Laminate, tube container body, and tube container

Abstract

To provide a laminate excellent in recyclability and opacity.SOLUTION: The laminate at least comprises a first resin layer, a second base material, a barrier resin layer, a first base material and a second resin layer in this order. The first resin layer, the second base material, the barrier resin layer, the first base material and the second resin layer each contain polyethylene as a major component. At least one of the second and first base materials is a polyethylene film having a total light transmittance from 10% to 40% inclusive.SELECTED DRAWING: Figure 4

Description

[Technical field]

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

[0002] Tube containers are known as packaging containers that are filled with semi-liquid paste-like substances such as toothpaste and face wash cream and are used by squeezing them out. Tube containers usually include a tube container body and a cap. The tube container body generally includes a body portion having one end closed and the other end open, and a head portion having a spout connected to the other open end of the body portion. The body portion is filled with the contents before closing one end of the body portion, and then the one end of the body portion is closed, thereby producing a tube container containing the contents.

[0003] Laminates obtained by laminating polyethylene films, polyester films, vapor-deposited films, aluminum foils, and the like are widely used as members constituting the barrels of tube container bodies (see, for example, Patent Documents 1 and 2).

[0004] In recent years, from the viewpoint of constructing a recycling-based society, packaging containers are required to have high recyclability. In addition, it is desirable for packaging containers to have barrier properties. However, as described above, the body of a conventional tube container body is composed of a laminate including, for example, a polyethylene film and an aluminum foil. It is generally difficult to separate the polyethylene film and the aluminum foil in the laminate. For this reason, such tube container bodies are not actively recycled at present.

[0005] In view of this, a laminate comprising a polyethylene film that has been subjected to a stretching treatment (stretched polyethylene film) as a substrate and a polyethylene film as a heat seal layer has been studied (see, for example, Patent Document 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2006-282184 A [Patent Document 2] JP 2014-231372 A [Patent Document 3] JP 2005-053223 A Summary of the Invention [Problem to be solved by the invention]

[0007] The present inventors have studied how to improve the barrier properties by providing a barrier resin layer containing a gas barrier resin as a main component while maintaining a high content of polyethylene in the laminate. It is believed that such a configuration can achieve both recyclability and barrier properties. Such a laminate is rolled into a cylindrical shape, and the inner heat seal layer at one end of the laminate is overlapped with the outer heat seal layer at the other end of the laminate, and the overlapped portion is heat sealed to form a joint (welded portion), thereby forming the body of the tube container body. However, the present inventors have found that in such a case, the joint strength at the joint may not be sufficient, resulting in delamination.

[0008] In addition, laminates using polyethylene films as the base material and heat seal layer are expected to have high recyclability, but when used as the main body of a tube container, it is desirable for the laminate to have concealing properties in layers other than the printed layer in order to protect the contents, such as toothpaste, which are sensitive to direct sunlight.

[0009] Therefore, an object of the present disclosure is to provide a laminate having excellent recyclability and hiding property.

[0010] Furthermore, an object of the present disclosure is to provide a laminate that is excellent in recyclability and barrier properties and can suppress the occurrence of delamination at the joint after heat sealing. [Means for solving the problem]

[0011] [1] At least a first resin layer, a second substrate, a barrier resin layer, the first substrate, and a second resin layer, in this order; the first resin layer, the second base material, the barrier resin layer, the first base material, and the second resin layer each contain polyethylene as a main component, A laminate, wherein at least one of the second substrate and the first substrate is a polyethylene film having a total light transmittance of 10% or more and 40% or less. [2] At least a first resin layer, a barrier resin layer, a first substrate, and a second resin layer, in this order; the first resin layer, the barrier resin layer, the first base material, and the second resin layer each contain polyethylene as a main component, A laminate, wherein at least one of the first base material and the first resin layer is a polyethylene film having a total light transmittance of 10% or more and 40% or less. [3] The laminate according to [1], further comprising an extruded resin layer between the first resin layer and the barrier resin layer, between the barrier resin layer and the first base material, and between the first base material and the second resin layer. [4] The laminate according to [2], further comprising an extruded resin layer between the first resin layer and the second substrate, between the second substrate and the barrier resin layer, between the barrier resin layer and the first substrate, and between the first substrate and the second resin layer. [5] The laminate according to any one of [1] to [4], wherein the barrier resin layer contains ethylene vinyl alcohol. [6] The laminate according to any one of [1] to [5], further comprising a printed layer provided on at least one surface of the second resin layer or the first base material. [7] The laminate according to any one of [1] to [6], wherein the first substrate is a uniaxially or biaxially oriented polyethylene substrate containing at least one selected from the group consisting of low-density polyethylene, medium-density polyethylene, and high-density polyethylene. [8] The laminate described in any one of [1] to [7], wherein the first resin layer and the second resin layer each independently contain at least one selected from medium density polyethylene, low density polyethylene, and linear low density polyethylene. [9] The laminate according to any one of [1] to [8], wherein the content of polyethylene in the entire laminate is 90 mass % or more.

[10] A laminate for forming a body of a tube container body, the laminate described in any of [1] to [9], wherein the second resin layer is a sealant layer on an outer surface side of the body, and the first resin layer is a sealant layer on an inner surface side of the body.

