High oxygen barrier type multilayer container and preparation method therefor

Abstract

The present invention belongs to the field of packaging materials, and relates to a high oxygen barrier type multilayer container, and a related preform thereof and a preparation method therefor. In particular, the present invention relates to a multilayer container and a preparation method therefor. The multilayer container comprises: an outer layer defining an outer surface and an inner layer defining an inner surface and an inner space, wherein optionally, a middle layer is further sandwiched between the outer layer and the inner layer. The outer layer, the middle layer and / or the inner layer comprise an oxygen-barrier molding material; the oxygen-barrier molding material is a combination of a 2,5-furandicarboxylate polyester material and an oxygen-absorbing material; the other corresponding layer materials comprise polyethylene terephthalate (PET); and the weight percentage of the oxygen-barrier molding material in the container is not higher than 5 wt%.

Description

Oxygen high barrier multilayer container and method for manufacturing the same

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to CN application No. 202410439551.1, filed on April 10, 2024, the contents of which are incorporated herein in their entirety. TECHNICAL FIELD

[0003] The present application belongs to the field of packaging materials, and relates to an oxygen high barrier multilayer container and a related preform and a manufacturing method thereof BACKGROUND

[0004] Existing plastic packaging containers, such as hard plastic packaging bottles, generally use polyethylene terephthalate (PET) as a packaging material. A preform (such as a PET formed bottle blank) can be formed by injection molding, and then a PET formed product bottle can be obtained by stretching and blowing after heating. The PET bottle stretched by heating retains a clear appearance and good mechanical properties. However, due to the certain oxygen basic transmission rate of the PET material bottle, its application in the packaging of sensitive products, such as dairy products, tea beverages, fruit juice and carbonated beverages, still has the defect of relatively short shelf life.

[0005] In the prior art, different barrier technologies have been developed for packaging based on PET, for example, nylon, other plastic resins that are easily oxidized, etc. are used as barrier materials to mix with PET materials to obtain single-mixed barrier bottles. By using the physical barrier or easy oxidation characteristics of these barrier materials, the oxygen barrier performance required by packaging is achieved. Another way to improve the gas barrier performance of PET is to add other compatible polyester resins to the PET preform stage, such as polyethylene naphthalate (PEN) or its copolymer (CN1167461A), or 2,5-furandicarboxylate polyester or its copolyester (CN107249885A). By forming a blended or multi-layer material distribution, the oxygen barrier efficiency of the PET packaging container can be improved, and the negative impact on packaging recycling is small. This approach is more environmentally friendly than single-mixed technology.

[0006] In addition, there are also multilayer bottles in the prior art in which the inner and outer layers are PET and the middle layer is nylon, but the middle layer of such multilayer bottles is prone to peeling and delamination. SUMMARY

[0007] In the above single or multi-layer technology, in order to achieve a relatively appropriate oxygen barrier efficiency, it is usually necessary to add in a high proportion (≥5wt%). High proportion of barrier material will reduce the transparency of PET bottles, for example, single-layer bottles formed by mixing PET with nylon and blow molding have the defect of high haze. In addition, high proportion of barrier material will cause greater pressure on the recycling and recycling of PET bottles, and bring problems such as cost increase.

[0008] In order to improve the oxygen barrier performance of PET resin-based containers and solve the problem of high addition amount of barrier materials in the prior art, the present application provides a multi-layer polyester container and a preparation method thereof. By combining 2,5-furandicarboxylate polyester or copolyester with oxygen-absorbing material as barrier material, the physical barrier performance and chemical reaction type barrier performance of the material are fully utilized, and excellent barrier performance of the container can be achieved under the condition of low addition amount of barrier material (not higher than 5wt%). In terms of preparation, a molding machine can be used to form a molded part through multi-layer injection molding process, different extrusion dies are used for injection molding, and then a bottle body with a barrier material layer is formed by heating and stretching blow molding. Therefore, the present application provides the following inventions:

[0009] In one aspect, the present application provides a multi-layer container, which comprises: an outer layer defining an outer surface and an inner layer defining an inner surface and an internal space, optionally, a middle layer is sandwiched between the outer layer and the inner layer; the outer layer, the middle layer and / or the inner layer comprise oxygen barrier forming material, which is a combination of 2,5-furandicarboxylate polyester material and oxygen-absorbing material; other corresponding layer materials (such as the outer layer, the middle layer and / or the inner layer) comprise polyethylene terephthalate (PET); the oxygen barrier forming material accounts for not more than 5wt% of the weight percentage of the container.

