Laminate, tube container body, and tube container

Abstract

The present invention provides a laminate that offers excellent recyclability and barrier properties, while also suppressing delamination at the joint after heat sealing. [Solution] A laminate comprising, in this order, at least a first heat seal layer, a barrier resin layer, and a second heat seal layer, wherein the first heat seal layer mainly contains polyethylene, the second heat seal layer mainly contains polyethylene, and the barrier resin layer mainly contains a gas barrier resin, and the laminate has a first surface and a second surface, wherein the first heat seal layer constitutes the first surface and the second heat seal layer constitutes the second surface, and ratio (T in / T b1 A laminate in which the ratio is 8.0 or higher, and the polyethylene content in the entire laminate is 90% by mass or higher.

Description

Technical Field

[0001] The present disclosure relates to a laminate, a tube container body, and a tube container.

Background Art

[0002] A tube container is known as a packaging container for filling and squeezing out paste-like semi-fluid substances such as toothpaste and facial cleansing cream for use. A tube container usually includes a tube container body and a cap. The tube container body generally includes a body portion with one end closed and the other end open, and a head portion having a spout connected to the open other end of the body portion. Before closing one end of the body portion, the body portion is filled with contents, and then one end of the body portion is closed, thereby manufacturing a tube container containing the contents.

[0003] As a member constituting the body portion of the tube container body, a laminate obtained by laminating a polyethylene film, a polyester film, a vapor-deposited film, an aluminum foil, etc. is widely used (see, for example, Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, from the perspective of building a circular economy, there has been a demand for high recyclability in packaging containers. Furthermore, it is desirable for packaging containers to possess barrier properties. However, as mentioned above, the body of conventional tube containers is composed of a laminate, for example, polyethylene film and aluminum foil. Separating the polyethylene film and aluminum foil within this laminate is generally difficult. Therefore, currently, such tube container bodies are not actively recycled.

[0006] The inventors investigated how to enhance barrier properties by providing a barrier resin layer containing a gas barrier resin as the main component while maintaining a high polyethylene content in the laminate. It is believed that such a configuration can achieve both recyclability and barrier properties. The laminate can be rolled into a cylindrical shape, the inner heat-seal layer of one end of the laminate and the outer heat-seal layer of the other end of the laminate can be overlapped, and the overlapped portion can be heat-sealed to form a joint (welded portion) and thus form the body of the tube container. However, the inventors found that in such cases, sufficient bonding strength at the joint may not be obtained, and delamination may occur.

[0007] This disclosure aims to provide a laminate that is excellent in recyclability and barrier properties, and that can suppress the occurrence of delamination at the joint after heat sealing. [Means for solving the problem]

[0008] The laminate of the present disclosure comprises, in this order, at least a first heat seal layer, a barrier resin layer, and a second heat seal layer, wherein the first heat seal layer mainly contains polyethylene, the second heat seal layer mainly contains polyethylene, and the barrier resin layer mainly contains a gas barrier resin, and the laminate has a first surface and a second surface, wherein the first heat seal layer constitutes the first surface, the second heat seal layer constitutes the second surface, and the total thickness (T) of the layers mainly containing polyethylene, including the first surface, located between the barrier resin layer and the first surface. in ) the thickness of the barrier resin layer (T b1 ) ratio (T in / T b1 The ratio is 8.0 or higher, and the polyethylene content in the entire laminate is 90% by mass or higher. [Effects of the Invention]

[0009] According to this disclosure, it is possible to provide a laminate that is excellent in recyclability and barrier properties, and that can suppress the occurrence of delamination at the joint after heat sealing. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 is a schematic cross-sectional view showing one embodiment of the laminate of the present disclosure. [Figure 2] Figure 2 is a schematic cross-sectional view showing one embodiment of the laminate of the present disclosure. [Figure 3] Figure 3 is a schematic cross-sectional view showing one embodiment of the laminate of the present disclosure. [Figure 4] Figure 4 is a schematic cross-sectional view showing one embodiment of the laminate of the present disclosure. [Figure 5] Figure 5 is a top view of the raw material for the cylindrical body of the tube container. [Figure 6] Figure 6 is a perspective view showing one embodiment of a tube container comprising a tube container body including the laminate of the present disclosure and a cap. [Figure 7] Figure 7 is a cross-sectional view of AA in Figure 6. [Modes for carrying out the invention]

[0011] In this specification, when multiple candidate upper limits and multiple candidate lower limits are given for a certain parameter, the numerical range of that parameter may be constructed by combining any one candidate upper limit and any one candidate lower limit. As an example, consider the statement, "Parameter B is preferably A1 or greater, more preferably A2 or greater, even more preferably A3 or greater. Parameter B is preferably A4 or less, more preferably A5 or less, even more preferably A6 or less." In this example, the numerical range of parameter B may be A1 or greater and A4 or less, A1 or greater and A5 or less, A1 or greater and A6 or less, A2 or greater and A4 or less, A2 or greater and A5 or less, A2 or greater and A6 or less, A3 or greater and A4 or less, A3 or greater and A5 or less, or A3 or greater and A6 or less.

[0012] The embodiments of this disclosure will be described in detail below. This disclosure can be implemented in many different forms and is not construed as being limited to the embodiments described below. The drawings may schematically represent the width, thickness, and shape of each layer, etc., compared to the embodiments, in order to clarify the explanation, but these are merely examples and do not limit the interpretation of this disclosure. In this specification and in each figure, elements similar to those already described in the previously shown figures are denoted by the same reference numerals, and detailed explanations may be omitted as appropriate.

[0013] Embodiments of the laminates of this disclosure will be described below with reference to drawings as appropriate. In the following description, the components described (e.g., polyethylene, gas barrier resin, additives, white pigment) may be used individually or in combination of two or more.

[0014] [Laminated structure] The laminate of this disclosure comprises at least a first heat seal layer, a barrier resin layer, and a second heat seal layer in this order. When the laminate is described as comprising each layer in this order, it means that the laminate comprises each layer in this order in the thickness direction of the laminate.

[0015] The laminate of the present disclosure has a first surface and a second surface facing the first surface in the thickness direction. In one embodiment, the first heat seal layer constitutes the first surface of the laminate, and the second heat seal layer constitutes the second surface of the laminate.

[0016] The first heat-seal layer is a layer mainly composed of polyethylene. The second heat-seal layer is a layer mainly composed of polyethylene. Therefore, the laminate of this disclosure has high recyclability. The tube container body equipped with this laminate also has similarly high recyclability. The polyethylene contained in the first heat-seal layer may be the same as or different from the polyethylene contained in the second heat-seal layer.

[0017] In this disclosure, "a layer containing polyethylene as the main component" means a layer in which the polyethylene content in 100% by mass of the layer is 50% by mass or more. The above content is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0018] The laminate of the present disclosure may further include a substrate containing polyethylene as a main component, selected from between the first heat seal layer and the barrier resin layer, and between the barrier resin layer and the second heat seal layer. The laminate of the present disclosure may further include a printing substrate, selected from between the first heat seal layer and the barrier resin layer, and between the barrier resin layer and the second heat seal layer. The printing substrate comprises a substrate and a printing layer provided on at least one surface of the substrate.

[0019] The laminate of this disclosure may include a barrier film comprising the barrier resin layer described above.

[0020] The laminate of the present disclosure may comprise, in this order, a first heat-seal layer, optionally an adhesive layer, a barrier film, optionally an adhesive layer, and a second heat-seal layer. In this embodiment, the first heat-seal layer may be a polyethylene film having a total light transmittance of 5% to 40%, or containing a white pigment. The laminate of the present disclosure may comprise, in this order, a first heat-seal layer, optionally an adhesive layer, a barrier film, optionally an adhesive layer, a printing substrate, optionally an adhesive layer, and a second heat-seal layer. In this embodiment, the first heat-seal layer may be a polyethylene film having a total light transmittance of 5% or more and 40% or less, or containing a white pigment. The laminate of the present disclosure may comprise, in this order, a first heat-seal layer, optionally an adhesive layer, a substrate, optionally an adhesive layer, a barrier film, optionally an adhesive layer, a printing substrate, optionally an adhesive layer, and a second heat-seal layer. In this embodiment, the first heat-seal layer and / or the substrate may be a polyethylene film having a total light transmittance of 5% to 40% or containing a white pigment.

[0021] One embodiment of the laminate of this disclosure is shown in Figures 1 to 4. The laminate 1 in Figure 1 comprises, in this order: a first heat seal layer 10 (first surface 1S), a barrier resin layer 32, and a second heat seal layer 20 (second surface 2S). The laminate 1 in Figure 2 comprises, in this order: (first surface 1S) a first heat seal layer 10, an adhesive layer Ad, a barrier film 30, another adhesive layer Ad, and a second heat seal layer 20 (second surface 2S). The laminate 1 in Figure 3 comprises, in this order: (first surface 1S) a first heat seal layer 10, an adhesive layer Ad, a barrier film 30, an adhesive layer Ad, a printing substrate 40, an adhesive layer Ad, and a second heat seal layer 20 (second surface 2S). The laminate 1 in Figure 4 comprises, in this order: (first surface 1S) a first heat seal layer 10, an adhesive layer Ad, a substrate 50, an adhesive layer Ad, a barrier film 30, an adhesive layer Ad, a printing substrate 40, an adhesive layer Ad, and a second heat seal layer 20 (second surface 2S).

[0022] In the examples shown in Figures 2 to 4, the barrier film 30 comprises a first polyethylene layer 34A, a first adhesive resin layer 36A, a barrier resin layer 32, a second adhesive resin layer 36B, and a second polyethylene layer 34B in this order. The barrier film 30 is not limited to this example and may consist of a barrier resin layer 32, or a barrier resin layer 32 and other layers not shown. In the examples shown in Figures 2 to 4, the printing substrate 40 comprises a substrate 42 and a printing layer 44 provided on one surface of the substrate. In the examples shown in Figures 3 to 4, the laminate 1 may further include an anchor coat layer (not shown) between the adhesive layer Ad and the printing layer 44.

[0023] The laminate of this disclosure has a high polyethylene content of 90% by mass or more, and exhibits excellent recyclability. The laminate of this disclosure also includes a barrier resin layer containing a gas barrier resin as its main component, and exhibits excellent barrier properties. In other words, the laminate of this disclosure can achieve both recyclability and barrier properties.

[0024] When a laminate having the above-mentioned barrier resin layer is heat-sealed to form the body of a tube container, delamination may occur at the joint (the part where the tube is joined). Delamination tends to occur more frequently after a certain period of time has elapsed since the contents were filled into the tube container. This is presumed to be because the barrier resin layer is exposed and stretched at the end face of the laminate at the joint, and the barrier resin layer absorbs moisture from the contents, for example, making it prone to peeling. However, in the laminate of this disclosure, by appropriately controlling the thickness of each layer as described below, such exposure of the end face of the barrier resin layer at the joint can be suppressed, and therefore the occurrence of delamination can be suppressed.

[0025] The total thickness of the layer containing polyethylene as the main component, including the first surface, located between the barrier resin layer and the first surface of the laminate is denoted as "T in ". The thickness of the barrier resin layer is denoted as "T b1 ". When there are two or more barrier resin layers, the barrier resin layer in the definition of "T in " means the barrier resin layer located closest to the first surface of the laminate among the barrier resin layers. In this case, the thickness (T b1 ) of the barrier resin layer means the thickness of the barrier resin layer located closest to the first surface of the laminate among the barrier resin layers. However, when there is one or more barrier resin layers laminated directly on the barrier resin layer located closest to the first surface of the laminate among the barrier resin layers without any other layers in between, it means the sum of the thicknesses of these barrier resin layers. The total thickness of the layer containing polyethylene as the main component, including the second surface, located between the barrier resin layer and the second surface of the laminate is denoted as "T out ". The thickness of the barrier resin layer is denoted as "T b2 ". When there are two or more barrier resin layers, the barrier resin layer in the definition of "T out " means the barrier resin layer located closest to the second surface of the laminate among the barrier resin layers. In this case, the thickness (T b2 ) of the barrier resin layer means the thickness of the barrier resin layer located closest to the second surface of the laminate among the barrier resin layers. However, when there is one or more barrier resin layers laminated directly on the barrier resin layer located closest to the second surface of the laminate among the barrier resin layers without any other layers in between, it means the sum of the thicknesses of these barrier resin layers.