[11] A tube container body having a head and a body, The head portion has a shoulder portion connected to one end of the body portion and a spout portion connected to the shoulder portion, and the body portion is composed of the laminate according to any one of [1] to

[10] . Tube container body.

[12] The tube container body according to

[11] , wherein the head portion is made of a resin composition containing polyethylene.

[13] A tube container body according to

[11] or

[12] , Cap and A tube container comprising:

[14] The tube container according to

[13] , wherein the cap is made of a resin composition containing polyethylene. Effect of the Invention

[0012] According to the present disclosure, a laminate having excellent recyclability and hiding power can be provided.

[0013] Furthermore, according to the present disclosure, it is possible to provide a laminate that is excellent in recyclability and barrier properties and can suppress the occurrence of delamination at the joint after heat sealing. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a cross-sectional schematic diagram showing one embodiment of a laminate according to the present disclosure. [Diagram 2] FIG. 2 is a cross-sectional schematic diagram showing one embodiment of a laminate of the present disclosure. [Diagram 3] FIG. 3 is a cross-sectional schematic diagram showing one embodiment of a laminate of the present disclosure. [Figure 4] FIG. 4 is a cross-sectional schematic diagram showing one embodiment of a laminate of the present disclosure. [Diagram 5] FIG. 5 is a top view of the original roll of the cylindrical body of the tube container body. [Figure 6] FIG. 6 is a perspective view showing one embodiment of a tube container including a tube container body including the laminate of the present disclosure and a cap. [Figure 7] FIG. 7 is a cross-sectional view taken along line AA in FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In this specification, when multiple upper limit candidates and multiple lower limit candidates are given for a certain parameter, the numerical range of the parameter may be configured by combining any one of the upper limit candidates and any one of the lower limit candidates. As an example, the description "Parameter B is preferably A1 or more, more preferably A2 or more, and even more preferably A3 or more. Parameter B is preferably A4 or less, more preferably A5 or less, and even more preferably A6 or less." will be explained. In this example, the numerical range of parameter B may be A1 or more and A4 or less, A1 or more and A5 or less, A1 or more and A6 or less, A2 or more and A4 or less, A2 or more and A5 or less, A2 or more and A6 or less, A3 or more and A4 or less, A3 or more and A5 or less, or A3 or more and A6 or less.

[0016] Hereinafter, the embodiments of the present disclosure will be described in detail. The present disclosure can be implemented in many different forms, and is not to be interpreted as being limited to the description of the embodiments exemplified below. In the drawings, the width, thickness, shape, etc. of each layer may be shown diagrammatically compared to the embodiments in order to make the explanation clearer, but these are merely examples and do not limit the interpretation of the present disclosure. In this specification and each figure, elements similar to those already explained with respect to the previous figures are given the same reference numerals, and detailed explanations may be omitted as appropriate.

[0017] Hereinafter, an embodiment of the laminate of the present disclosure will be described with reference to the drawings as appropriate. In the following description, the components described (e.g., polyethylene, gas barrier resin, additive, white pigment) may be used alone or in combination of two or more.

[0018] [Laminate] The laminate of the present disclosure includes at least a first heat seal layer (first resin layer), a barrier resin layer, and a second heat seal layer (second resin layer) in this order. The laminate includes each layer "in this order" means that the laminate includes each layer in this order in the thickness direction of the laminate.

[0019] The laminate of the present disclosure has a first surface and a second surface opposite to 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.

[0020] The first heat seal layer (first resin layer) is a layer containing polyethylene as a main component. The second heat seal layer (second resin layer) is a layer containing polyethylene as a main component. Therefore, the laminate of the present disclosure has high recyclability. The tube container body including this laminate also has 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.

[0021] In the present disclosure, a "layer containing polyethylene as a main component" refers to a layer in which the polyethylene content in 100% by mass of the layer is 50% by mass or more. The content is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0022] The laminate of the present disclosure may further include a substrate containing polyethylene as a main component at one or more 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 at one or more 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 includes a substrate and a printing layer provided on at least one surface of the substrate.

[0023] The laminate of the present disclosure may include a barrier film including the above-mentioned barrier resin layer.

[0024] The laminate of the present disclosure may include, in this order, a first heat seal layer, an optional adhesive layer, a barrier film, an optional 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 include, in this order, a first heat seal layer, an optional adhesive layer, a barrier film, an optional adhesive layer, a printing substrate, an optional 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 include, in this order, a first heat seal layer, an optional adhesive layer, a substrate, an optional adhesive layer, a barrier film, an optional adhesive layer, a printing substrate, an optional 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% or more and 40% or less, or containing a white pigment. The laminate of the present disclosure may include, in this order, a first heat seal layer (first resin layer), an optional adhesive layer, a substrate, an optional adhesive layer, a barrier film, an optional adhesive layer, a printing substrate, an optional adhesive layer, and a second heat seal layer (second resin layer). In this embodiment, the substrate may be a polyethylene film containing a white pigment and having a total light transmittance of 5% or more and 40% or less.

