on the substrate is... / Second- Within the range of / second, and thus the mesh moves at a suitable rate to obtain the desired film thickness. Once the inorganic coating is applied, the substrate is rolled up again. Overall, 100nm of aluminum is applied to the top surface of the substrate to prepare this particular sample. The aluminum source needs to be cooled to prevent oxidation before the vacuum chamber can be opened, so approximately 30 minutes must be waited. After this time, air is allowed to enter the chamber and the substrate roll can be removed.

[0667] The next step differed among the following five samples. Using a laboratory coater with a wire bar for controlling coating thickness and an oven with a convection dryer, different compositions were used as heat-sealing layers to produce different novel structures: HPX-O-A100-P1, HPX-O-A100-P2, HPX-A100-P1-A4, and HPX-A100-3C and HPX-A100-3B. Water from these solutions was dried at 90°C for 3 minutes using a steady-state convection dryer / heater, producing a solid layer during drying.

[0668] HPX-O-A100-P1: As the next step, a protective layer of liquid PVOH paint / primer is applied directly to the top of the aluminum layer.

[0669] HPX-O-A100-P2: As the next step, it will be used as a PVOH paint / primer with 50% liquid. A protective layer of liquid primer, consisting of 50% blend of the two components, is applied directly to the top of the aluminum layer.

[0670] HPX-O-A100-P1-4A: As the next step, a protective layer of liquid PVOH paint / primer is applied directly to the top of the aluminum layer.

[0671] HPX-O-A100-P1-3C: As the next step, a protective layer of liquid PVOH paint / primer is applied directly to the top of the aluminum layer. Finally, the structure is coated with a water-based heat-sealing composition, FROZEN 3C (PVOH with talc), maintained at 85°C. A wet layer of approximately 55 μm thickness is laid. A convection dryer / heater (from...) The solution was dried at 90°C using Drytec (a brand of styrene), producing a heat-sealing layer approximately 18 μm thick when dry. The resulting dry heat-sealing layer consisted of 48% Selvol 205 (obtained from Sekisui Chemicals), 40% microtalc, 6% glycerol, and 6% sorbitol.

[0672] HPX-O-A100-3B: As a next step, aluminum is coated with the aqueous heat-sealing composition FROZEN 3B, maintained at 85°C, to produce a heat-sealing layer approximately 18 μm thick when dry. The resulting dry heat-sealing layer consists of 80% PVOH, 10% glycerol, and 10% sorbitol.

[0673] The details of each layer and their purpose within the resulting structure are summarized in Table 19 below:

[0674] Table 19: Structural Details :

[0675]

[0676]

[0677] The resulting structure was then subjected to a series of physical tests to assess its suitability for the application. These tests included moisture permeability testing, oxygen permeability testing, grease resistance testing, heat seal strength testing, recyclability testing, and biodegradability testing. The results of these samples are summarized in Table 20 below:

[0678] Table 20: Results of physical tests on the structure :

[0679]

[0680] Results to date indicate that using PVOH varnish as a top primer still provides below-target moisture transmittance, suggesting that the structure can be used for packaging even highly humidity-sensitive dry products. It also shows that PVOH varnish can be used as a heat-sealing layer in the structure, potentially eliminating the need to add additional heat-sealing polymers to the structure. We also found that PVOH varnish is less sensitive to moisture than PVOH alone.

[0681] Results with HPX-O-A100-3B suggest that a primer may not be necessary as a topcoat, although given the results already shown, a bottom primer would be required if both primers were removed. Instead, a soluble polymer layer can be used to cover aluminum and maintain a moisture barrier below the target of <5 g / m².day at 38°C / 90% RH.

[0682] Example 7: Based on paper, polyvinyl alcohol laminate, Primer, SiOx barrier layer and polyethylene Enol heat-sealing layer biodegradable barrier paper composite

[0683] We also explored the use of SiOx barrier layers instead of aluminum barrier layers. SiOx barrier layers tend to be significantly more expensive than aluminum barrier layers and are more brittle, making them difficult to maintain during processing, transportation, and use. However, one advantage is their transparency. One advantage of having transparent barrier layers includes potentially easier visual evaluation in paper recycling program testing. Another advantage is that if translucent paper packaging is required, this can be achieved by combining kraft paper-based transparent paper with a SiOx-based barrier layer. Figure 11 shows a photograph comparing paper samples produced using aluminum barrier layers with those produced using SiOx barrier layers, demonstrating that you can see the paper underneath directly through the SiOx barrier layer—while the aluminum barrier layer is so opaque that you cannot see the paper underneath.