[0026] The ratio (T in ) of the total thickness (T b1 ) to the thickness (T in / T b1The ratio (T) is preferably 8.0 or higher, more preferably 8.5 or higher, even more preferably 9.0 or higher, even more preferably 9.5 or higher, and particularly preferably 10.0 or higher, 11.0 or higher, or 12.0 or higher. in / T b1 The coefficient of gravity is preferably 15.0 or less, more preferably 14.5 or less, and even more preferably 14.0 or less. In this embodiment, at the joint (tube bonding location) on the inner surface of the body of the tube container, the layer mainly containing polyethylene can sufficiently cover the end face of the barrier resin layer, and thus the occurrence of delamination can be suppressed. In one embodiment, at the joint, the first heat seal layer of the laminate located on the radially inner side of the body (hereinafter simply referred to as "inside") melts during heat sealing, covering the end face of the barrier resin layer of the laminate located on the inside, and adhering to the first heat seal layer of the laminate located on the radially outer side of the body (hereinafter simply referred to as "outside"). This increases the bonding strength between the laminate located on the inside and the laminate located on the outside. Therefore, the occurrence of delamination at the joint tends to be suppressed.

[0027] Total thickness (T in The thickness is preferably 120 μm or more, more preferably 130 μm or more, even more preferably 140 μm or more, even more preferably 150 μm or more, and particularly preferably 160 μm or more, 170 μm or more, or 180 μm or more. Total thickness (T in The thickness of the layer is preferably 250 μm or less, more preferably 230 μm or less, and even more preferably 210 μm or less. In this configuration, the layer containing polyethylene as the main component can sufficiently cover the barrier resin layer at the joint (tube bonding) on ​​the inner surface of the body of the tube container, and therefore tends to suppress the occurrence of delamination.

[0028] Total thickness (T out ) thickness (T b2 ) ratio (T out / T b2 The ratio (T) is preferably 6.0 or higher, more preferably 7.0 or higher, and even more preferably 8.0 or higher.out / T b2 The coefficient of gravity is preferably 14.0 or less, more preferably 13.0 or less, even more preferably 12.0 or less, even more preferably 11.0 or less, and particularly preferably 10.0 or less. In this embodiment, at the joint (tube bonding area) on the outer surface of the body of the tube container, the layer containing polyethylene as the main component can sufficiently cover the end face of the barrier resin layer, and thus the occurrence of delamination can be suppressed. In one embodiment, at the joint, the second heat seal layer of the laminate located on the outside of the body melts during heat sealing, covering the end face of the barrier resin layer of the outer laminate and adhering to the second heat seal layer of the laminate located on the inside of the body. This increases the bonding strength between the outer laminate and the inner laminate. Therefore, the occurrence of delamination at the joint tends to be suppressed.

[0029] Total thickness (T out The thickness is preferably 100 μm or more, more preferably 110 μm or more, and even more preferably 120 μm or more. Total thickness (T out The thickness of the layer is preferably 220 μm or less, more preferably 210 μm or less, even more preferably 200 μm or less, even more preferably 190 μm or less, and particularly preferably 180 μm or less, 170 μm or less, or 160 μm or less. In this configuration, the layer mainly containing polyethylene can sufficiently cover the barrier resin layer at the joint (tube bonding) on ​​the outer surface of the body of the tube container, and therefore tends to suppress the occurrence of delamination.

[0030] Thickness (T b1 ) and thickness (T b2 Each of these is independently preferably 3 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. Thickness (T b1 ) and thickness (T b2Each of these layers is preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. When the laminate has only one barrier resin layer, or when the laminate has two or more barrier resin layers, but these barrier resin layers are laminated without any other layers in between, T b1 =T b2 In this case, simply "T b It is also written as ".

[0031] The total thickness of the laminate of the present disclosure is preferably 260 μm or more, more preferably 280 μm or more, even more preferably 300 μm or more, even more preferably 320 μm or more, and particularly preferably 340 μm or more. The total thickness of the laminate of the present disclosure is preferably 440 μm or less, more preferably 420 μm or less, even more preferably 400 μm or less, even more preferably 380 μm or less, and particularly preferably 360 μm or less.

[0032] The polyethylene content in the entire laminate of this disclosure is preferably 90% by mass or more, more preferably 92% by mass or more, even more preferably 93% by mass or more, and particularly preferably 94% by mass or more. This improves the recyclability of the laminate of this disclosure and the tube container (especially the laminated tube container) body equipped with the laminate.

[0033] In one embodiment, the laminate of the present disclosure does not include polyethylene terephthalate film, aluminum foil, vapor-deposited film, or vapor-deposited film formed on a resin film. This improves the recyclability of the laminate of the present disclosure and the tube container (particularly laminated tube container) body equipped with the laminate.

[0034] In this specification, "laminated body" may refer to the raw material itself manufactured on a production line having the layer structure described above, or to each individual laminated body obtained by cutting the raw material, and is not particularly limited as long as it has the layer structure described above. The laminated body pieces are used, for example, to form the body of a tube container.

[0035] Figure 5 shows a top view of the raw material as a laminate of the present disclosure before cutting along the cutting line L. This raw material contains a plurality of continuous laminates (individual pieces) for forming the body of a tube container. By cutting this raw material along the cutting line L, a plurality of laminate pieces for forming the body of a tube container can be obtained. When viewing these laminate pieces in plan view, it is preferable that no printed layer is formed in the regions corresponding to both ends perpendicular to the raw material flow direction. This makes it possible to further suppress delamination from the tube bonding area in the body, for example.

[0036] The oxygen permeability of the laminate of this disclosure, measured in accordance with JIS K7126-2:2006 under conditions of 23°C and 90% RH, is preferably 2.0 cc / m². 2 • Less than 1.5 cc / m³ per day atm, more preferably 1.5 cc / m³ 2 Less than or equal to 1.0 cc / m³ per day·atm, more preferably 1.0 cc / m³. 2 The oxygen permeability should be less than or equal to 0.01 cc / m³. A lower oxygen permeability is preferable, but its lower limit is, for example, 0.01 cc / m³. 2 "day" or "atm" would also be acceptable.

[0037] The water vapor transmission rate of the laminate of this disclosure, measured in accordance with JIS K7129-2:2019 under conditions of 40°C and 90% RH, is preferably 3.0 g / m². 2 • Less than 2.0 g / m² per day, more preferably 2.0 g / m² 2 • Less than 1.5 g / m², more preferably 1.5 g / m² 2 It is less than or equal to 0.01 g / m³. A lower water vapor permeability is preferable, but its lower limit is, for example, 0.01 g / m³. 2 "Day" is also acceptable.

[0038] The total light transmittance of the laminate of this disclosure, as measured in accordance with JIS K7375:2008, is preferably 40% or less, more preferably 30% or less, even more preferably 20% or less, and particularly preferably 15% or less. The above total light transmittance of the laminate of this disclosure may be, for example, 5% or more, or 8% or more.

[0039] <First heat seal layer and second heat seal layer> The first heat seal layer contains polyethylene as its main component. The second heat seal layer contains polyethylene as its main component. The polyethylene contained in the first heat seal layer and the polyethylene contained in the second heat seal layer may be the same or different. The first heat seal layer and the second heat seal layer can melt and fuse together upon heating.

[0040] When the laminate of this disclosure is used to form the body of a tube container, the first heat seal layer is a sealant layer on the inner surface of the body, and the second heat seal layer is a sealant layer on the outer surface of the body. That is, the body comprises, from the inside to the outside, the first heat seal layer, a barrier resin layer, and the second heat seal layer in this order. In one embodiment, the first heat seal layer constitutes the first surface of the laminate, and the second heat seal layer constitutes the second surface of the laminate.

[0041] Examples of polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Among these, low-density polyethylene and linear low-density polyethylene are preferred from the viewpoint of heat sealability. In this disclosure, high-density polyethylene has a density of 0.945 g / cm³. 3 Ultra-high density polyethylene may also be used, and as medium-density polyethylene, the density is 0.932 g / cm³. 3 Super 0.945g / cm 3 The following polyethylenes may be used, and as low-density polyethylene, a density of 0.900 g / cm³ may be used. 3 Super 0.932g / cm 3 The following polyethylenes may be used, and as linear low-density polyethylene, a density of 0.900 g / cm³ may be used. 3 Super 0.932g / cm 3 The following polyethylenes may be used, and as ultra-low density polyethylene, a density of 0.900 g / cm³ may be used.3 The following polyethylenes may be used. The density of the polyethylene shall be measured in accordance with Method D (density gradient pipe method, 23°C) of JIS K7112:1999.

[0042] Low-density polyethylene is typically polyethylene obtained by polymerizing ethylene using a high-pressure polymerization method (high-pressure low-density polyethylene). Linear low-density polyethylene is typically polyethylene obtained by polymerizing ethylene and a small amount of α-olefin using a low-pressure polymerization method (e.g., polymerization using a Ziegler-Natta catalyst or a metallocene catalyst).

[0043] Polyethylenes with different densities or branching can be obtained by appropriately selecting a polymerization method. For example, it is preferable to use a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as the polymerization catalyst, and to carry out polymerization in one or more stages using one of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, or high-pressure ionic polymerization.

[0044] In this disclosure, polyethylene includes copolymers of ethylene and other monomers (hereinafter also referred to as "ethylene copolymers"). In this disclosure, the content of ethylene-derived constituent units in polyethylene is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The above content is measured by nuclear magnetic resonance (NMR) spectroscopy.

[0045] Examples of ethylene copolymers include copolymers of ethylene with α-olefins having 3 to 20 carbon atoms. Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene. Polyethylene may also be a copolymer of ethylene with vinyl acetate or (meth)acrylic acid esters, etc.

[0046] As polyethylene, biomass-derived polyethylene (hereinafter also referred to as "biomass polyethylene") obtained by polymerizing monomers containing biomass-derived ethylene may be used. Since such biomass polyethylene is a carbon-neutral material, it can reduce the environmental burden in the production of the laminates of this disclosure.

[0047] As polyethylene, recycled polyethylene (hereinafter also referred to as "recycled polyethylene") may be used. Examples of recycled polyethylene include polyethylene recycled by mechanical recycling or chemical recycling. Mechanical recycling generally involves crushing the collected polyethylene film, washing it with alkali to remove dirt and foreign matter from the film surface, drying it at high temperature and reduced pressure for a certain period of time to disperse contaminants remaining inside the film and decontaminate it, removing the dirt from the film and returning it to polyethylene. Chemical recycling generally involves decomposing the collected polyethylene film to the monomer level and then repolymerizing the monomers to obtain polyethylene.

[0048] In this disclosure, the melt flow rate (MFR) of polyethylene is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, even more preferably 0.5 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and even more preferably 10 g / 10 min or less, from the viewpoint of film-forming properties and processability. The MFR of polyethylene is measured by Method A in accordance with JIS K7210:1999, under conditions of a temperature of 190°C and a load of 2.16 kg.

[0049] The above explanation regarding polyethylene can also be applied to polyethylene contained in other layers.