[0025] One embodiment of the laminate of the present disclosure is shown in FIGS. The laminate 1 in FIG. 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 FIG. 2 comprises, in this order, a first heat seal layer 10 (first surface 1S), an adhesive layer Ad, a barrier film 30, an adhesive layer Ad, and a second heat seal layer 20 (second surface 2S). The laminate 1 in FIG. 3 comprises, in this order, (first surface 1S) a first heat seal layer (first resin layer) 10, an adhesive layer (extruded resin layer) Ad, a barrier film 30, an adhesive layer (extruded resin layer) Ad, a printing substrate 40, an adhesive layer (extruded resin layer) Ad, and a second heat seal layer (second resin layer) 20 (second surface 2S). The laminate 1 in FIG. 4 comprises, in this order, (first surface 1S) a first heat seal layer (first resin layer) 10, an adhesive layer (extruded resin layer) Ad, a substrate (second substrate) 50, an adhesive layer (extruded resin layer) Ad, a barrier film 30, an adhesive layer (extruded resin layer) Ad, a printing substrate 40, an adhesive layer (extruded resin layer) Ad, and a second heat seal layer (second resin layer) 20 (second surface 2S).

[0026] In the example shown in Figs. 2 to 4, the barrier film 30 includes 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 present invention is not limited to this example, and the barrier film 30 may include the barrier resin layer 32, or may include the barrier resin layer 32 and another layer (not shown). In the example shown in Figs. 2 to 4, the printing substrate 40 includes a substrate (first substrate) 42 and a printing layer 44 provided on one surface of the substrate. In the example shown in Figs. 3 to 4, the laminate 1 may further include an anchor coat layer (not shown) between the adhesive layer (extruded resin layer) Ad and the printing layer 44.

[0027] The laminate of the present disclosure has a high polyethylene content of 90% by mass or more and is excellent in recyclability. The laminate of the present disclosure has a barrier resin layer containing a gas barrier resin as a main component and is excellent in barrier property. In other words, the laminate of the present disclosure can achieve both recyclability and barrier property.

[0028] When the laminate having the barrier resin layer is heat-sealed to form the body of the tube container body, delamination may occur at the joint (tube attachment point). Delamination tends to occur more after a certain period of time has passed since the tube container is filled with the contents. This is presumably due to the barrier resin layer being exposed and extending from the end face of the laminate at the joint, and the barrier resin layer absorbing, for example, moisture from the contents and becoming more likely to peel off. However, in the laminate of the present disclosure, by appropriately controlling the thickness of each layer as described below, it is possible to suppress the end face exposure of the barrier resin layer at the joint, and therefore the occurrence of delamination can be suppressed.

[0029] The total thickness of the layers containing polyethylene as a main component and located between the barrier resin layer and the first surface of the laminate is defined as "T in The thickness of the barrier resin layer is described as "T b1 " When there are two or more barrier resin layers, it is written as "T inThe barrier resin layer in the definition of "is the barrier resin layer that is located closest to the first surface of the laminate among the barrier resin layers. In this case, the thickness of the barrier resin layer (T b1 ) means the thickness of the barrier resin layer that is located closest to the first surface of the laminate, provided that, in the case where one or more barrier resin layers are present on the barrier resin layer that is located closest to the first surface of the laminate without any intervening layer, it means the total thickness of these barrier resin layers. The total thickness of the layers containing polyethylene as a main component and located between the barrier resin layer and the second surface of the laminate is defined as "T out The thickness of the barrier resin layer is described as "T b2 " When there are two or more barrier resin layers, it is written as "T out The barrier resin layer in the definition of "the barrier resin layer" means the barrier resin layer located closest to the second surface of the laminate. In this case, the thickness of the barrier resin layer (T b2 ) means the thickness of the barrier resin layer that is located closest to the second surface of the laminate, provided that, in the case where one or more barrier resin layers are present on the barrier resin layer that is located closest to the second surface of the laminate without any intervening layer, it means the total thickness of these barrier resin layers.

[0030] Total thickness (T in ) of the thickness (T b1 ) to the ratio (T in / T b1 ) is preferably 8.0 or more, more preferably 8.5 or more, even more preferably 9.0 or more, still more preferably 9.5 or more, particularly preferably 10.0 or more, 11.0 or more, or 12.0 or more. in / T b1) 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 attachment portion) on the inner surface of the body of the tube container body, the layer containing polyethylene as a main component can sufficiently cover the end face of the barrier resin layer, and therefore 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 the inner side) melts during heat sealing to cover the end face of the barrier resin layer of the laminate located on the inner side and is bonded to the first heat seal layer of the laminate located on the radially outer side of the body (hereinafter simply referred to as the outer side). This makes it possible to increase the bonding strength between the laminate located on the inner side and the laminate located on the outer side. This tends to suppress the occurrence of delamination at the joint.

[0031] Total thickness (T in ) 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, particularly preferably 160 μm or more, 170 μm or more, or 180 μm or more. in ) is preferably 250 μm or less, more preferably 230 μm or less, and further preferably 210 μm or less. In such an embodiment, the layer containing polyethylene as a main component can sufficiently cover the barrier resin layer at the joint (tube bonding portion) on the inner surface of the barrel of the tube container body, and therefore the occurrence of delamination tends to be suppressed.