[0684] The structure of Example 7 was prepared at The Fraunhofer Institute IVV, Freiburg, Germany. :

[0685] In the non-limiting embodiments (HPX-O6-SiOx-3B and HPX-O3-SiOx-3B), a 62 μm thick biodegradable and recyclable paper grade, sold in PackPro 7.0 from Brigland Bergmeister (B&B), was used. This paper has two sides; one side was sized by Brigland and Bergmeister using a mineral coating to prepare for subsequent coatings, while the other side was unsized. The sized side of the paper was then coated with a PVOH-based aqueous laminate composition, FROZEN 3A (see formulation above), maintained at 85°C, using an anilox roller. Moisture from the solution was partially absorbed into the paper, but also removed using a convection dryer / heater (from...). The liquid (Drytec brand) was dried at 90°C to produce a PVOH layer approximately 9 μm thick upon drying. The resulting dried laminate consisted of 80% Selvol 205PVOH (from Sekisui Chemicals) and 20% glycerol (from Cremer). As a next step, an anilox roller was also used to dry the liquid... A primer layer is added on top of the first layer. Then, the same convection dryer / heater (obtained from [source]) is used, maintained at 100°C. Drytec brand) cured The substrate is moved through the dryer at a speed of 5 meters per minute to ensure that the coating remains in the dryer for approximately 1 minute. This curing process forms... The primer layer has a very flat surface, and once dried, it is approximately 3 μm thick. The HPX-O3-SiOx-3B sample only has this first layer added. For sample HPX-O6-SiOx-3B, in order to prepare an even more perfect and rigid support layer for depositing the SiOx layer, we then repeated... The primer layer is applied and cured to create a layer approximately 6 μm thick once cured. During the second curing... After the first layer, an extremely flat and stable surface is formed, which is excellent for receiving subsequent SiOx coatings. The prepared roll is then placed in the vacuum system of the electron beam evaporation unit (manufactured by Leybold) and evacuated to create a vacuum—a process that takes several hours due to the porosity of the paper layers within the substrate. Typically, the system is evacuated to 12 × 10⁻⁶. -5 A vacuum of mbar (approximately 0.01 Torr) is applied. Once inside the system, the substrate is cooled to a temperature range of -5°C to -10°C with liquid nitrogen before deposition, causing any residual water to freeze in situ. The system then unfolds the substrate, moving at a web speed in the range of 4 m / min, using a web tension of approximately 50 N. Electron beam evaporation using a SiOx source is used to generate vapor, which is then deposited onto the substrate as it unfolds. The SiOx target used has a purity of >99% (single crystal from Amcor). To evaporate the SiOx target, a current of 85 mA–90 mA is applied to the electron source to form an electron beam focused onto the SiOx target, which is much lower than that required for aluminum coating. The SiOx coating rate on the substrate is... Within the range of / second (greater than aluminum coating), the web is moved at a suitable rate to achieve the desired thickness. Once the SiOx coating is applied, the substrate is rolled up again. Overall, 50nm-60nm of SiOx is applied to the top surface of the substrate to prepare this particular sample. The SiOx source needs to be cooled to prevent thermal shock before the vacuum chamber can be opened, so approximately 30 minutes must be waited. After this time, air is allowed into the chamber and the substrate roll can be removed. As a next step, an anilox roller is also used to apply liquid... Another layer of primer is added directly on top of the SiOx layer. The same convection dryer / heater (obtained from [source missing]) is used, maintained at 120°C. The layer was cured using a Drytec brand, while the substrate was moved through the dryer at a speed of 5 m / min to ensure the coating's residence time within the dryer was approximately 1 minute. Finally, the structure was coated with a water-based heat-sealing composition, FROZEN3B, maintained at 85°C, using an anilox roller. A wet layer of approximately 55 μm thickness was laid. A convection dryer / heater (from Drytec) was used. The solution was dried at 90°C using Drytec (a brand of dry heat sealant) to produce a heat-sealing layer approximately 18 μm thick when dry. The resulting dry heat-sealing layer consisted of 80% Selvol 205 (obtained from Sekisui Chemicals), 10% glycerol, and 10% sorbitol.