[0050] In one embodiment, the first heat-seal layer and the second heat-seal layer may each be a polyethylene film having a total light transmittance, as measured in accordance with JIS K7375:2008, preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more.

[0051] The polyethylene content in the first heat seal layer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, and may be 99% by mass or less, 97.5% by mass or less, or 95% by mass or less. With such a configuration, for example, the recyclability of a packaging container comprising the laminate of this disclosure can be improved. The polyethylene content in the second heat seal layer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, and may be 99% by mass or less, 97.5% by mass or less, or 95% by mass or less. With such a configuration, for example, the recyclability of a packaging container comprising the laminate of this disclosure can be improved.

[0052] In one embodiment, the first heat-seal layer contains a white pigment. This configuration allows for the imparting of opacity (e.g., a white opacity) to the laminate without using inks such as white ink. For example, if the contents of the packaging container are toothpaste, the packaging container can be given a design that expresses the whiteness of teeth. Furthermore, while the use of inks requires the evaporation and removal of solvents, which can place an environmental burden during the manufacturing of the laminate, the above configuration can further reduce the environmental burden during the manufacturing of the laminate.

[0053] Examples of white pigments include titanium dioxide, barium titanate, strontium titanate, aluminum oxide, magnesium oxide, zinc oxide, barium sulfate, magnesium carbonate, barium carbonate, zirconium oxide, calcium carbonate, white carbon, clay, talc, and barium sulfate.

[0054] The content of the white pigment in the first heat seal layer containing the white pigment is preferably 1% by mass or more, more preferably 2.5% by mass or more, even more preferably 5% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. This can further improve the effects described above.

[0055] In one embodiment, the first heat-seal layer may be a polyethylene film having a total light transmittance of 5% or more and 40% or less as measured in accordance with JIS K7375:2008, or, for example, a milky white polyethylene film. This can, for example, impart opacity to the laminate.

[0056] The first heat seal layer may contain additives. The second heat seal layer may contain additives. Examples of additives include crosslinking agents, antioxidants, antiblocking agents, lubricants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0057] The first heat seal layer may have a multilayer structure. The second heat seal layer may also have a multilayer structure. Examples of multilayer structures include a layer containing medium-density polyethylene, a layer containing medium-density polyethylene, and a layer containing medium-density polyethylene.

[0058] The first heat-seal layer may be a film containing polyethylene. The second heat-seal layer may also be a film containing polyethylene. The film may be a stretched film or an unstretched film. From the viewpoint of heat-sealability, the film is preferably an unstretched film.

[0059] The surface of the first heat seal layer may be surface-treated. The surface of the second heat seal layer may also be surface-treated. This improves the adhesion between these heat seal layers and the layers adjacent to them. Examples of surface treatment methods include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, glow discharge treatment, and chemical treatments such as oxidation treatment using chemicals.

[0060] An anchor coat layer may be formed on the surface of the first heat seal layer using a conventionally known anchor coat agent. An anchor coat layer may also be formed on the surface of the second heat seal layer using a conventionally known anchor coat agent.

[0061] The thickness of the first heat seal layer is preferably 30 μm or more, more preferably 50 μm or more, preferably 150 μm or less, and more preferably 130 μm or less. The thickness of the second heat seal layer is preferably 20 μm or more, more preferably 40 μm or more, preferably 140 μm or less, and more preferably 120 μm or less. If the above thickness is above the lower limit, the heat sealability can be further improved. If the above thickness is below the upper limit, the processability of the laminate can be improved.

[0062] The first heat seal layer and the second heat seal layer may each be formed by, for example, making a film from a resin composition containing at least polyethylene using a T-die method or an inflation method. The first heat seal layer and the second heat seal layer may each be laminated via, for example, an extruded polyethylene layer, as described later.

[0063] <Barrier resin layer and barrier film> The laminate of this disclosure comprises a barrier resin layer. The barrier resin layer is a layer mainly composed of a gas barrier resin. Such a laminate exhibits excellent barrier properties, such as oxygen barrier properties and water vapor barrier properties, without comprising dissimilar layers such as vapor-deposited films and aluminum foils.

[0064] Examples of gas barrier resins include ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile; polyamides such as nylon 6, nylon 6,6 and polymethaxylylene adipamide (MXD6); polyesters; polyurethanes; and (meth)acrylic resins. Among these, EVOH is preferred from the viewpoint of heat resistance and gas barrier properties.

[0065] EVOH can be obtained, for example, by copolymerizing ethylene with a vinyl ester monomer and then saponifying the copolymer. The copolymerization of ethylene with a vinyl ester monomer can be carried out by any known polymerization method, such as solution polymerization, suspension polymerization, or emulsion polymerization. Vinyl acetate is generally used as the vinyl ester monomer, but other vinyl ester monomers may also be used. Examples of other vinyl ester monomers include aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl versatate; and aromatic vinyl esters such as vinyl benzoate. EVOH may be modified by known methods, such as urethaneization, acetalization, cyanoethylation, or oxyalkyleneization.

[0066] In ethylene-vinyl alcohol copolymer (EVOH), the content of ethylene-derived constituent units (ethylene content) is preferably 20 mol% or more, more preferably 25 mol% or more, preferably 60 mol% or less, and more preferably 50 mol% or less. If the ethylene content is above the lower limit, for example, the processability of the laminate can be improved. If the ethylene content is below the upper limit, for example, the oxygen barrier and / or water vapor barrier properties of the laminate can be improved. The ethylene content is measured by NMR spectroscopy.

[0067] The melting point (Tm) of EVOH is preferably 140°C or higher, more preferably 145°C or higher, even more preferably 150°C or higher, preferably 200°C or lower, more preferably 195°C or lower, and even more preferably 190°C or lower, from the viewpoint of heat resistance. The Tm of EVOH is the melting peak temperature obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121:2012.

[0068] From the viewpoint of gas barrier properties, the average degree of saponification of the vinyl ester component in EVOH is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more. The average degree of saponification is measured in accordance with JIS K6726-1994 (provided that EVOH is a solution uniformly dissolved in water / methanol solvent).

[0069] The melt flow rate (MFR) of EVOH is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, even more preferably 0.5 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and even more preferably 10 g / 10 min or less, from the viewpoint of film-forming properties and processability. The MFR of EVOH is measured by Method A in accordance with JIS K7210:1999, under conditions of a temperature of 190°C and a load of 2.16 kg, although the measurement temperature may be 210°C depending on the melting point of EVOH.

[0070] The gas barrier resin content in the barrier resin layer is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more, 85% by mass or more, or 90% by mass or more. This improves the barrier properties of the laminate, such as oxygen barrier properties and water vapor barrier properties.

[0071] The barrier resin layer may contain resins other than gas barrier resins. Examples of such resins include polyolefins such as polyethylene and polypropylene; vinyl resins; and cellulose resins. The barrier resin layer may contain the above-mentioned additives.

[0072] The barrier resin layer may be formed, for example, by forming a film from a resin composition containing at least a gas barrier resin using a T-die method or an inflation method.

[0073] The thickness of the barrier resin layer is preferably 3 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. If the thickness is above the lower limit, for example, the effect of the barrier resin layer can be improved. If the thickness is below the upper limit, for example, the recyclability of the laminate can be improved. The ratio of the thickness of the barrier resin layer to the total thickness of the barrier film described below is preferably 5% or more, more preferably 10% or more, even more preferably 15% or more, preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less.

[0074] The laminate of the present disclosure may include a barrier film comprising the barrier resin layer described above. The barrier film may, for example, comprise a polyethylene layer and a barrier resin layer, with an adhesive resin layer between the polyethylene layer and the barrier resin layer. In one embodiment, the barrier film comprises a first polyethylene layer, a first adhesive resin layer, a barrier resin layer, a second adhesive resin layer, and a second polyethylene layer in this order. For example, a barrier film may comprise a linear low-density polyethylene layer, an adhesive resin layer, an ethylene-vinyl alcohol copolymer layer, an adhesive resin layer, and a linear low-density polyethylene layer in this order, as well as a barrier film may comprise a medium-density polyethylene layer, an adhesive resin layer, an ethylene-vinyl alcohol copolymer layer, an adhesive resin layer, and a medium-density polyethylene layer in this order. In the following description, unless specifically distinguished between the first polyethylene layer and the second polyethylene layer, they will simply be referred to as the polyethylene layer.

[0075] The polyethylene layers, such as the first polyethylene layer and the second polyethylene layer, contain polyethylene as the main component. Examples of polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. The polyethylene contained in the first polyethylene layer and the polyethylene contained in the second polyethylene layer may be the same or different.

[0076] The polyethylene layer may contain biomass polyethylene. The polyethylene layer may contain recycled polyethylene. The polyethylene layer may contain the above-mentioned additives.

[0077] The polyethylene content in the polyethylene layer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. With such a configuration, for example, the recyclability of a packaging container comprising the laminate of this disclosure can be improved.

[0078] The ratio of the thickness of the first polyethylene layer to the total thickness of the barrier film is preferably 10% or more, more preferably 15% or more, even more preferably 20% or more, preferably 45% or less, more preferably 43% or less, and even more preferably 40% or less. The ratio of the thickness of the second polyethylene layer to the total thickness of the barrier film is preferably 10% or more, more preferably 15% or more, even more preferably 20% or more, preferably 45% or less, more preferably 43% or less, and even more preferably 40% or less.

[0079] The adhesive resin layer contains adhesive resin. Examples of adhesive resins include polyolefins such as polyethylene, modified polyolefins, vinyl resins, polyethers, polyesters, polyamides, polyurethanes, silicone resins, epoxy resins, and phenolic resins. Among these, polyolefins and modified polyolefins are preferred from the viewpoint of recyclability and adhesion, and modified polyolefins such as acid-modified polyolefins are more preferred. Examples of modified polyolefins include modified polyolefins (particularly graft-modified polyolefins) using unsaturated carboxylic acids such as maleic acid and fumaric acid, or their acid anhydrides, esters, or metal salts. Among adhesive resins, modified polyolefins such as modified polyethylene are preferred from the viewpoint of obtaining a composition suitable for monomaterial packaging materials, acid-modified polyolefins such as acid-modified polyethylene are more preferred, and maleic anhydride-modified polyethylene is even more preferred.

[0080] The adhesive resin layer may contain the above-mentioned additives.

[0081] The ratio of the thickness of the first adhesive resin layer to the total thickness of the barrier film is preferably 1% or more, more preferably 3% or more, even more preferably 5% or more, preferably 20% or less, more preferably 18% or less, and even more preferably 15% or less. The ratio of the thickness of the second adhesive resin layer to the total thickness of the barrier film is preferably 1% or more, more preferably 3% or more, even more preferably 5% or more, preferably 20% or less, more preferably 18% or less, and even more preferably 15% or less.

[0082] The barrier film having a barrier resin layer may also be a co-extruded resin film. The co-extruded resin film may be manufactured by forming a film using, for example, an inflation method or a T-die method. The barrier film having a barrier resin layer may be, for example, a co-extruded resin film comprising a linear low-density polyethylene layer, an adhesive resin layer, an ethylene-vinyl alcohol copolymer layer, an adhesive resin layer, and a linear low-density polyethylene layer in this order. Lamination of the barrier film and the heat seal layer, etc., can be carried out via an extruded polyethylene layer, as described later.

[0083] The barrier film may contain a compatibilizer. Two or more layers in the barrier film may contain a compatibilizer. By containing a compatibilizer in the barrier film, when the tube container body made using the laminate of this disclosure is heated, melted, and recycled, the miscibility between the gas barrier resin contained in the barrier resin layer and the polyethylene contained in the heat seal layer, etc., can be improved. This effectively suppresses a decrease in its physical properties. It also effectively suppresses a decrease in its transparency.