[0032] Total thickness (T out ) of the thickness (T b2 ) to the ratio (T out / T b2 ) is preferably 6.0 or more, more preferably 7.0 or more, and even more preferably 8.0 or more. out / T b2) 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 attachment location) on the outer surface of the body of the tube container body, the layer containing polyethylene as a main component can sufficiently cover the end face of the barrier resin layer, and therefore 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 laminate located on the outside and adhering to the second heat seal layer of the laminate located on the inside of the body. This can increase the bonding strength between the laminate located on the outside and the laminate located on the inside. Therefore, there is a tendency that the occurrence of delamination at the joint can be suppressed.

[0033] Total thickness (T out ) is preferably 100 μm or more, more preferably 110 μm or more, and even more preferably 120 μm or more. out ) is preferably 220 μm or less, more preferably 210 μm or less, even more preferably 200 μm or less, still more preferably 190 μm or less, and particularly preferably 180 μm or less, 170 μm or less, or 160 μm or less. In such an embodiment, the layer containing polyethylene as a main component can sufficiently cover the barrier resin layer at the joint (tube bonding portion) on the outer surface of the barrel of the tube container body, and therefore the occurrence of delamination tends to be suppressed.

[0034] Thickness (T b1 ) and thickness (T b2 ) are each independently preferably 3 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. b1 ) and thickness (T b2) are each independently 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 that are laminated without any other layers therebetween, T b1 =T b2 In this case, simply "T b " is also written.

[0035] 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.

[0036] The content of polyethylene in the entire laminate of the present disclosure is preferably 90% by mass or more, more preferably 92% by mass or more, further preferably 93% by mass or more, and particularly preferably 94% by mass or more, which can improve the recyclability of the laminate of the present disclosure and the tube container (particularly laminated tube container) body including the laminate.

[0037] In one embodiment, the laminate of the present disclosure does not include any of a polyethylene terephthalate film, an aluminum foil, a vapor deposition film, and a vapor deposition film formed on a resin film, thereby improving the recyclability of the laminate of the present disclosure and a tube container (particularly a laminated tube container) body including the laminate.

[0038] In this specification, the term "laminate" may refer to the raw roll itself produced on a production line having the above-mentioned layer structure, or may refer to each individual laminate piece obtained by cutting the raw roll, and is not particularly limited as long as it has the above-mentioned layer structure. The individual laminate pieces are used, for example, to form the body of a tube container body.

[0039] 5 shows a top view of an original roll as a laminate of the present disclosure before being cut along cutting line L. This original roll includes a plurality of continuous laminates (individual pieces) for forming the body of the tube container body. By cutting this original roll along cutting line L, a plurality of laminate pieces for forming the body of the tube container body can be obtained. When this laminate piece is viewed in plan, it is preferable that no printed layer is formed in the regions corresponding to both ends in the direction perpendicular to the original roll flow direction. This can, for example, further suppress delamination from the tube attachment point in the body.

[0040] The oxygen permeability of the laminate of the present disclosure, measured in accordance with JIS K7126-2:2006, in an environment of a temperature of 23° C. and a humidity of 90% RH is preferably 2.0 cc / m 2 ·day·atm or less, preferably 1.5cc / m 2 ·day·atm or less, more preferably 1.0cc / m 2 The lower the oxygen permeability, the better. The lower limit is, for example, 0.01 cc / m 2 ·day·atm is also acceptable.

[0041] The water vapor permeability of the laminate of the present disclosure, measured in accordance with JIS K7129-2:2019, under an environment of a temperature of 40°C and a humidity of 90% RH is preferably 3.0 g / m 2 ·day or less, preferably 2.0g / m 2 ·day or less, more preferably 1.5 g / m 2 The lower the water vapor permeability, the better. The lower limit is, for example, 0.01 g / m 2 ·day is also acceptable.

[0042] The total light transmittance of the laminate of the present disclosure, 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 total light transmittance of the laminate of the present disclosure may be, for example, 5% or more, or 8% or more.

[0043] <First heat seal layer and second heat seal layer> The first heat seal layer contains polyethylene as a main component. The second heat seal layer contains polyethylene as a 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 be melted by heating and fused to each other.

[0044] When the laminate of the present disclosure is used to form the body of a tube container body, 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. That is, the body includes, from the inside to the outside of the body, a first heat seal layer, a barrier resin layer, and a second heat seal layer, in this order. In one embodiment, the first heat seal layer constitutes a first surface of the laminate, and the second heat seal layer constitutes a second surface of the laminate.

[0045] Examples of polyethylene include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, and very low density polyethylene. Among these, low density polyethylene and linear low density polyethylene are preferred from the viewpoint of heat sealability. In the present disclosure, high density polyethylene refers to polyethylene having a density of 0.945 g / cm 3 Polyethylene having a density of 0.932 g / cm3 or more may be used. Medium density polyethylene has a density of 0.932 g / cm3 or more. 3 Super 0.945g / cm 3 The following polyethylenes may be used: low density polyethylenes having a density of 0.900 g / cm 3 Super 0.932g / cm 3 The following polyethylenes may be used: linear low density polyethylenes having a density of 0.900 g / cm 3 Super 0.932g / cm 3 The following polyethylenes may be used: ultra-low density polyethylenes with a density of 0.900 g / cm3 The following polyethylene may be used. The density of polyethylene is measured in accordance with JIS K7112:1999, Method D (density gradient tube method, 23°C).