[0010] The present application improves the oxygen barrier performance of the package by combining 2,5-furandicarboxylate polyester material and oxygen-absorbing material at a low proportion (<5wt%), to improve the shelf life level of PET packaging products in the prior art.

[0011] Polyester materials based on 2,5-furan dicarboxylic acid (2,5-FDCA) are a new type of bio-based polymers that can be used as a substitute for petroleum-based or terephthalic acid (TPA)-based polyesters, with good manufacturability, heat resistance, mechanical properties and barrier properties. The 2,5-furan dicarboxylate polyester materials that can be used in the present application include 2,5-furan dicarboxylate polyesters or copolyesters, including but not limited to: poly(ethylene-2,5-furan dicarboxylate) (PEF); poly(trimethylene-2,5-furan dicarboxylate) (PTF); poly(butylene-2,5-furan dicarboxylate) (PBF); poly(isosorbide-2,5-furan dicarboxylate) (PISF); poly(isoidide-2,5-furan dicarboxylate) (PIIF); poly(isomannide-2,5-furan dicarboxylate) (PIMF); poly(neopentylene-2,5-furan dicarboxylate) (PNPGF); poly(ethylene-2,5-furan dicarboxylate) with 1,8-naphthalene dicarboxylate (PEF-PEN); poly(1,4-phenylene-2,5-furan dicarboxylate) (PCHF); poly(1,2-dimethylphenylene-2,5-furan dicarboxylate) (PDMFF); and any combination thereof, mixtures thereof, or copolymers thereof.

[0012] In some embodiments, the 2,5-furan dicarboxylate polyester material used in the present application is poly(ethylene-2,5-furan dicarboxylate) (PEF), which can be obtained by direct esterification or ester exchange reaction using 2,5-furan dicarboxylic acid (2,5-FDCA) or its derivatives and ethylene glycol (EG) as raw materials. The chemical structural formulas of PEF, EG and 2,5-FDCA are as follows, respectively:

[0013] Poly(ethylene-2,5-furan dicarboxylate) (PEF)

[0014] In some embodiments, the 2,5-furan dicarboxylate polyester material used in the present application is a random copolymer of 2,5-furan dicarboxylic acid glycol ester, terephthalic acid (PTA) and / or isophthalic acid (IPA), and ethylene glycol, wherein the 2,5-furan dicarboxylic acid accounts for 30%-80% of the total acid moles.

[0015] In some embodiments, the 2,5-furan dicarboxylate polyester material used in the present application has a number average molecular weight of 30,000-40,000 and a intrinsic viscosity of 0.75-0.9 dL / g.

[0016] The oxygen absorbing material used in the present application refers to a polymer material having oxygen capturing / cleaning effect. The oxygen absorbing mechanism mainly has two types: one is to use the oxidation reaction of the low molecular weight oxygen absorber (such as inorganic or organic small molecules) added in the polymer matrix, and the other is to use the self-oxidation of the oxygen absorbing resin with specific structure (such as the polymer chain containing double bond, carbonyl and other active groups). In some embodiments, the oxygen absorbing material used in the present application comprises a resin matrix and a low molecular active ingredient for cleaning oxygen. In some embodiments, the oxygen absorbing material comprises a nylon matrix and a transition metal, a salt thereof or a complex thereof, which can be selected from the first, second or third transition metal series in the periodic table, including but not limited to cobalt, iron, nickel, copper, manganese or any combination thereof.

[0017] In the multilayer container of the present application, the 2,5-furandicarboxylate polyester or copolyester is used in combination with the oxygen absorbing material, which can have a synergistic and reducing effect, and the total amount of the two in the container is not higher than 5wt%.