[0084] While conventionally known compatibilizers can be appropriately selected and used, from the viewpoint of recyclability, unsaturated carboxylic acid-modified polyolefins are preferred, and maleic anhydride-modified polyethylene is more preferred.

[0085] The content of the compatibilizer in the entire barrier film is preferably 5% by mass or more, more preferably 20% by mass or less. When the content is 5% by mass or more, the above-mentioned deterioration in physical properties and transparency can be suppressed more effectively. When the content is 20% by mass or less, the moldability of the barrier film can be improved, and the deterioration in strength of the film made using the resin obtained by recycling the laminate of this disclosure can be suppressed.

[0086] The barrier film may be a stretched film or an unstretched film. From the viewpoint of the strength of the laminate, the barrier film may be a stretched film. The stretched film may be a uniaxially oriented film or a biaxially oriented film.

[0087] It is preferable that the surface of the barrier film is treated with the above-mentioned surface treatment. This improves the adhesion between the barrier film and the layer adjacent to the barrier film.

[0088] The total thickness of the barrier film is preferably 20 μm or more, more preferably 30 μm or more, preferably 100 μm or less, and more preferably 90 μm or less. A thickness of 20 μm or more can further improve the gas barrier properties of the laminate. A thickness of 100 μm or less can further improve the recyclability of the laminate.

[0089] <Base material> The laminate of this disclosure may further comprise one or more substrates selected from between the first heat seal layer and the barrier resin layer, and between the barrier resin layer and the second heat seal layer. The laminate of this disclosure may further comprise one or more substrates selected from between the first heat seal layer and the barrier film, and between the barrier film and the second heat seal layer. The substrate mainly contains polyethylene.

[0090] Examples of polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Among these, high-density polyethylene and medium-density polyethylene are preferred from the viewpoint of the strength and heat resistance of the substrate, and medium-density polyethylene is more preferred from the viewpoint of the stretchability of the substrate.

[0091] The polyethylene content in the base material is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. With such a configuration, for example, the recyclability of a packaging container comprising the laminate of this disclosure can be improved.

[0092] The base material may contain biomass polyethylene. The base material may contain recycled polyethylene. The base material may contain the above-mentioned additives.

[0093] In one embodiment, the substrate may be a polyethylene film having a total light transmittance, as measured in accordance with JIS K7375:2008, preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more.

[0094] The laminate of this disclosure may further include a substrate containing a white pigment between the printing substrate and the first heat-seal layer. With such a configuration, the laminate can be given opacity (e.g., a white opacity) without using inks such as white ink, and the environmental impact can be reduced.

[0095] Examples of white pigments include titanium dioxide, barium titanate, strontium titanate, aluminum oxide, magnesium oxide, zinc oxide, barium sulfate, magnesium carbonate, barium carbonate, zirconium oxide, calcium carbonate, white carbon, clay, talc, and barium sulfate.

[0096] The content of the white pigment in the substrate containing the white pigment is preferably 1% by mass or more, more preferably 2.5% by mass or more, even more preferably 5% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. This can further improve the effects described above.

[0097] In one embodiment, the substrate may be a polyethylene film having a total light transmittance of 5% or more and 40% or less as measured in accordance with JIS K7375:2008, or, for example, a milky white polyethylene film. This allows, for example, the laminate to be imparted with opacity.

[0098] The substrate may have a multilayer structure. Examples of multilayer structures include a layer containing linear low-density polyethylene, a layer containing high-density polyethylene, and a layer containing linear low-density polyethylene.

[0099] The base material may be a film containing polyethylene. The film may be a stretched film or an unstretched film. From the viewpoint of the strength of the laminate, a stretched film is preferred. The stretched film may be a uniaxially oriented film or a biaxially oriented film. In one embodiment, the stretching ratio in the longitudinal direction (MD) of the stretched film is preferably 2 times or more and 10 times or less, more preferably 3 times or more and 7 times or less. In one embodiment, the stretching ratio in the transverse direction (TD) of the stretched film is preferably 2 times or more and 10 times or less, more preferably 3 times or more and 7 times or less. When the stretching ratio is 2 times or more, for example, the rigidity, strength and heat resistance of the polyethylene film can be improved, the printability of the polyethylene film can be improved, and the transparency of the polyethylene film can be improved. When the stretching ratio is 10 times or less, for example, good stretching can be performed without causing the film to break. In one embodiment, the stretched film is a uniaxially oriented film, and more specifically, a uniaxially oriented film that has been stretched in the longitudinal direction (MD).

[0100] The surface of the substrate may be treated with the above-mentioned surface treatment. This can improve the adhesion between the substrate and the layer adjacent to the substrate. An anchor coat layer may be formed on the surface of the substrate using a conventionally known anchor coat agent.

[0101] The thickness of the substrate is preferably 10 μm or more, more preferably 20 μm or more, preferably 100 μm or less, and more preferably 70 μm or less. A substrate thickness of 10 μm or more can further improve its strength and heat resistance. A substrate thickness of 100 μm or less can improve the processability of the laminate.

[0102] The base material may be prepared, for example, by forming a film from a resin composition containing at least polyethylene using a T-die method or an inflation method.

[0103] <Print layer> The laminate of this disclosure may include a printed layer, which includes an image. Examples of images include text, shapes, symbols, patterns, and combinations thereof. Images may also include textual information such as product name, name of contents in the packaging, manufacturer, and ingredients. Images may be solid color (so-called solid images).

[0104] The printed layer may be formed using a printing layer composition such as a thermoplastic resin composition, a thermosetting resin composition, and an energy-ray curable resin composition, each containing a colorant. Specifically, the printed layer contains a resin component such as a thermoplastic resin, a cured thermosetting resin, or a cured energy-ray curable resin, and a colorant.

[0105] Examples of colorants include pigments such as inorganic and organic pigments; and dyes such as acid dyes, direct dyes, disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes, and sublimation dyes. Specific examples of pigments include titanium dioxide, zinc oxide, carbon black, iron oxide, iron yellow, ultramarine, metallic pigments, pearl pigments, and fluorescent pigments. The printed layer may be a high-luminosity layer with a high metallic sheen.

[0106] The resin component content in the printed layer may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 99% by mass or less, 97% by mass or less, or 95% by mass or less. The colorant content in the printed layer may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 90% by mass or less, 70% by mass or less, or 50% by mass or less.

[0107] The printing layer composition may contain an organic solvent and / or water from the viewpoint of improving coatability and other properties. Examples of organic solvents include hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, cellosolve acetate and butyl cellosolve acetate; and alcohols such as propanol.

[0108] The printed layer may be provided on, for example, at least one surface of the substrate. For example, the laminate of the present disclosure may include a printed substrate between the second heat seal layer and the barrier resin layer, specifically between the second heat seal layer and the barrier film. The printed substrate comprises a substrate mainly composed of polyethylene and a printed layer provided on at least one surface of the substrate. The printed layer on the printed substrate may be provided on the surface of the substrate facing the second heat seal layer, or on the surface of the substrate facing the first heat seal layer. Preferably, the printed layer on the printed substrate is provided on the surface of the substrate facing the second heat seal layer.

[0109] The thickness of the printed layer is preferably 0.01 μm or more, more preferably 0.5 μm or more, even more preferably 1 μm or more, preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

[0110] Printing methods for the printed layer include, for example, letterpress printing, flexographic printing, gravure printing, offset printing, screen printing, inkjet printing, and thermal transfer printing. When the printed layer is formed by letterpress printing or flexographic printing, it is preferable to use an energy-ray curable resin composition, and more preferable to use an ultraviolet-curable resin composition.

[0111] When the laminate of this disclosure is viewed from above, it is preferable that no printed layer is formed in the area corresponding to the area where heat sealing is planned to form the body of the tube container. "View from above" means viewing the laminate from the direction normal to the second surface of the laminate. In addition to suppressing the exposure of the end face of the barrier resin layer at the joint as described above, this configuration of the printed layer can suppress the occurrence of delamination at the joint (tube bonding area) starting from the printed layer.

[0112] <Anchor Coat Layer> The laminate of this disclosure may further include an anchor coat layer between the printed layer and the extruded polyethylene layer. Such a laminate has, for example, excellent interlayer adhesion. The anchor coat layer is formed, for example, by an anchor coat agent.

[0113] Examples of anchor coating agents include polyurethane-based, polyolefin-based, polyethyleneimine-based, or epoxy resin-based anchor coating agents. In one embodiment, the anchor coating agent is a two-component curable resin, consisting, for example, a polyol as the main component and a polyisocyanate as the curing agent. Examples of polyols include polyether polyols, polyester polyols, and (meth)acrylic polyols. Examples of polyisocyanates include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenylene polyisocyanate, as well as aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate. In one embodiment, the anchor coating layer consists of polyurethane obtained by the reaction of the polyol and the polyisocyanate. Specific examples of polyurethanes include polyether polyurethane, polyester polyurethane, and poly(meth)acrylic polyurethane.

[0114] The anchor coat layer can be formed, for example, by applying an anchor coat agent to a printing substrate. The anchor coat agent can be applied by coating methods such as the roll coating method, gravure roll coating method, and kiss coating method, or by printing methods.

[0115] The thickness of the anchor coat layer is preferably 0.01 μm or more, more preferably 0.3 μm or more, even more preferably 0.5 μm or more, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less.

[0116] <Adhesive layer> The laminate of this disclosure may have adhesive layers between any layers, for example, between the second heat seal layer and the barrier film, between the barrier film and the first heat seal layer, between the second heat seal layer and the substrate, between the substrate and the barrier film, and between the substrate and the first heat seal layer. This improves the interlayer adhesion strength in the laminate and therefore suppresses delamination in, for example, the laminate and the tube container.

[0117] As the adhesive layer, for example, an extruded polyethylene layer containing polyethylene as the main component is preferred. Laminates having an extruded polyethylene layer have a high polyethylene content and excellent recyclability.

[0118] Examples of polyethylene included in the extruded polyethylene layer include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Among these, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene are preferred from the viewpoint of interlayer adhesion, and low-density polyethylene is more preferred.

[0119] The melt flow rate (MFR) of polyethylene contained in the extruded polyethylene layer is preferably 1 g / 10 min or more, more preferably 2 g / 10 min or more, even more preferably 3 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and even more preferably 20 g / 10 min or less, from the viewpoint of film-forming properties and processability. The MFR of polyethylene is measured by Method A in accordance with JIS K7210:1999, under conditions of a temperature of 190°C and a load of 2.16 kg.

[0120] The melting point (Tm) of the polyethylene contained in the extruded polyethylene layer is preferably 100°C or higher, preferably 140°C or lower, more preferably 130°C or lower, and even more preferably 120°C or lower, from the viewpoint of balancing heat resistance and adhesiveness. The Tm of polyethylene is the melting peak temperature obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121:2012.

[0121] The extruded polyethylene layer may contain biomass polyethylene. The extruded polyethylene layer may contain recycled polyethylene. The extruded polyethylene layer may contain the above-mentioned additives.

[0122] The polyethylene content in the extruded polyethylene layer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. This configuration can improve, for example, adhesion and recyclability.

[0123] The thickness of the extruded polyethylene layer is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, preferably 40 μm or less, more preferably 35 μm or less, and even more preferably 30 μm or less. When the thickness is 5 μm or more, interlayer adhesion can be further improved. When the thickness is 40 μm or less, the production cost of the laminate can be reduced and its productivity can be improved.

[0124] The extruded polyethylene layer may be formed, for example, by melt-extruding a resin composition containing at least polyethylene onto the target film. The melting temperature at this time is preferably 280°C or higher, more preferably 290°C or higher, preferably 340°C or lower, and more preferably 335°C or lower.