[0046] Low-density polyethylene is usually polyethylene obtained by polymerizing ethylene using a high-pressure polymerization process (high-pressure low-density polyethylene). Linear low-density polyethylene is usually polyethylene obtained by polymerizing ethylene and a small amount of α-olefins using a low-pressure polymerization process (e.g., polymerization using a Ziegler-Natta catalyst or a metallocene catalyst).

[0047] Polyethylenes with different densities or branches can be obtained by appropriately selecting a polymerization method. For example, it is preferable to carry out polymerization in one or more stages by using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization.

[0048] In the present disclosure, polyethylene includes copolymers of ethylene and other monomers (hereinafter also referred to as "ethylene copolymers"). In the present disclosure, the content of ethylene-derived structural 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 content is measured by nuclear magnetic resonance (NMR) method.

[0049] Examples of ethylene copolymers include copolymers of ethylene and 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. The polyethylene may be a copolymer of ethylene and vinyl acetate or (meth)acrylic acid ester.

[0050] As the polyethylene, biomass-derived polyethylene (hereinafter also referred to as "biomass polyethylene") obtained by polymerizing a monomer containing biomass-derived ethylene may be used. Since such biomass polyethylene is a carbon-neutral material, the environmental load in producing the laminate of the present disclosure can be reduced.

[0051] As the 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 is generally a method in which recovered polyethylene films, etc. are crushed, washed with an alkali to remove dirt and foreign matter from the film surface, and then dried at high temperature and reduced pressure for a certain period of time to diffuse contaminants remaining inside the film, thereby decontaminating the film and removing the dirt from the film, and returning it to polyethylene. Chemical recycling is generally a method in which recovered polyethylene films, etc. are decomposed to the monomer level, and the monomers are polymerized again to obtain polyethylene.

[0052] In the present disclosure, from the viewpoint of film-forming and processability, the melt flow rate (MFR) of the 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, and 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. The MFR of the 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.

[0053] The above discussion of polyethylene also applies to the polyethylene contained in the other layers.

[0054] In one embodiment, the first heat seal layer and the second heat seal layer may each independently be a polyethylene film having a total light transmittance measured in accordance with JIS K7375:2008 of 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.

[0055] The content of polyethylene 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, 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 including the laminate of the present disclosure can be improved. The content of polyethylene 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, 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 including the laminate of the present disclosure can be improved.

[0056] In one embodiment (for example, laminate 1 shown in FIG. 3), the first heat seal layer contains a white pigment. With this configuration, for example, it is possible to impart hiding power (for example, a sense of hiding of a white color) to the laminate without using ink such as white ink. For example, when the contents of the packaging container are toothpaste or the like, a design expressing the whiteness of teeth can be imparted to the packaging container. In addition, when ink is used, the solvent needs to be removed by volatilization, which may impose a burden on the environment during the production of the laminate, but the above configuration can further reduce the environmental burden during the production of the laminate.

[0057] Examples of white pigments include titanium oxide, 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.

[0058] 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, and is 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, thereby further improving the above-mentioned effects.

[0059] In one embodiment, the first heat seal layer may be a polyethylene film having a total light transmittance of 5% to 40%, preferably 10% to 40%, as measured in accordance with JIS K7375:2008, and may be, for example, a milky white polyethylene film, which can impart, for example, hiding power to the laminate.

[0060] The first heat seal layer may contain an additive. The second heat seal layer may contain an additive. Examples of the additive include a crosslinking agent, an antioxidant, an antiblocking agent, a lubricant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and a modifying resin.

[0061] The first heat seal layer may have a multi-layer structure. The second heat seal layer may have a multi-layer structure. The multi-layer structure may include, for example, a structure including a layer containing medium density polyethylene, a layer containing medium density polyethylene, and a layer containing medium density polyethylene.

[0062] The first heat seal layer may be a film containing polyethylene. The second heat seal layer may 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.

[0063] The surface of the first heat seal layer may be subjected to a surface treatment. The surface of the second heat seal layer may be subjected to a surface treatment. This can improve the adhesion between these heat seal layers and the layer adjacent to the heat seal layer. Examples of the surface treatment method 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.

[0064] 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 be formed on the surface of the second heat seal layer using a conventionally known anchor coat agent.

[0065] The thickness of the first heat seal layer is preferably 30 μm or more, more preferably 50 μm or more, and is preferably 150 μm or less, 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, and is preferably 140 μm or less, more preferably 120 μm or less. When the thickness is equal to or greater than the lower limit, the heat sealability can be improved, whereas when the thickness is equal to or less than the upper limit, the processability of the laminate can be improved.

[0066] Specifically, as shown in Fig. 3 and Fig. 4, in the laminate 1, the thickness of the first heat seal layer is preferably 30 µm or more and 250 µm or less, more preferably 50 µm or more and 200 µm or less. The thickness of the second heat seal layer is preferably 30 µm or more and 250 µm or less, more preferably 50 µm or more and 200 µm or less. When the thickness is 30 µm or more, the heat sealability can be further improved. When the thickness is 250 µm or less, the processability of the laminate can be improved.