[0018] In some embodiments, the 2,5-furandicarboxylate polyester or copolyester accounts for 0.1wt%-5wt% of the weight percentage of the container, for example 0.1wt%-0.5wt%, 0.5wt%-1wt%, 1wt%-2wt%, 2wt%-3wt%, 3wt%-4wt% or 4wt%-5wt%. In some embodiments, the oxygen absorbing material accounts for 0.1wt%-5wt% of the weight percentage of the container, for example 0.1wt%-0.5wt%, 0.5wt%-1wt%, 1wt%-2wt%, 2wt%-3wt%, 3wt%-4wt% or 4wt%-5wt%.

[0019] In some embodiments, the polyethylene terephthalate (PET) accounts for 90%-99.8% (for example 90%-91%, 91%-93%, 93%-95%, 95%-96%, 96%-98%, 98%-99% or 99%-99.8%) of the weight percentage of the container.

[0020] 2,5-furandicarboxylate polyester or copolyester to oxygen absorbing material weight ratio is not limited and can be (1-99):(1-99), for example (1-10):(90-99), (10-20):(80-90), (20-30):(70-80), (30-40):(60-70), (40-50):(50-60), (50-60):(40-50), (60-70):(30-40), (70-80):(20-30), (80-90):(10-20), (90-99):(1-10). In some embodiments, the oxygen absorbing material:2,5-furandicarboxylate polyester or copolyester weight ratio is (0.1-5):(0.5-5), for example 0.1:(3-5), 0.5:(2-5), 1:(0.5-5), 3:(0.5-5), 5:(0.5-5), for example 0.1:3, 0.1:5, 0.5:2, 0.5:3, 0.5:5, 1:0.5, 1:1, 1:2, 1:3, 1:5, 3:0.5, 3:1, 3:2, 3:3, 3:5, 5:0.5, 5:1, 5:2, 5:3.

[0021] In some embodiments, the total added amount of 2,5-furandicarboxylate polyester or copolyester in the container is not less than 3 wt%, for example 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.8 wt%, 3.9 wt%, 4.0 wt%, 4.1 wt%, 4.2 wt%, 4.3 wt%, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, or 4.9 wt%.

[0022] In some embodiments, the total added amount of 2,5-furandicarboxylate polyester or copolyester in the container is not less than 3 wt% and less than 5 wt%, for example 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.8 wt%, 3.9 wt%, 4.0 wt%, 4.1 wt%, 4.2 wt%, 4.3 wt%, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, or 4.9 wt%.

[0023] In some embodiments, the total added amount of oxygen absorbing material in the container is 1 wt%-2 wt%, for example 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, or 1.9 wt%.

[0024] In some embodiments, the weight ratio of oxygen absorbing material: 2,5-furandicarboxylate polyester or copolyester is 0.1 :3 to 3:2, for example, 0.1 :3, 0.5:1, 0.5:2, 0.5:3, 1 :0.5, 1 :1, 1 :2, 1 :3, 3:0.5, 3:1, 3:2.

[0025] The above-mentioned amounts of the additives in the embodiments can provide the container with better oxygen barrier properties and the lowest overall cost. Both the oxygen absorbing material and the 2,5-furandicarboxylate polyester or copolyester used in the present application are commercially available.

[0026] In the multilayer container of the present application, the oxygen barrier forming material comprising the 2,5-furandicarboxylate polyester or copolyester and the oxygen absorbing material can be included in any one or more of the inner layer, the outer layer, and the optional intermediate layer. In some embodiments, the layer comprising the oxygen barrier forming material is formed entirely of the oxygen barrier forming material. In some embodiments, the layer comprising the oxygen barrier forming material can also include other materials, preferably also including the materials forming the other layers (i.e., the layers not comprising the oxygen barrier forming material).

[0027] In some embodiments, the other layers (i.e., the layers not comprising the oxygen barrier forming material) can be formed entirely of PET or can include other materials in addition to PET.

[0028] In some embodiments, the multilayer container of the present application comprises an outer layer defining an outer surface and an inner layer defining an inner surface and an interior space, wherein the outer layer is formed of a polyester or a combination of a polyester and an oxygen absorbing material, and the inner layer comprises the oxygen barrier forming material.