[0125] [Tube container body] The tube container body of this disclosure comprises the laminate described above. The tube container body of this disclosure will now be described with reference to the drawings. Figure 6 is a simplified diagram showing the configuration of the tube container 100, and Figure 7 is a cross-sectional view AA of Figure 6. As shown in Figure 6, the tube container body 101 comprises a head portion 102 and a body portion 103, and the body portion 103 is made of the laminate of this disclosure.

[0126] <Head> The head portion 102 includes a shoulder portion 104 connected to one end of the body portion 103, and an outlet portion 105 connected to the shoulder portion 104. In one embodiment, the spout portion 105 is provided with a thread 107 for screwing on a cap 106.

[0127] In one embodiment, the head is formed from a resin composition containing polyethylene. This improves the recyclability of the tube container body. Examples of polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Among these, high-density polyethylene is preferred from the viewpoint of shape retention and moldability.

[0128] The above resin composition may contain at least one selected from biomass polyethylene and recycled polyethylene. The above resin composition may contain the above additives.

[0129] The head can be manufactured by conventionally known methods. For example, the head can be manufactured by compression molding or injection molding and then joined to the body.

[0130] When manufacturing a tube container body using a compression molding method, the body may be attached to a male mold having a protrusion at the top, the male and female molds may be placed opposite each other, molten resin composition may be supplied into the male and female molds and compressed to form the head, and the head may be joined to one of the openings of the body, thereby manufacturing a tube container body comprising a head and a body.

[0131] When manufacturing a tube container body using injection molding, the body may be attached to a male mold having a protrusion at the top, the male and female molds may be placed opposite each other, molten resin composition may be supplied from the gate and injection molded to form the head, and the head may be joined to one of the openings of the body, thereby manufacturing a tube container body comprising a head and a body.

[0132] <torso> In the tube container body 101 of the present disclosure, the body portion 103 is connected to the shoulder portion 104 of the head portion 102. The body portion 103 includes a joint portion 108 formed by overlapping the first heat-seal layer side surface of one end of the laminate of the present disclosure with the second heat-seal layer side surface of the other end so that they are in contact, rolling it into a cylindrical shape, and then heat-sealing the overlapped portion. The body portion 103 also includes a bottom joint portion 109 formed by heat-sealing the opening of the rolled-in-cylindrical laminate.

[0133] Examples of conventional heat sealing methods include bar seals, rotary roll seals, belt seals, impulse seals, high-frequency seals, ultrasonic seals, and flame seals.

[0134] For example, a cylindrical body may be manufactured by overlapping the laminate of the present disclosure so that the surface of the first heat seal layer at one end and the surface of the second heat seal layer at the other end are in contact, rolling them into a cylindrical shape, and then heat sealing the overlapped portion. From the viewpoint of heat sealability, it is preferable that one end of the overlapping assembly is the first heat seal layer and the other end is the second heat seal layer. In this case, the first heat seal layer and the second heat seal layer melt and join together, forming a joint.

[0135] In the above embodiment, the joint is formed by overlapping, but the first heat-seal layers may also be joined by butting the same surfaces at both ends of the laminate together and heat-sealing them.

[0136] [Tube container] The tube container of this disclosure will now be described with reference to the drawings. As shown in Figure 6, the tube container 100 of this disclosure comprises a tube container body 101 and a cap 106 attached to the head 102. In the tube container made from the laminate of this disclosure, the thickness of each layer constituting the laminate can be measured in the cross-section of the body portion 103 in Figure 7, excluding the joint portion 108. For example, as shown in Figure 7, the portion enclosed by the dotted line may be measured.

[0137] <Tube container body> As the tube container itself has been described above, it will not be described here.

[0138] <Cap> The cap is detachably attached to the dispensing port at the top and serves to close the dispensing port. In one embodiment, the cap is formed from a resin composition containing a thermoplastic resin. Examples of thermoplastic resins include polyethylene and polyolefins such as polypropylene, polyester, cellulose resin, and vinyl resin. From the viewpoint of recyclability, polyethylene is particularly preferred. Examples of polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Among these, high-density polyethylene is preferred from the viewpoint of shape retention and ease of opening.

[0139] The above resin composition may contain at least one selected from biomass polyethylene and recycled polyethylene. The above resin composition may contain the above additives.

[0140] As shown in Figure 6, the cap may be a screw type with a groove on the inner surface of the cap that screws onto the threads 107 of the dispensing port 105, or it may be a cap that is fitted by pressing it onto the dispensing port 105.

[0141] This disclosure relates, for example, to the following [1] to

[22] . [1] A laminate comprising, in this order, at least a first heat seal layer, a barrier resin layer, and a second heat seal layer, wherein the first heat seal layer mainly contains polyethylene, the second heat seal layer mainly contains polyethylene, the barrier resin layer mainly contains a gas barrier resin, the laminate has a first surface and a second surface, the first heat seal layer constitutes the first surface, the second heat seal layer constitutes the second surface, and the total thickness (T) of the layers mainly containing polyethylene, including the first surface, located between the barrier resin layer and the first surface. in The thickness (T) of the barrier resin layer b1 ) ratio (T in / Tb1 A laminate in which the ratio is 8.0 or higher, and the polyethylene content in the entire laminate is 90% by mass or higher. [2] The laminate according to [1], wherein the barrier resin layer contains an ethylene-vinyl alcohol copolymer as the main component. [3] The laminate according to [1] or [2], wherein the laminate comprises a barrier film comprising a first polyethylene layer, a first adhesive resin layer, the barrier resin layer, a second adhesive resin layer, and a second polyethylene layer. [4] The laminate according to [3], wherein the thickness of the barrier film is 20 μm or more and 100 μm or less. [5] The total thickness (T in A laminate according to any one of the above [1] to [4], wherein the thickness of the slab is 120 μm or more and 250 μm or less. [6] The total thickness (T) of the layer located between the barrier resin layer and the second surface, which mainly contains polyethylene including the second surface. out The thickness (T) of the barrier resin layer b2 ) ratio (T out / T b2 A laminate according to any one of the above [1] to [5], wherein the ratio is 6.0 or more and 14.0 or less. [7] The total thickness (T out The laminate according to [6] above, wherein the thickness of the slab is 100 μm or more and 220 μm or less. [8] The laminate according to any one of the claims [1] to [7], wherein the laminate further comprises a printing substrate between the first heat seal layer and the barrier resin layer and / or between the barrier resin layer and the second heat seal layer, the printing substrate comprising a substrate mainly composed of polyethylene and a printing layer provided on at least one surface of the substrate. [9] The laminate according to [8], wherein the laminate comprises, in this order, the barrier resin layer, the substrate of the printing substrate, the printing layer of the printing substrate, and the second heat seal layer.

[10] The laminate according to [8] or [9], wherein the substrate in the printing substrate is a stretched film containing at least one selected from medium-density polyethylene and high-density polyethylene.

[11] A laminate for forming the body of a tube container, wherein the first heat seal layer is a sealant layer on the inner surface of the body, and the second heat seal layer is a sealant layer on the outer surface of the body, according to any one of the claims [1] to

[10] .

[12] The laminate according to

[11] , wherein the laminate further comprises a printing substrate between the first heat seal layer and the barrier resin layer and / or between the barrier resin layer and the second heat seal layer, the printing substrate comprising a substrate mainly composed of polyethylene and a printing layer provided on at least one surface of the substrate, the printing layer not formed in the printing substrate in a region corresponding to the area to be heat-sealed for forming the body of the tube container body.

[13] The laminate according to

[11] or

[12] , wherein the laminate comprises, in order from the inner surface, the first heat seal layer, optionally an extruded polyethylene layer, a barrier film having the barrier resin layer, optionally an extruded polyethylene layer, a substrate mainly containing polyethylene, and a printing substrate having a printing layer, optionally an extruded polyethylene layer, and the second heat seal layer.

[14] The laminate according to

[13] , wherein the first heat-seal layer contains a white pigment.

[15] The laminate according to

[13] or

[14] , wherein the first heat-seal layer is a polyethylene film having a total light transmittance of 5% or more and 40% or less (measured in accordance with JIS K7375:2008).

[16] The laminate according to any one of the above

[11] to

[15] , wherein the laminate comprises, in order from the inner surface, the first heat seal layer, optionally an extruded polyethylene layer, a substrate mainly containing polyethylene, optionally an extruded polyethylene layer, a barrier film comprising the barrier resin layer, optionally an extruded polyethylene layer, a substrate mainly containing polyethylene, and a printing substrate comprising a printing layer, optionally an extruded polyethylene layer, and the second heat seal layer.

[17] The laminate according to

[16] , wherein at least one selected from the first heat seal layer and the substrate containing polyethylene as the main component contains a white pigment.

[18] The laminate according to

[16] or

[17] , wherein at least one selected from the first heat seal layer and the substrate containing polyethylene as the main component is a polyethylene film having a total light transmittance of 5% or more and 40% or less (measured in accordance with JIS K7375:2008).

[19] A tube container body comprising a head and a body, wherein the head comprises a shoulder portion connected to one end of the body and an extraction port portion connected to the shoulder portion, and the body is composed of a laminate as described in any one of the items [1] to

[18] above.

[20] The tube container body according to

[19] , wherein the head is formed of a resin composition containing polyethylene.

[21] A tube container comprising the tube container body described in

[19] or

[20] above, and a cap.

[22] The tube container according to

[21] , wherein the cap is formed of a resin composition containing polyethylene. [Examples]

[0142] The laminates of the present disclosure will be described in more detail below with reference to examples, but the laminates of the present disclosure are not limited to the following examples. In the following description, polyethylene will also be referred to as "PE", linear low-density polyethylene as "LLDPE", high-density polyethylene as "HDPE", low-density polyethylene as "LDPE", ethylene-vinyl alcohol copolymer as "EVOH", polyethylene terephthalate as "PET", polyethylene film as "PEF", barrier film as "BF", and extruded polyethylene layer as "EC-PE".