[0686] The details of each layer and their purpose within the resulting structure are summarized in Table 21 below:

[0687] Table 21: Structural Details :

[0688]

[0689]

[0690] The resulting structure was then subjected to a series of physical tests, including a water permeability test. The results of these samples are summarized in Table 22 below:

[0691] Table 22: Results of physical tests on the structure :

[0692]

[0693] As can be seen from the table, when using a SiOx barrier layer instead of an aluminum barrier layer, the barrier performance is worse than the target of <5 g / m²·day. Therefore, it cannot be used for products with the highest packaging requirements. However, if the higher cost and more fragile structure can be managed, it is still useful for some products with lower requirements. If a stiffer or higher GSM paper can be used, it can help protect fragile structures to some extent. The table above shows that the brittleness of the samples increases as the primer layer thickness decreases; the HPX-O6-SiOx-3B sample contains a 6 μm thick... The layer, but HPX-O3-SiOx-3B only contains a 3μm thick layer. It has a layer and a much higher water permeability. Besides... Aside from thickness, the two structures are identical in construction. Furthermore, when measured at lower humidity (40°C / 50% RH), the MVTR of this structure is exceptionally low, at 0.732. This clearly demonstrates that humidity significantly impacts the value of this structure.

[0694] Example 8: Based on paper and PHA laminate, Biodegradable barrier paper with SiOx laminate

[0695] Based on the SiOx barrier layer example described in Example 7, we prepared another form of this structure, but using PHA instead of PVOH for heat sealing. The reason for testing PHA is that it actually exhibits better biodegradation kinetics than PVOH, and it may also be less sensitive to humidity than PVOH. We also rearranged these layers in the structure, and their purpose in this structure is summarized in Table 23 below.

[0696] Example 8 was prepared at The Fraunhofer Institute IVV, Freiburg, Germany. :

[0697] In one non-limiting embodiment (HPX-O-A100-3B:KOTH1), a 62 μm thick biodegradable and recyclable paper grade, sold in PackPro 7.0 format by Birgl & Bergmeister (B&B), was used. The paper had two sides; one side was sized by Birgl & Bergmeister using a mineral coating to prepare for subsequent coating, while the other side was unsized. The sized side of the paper was then coated with an aqueous suspension of PHA from Danimer using a laboratory coater equipped with a wire bar coating tool and a convection dryer. Water from the solution was partially absorbed into the paper, but also dried at 120°C using a steady-state convection dryer / heater, producing a PHA layer approximately 9 μm thick when dry. The PHA layer was then heated to a higher temperature of 170°C for 30 seconds using a hot press to form a continuous PHA layer. As a next step, the liquid was also applied using a moving wire bar coating tool. A primer layer is added on top of the PHA layer. Then, the same convection dryer / heater maintained at 120°C is used to dry the product. The layer cures for 5 minutes. This curing process forms a solidified layer. The primer layer has a very flat surface, and once dried, it is approximately 4.5 μm thick. The prepared sheet is then fixed onto a continuous paper roll, placed in the vacuum system of an electron beam evaporation unit (manufactured by Leybold), and evacuated to create a vacuum—a process that takes several hours due to the porosity of the paper layers within the substrate. Typically, the system is evacuated to 1.5 × 10⁻⁶. -5 A vacuum of mbar (approximately 0.01 Torr) is applied. Once inside the system, the substrate is cooled to a temperature range of -5°C to -10°C with liquid nitrogen before deposition, causing any residual water to freeze in situ. The system then unfolds the substrate, moving at a web speed in the range of 4 m / min, using a web tension of approximately 50 N. Electron beam evaporation using a SiOx source is used to generate vapor, which is then deposited onto the substrate as it unfolds. The purity of the SiOx target used is >99%. To evaporate the SiOx target, a current of 85 mA–90 mA is applied to the electron source to form an electron beam focused on the SiOx target, which is much lower than that required for aluminum coating. The SiOx coating rate on the substrate is... The speed is within the range of / second (much slower than aluminum coating), so the web is moved at a suitable rate to achieve the desired thickness. Once the SiOx coating is applied, the substrate is rolled up again. Overall, 50nm-60nm of SiOx is applied to the top surface of the substrate to prepare this particular sample. The SiOx source needs to be cooled to prevent thermal shock before the vacuum chamber can be opened, so approximately 30 minutes must be waited. After this time, air is allowed into the chamber and the substrate roll can be removed. Finally, using a laboratory coater with wire bar coating tools and a convection dryer at 120°C, the SiOx is recoated with an aqueous suspension of PHA from Danimer, producing a PHA layer approximately 10μm thick upon drying.