[0067] The first heat seal layer and the second heat seal layer may each be formed by, for example, forming a resin composition containing at least polyethylene into a film using a T-die method, an inflation method, etc. The first heat seal layer and the second heat seal layer may each be laminated via, for example, an extruded resin layer described later.

[0068] <Barrier resin layer and barrier film> The laminate of the present disclosure includes a barrier resin layer. The barrier resin layer is a layer containing a gas barrier resin as a main component. Such a laminate has excellent barrier properties such as oxygen barrier property and water vapor barrier property without including a different layer such as a vapor deposition film, a vapor deposition film, or an aluminum foil.

[0069] Examples of gas barrier resins include ethylene-vinyl alcohol copolymers (EVOH), polyvinyl alcohol, polyacrylonitrile, polyamides such as nylon 6, nylon 6,6, and polymetaxylylene adipamide (MXD6), polyesters, polyurethanes, and (meth)acrylic resins. Among these, EVOH is preferred from the viewpoints of heat resistance and gas barrier properties.

[0070] 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, for example, solution polymerization, suspension polymerization, emulsion polymerization, etc. As the vinyl ester monomer, vinyl acetate is generally used, but other vinyl ester monomers may be used. As the other vinyl ester monomers, for example, 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; aromatic vinyl esters such as vinyl benzoate. EVOH may be modified by known methods, such as urethanization, acetalization, cyanoethylation, and oxyalkylenation.

[0071] In the ethylene-vinyl alcohol copolymer (EVOH), the content of structural units derived from ethylene (ethylene content) is preferably 20 mol% or more, more preferably 25 mol% or more, and preferably 60 mol% or less, more preferably 50 mol% or less. When the ethylene content is equal to or more than the lower limit, for example, the processability of the laminate can be improved. When the ethylene content is equal to or less than the upper limit, for example, the oxygen barrier property and / or water vapor barrier property of the laminate can be improved. The ethylene content is measured by NMR.

[0072] From the viewpoint of heat resistance, 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, and preferably 200° C. or lower, more preferably 195° C. or lower, even more preferably 190° C. or lower. The Tm of EVOH is the melting peak temperature obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121:2012.

[0073] From the viewpoint of gas barrier properties, the average saponification degree 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 saponification degree is measured in accordance with JIS K6726-1994 (wherein EVOH is used as a solution uniformly dissolved in a water / methanol solvent).

[0074] From the viewpoint of film-forming and processability, 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, and 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. 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, but the measurement temperature may be 210°C depending on the melting point of EVOH.

[0075] The content of the gas barrier resin 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, which can improve the barrier properties, such as the oxygen barrier property and water vapor barrier property, of the laminate.

[0076] The barrier resin layer may contain a resin other than the gas barrier resin, such as polyolefins such as polyethylene and polypropylene, vinyl resins, and cellulose resins. The barrier resin layer may contain the above-mentioned additives.

[0077] The barrier resin layer may be formed, for example, by forming a resin composition containing at least a gas barrier resin into a film using a T-die method, an inflation method, or the like.

[0078] The thickness of the barrier resin layer is preferably 3 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more, and is preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. When the thickness is equal to or more than the lower limit, for example, the effect of the barrier resin layer can be improved. When the thickness is equal to or less than 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, and even more preferably 15% or more, and is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less.

[0079] The laminate of the present disclosure may include a barrier film including the above-mentioned barrier resin layer. The barrier film may include, for example, a polyethylene layer and a barrier resin layer, and an adhesive resin layer between the polyethylene layer and the barrier resin layer. In one embodiment, the barrier film includes 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, the barrier film may include 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, and 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, when the first polyethylene layer and the second polyethylene layer are not particularly distinguished from each other, they are simply referred to as polyethylene layers.

[0080] The polyethylene layers, such as the first polyethylene layer and the second polyethylene layer, contain polyethylene as a main component. Examples of polyethylene include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, and very low density polyethylene. From the viewpoint of heat sealability, medium density polyethylene, low density polyethylene, and linear low density polyethylene are preferred. The polyethylene contained in the first polyethylene layer and the polyethylene contained in the second polyethylene layer may be the same or different.

[0081] The polyethylene layer may contain biomass polyethylene. The polyethylene layer may contain recycled polyethylene. The polyethylene layer may contain the additives described above.

[0082] 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 including the laminate of the present disclosure can be improved.

[0083] 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, and preferably 45% or less, more preferably 43% or less, 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, and preferably 45% or less, more preferably 43% or less, even more preferably 40% or less.

[0084] The adhesive resin layer contains an adhesive resin. Examples of adhesive resins include polyolefins such as polyethylene, modified polyolefins, vinyl resins, polyethers, polyesters, polyamides, polyurethanes, silicone resins, epoxy resins, and phenol 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 polyolefins modified with unsaturated carboxylic acids such as maleic acid and fumaric acid, or their acid anhydrides, esters, or metal salts (particularly graft-modified polyolefins). Among adhesive resins, modified polyolefins such as modified polyethylene are preferred from the viewpoint of obtaining a structure suitable for mono-material packaging materials, acid-modified polyolefins such as acid-modified polyethylene are more preferred, and maleic anhydride-modified polyethylene is even more preferred.

[0085] The adhesive resin layer may contain the above-mentioned additives.