[0143] [Film used] The films used in the examples or comparative examples are listed below. • Uniaxially oriented HDPE film Tokyo Ink Co., Ltd., Hybron SMKQW, HDPE, 25μm thickness • Biaxially oriented PET film Toyobo Co., Ltd., E5200, 12μm thickness • Aluminum-coated biaxially oriented PET film Manufactured by Toray Film Processing, BR-PET1312, 12μm thick • Transparent vapor-deposited biaxially oriented PET film A film in which a silica vapor-deposited film is formed on one surface of a PET film with a thickness of 12 μm by the CVD method. • Polyethylene film Made by Aicello, Suzuron L-100N, LLDPE, Thickness 30 μm, 50 μm, or 80 μm • Polyethylene film A 50 μm or 80 μm thick, polyethylene (density: 0.931 g / cm³) 3 A film obtained by forming a film with MFR: 2.1g / 10min. • Polyethylene film B Thickness: 180 μm, polyethylene (density: 0.920 g / cm³) 3 A film obtained by forming a film with MFR: 1.9g / 10min. • Opaque polyethylene film A Thickness 130μm, 100μm, 80μm, or 50μm, polyethylene (density: 0.920g / cm³) 3 A film obtained by forming a film of a mixture of 94% by mass (MFR: 1.9g / 10min) and 6% by mass of a white pigment (titanium dioxide-based pigment). • Milky white polyethylene film B Thickness: 80 μm, polyethylene (density: 0.924 g / cm³) 3 A film obtained by forming a film of a mixture of 85% by mass (MFR: 2.0g / 10 min) and 15% by mass of a white pigment (titanium dioxide-based pigment). • Antistatic agent-containing polyethylene film A Thickness 110 μm, 80 μm, 50 μm, or 30 μm, polyethylene (density: 0.920 g / cm³) 3 A film obtained by forming a film of a mixture of (MFR: 1.9g / 10min) 98% by mass and 2% by mass of an antistatic agent. • Antistatic agent-containing polyethylene film B 50 μm or 30 μm thick, polyethylene (density: 0.930 g / cm³) 3 A film obtained by forming a film of a mixture of 98.5% by mass (MFR: 2.1g / 10min) and 1.5% by mass of an antistatic agent and an antiblocking agent. • Antistatic agent-containing polyethylene film C Thickness 130 μm, 50 μm, or 30 μm, polyethylene (density: 0.920 g / cm³) 3 A film obtained by forming a film of a mixture of (MFR: 1.9g / 10min) 98% by mass and 2% by mass of an antistatic agent. • EVOH-based barrier film A LLDPE (Dow Chemical, DOWLEX2045G, Density: 0.920 g / cm³) 3 ) and adhesive resin (Mitsui Chemicals, Admer NF557) and EVOH (Kuraray, EVAL H171B, density: 1.17 g / cm³) 3 , ethylene content: 38 mol%, adhesive resin (Mitsui Chemicals, Admer NF557), and LLDPE (Dow Chemical, DOWLEX2045G, density: 0.920 g / cm³) 3A barrier film was obtained by co-extruding five layers of the following materials using an inflation method. The barrier film comprises, in this order, a 30 μm thick LLDPE layer and an adhesive resin layer (LLDPE layer: 26 μm, adhesive resin layer: 4 μm), a 15 μm thick EVOH layer, and a 30 μm thick adhesive resin layer and LLDPE layer (adhesive resin layer: 4 μm, LLDPE layer: 26 μm), with a total thickness of approximately 75 μm. EVOH-based barrier film B LLDPE (Dow Chemical, DOWLEX2045G, Density: 0.920 g / cm³) 3 ) and adhesive resin (Mitsui Chemicals, Admer NF528T) and EVOH (Kuraray, F171B, density: 1.19 g / cm³) 3 , ethylene content: 32 mol%, adhesive resin (Mitsui Chemicals, Admer NF528T), and LLDPE (Dow Chemical, DOWLEX2045G, density: 0.920 g / cm³). 3 A barrier film was obtained by co-extruding five layers of the following materials using an inflation method. The barrier film comprises, in this order, a 30 μm LLDPE layer and an adhesive resin layer (LLDPE layer: 26 μm, adhesive resin layer: 4 μm), a 15 μm thick EVOH layer, and a 30 μm thick adhesive resin layer and LLDPE layer (adhesive resin layer: 4 μm, LLDPE layer: 26 μm), with a total thickness of approximately 75 μm.

[0144] [Example A1-1] A 1 μm thick printed layer was formed on one surface of a 25 μm thick uniaxially oriented HDPE film (Hybron SMKQW) by gravure printing and drying using a urethane-based gravure ink (manufactured by Toyo Ink). In this way, a printed substrate was obtained. However, no printed layer was formed in the areas corresponding to 4.0 mm at one end and 2.0 mm at the other end of the laminate individual pieces obtained by the processing described later (areas intended for tube bonding).

[0145] The following lamination process was performed using a single extrusion lamination method: One surface of EVOH-based barrier film A was laminated with LDPE (Novatec LD LC602A, manufactured by Nippon Polyethylene, MFR: 8.2 g / 10 min, density: 0.919 g / cm³). 3 A 30 μm thick extruded polyethylene layer was formed by melting and extruding a polyethylene film (melting point: 107°C) at 330°C, and a 100 μm thick milky white polyethylene film A was laminated to this extruded polyethylene layer.

[0146] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on the other surface of EVOH-based barrier film A by melt-extruding LDPE (LC602A) at 330°C, and the non-printed surface of the printing substrate was laminated to this extruded polyethylene layer. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed surface of the printing substrate and dried to form a 1 μm thick anchor coat layer. A 20 μm thick extruded polyethylene layer was formed on the surface of the anchor coat layer by melt-extruding LDPE (LC602A) at 330°C, and an 80 μm thick antistatic agent-containing polyethylene film A was laminated via this extruded polyethylene layer.

[0147] In this way, a laminate was obtained. The laminate comprises, in this order: (outermost layer) an antistatic agent-containing polyethylene film (80 μm, second heat-seal layer), an extruded polyethylene layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented HDPE film (25 μm), an extruded polyethylene layer (20 μm), an EVOH-based barrier film A (75 μm), an extruded polyethylene layer (30 μm), and a milky white polyethylene film (100 μm, first heat-seal layer) (innermost layer). The numbers in parentheses indicate the thickness.

[0148] [Examples A1-2 to A1-4] A laminate was prepared in the same manner as in Example A1, except that the outermost layer of the antistatic agent-containing polyethylene film and / or the innermost layer of the milky white polyethylene film were changed as shown in Table 1. [Examples A1-5] The laminate was fabricated in the same manner as in Example A1-1, except that a printed layer was also formed on the area where the tube was to be attached.

[0149] [Example A2-1] A 1 μm thick printed layer was formed on one surface of a 25 μm thick uniaxially oriented HDPE film (Hybron SMKQW) by gravure printing and drying using a urethane-based gravure ink (manufactured by Toyo Ink). In this way, a printed substrate was obtained. However, no printed layer was formed in the area where the product was to be attached to the tube.

[0150] Lamination was performed using the tandem extrusion lamination method as follows: A 20 μm thick extruded polyethylene layer was formed on one surface of EVOH-based barrier film A by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick milky white polyethylene film A was laminated to this extruded polyethylene layer. A 30 μm thick extruded polyethylene layer was formed on the surface of the laminated milky white polyethylene film by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick polyethylene film (Suzuron L-100N) was laminated to this extruded polyethylene layer.

[0151] Lamination was performed as follows using the tandem extrusion lamination method. On the other surface of EVOH-based barrier film A, LDPE (LC602A) was melt-extruded at 330°C to form a 20 μm thick extruded polyethylene layer, and the non-printed surface of the printing substrate was laminated to this extruded polyethylene layer. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied and dried to the printed surface of the printing substrate to form an anchor coat layer with a thickness of 1 μm. On the surface of the anchor coat layer, LDPE (LC602A) was melt-extruded at 330°C to form a 20 μm thick extruded polyethylene layer, and a 50 μm thick antistatic agent-containing polyethylene film A was laminated via this extruded polyethylene layer.

[0152] In this way, a laminate was obtained. The laminate comprises, in order, an antistatic agent-containing polyethylene film (50 μm, second heat-seal layer) (outermost layer), an extruded polyethylene layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented HDPE film (25 μm), an extruded polyethylene layer (20 μm), an EVOH-based barrier film A (75 μm), an extruded polyethylene layer (20 μm), a milky white polyethylene film (50 μm), an extruded polyethylene layer (30 μm), and a polyethylene film (50 μm, first heat-seal layer) (innermost layer).

[0153] [Examples A2-2 to A2-3] A laminate was prepared in the same manner as in Example A2-1, except that the outermost layer of the polyethylene film containing an antistatic agent and / or the innermost layer of polyethylene film were changed as shown in Table 1.

[0154] [Examples A2-4] The laminate was fabricated in the same manner as in Example A2-1, except that a printed layer was also formed on the area where the tube was to be attached.

[0155] [Example A3-1] A 1 μm thick printed layer was formed on one surface of a 25 μm thick uniaxially oriented HDPE film (Hybron SMKQW) by gravure printing and drying using a urethane-based gravure ink (manufactured by Toyo Ink). In this way, a printed substrate was obtained. However, no printed layer was formed in the area where the product was to be attached to the tube.

[0156] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on one surface of EVOH-based barrier film A by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick milky white polyethylene film A was laminated through this extruded polyethylene layer. A 30 μm thick extruded polyethylene layer was formed on the surface of the laminated milky white polyethylene film by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick polyethylene film A was laminated through this extruded polyethylene layer.

[0157] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on the other surface of EVOH-based barrier film A by melt-extruding LDPE (LC602A) at 330°C, and the non-printed surface of the printing substrate was laminated to this extruded polyethylene layer. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed surface of the printing substrate and dried to form a 1 μm thick anchor coat layer. A 20 μm thick extruded polyethylene layer was formed on the surface of the anchor coat layer by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick antistatic agent-containing polyethylene film B was laminated through this extruded polyethylene layer.

[0158] In this way, a laminate was obtained. The laminate comprises, in order, an antistatic agent-containing polyethylene film (50 μm, second heat-seal layer) (outermost layer), an extruded polyethylene layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented HDPE film (25 μm), an extruded polyethylene layer (20 μm), an EVOH-based barrier film A (75 μm), an extruded polyethylene layer (20 μm), a milky white polyethylene film (50 μm), an extruded polyethylene layer (30 μm), and a polyethylene film (50 μm, first heat-seal layer) (innermost layer).

[0159] [Examples A3-2 to A3-3] A laminate was prepared in the same manner as in Example A3-1, except that the outermost layer of the polyethylene film containing an antistatic agent and / or the innermost layer of polyethylene film were changed as shown in Table 1. [Examples A3-4] The laminate was fabricated in the same manner as in Example A3-1, except that a printed layer was also formed on the area where the tube was to be attached.

[0160] [Comparative Example A1-1] A 1 μm thick printed layer was formed on one surface of a 25 μm thick uniaxially oriented HDPE film (Hybron SMKQW) by gravure printing and drying using a urethane-based gravure ink (manufactured by Toyo Ink). In this way, a printed substrate was obtained. However, no printed layer was formed in the area where the product was to be attached to the tube.

[0161] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on one surface of a 50 μm thick milky white polyethylene film A by melt-extruding LDPE (LC602A) at 330°C, and an EVOH-based barrier film A was laminated to this extruded polyethylene layer. A 30 μm thick extruded polyethylene layer was formed on the surface of the laminated EVOH-based barrier film A by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick polyethylene film (Suzuron L-100N) was laminated to this extruded polyethylene layer.

[0162] Lamination was performed as follows using the tandem extrusion lamination method. On the other surface of the milky white polyethylene film A, LDPE (LC602A) was melt-extruded at 330°C to form an extruded polyethylene layer with a thickness of 20 μm, and the non-printed surface of the printing substrate was laminated to this extruded polyethylene layer. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed surface of the printing substrate and dried to form an anchor coat layer with a thickness of 1 μm. On the surface of the anchor coat layer, LDPE (LC602A) was melt-extruded at 330°C to form an extruded polyethylene layer with a thickness of 20 μm, and a 50 μm thick antistatic polyethylene film C was laminated through this extruded polyethylene layer.

[0163] In this way, a laminate was obtained. The laminate comprises, in order, an antistatic agent-containing polyethylene film (50 μm, second heat-seal layer) (outermost layer), an extruded polyethylene layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented HDPE film (25 μm), an extruded polyethylene layer (20 μm), a milky white polyethylene film (50 μm), an extruded polyethylene layer (20 μm), an EVOH-based barrier film A (75 μm), an extruded polyethylene layer (30 μm), and a polyethylene film (50 μm, first heat-seal layer) (innermost layer).

[0164] [Comparative Examples A1-2~A1-3] A laminate was prepared in the same manner as in Comparative Example A1-1, except that the outermost layer of polyethylene film containing an antistatic agent and / or the innermost layer of polyethylene film were changed as shown in Table 1.

[0165] [Comparative Examples A1-4] The laminate was prepared in the same manner as in Comparative Example A1-1, except that a printed layer was also formed on the area where the tube was to be attached.