[0698] Table 23: Structural Details :

[0699]

[0700] The resulting structure was then subjected to a series of physical tests to assess its suitability for the application. These tests included moisture permeability testing, oxygen permeability testing, grease resistance testing, heat seal strength testing, recyclability testing, and biodegradability testing. The results of these samples are summarized in Table 24 below:

[0701] Table 24: Results of Physical Tests of the Structure :

[0702]

[0703] The data above indicate that the specific arrangement actually used did not provide better barrier protection than that of Example 7.

[0704] Preparation of Example 9: Based on paper, polyvinyl alcohol laminate, Primer and no sealant Biodegradable and recyclable barrier paper laminate with aluminum barrier layer :

[0705] HPX-KOTH-IS-1 was constructed on an industrial scale in Example 5. Figure 12 In the process of manufacturing larger rolls of material, additional samples of Example 9 were also produced. These samples were made of the same material as Example 5, but without the adhesive and heat-sealing layers. For this material, details of each layer and their purpose within the resulting structure are summarized in Table 26 below. We used a film converter from Jura-Plast GmbH / Jura-Tech GmbH (Bavaria, Germany) to prepare materials 1 meter wide × 500 meters long for us. This converter has the ability to coat solutions onto paper and other substrates, blow-form films, and bond different layers together. Layer 2 (PVOH FROZEN 3A layer) and layer 3 (…) were bonded together at Jura-Plast GmbH / Jura-Tech GmbH. A layer is coated onto the paper layer. The substrate roll is then sent to a third-party metallizing equipment manufacturer, ROWOCoatings GmbH (Baden-Württemberg, Germany), to apply an aluminum vapor-deposited layer. The substrate roll is then sent back to Jura-Plast GmbH / Jura-Tech GmbH, and then to P&G for further testing. This material can be used to produce samples with different sealing layers.

[0706] Table 25: Example 9 in Jura-Plast GmbH / Jura-Tech GmbH and ROWO Coatings GmbH Group Structural details of the laminated structure at the junction

[0707]

[0708]

[0709] Preparation of Examples 10-12: Based on paper, polyvinyl alcohol laminate, end Paint and having A biodegradable and recyclable barrier paper laminate with a PBAT / TPS blended sealing layer and an aluminum barrier layer. :

[0710] In the non-limiting embodiments of Examples 10-12 described below, which have a PBAT / TPS blend as a sealing layer, HPX-KOTH-IS-1 without an adhesive and sealing layer was prepared from Example 9. A compostable adhesive layer (Epotal CF 430 supplied by BASF) was coated onto the Example 9 material on a vacuum metallized aluminum layer and dried at 80°C for 5 minutes; these samples used a coating weight of 5 gsm. A PBAT film blended with TPS obtained from BiologiQ was then laminated onto the structure at 80°C in a benchtop laminator. The BiologiQ PBAT / TPS samples had a thickness of 20-25 μm and different PBAT:TPS ratios of 95:5, 90:10, and 75:25. The samples were named BQ PBAT / TPS (5%), BQ PBAT / TPS (10%), and BQ PBAT / TPS (25%), and were respectively Examples 10, 11, and 12.

[0711] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the precise numerical values ​​cited. Rather, unless otherwise specified, each such dimension is intended to represent the stated value and a range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “approximately 40 mm”.

[0712] Unless expressly excluded or otherwise limited, every reference cited herein, including any cross-references or related patents or patent applications, and any patent application or patent claiming priority to or benefiting from it, is incorporated herein by reference in its entirety. Reference to any reference is not an endorsement of it as prior art to any disclosed or protected art herein, nor is it an endorsement of any such invention, either on its own or in combination with any one or more references. Furthermore, where any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in referenced documents, the meaning or definition given to that term in this invention shall prevail.

[0713] While specific embodiments of the invention have been illustrated and described by way of example, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications falling within the scope of the invention be covered by the appended claims.