[0086] 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, and preferably 20% or less, more preferably 18% or less, 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, and preferably 20% or less, more preferably 18% or less, even more preferably 15% or less.

[0087] The barrier film having a barrier resin layer may be a coextruded resin film. The coextruded resin film may be produced by film formation using, for example, an inflation method or a T-die method. The barrier film having a barrier resin layer may be a coextruded resin film having, for example, 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. The barrier film and the heat seal layer or the like may be laminated via an extruded resin layer described later.

[0088] 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 produced using the laminate of the present disclosure is heated and melted for recycling, the mixability of the gas barrier resin contained in the barrier resin layer and the polyethylene contained in the heat seal layer or the like can be improved. This can effectively prevent the physical properties from decreasing. In addition, it can effectively prevent the transparency from decreasing.

[0089] The compatibilizer can be appropriately selected from conventionally known compatibilizers. From the viewpoint of recyclability, however, unsaturated carboxylic acid-modified polyolefins are preferred, and maleic anhydride-modified polyethylenes are more preferred.

[0090] 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 deterioration in transparency can be more effectively suppressed. When the content is 20% by mass or less, the moldability of the barrier film can be improved, and the strength reduction of the film produced using the resin obtained by recycling the laminate of the present disclosure can be suppressed.

[0091] 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 stretched film or a biaxially stretched film.

[0092] The surface of the barrier film is preferably subjected to the above-mentioned surface treatment, which can improve the adhesion between the barrier film and a layer adjacent to the barrier film.

[0093] The total thickness of the barrier film is preferably 20 μm or more, more preferably 30 μm or more, and preferably 100 μm or less, more preferably 90 μm or less. When the thickness is 20 μm or more, the gas barrier properties of the laminate can be further improved. When the thickness is 100 μm or less, the recyclability of the laminate can be further improved.

[0094] <Base material> The laminate of the present disclosure may further include a substrate between one or more of the first heat seal layer and the barrier resin layer, and between the barrier resin layer and the second heat seal layer. Specifically, as shown in Fig. 3, the laminate 1 preferably has a structure including a substrate (first substrate) 42 between the barrier resin layer 32 and the second heat seal layer 20. Also, as shown in Fig. 4, the laminate 1 preferably has a structure including a substrate (second substrate) 50 between the first heat seal layer 10 and the barrier resin layer 32, and a substrate (first substrate) 42 between the barrier resin layer 32 and the second heat seal layer 20. The laminate of the present disclosure may further include a substrate between one or more of the following: the first heat seal layer and the barrier film; and the barrier film and the second heat seal layer. Specifically, as shown in Fig. 3, the laminate 1 of the present disclosure preferably has a configuration in which a printed substrate 40 is provided between the barrier film 30 and the second heat seal layer 20. Also, as shown in Fig. 4, the laminate 1 of the present disclosure preferably has a configuration in which a substrate (second substrate) 50 is provided between the first heat seal layer 10 and the barrier film 30, and a printed substrate 40 is provided between the barrier film 30 and the second heat seal layer 20.

[0095] The substrate contains polyethylene as a main component. Since the resin material constituting the base material is polyethylene, which is the same type of resin material as the resin material constituting the first heat seal layer and the second heat seal layer, a laminate having such a configuration can be suitably used as a packaging material for producing mono-material packaging containers.

[0096] Examples of polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and very 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.

[0097] The content of polyethylene in the substrate is preferably 50% by mass or more, more preferably 60% by mass or more, further 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 including the laminate of the present disclosure can be improved.

[0098] The substrate may contain biomass polyethylene. The substrate may contain recycled polyethylene. The substrate may contain the above-mentioned additives.

[0099] In one embodiment, the substrate may be a polyethylene film having a total light transmittance measured in accordance with JIS K7375:2008 of preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more.

[0100] The laminate of the present disclosure (for example, laminate 1 shown in FIG. 4) may further include a substrate (second substrate) containing a white pigment between the printing substrate and the first heat seal layer. Furthermore, the laminate of the present disclosure (for example, laminate 1 shown in FIG. 3) may be configured such that the substrate (first substrate) constituting the printing substrate contains a white pigment. With such a configuration, for example, it is possible to impart hiding power (for example, a white hiding effect) to the laminate without using ink such as white ink, thereby reducing the environmental load.

[0101] Examples of white pigments include titanium oxide, 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.

[0102] The content of the white pigment in the base material 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, and is 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, thereby further improving the above-mentioned effects.

[0103] In one embodiment, the substrate may be a polyethylene film having a total light transmittance of 5% to 40%, preferably 10% to 40%, as measured in accordance with JIS K7375:2008, and may be, for example, a milky white polyethylene film, which can impart, for example, hiding power to the laminate.

[0104] In addition, when the laminate of the present disclosure (for example, laminate 1 shown in FIG. 4) further includes a substrate (second substrate) containing a white pigment between the printing substrate and the first heat seal layer, it is preferable that the first heat seal layer does not contain a white pigment. With this configuration, as described below, when a tube container body is manufactured using the laminate of the present disclosure, there is no risk of the white pigment being exposed on the surface layer (first surface layer 1S) of the first heat seal layer due to contact between the metal parts of the manufacturing device such as rollers and the first heat seal layer. This makes it possible to prevent the contents in the tube container from coming into contact with the white pigment and deteriorating the contents (for example, changing the taste of toothpaste, etc.).