[0029] In some embodiments, the multilayer container of the present application comprises an outer layer defining an outer surface and an inner layer defining an inner surface, and an intermediate layer between the outer layer and the inner layer, wherein the inner layer and the outer layer are each formed of PET, and the intermediate layer is formed of the oxygen barrier forming material.

[0030] In some embodiments, both the 2,5-furandicarboxylate polyester or copolyester and the oxygen absorbing material are added to the intermediate layer of the container, and the intermediate layer of the container comprises 5% of the total weight of the container. In some embodiments, the intermediate layer of the container comprises PET in addition to the 2,5-furandicarboxylate polyester or copolyester and the oxygen absorbing material.

[0031] In the multilayer container of the present application, the inner layer, the outer layer, or the optional intermediate layer can further comprise a colorant, a UV blocker, a lubricant, a slip agent, a processing aid, an antioxidant, an antimicrobial agent, a heat stabilizer, or any combination thereof.

[0032] In the multilayer container of the present application, the inner layer, the outer layer, and optionally the intermediate layer each independently can have a thickness of 0.1 mm to 1.5 mm, such as 0.1 mm to 0.5 mm, 0.5 mm to 1.0 mm, or 1.0 mm to 1.5 mm.

[0033] In one aspect, the present application provides a preform comprising: an outer layer defining an outer surface and an inner layer defining an inner surface and an interior space, optionally with an intermediate layer sandwiched between the outer layer and the inner layer; the outer layer, the intermediate layer, and / or the inner layer comprising an oxygen barrier molding material, the oxygen barrier molding material being a combination of a 2,5-furandicarboxylate polyester material and an oxygen absorbing material; other corresponding layer materials comprising polyethylene terephthalate (PET); the poly oxygen barrier molding material being no more than 5 wt% of the weight of the container.

[0034] The preform of the present application can have the same features as the multilayer container of any of the embodiments described above, except for the thickness.

[0035] In one aspect, the present application provides a method of making the multilayer container of the present application, the method comprising:

[0036] a) providing a preform; and

[0037] b) blow stretch molding the preform to provide the multilayer container.

[0038] In step a), the preform can be obtained by injection molding or the like. Since PET contains a lipid group and has a certain hydrophilicity, the granules are sensitive to water at high temperatures. When the water content exceeds the limit, it can cause the molecular weight of PET to decrease, which can cause the product to be colored and brittle. Therefore, in some embodiments, step a) comprises drying the raw material before processing, and the drying temperature can be 160°C to 185°C.

[0039] The injection molding machine can be used to obtain the preform by a multi-layer injection molding process, in which the raw materials of each layer are injected through different extrusion dies. In some embodiments, the material melting temperature is set to 260°C to 290°C, and the mold temperature is less than 15°C during the injection molding step. Using the above process conditions, the crystallization of the polymer can be reduced, and the product has good transparency. In some embodiments, the back pressure of the injection molding machine is controlled at 800 to 2000 psi to uniformly compact the melt, so that the product has good weight and dimensional stability, and the gas in the melt is extruded to improve the uniformity of the product gloss.

[0040] In some embodiments, the multilayer container is a bottle. In step b), a blow molding machine can be used to make the preform into a bottle with a certain shape and size. By applying air pressure, the blow molding machine blows air into the heated bottle blank and shapes it with a specific mold wrapped outside.

[0041] In some embodiments, step b) comprises:

[0042] Preheating: the preform is heated to a suitable forming temperature, and the inner and outer walls of the preform are kept uniformly heated. The finish does not need to be heated because it is already shaped. Therefore, the finish needs to be cooled during the heating of the preform.

[0043] Blow molding: the uniformly heated preform is sent to a blow mold by a chain, and a sterile high-pressure gas is blown into the preform through the middle of the core rod to stretch it in a circular direction, so that it is blown to tightly fit the mold wall, and then cooled.

[0044] Demolding: after the blow molding is completed, the machine starts to exhaust and demold.

[0045] Conveying: the molded bottle is sent to the next bottle station by a conveyor belt, and is pulled up and blown out by a bottle ejection cylinder.

[0046] In some embodiments, the preform heating temperature is set to 90-110°C (for example, 92°C), the pre-blowing pressure is set to 5-10 bar (for example, 7.2 bar), the final blowing pressure is set to 15-25 bar (for example, 22 bar), and the stretching speed is set to 0.8-1.5 m / s (for example, 1.1 m / s). Using the above process parameters can make the intermediate layer material more evenly distributed, and the container has better barrier properties.