Claims

1. Biodegradable and recyclable barrier paper laminates, including: a) A biodegradable and recyclable paper layer with an outer and inner surface; b) A first biodegradable polymer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable and recyclable paper layer; c) A first biodegradable primer layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable polymer layer; d) An inorganic barrier layer having an outer surface and an inner surface, the outer surface being disposed on the inner surface of the biodegradable primer layer; wherein the inorganic barrier layer comprises at least one of aluminum, alumina, or silicon oxide; e) A second biodegradable primer layer having an outer surface and an inner surface, the inner surface being disposed on the inner surface of the inorganic barrier layer; f) A second biodegradable polymer layer having an outer surface and an inner surface, the inner surface being disposed on the outer surface of the biodegradable primer layer and acting as a heat-sealing layer; The biodegradable and recyclable barrier paper laminate, as determined by test method PTS-RH:021 / 97 (October 2019 draft), is recyclable and exhibits a recyclability percentage of at least 50%; and The biodegradable and recyclable barrier paper laminate described herein exhibits at least 60% biodegradation within 60 days in the OECD 301B test. The primer layer described above is bio-ORMOCER. ® It is at least one of polyvinyl alcohol paint or shellac paint, and has a thickness of 0.1 µm to 30 µm.

2. The biodegradable and recyclable barrier paper laminate according to claim 1, wherein at least one of the biodegradable polymer layers comprises at least one biodegradable polymer, said biodegradable polymer being at least one of polyvinyl alcohol, polyethylene oxide, methylcellulose, sodium alginate, polyhydroxyalkanoates, polybutyl succinate, polybutylene adipate, polybutylene adipate-co-butylene terephthalate, polylactic acid, thermoplastic starch, or blends thereof.

3. The biodegradable and recyclable barrier paper laminate according to claim 2, wherein the polyvinyl alcohol is a partially or completely hydrolyzed homopolymer or copolymer.

4. The biodegradable and recyclable barrier paper laminate according to claim 3, wherein the polyvinyl alcohol is a homopolymer with a degree of hydrolysis of 70% to 100%.

5. The biodegradable and recyclable barrier paper laminate according to claim 2, wherein the polyvinyl alcohol has an average molecular weight of 20,000 Da to 150,000 Da.

6. The biodegradable and recyclable barrier paper laminate according to claim 2, wherein the polyethylene oxide has an average molecular weight of 50,000 Da to 400,000 Da.

7. The biodegradable and recyclable barrier paper laminate according to claim 2, wherein the methylcellulose has an average molecular weight of 10,000 Da to 100,000 Da.

8. The biodegradable and recyclable barrier paper laminate according to claim 2, wherein at least one of the first biodegradable polymer layer or the second biodegradable polymer layer comprises at least one plasticizer.

9. The biodegradable and recyclable barrier paper laminate according to claim 8, wherein the plasticizer is at least one of glycerol, sorbitol, propylene glycol (PG), trimethylene glycol (PDO), trimethylolpropane (TMP), methylpropanediol (MPD), 2-methyl-1,3-propanediol (MPO), and mixtures thereof.

10. The biodegradable and recyclable barrier paper laminate according to claim 1, wherein the basis weight of the biodegradable and recyclable barrier paper laminate is 20 g / m³. 2 Up to 1000g / m 2 .

11. The biodegradable and recyclable barrier paper laminate according to claim 1, wherein the WVTR of the biodegradable and recyclable barrier paper laminate is 0.001 g / m³ when measured according to ASTM method F1249-13 or E96 at 38°C and 50% relative humidity. 2 / 50g / m 2 / sky.

12. The biodegradable and recyclable barrier paper laminate according to claim 1, wherein the WVTR of the biodegradable and recyclable barrier paper laminate is 0.1 g / m³ when measured according to ASTM method F1249-13 or E96 at 38°C and 90% relative humidity. 2 / 100g / m 2 / sky.

13. The biodegradable and recyclable barrier paper laminate according to claim 1, wherein the grease resistance level of the biodegradable and recyclable barrier paper laminate is >12 according to the TAPPI T 559cm-12 grease resistance test for paper and paperboard.

14. The biodegradable and recyclable barrier paper laminate according to claim 1, wherein the average thickness of the inorganic barrier layer is from 2 nm to 1000 nm.

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