[0166] [Example B1-1] A 1 μm thick printed layer was formed on one surface of a 25 μm thick uniaxially oriented HDPE film (Hybron SMKQW) by gravure printing and drying using a urethane-based gravure ink (manufactured by Toyo Ink). In this way, a printed substrate was obtained. However, no printed layer was formed in the areas corresponding to 4.0 mm at one end and 2.0 mm at the other end of the laminate individual pieces obtained by the processing described later (areas intended for tube bonding).

[0167] The following lamination process was performed using a single extrusion lamination method: On one surface of EVOH-based barrier film B, LDPE (Novatec LD LC602A, manufactured by Nippon Polyethylene, MFR: 8.2 g / 10 min, density: 0.919 g / cm³) was applied. 3 A 30 μm thick extruded polyethylene layer was formed by melting and extruding a polyethylene film (melting point: 107°C) at 330°C, and a 100 μm thick milky white polyethylene film A was laminated to this extruded polyethylene layer.

[0168] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on the other surface of EVOH-based barrier film B by melt-extruding LDPE (LC602A) at 330°C, and the non-printed surface of the printing substrate was laminated to this extruded polyethylene layer. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed surface of the printing substrate and dried to form a 1 μm thick anchor coat layer. A 20 μm thick extruded polyethylene layer was formed on the surface of the anchor coat layer by melt-extruding LDPE (LC602A) at 330°C, and an 80 μm thick antistatic agent-containing polyethylene film A was laminated through this extruded polyethylene layer.

[0169] In this way, a laminate was obtained. The laminate comprises, in this order: (outermost layer) an antistatic agent-containing polyethylene film (80 μm, second heat-seal layer), an extruded polyethylene layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented HDPE film (25 μm), an extruded polyethylene layer (20 μm), an EVOH-based barrier film B (75 μm), an extruded polyethylene layer (30 μm), and a milky white polyethylene film (100 μm, first heat-seal layer) (innermost layer). The numbers in parentheses indicate the thickness.

[0170] [Examples B1-2 to B1-4] A laminate was prepared in the same manner as in Example B1, except that the outermost layer of the antistatic agent-containing polyethylene film and / or the innermost layer of the milky white polyethylene film were changed as shown in Table 3. [Examples B1-5] The laminate was fabricated in the same manner as in Example B1-1, except that a printed layer was also formed on the area where the tube was to be attached.

[0171] [Example B2-1] A 1 μm thick printed layer was formed on one surface of a 25 μm thick uniaxially oriented HDPE film (Hybron SMKQW) by gravure printing and drying using a urethane-based gravure ink (manufactured by Toyo Ink). In this way, a printed substrate was obtained. However, no printed layer was formed in the area where the product was to be attached to the tube.

[0172] Lamination was performed as follows using the tandem extrusion lamination method. On one surface of EVOH-based barrier film B, an extruded polyethylene layer with a thickness of 20 μm was formed by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick milky white polyethylene film A was laminated through this extruded polyethylene layer. On the surface of the laminated milky white polyethylene film, an extruded polyethylene layer with a thickness of 30 μm was formed by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick polyethylene film (Suzuron L-100N) was laminated through this extruded polyethylene layer.

[0173] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on the other surface of EVOH-based barrier film B by melt-extruding LDPE (LC602A) at 330°C, and the non-printed surface of the printing substrate was laminated to this extruded polyethylene layer. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed surface of the printing substrate and dried to form a 1 μm thick anchor coat layer. A 20 μm thick extruded polyethylene layer was formed on the surface of the anchor coat layer by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick antistatic agent-containing polyethylene film A was laminated through this extruded polyethylene layer.

[0174] In this way, a laminate was obtained. The laminate comprises, in order, an antistatic agent-containing polyethylene film (50 μm, second heat-seal layer) (outermost layer), an extruded polyethylene layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented HDPE film (25 μm), an extruded polyethylene layer (20 μm), an EVOH-based barrier film B (75 μm), an extruded polyethylene layer (20 μm), a milky white polyethylene film (50 μm), an extruded polyethylene layer (30 μm), and a polyethylene film (50 μm, first heat-seal layer) (innermost layer).

[0175] [Examples B2-2 to B2-3] A laminate was prepared in the same manner as in Example B2-1, except that the outermost layer of the polyethylene film containing an antistatic agent and / or the innermost layer of polyethylene film were changed as shown in Table 3.

[0176] [Examples B2-4] The laminate was fabricated in the same manner as in Example B2-1, except that a printed layer was also formed on the area where the tube was to be attached.

[0177] [Example B3-1] A 1 μm thick printed layer was formed on one surface of a 25 μm thick uniaxially oriented HDPE film (Hybron SMKQW) by gravure printing and drying using a urethane-based gravure ink (manufactured by Toyo Ink). In this way, a printed substrate was obtained. However, no printed layer was formed in the area where the product was to be attached to the tube.

[0178] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on one surface of EVOH-based barrier film B by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick milky white polyethylene film A was laminated through this extruded polyethylene layer. A 30 μm thick extruded polyethylene layer was formed on the surface of the laminated milky white polyethylene film by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick polyethylene film A was laminated through this extruded polyethylene layer.

[0179] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on the other surface of the EVOH-based barrier film B by melt-extruding LDPE (LC602A) at 330°C, and the non-printed surface of the printing substrate was laminated to this extruded polyethylene layer. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed surface of the printing substrate and dried to form a 1 μm thick anchor coat layer. A 20 μm thick extruded polyethylene layer was formed on the surface of the anchor coat layer by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick antistatic agent-containing polyethylene film B was laminated through this extruded polyethylene layer.

[0180] In this way, a laminate was obtained. The laminate comprises, in order, an antistatic agent-containing polyethylene film (50 μm, second heat-seal layer) (outermost layer), an extruded polyethylene layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented HDPE film (25 μm), an extruded polyethylene layer (20 μm), an EVOH-based barrier film B (75 μm), an extruded polyethylene layer (20 μm), a milky white polyethylene film (50 μm), an extruded polyethylene layer (30 μm), and a polyethylene film (50 μm, first heat-seal layer) (innermost layer).

[0181] [Examples B3-2 to B3-3] A laminate was prepared in the same manner as in Example B3-1, except that the outermost layer of the polyethylene film containing the antistatic agent and / or the innermost layer of the polyethylene film were changed as shown in Table 3. [Examples B3-4] The laminate was fabricated in the same manner as in Example B3-1, except that a printed layer was also formed on the area where the tube was to be attached.

[0182] [Comparative Example B1-1] A 1 μm thick printed layer was formed on one surface of a 25 μm thick uniaxially oriented HDPE film (Hybron SMKQW) by gravure printing and drying using a urethane-based gravure ink (manufactured by Toyo Ink). In this way, a printed substrate was obtained. However, no printed layer was formed in the area where the product was to be attached to the tube.

[0183] Lamination was performed as follows using the tandem extrusion lamination method. A 20 μm thick extruded polyethylene layer was formed on one surface of a 50 μm thick milky white polyethylene film A by melt-extruding LDPE (LC602A) at 330°C, and an EVOH-based barrier film B was laminated to this extruded polyethylene layer. A 30 μm thick extruded polyethylene layer was formed on the surface of the laminated EVOH-based barrier film B by melt-extruding LDPE (LC602A) at 330°C, and a 50 μm thick polyethylene film (Suzuron L-100N) was laminated to this extruded polyethylene layer.

[0184] Lamination was performed as follows using the tandem extrusion lamination method. On the other surface of the milky white polyethylene film A, LDPE (LC602A) was melt-extruded at 330°C to form an extruded polyethylene layer with a thickness of 20 μm, and the non-printed surface of the printing substrate was laminated to this extruded polyethylene layer. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed surface of the printing substrate and dried to form an anchor coat layer with a thickness of 1 μm. On the surface of the anchor coat layer, LDPE (LC602A) was melt-extruded at 330°C to form an extruded polyethylene layer with a thickness of 20 μm, and a 50 μm thick antistatic polyethylene film C was laminated through this extruded polyethylene layer.

[0185] In this way, a laminate was obtained. The laminate comprises, in order, an antistatic agent-containing polyethylene film (50 μm, second heat-seal layer) (outermost layer), an extruded polyethylene layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented HDPE film (25 μm), an extruded polyethylene layer (20 μm), a milky white polyethylene film (50 μm), an extruded polyethylene layer (20 μm), an EVOH-based barrier film B (75 μm), an extruded polyethylene layer (30 μm), and a polyethylene film (50 μm, first heat-seal layer) (innermost layer).

[0186] [Comparative examples B1-2~B1-3] A laminate was prepared in the same manner as in Comparative Example B1-1, except that the outermost layer of polyethylene film containing an antistatic agent and / or the innermost layer of polyethylene film were changed as shown in Table 3.

[0187] [Comparative Example B1-4] The laminate was prepared in the same manner as in Comparative Example B1-1, except that a printed layer was also formed on the area where the tube was to be attached.

[0188] [Comparative Example 2] A 1 μm thick biaxially oriented PET film (E5200) was used as a substrate. A urethane-based gravure ink (manufactured by Toyo Ink) was applied to one surface of the film by gravure printing and then dried to form a 1 μm thick printed layer. In this way, a printing substrate was obtained.

[0189] Lamination was performed using the tandem dry lamination method as follows: A 3 μm thick adhesive layer was formed by applying and drying a urethane-based two-component curing adhesive (manufactured by Rock Paint, main component: RU-80, hardener: H-5) to the surface of the printing layer on the printing substrate, and then laminating a 12 μm thick aluminum-metallized biaxially oriented PET film (BR-PET1312) through this adhesive layer. The same urethane-based two-component curing adhesive was applied and dried to the surface of the laminated aluminum-metallized PET film to form a 3 μm thick adhesive layer, and then laminating a 180 μm thick polyethylene film B through this adhesive layer.

[0190] The lamination process was performed as follows using the single-dry lamination method. The above-mentioned urethane-based two-component curing adhesive was applied to the non-printed surface of the printed substrate and dried to form a 3 μm thick adhesive layer, and a 130 μm thick polyethylene film C containing an antistatic agent was laminated to it via this adhesive layer.

[0191] In this way, a laminate was obtained. The laminate comprises, in order, an antistatic agent-containing polyethylene film (130 μm, second heat-seal layer) (outermost layer), an adhesive layer (3 μm), a biaxially oriented PET film (12 μm), a printed layer (1 μm), an adhesive layer (3 μm), an aluminum-deposited biaxially oriented PET film (12 μm), an adhesive layer (3 μm), and a polyethylene film (180 μm, first heat-seal layer) (innermost layer).

[0192] [Comparative Example 3] A 1 μm thick biaxially oriented PET film (E5200) was used as a substrate. A urethane-based gravure ink (manufactured by Toyo Ink) was applied to one surface of the film by gravure printing and then dried to form a 1 μm thick printed layer. In this way, a printing substrate was obtained.

[0193] The following lamination process was performed using the single-dry lamination method. A 3 μm thick adhesive layer was formed on one surface of an 80 μm thick milky white polyethylene film B by applying and drying a two-component urethane-based curing adhesive (manufactured by Mitsui Chemicals, main component: XA-311, curing agent: A-3). A 12 μm thick transparent vapor-deposited biaxially oriented PET film was then laminated to this adhesive layer.

[0194] Lamination was performed as follows using the tandem extrusion lamination method. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the surface of the laminated transparent vapor-deposited biaxially oriented PET film and dried to form a 1 μm thick anchor coat layer. An extruded resin layer with a thickness of 25 μm was formed on the surface of the anchor coat layer by melt-extruding ethylene-methacrylic acid copolymer (Mitsui Dow Polychemicals, Nucrel N0908C) at 290°C, and an 80 μm thick polyethylene film (Suzuron L-100N) was laminated through this extruded resin layer. An extruded polyethylene layer with a thickness of 25 μm was formed on the other surface of the milky white polyethylene film B by melt-extruding LDPE (LC602A) at 330°C, and the surface on which the printing layer of the printing substrate is formed was laminated to this extruded polyethylene layer.