[0047] In some embodiments, the multi-layer container is prepared using a blow-label-filling-capping integrated machine, which can continuously complete blow molding, labeling, filling, and capping. Therefore, in some embodiments, the method further comprises, after step b), sticking a label on the bottle, filling the bottle with a liquid, and capping the bottle.

[0048] In one aspect, the present application provides a commodity comprising the multi-layer container of the present application and a content arranged in the inner space of the multi-layer container. In some embodiments, the content is a liquid. In some embodiments, the content is a beverage.

[0049] Advantages of the application

[0050] The present application realizes excellent barrier properties of the PET container with a low amount of barrier material (not higher than 5 wt%), reduces production costs, and is more environmentally friendly than single-mixing technology, which is conducive to the recycling of containers. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 exemplarily shows a multi-layer container of the present application and its outer layer, intermediate layer, and inner layer. DETAILED DESCRIPTION

[0052] The embodiments of the present application will be described in detail below with reference to the examples, but those skilled in the art will understand that the following examples are only for illustration of the present application and should not be regarded as limiting the scope of the present application. The specific conditions not noted in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments not noted for the manufacturer are all the conventional products which can be obtained commercially.

[0053] I. General preparation method:

[0054] Raw materials: The oxygen absorbing material contains a nylon matrix and a transition metal, which are commercially available products; the PEF has a number average molecular weight of 30,000-40,000 and a specific viscosity of 0.75-0.9 dL / g, which are commercially available products; the PET is a commercially available product.

[0055] A molding machine is used to form a molded part through a multi-layer injection molding process by using different extrusion dies, and then a bottle body with a barrier material layer is formed by heating and stretching to blow the bottle.

[0056] 1. Bottle blank injection molding process:

[0057] The material drying temperature is set to 160-185°C; the material melting temperature for injection molding is 260-290°C, the material plasticizing back pressure is 800-2000 psi; and the mold temperature is lower than 15°C.

[0058] 2. Bottle blowing process:

[0059] The bottle blank heating temperature is 92°C, the pre-blowing pressure is 7.2 bar, the final blowing pressure is 22 bar, and the stretching speed is 1.1 m / s.

[0060] II. Oxygen transmission rate test:

[0061] Test instrument: MOCON oxygen transmission rate tester 2 / 22(H),

[0062] Test temperature: 23°C,

[0063] The results are expressed by the oxygen transmission rate (OTR).

[0064] The raw material ratio and test results of each example are shown in Table 1.

[0065] Table 1

[0066] Comparative example

[0067] From the examples and comparative examples, it can be seen that the combination of oxygen-absorbing material and PEF in the middle layer of the bottle can achieve better oxygen barrier property with the total amount of the two being reduced.

[0068] The tea beverage contains tea polyphenols, catechin and other substances, which are easy to oxidize, change the color of the tea soup and change the flavor. After the product shelf life test, the bottle with OTR below 0.1 can keep the original flavor of the tea beverage during the shelf life, and the tea soup is transparent and not easy to change color. Therefore, the bottle with OTR below 0.1 is particularly suitable for packaging tea beverage.

[0069] When the inner and outer layers comprise 95% of PET, and the middle layer comprises 1% of oxygen-absorbing material and 2% to 3% of PEF, the oxygen barrier property of the prepared bottle meets the requirements of tea beverage products, and the comprehensive cost is the lowest.

[0070] Although the specific embodiments of the present application have been described in detail, those skilled in the art will understand that various modifications and changes can be made to the details according to all the teachings disclosed herein, and these changes are within the scope of protection of the present application. The entire scope of the present application is given by the appended claims and any equivalents thereof.

Claims

1. A multi-layer container, comprising: an outer layer defining an outer surface; and an inner layer defining an inner surface and an inner space, optionally comprising an intermediate layer between the outer layer and the inner layer; the outer layer, the intermediate layer, and / or the inner layer comprising an oxygen-barrier molding material, wherein the oxygen-barrier molding material is a combination of a 2,5-furandicarboxylic acid ester polyester material and an oxygen-absorbing material; the material of the other corresponding layers comprises polyethylene terephthalate (PET); and the oxygen-barrier molding material accounts for no more than 5 wt % of the weight of the container.

2. The multi-layer container according to claim 1, wherein The 2,5-furandicarboxylate polyester material is a 2,5-furandicarboxylate polyester or copolyester, such as: poly(ethylene-2,5-furandicarboxylate) (PEF); poly(trimethylene-2,5-furandicarboxylate) (PTF); poly(butylene-2,5-furandicarboxylate) (PBF); poly(isosorbide-2,5-furandicarboxylate) (PISF); poly(isoidoyl-2,5-furandicarboxylate) (PIIF); poly(isomannose-2,5-furandicarboxylate) (PIIF); poly(1,4-phenylene-2,5-furandicarboxylate) (PCHF); poly(1,2-dimethylphenylene-2,5-furandicarboxylate) (PDMFF); and any combination, mixture, or copolymer thereof; Preferably, the 2,5-furandicarboxylate polyester material is poly(ethylene-2,5-furandicarboxylate) (PEF).

3. The multi-layer container according to claim 1 or 2, wherein The oxygen absorbing material comprises a resin matrix and a low molecular active component for scavenging oxygen; Preferably, the oxygen absorbing material comprises a nylon matrix and a transition metal, a salt thereof or a complex thereof.

4. The multi-layer container according to any one of claims 1 to 3, wherein It has one or more of the following characteristics: (1) The total amount of 2,5-furandicarboxylic acid ester polyester or copolyester and oxygen absorbing material added to the container is not less than 3wt%; (2) The total amount of 2,5-furandicarboxylate polyester or copolyester added to the container is not less than 3 wt% and less than 5 wt%; (3) The total amount of oxygen absorbing material added to the container is 1wt%-2wt%; (4) The weight ratio of oxygen absorbing material: 2,5-furandicarboxylic acid ester polyester or copolyester is 0.1:3 to 3:

2.

5. The multi-layer container according to any one of claims 1 to 4, comprising an outer layer defining an outer surface, an inner layer defining an inner surface, and an intermediate layer between the outer layer and the inner layer, wherein the inner layer and the outer layer are respectively formed of PET, and the intermediate layer is formed of an oxygen barrier molding material.

6. The multi-layer container according to any one of claims 1 to 5, wherein The 2,5-furandicarboxylate polyester or copolyester and the oxygen absorbing material are both added to the middle layer of the container, and the middle layer of the container accounts for 5% of the total weight of the container; preferably, the middle layer of the container includes PET in addition to the 2,5-furandicarboxylate polyester or copolyester and the oxygen absorbing material.

7. The multi-layer container according to any one of claims 1 to 6, wherein The inner layer, outer layer or optional middle layer may further comprise a colorant, a UV blocker, a lubricant, a slip agent, a processing aid, an antioxidant, an antimicrobial agent, a thermal stabilizer, or any combination thereof.

8. The multi-layer container according to any one of claims 1 to 7, wherein The inner layer, outer layer and optional intermediate layer each independently have a thickness of 0.1 mm to 1.5 mm.

9. A preform, comprising: an outer layer defining an outer surface; and an inner layer defining an inner surface and an interior space, optionally comprising an intermediate layer between the outer layer and the inner layer; wherein the outer layer, the intermediate layer, and / or the inner layer comprise an oxygen-barrier molding material, wherein the oxygen-barrier molding material is a combination of a 2,5-furandicarboxylate polyester material and an oxygen-absorbing material; and wherein the material of the other corresponding layers comprises polyethylene terephthalate (PET); and wherein the oxygen-barrier molding material accounts for no more than 5 wt % of the weight of the container; Preferably, the preform has the features defined in any one of claims 2-7.

10. A method for preparing the multi-layer container according to any one of claims 1 to 8, the method comprising: a) providing a preform; and b) blow stretch molding the preform to provide the multilayer container.

11. A commercial product comprising the multi-layer container according to any one of claims 1 to 8 and contents arranged in the interior space of the multi-layer container; Preferably, the content is liquid; Preferably, the content is a beverage.

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