[0195] The following lamination process was performed using a single extrusion lamination method. An anchor coating agent (Toyo Morton Co., Ltd., EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the non-printed surface of the printed substrate and dried to form a 1 μm thick anchor coating layer. An extruded polyethylene layer with a thickness of 25 μm was formed on the surface of the anchor coating layer by melt-extruding LDPE (LC602A) at 330°C, and an 80 μm thick antistatic polyethylene film A was laminated to this extruded polyethylene layer.

[0196] In this way, a laminate was obtained. The laminate comprises, in order, an antistatic agent-containing polyethylene film (80 μm, second heat-seal layer) (outermost layer), an extruded polyethylene layer (25 μm), an anchor coat layer (1 μm), a biaxially oriented PET film (12 μm), a printed layer (1 μm), an extruded polyethylene layer (25 μm), a milky white polyethylene film (80 μm), an adhesive layer (3 μm), a transparent vapor-deposited biaxially oriented PET film (12 μm), an anchor coat layer (1 μm), an extruded resin layer (25 μm), and a polyethylene film (80 μm, first heat-seal layer) (innermost layer).

[0197] [Preparation of tube containers] The laminates obtained in the examples and comparative examples were processed into individual laminate pieces with a width of 120.0 mm using a bobbin cutter. The ends in the width direction were overlapped so that the overlap width was approximately 1.2 mm, and then the overlapped ends were heat-sealed under the conditions of 0.1 MPa, 120°C, and 1.0 second to obtain a cylindrical raw material. The obtained raw material was cut to a length of 141.6 mm in the length direction to produce a cylindrical body that would become the body of the tube container. The cylindrical body was mounted on a mandrel for forming the tube container, and a head consisting of a frustoconical shoulder and a cylindrical extraction port continuous therewith was attached to one end of the cylindrical body using high-density polyethylene (Suntec J345, manufactured by Asahi Kasei, density 0.956 g / cm³). 3A tube container body was fabricated using a compression molding method with the material shown in Figure 6. Next, the high-density polyethylene was injected into a mold for cap molding and molded to produce a cap. In this way, a tube container was obtained.

[0198] 180g of Lux Super Rich Treatment (Unilever Japan) and 100g of Dentor Spearmint (Lion) were filled into tube containers and stored at 50°C dry for one month. The physical properties of the tube containers before and after storage were measured as follows.

[0199] [Side seam tensile test] Test specimens were obtained by cutting the body of the above-mentioned tube container into strips 15 mm wide, perpendicular to the side seam (tube bonding area) (TD direction of the laminate). These test specimens were pulled at a test speed of 300 mm / min using a tensile testing machine (Orientec Co., Ltd., STA-1150). If there were no cosmetic defects such as peeling at the end face when the side seam was pulled, it was described as "A," and if there were cosmetic defects such as peeling at the end face when the side seam was pulled, it was described as "B."

[0200] [Shoulder Tensile Test] Test specimens were obtained by cutting strips 15 mm wide from two locations on the adhesive joint between the body and shoulder of the tube container: the side seam (tube bonding area) and the location 180° opposite to it, in the direction of the hem (MD direction of the laminate). These test specimens were pulled at a test speed of 300 mm / min using a tensile testing machine (Orientec Co., Ltd., STA-1150). If there were no cosmetic defects such as peeling at the end of the side seam when the shoulder was pulled, it was described as "A," and if there were cosmetic defects such as peeling at the end of the side seam when the shoulder was pulled, it was described as "B."

[0201] [Edge exposure] A 60mm square test specimen, including the tubular section of the body, was cut from the tube container. The area around the tubular section of the test specimen was folded in a mountain fold along the tubular section, viewed from the outer surface of the body, and pressure was applied to create a crease. A cross-section of the test specimen perpendicular to the tubular section (TD direction of the laminate) was photographed with a microscope to obtain an image, and the captured image was visually examined to confirm whether or not the barrier resin layer was exposed on the outer surface of the tubular section. Similarly, a 60mm square test specimen, including the tubular section of the body, was cut from the tube container. The area around the tubular section of the test specimen was folded in a valley fold along the tubular section, viewed from the outer surface of the body, and pressure was applied to create a crease. A cross-section of the test specimen perpendicular to the tubular section (TD direction of the laminate) was photographed with a microscope to obtain an image, and the captured image was visually examined to confirm whether or not the barrier resin layer was exposed on the inner surface of the tubular section. "A" indicates that the barrier resin layer is not exposed at the end face of the laminate at the tubular bonding location. "B" indicates that the barrier resin layer is exposed at the end face of the laminate at the tubular bonding location, and "C" indicates that end face coating is difficult.

[0202] [Monomaterial] The polyethylene content (monomaterial ratio) was calculated from the specific gravity of the material constituting each layer of the laminates obtained in the examples and comparative examples, and the thickness of each layer. For the laminates obtained in the examples and comparative examples, a determination was made as to whether or not they were monomaterials, in accordance with the CEFLEX guidelines (2020). A rating of "A" was given if they conformed to the CEFLEX guidelines (2020), and a rating of "B" was given if they did not.

[0203] [Total light transmittance] In accordance with JIS K7375:2008, the total light transmittance was measured using a haze meter (HM-150, manufactured by Murakami Color Technology Laboratory Co., Ltd.). Measurements were performed on three test specimens, and the average value of the obtained values ​​was calculated.

[0204] [Measurement of oxygen permeability and water vapor permeability] Test pieces with a size of 100 mm × 100 mm were cut out from the laminates obtained in the examples and comparative examples, and the oxygen permeability and water vapor permeability were measured. The oxygen permeability of the laminate measured in accordance with JIS K7126-2:2006 under the environment of 23°C and 90% RH was all 1.0 cc / m 2 ·day·atm or less. The water vapor permeability of the laminate measured in accordance with JIS K7129-2:2019 under the environment of 40°C and 90% RH was all 2.0 g / m 2 ·day or less.

[0205]

Table 1

[0206]

Table 2

[0207]

Table 3

[0208]

Table 4

Explanation of Symbols

[0209] 1: Laminate 1S: First surface 2S: Second surface 10: First heat-sealing layer 20: Second heat-sealing layer 30: Barrier film 34A: First polyethylene layer 34B: Second polyethylene layer 36A: First adhesive resin layer 36B: Second adhesive resin layer 32: Barrier resin layer 40: Printing substrate 42: Substrate 44: Printing layer 50: Base material Ad: Adhesive layer 100: Tube container 101: Tube container body 102:Head 103: Torso 104: Shoulder 105:Extraction port 106: Cap 107: Spiral 108: Joint 109:Bottom joint

Claims

1. A laminate comprising, at least, a first heat seal layer, a barrier resin layer, and a second heat seal layer in this order, The first heat seal layer contains polyethylene as its main component, The second heat seal layer contains polyethylene as its main component, The barrier resin layer contains a gas barrier resin as its main component, The laminate has a first surface and a second surface, wherein the first heat seal layer constitutes the first surface, and the second heat seal layer constitutes the second surface. The total thickness (T) of the layer located between the barrier resin layer and the first surface, which mainly contains polyethylene including the first surface. ｉｎ The thickness (T) of the barrier resin layer ｂ１ ) Ratio (T ｉｎ / T ｂ１ ) is 8.0 or higher, The polyethylene content in the entire laminate is 90% by mass or more. Laminated structure.

2. The laminate according to claim 1, wherein the barrier resin layer contains an ethylene-vinyl alcohol copolymer as the main component.

3. The laminate according to claim 1, wherein the laminate comprises a barrier film comprising a first polyethylene layer, a first adhesive resin layer, the barrier resin layer, a second adhesive resin layer, and a second polyethylene layer.

4. The laminate according to claim 3, wherein the thickness of the barrier film is 20 μm or more and 100 μm or less.

5. The total thickness (T) ｉｎ The laminate according to claim 1, wherein the thickness of the ) is 120 μm or more and 250 μm or less.

6. The total thickness (T ｏｕｔ ), of the layer containing polyethylene as a main component including the second surface, which is located between the barrier resin layer and the second surface ｂ２ ), to the thickness (T ｏｕｔ / T ｂ２ ) of the barrier resin layer is 6.0 or more and 14.0 or less. The laminate according to claim 1.

7. The total thickness (T) ｏｕｔ The laminate according to claim 6, wherein the thickness of the ) is 100 μm or more and 220 μm or less.

8. The laminate further comprises a printing substrate between the first heat seal layer and the barrier resin layer, and / or between the barrier resin layer and the second heat seal layer. The printing substrate comprises a substrate containing polyethylene as the main component, and a printing layer provided on at least one surface of the substrate. The laminate according to claim 1.

9. The laminate according to claim 8, wherein the laminate comprises the barrier resin layer, the substrate of the printing substrate, the printing layer of the printing substrate, and the second heat seal layer in this order.

10. The laminate according to claim 8, wherein the substrate in the printing substrate is a stretched film containing at least one selected from medium-density polyethylene and high-density polyethylene.

11. A laminate for forming the body of a tube container, wherein the first heat seal layer is a sealant layer on the inner surface side of the body, and the second heat seal layer is a sealant layer on the outer surface side of the body, according to claim 1.

12. The laminate further comprises a printing substrate between the first heat seal layer and the barrier resin layer, and / or between the barrier resin layer and the second heat seal layer. The printing substrate comprises a substrate containing polyethylene as the main component, and a printing layer provided on at least one surface of the substrate. In the aforementioned printing substrate, the printing layer is not formed in the region corresponding to the area where heat sealing is planned to form the body of the tube container. The laminate according to claim 11.

13. The laminated body, in order from the inner surface, The first heat seal layer and, An extruded polyethylene layer is provided as desired. A barrier film comprising the barrier resin layer, An extruded polyethylene layer is provided as desired. A printing substrate comprising a substrate containing polyethylene as the main component, and a printing layer, An extruded polyethylene layer is provided as desired. The second heat seal layer and The laminate according to claim 11, comprising the elements in this order.

14. The laminate according to claim 13, wherein the first heat-seal layer contains a white pigment.

15. The laminate according to claim 13, wherein the first heat-seal layer is a polyethylene film having a total light transmittance of 5% or more and 40% or less (measured in accordance with JIS K7375:2008).

16. The laminated body, in order from the inner surface, The first heat seal layer and, An extruded polyethylene layer is provided as desired. A base material containing polyethylene as the main component, An extruded polyethylene layer is provided as desired. A barrier film comprising the barrier resin layer, An extruded polyethylene layer is provided as desired. A printing substrate comprising a substrate containing polyethylene as the main component, and a printing layer, An extruded polyethylene layer is provided as desired. The second heat seal layer and The laminate according to claim 11, comprising the elements in this order.

17. The laminate according to claim 16, wherein at least one selected from the first heat seal layer and the substrate containing polyethylene as a main component contains a white pigment.

18. The laminate according to claim 16, wherein at least one selected from the first heat-seal layer and the substrate containing polyethylene as a main component is a polyethylene film having a total light transmittance of 5% or more and 40% or less (measured in accordance with JIS K7375:2008).

19. A tube container body comprising a head and a body, The head comprises a shoulder portion connected to one end of the body and an extraction port portion connected to the shoulder portion, and the body is made of a laminate according to any one of claims 1 to 18. The tube container itself.

20. The tube container body according to claim 19, wherein the head portion is formed of a resin composition containing polyethylene.

21. The tube container body according to claim 19, The cap and A tube container equipped with the following features.

22. The tube container according to claim 21, wherein the cap is formed of a resin composition containing polyethylene.

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