[0105] The substrate may have a multi-layer structure, for example, a structure including a layer containing a linear low density polyethylene, a layer containing a high density polyethylene, and a layer containing a linear low density polyethylene.

[0106] The substrate 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, the film is preferably a stretched film. The stretched film may be a uniaxially stretched film or a biaxially stretched film. In one embodiment, the stretching ratio in the longitudinal direction (MD) of the stretched film is preferably 2 to 10 times, more preferably 3 to 7 times. In one embodiment, the stretching ratio in the transverse direction (TD) of the stretched film is preferably 2 to 10 times, more preferably 3 to 7 times. 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 breakage of the film. In one embodiment, the stretched film is a uniaxially stretched film, more specifically, a uniaxially stretched film that has been stretched in the machine direction (MD).

[0107] The surface of the substrate may be subjected to 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.

[0108] The thickness of the substrate is preferably 10 μm or more, more preferably 20 μm or more, and preferably 100 μm or less, more preferably 70 μm or less. When the thickness of the substrate is 10 μm or more, the strength and heat resistance can be further improved. When the thickness of the substrate is 100 μm or less, the processability of the laminate can be improved.

[0109] The substrate may be prepared, for example, by forming a resin composition containing at least polyethylene into a film using a T-die method, an inflation method, or the like.

[0110] Specifically, for example, as shown in Figures 3 and 4, the MFR of the polyethylene constituting the substrate (first substrate) 42 in the printing substrate 40 is, from the viewpoint of film-forming and processability, preferably 0.1 g / 10 min or more and 50 g / 10 min or less, more preferably 0.2 g / 10 min or more and 30 g / 10 min or less, even more preferably 0.2 g / 10 min or more and 10 g / 10 min or less, and particularly preferably 0.2 g / 10 min or more and 5.0 g / 10 min or less.

[0111] For example, when the substrate 42 is produced by the T-die method, the MFR of the polyethylene constituting the substrate 42 is preferably 3.0 g / 10 min or more and 20 g / 10 min or less from the viewpoints of film-formability and processability. For example, when the substrate 42 is produced by the inflation method, the MFR of the polyethylene constituting the substrate 42 is preferably 0.2 g / 10 min or more and 5.0 g / 10 min or less from the viewpoints of film-formability and processability.

[0112] From the viewpoint of heat resistance, the melting point of the polyethylene constituting the base material 42 is preferably 100°C or more and 140°C or less, more preferably 110°C or more and 140°C or less, and even more preferably 120°C or more and 140°C or less.

[0113] The polyethylene content in the base material 42 constituting the printing base material 40 is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. With this configuration, for example, the recyclability of the laminate 1 can be improved. When the base material 42 has a multi-layer structure, the polyethylene content in each layer constituting the base material 42 is independently preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. With this configuration, for example, the recyclability of the laminate 1 can be improved.

[0114] The haze of the substrate 42 may be 25% or less, 15% or less, or 10% or less. The lower limit of the haze may be 0.1% or 1%. The haze of the substrate 42 is measured in accordance with JIS K7136.

[0115] The substrate 42 is preferably a polyethylene substrate that has been subjected to a stretching process (stretched substrate). The stretching process can improve, for example, the printability, heat resistance, and strength of the polyethylene substrate. Such a stretched substrate can satisfy the physical properties required for a substrate that constitutes, for example, the body of a tube container.

[0116] The thickness of the stretched substrate is preferably 10 μm or more and 60 μm or less, more preferably 15 μm or more and 50 μm or less. When the thickness of the stretched substrate is 10 μm or more, the rigidity and strength can be improved. When the thickness of the stretched substrate is 60 μm or less, the processability can be improved.

[0117] The stretched substrate may have a single layer structure or a multilayer structure. Hereinafter, a stretched substrate having a multilayer structure is also referred to as a "stretched multilayer substrate". A stretched multilayer substrate is preferable from the viewpoint of improving its strength, heat resistance, and stretchability.

[0118] The stretched multi-layer substrate has a multi-layer structure of two or more layers. In one embodiment, the number of layers of the stretched multi-layer substrate is 2 to 7 layers, for example, 3 to 7 layers, or 3 to 5 layers. The number of layers of the stretched multi-layer substrate is preferably an odd number, for example, 3, 5, or 7 layers. The stretched multi-layer substrate has a multi-layer structure, which can improve the balance of rigidity, strength, heat resistance, printability, and stretchability. Each layer of the stretched multi-layer substrate also preferably contains polyethylene as a main component.

[0119] Hereinafter, several examples of the embodiment of the stretched multilayer base material will be described. Hereinafter, a layer containing 80% or more of high-density polyethylene will be referred to as a "high-density polyethylene layer", a layer containing 80% or more of medium-density polyethylene will be referred to as a "medium-density polyethylene layer", a layer containing 80% or more of low-density polyethylene will be referred to as a "low-density polyethylene layer", a layer containing 80% or more of linear low-density polyethylene will be referred to as a "linear low-density polyethylene layer", and a layer containing 80% or more of very-low-density polyethylene will be referred to as a "very-low-density polyethylene layer".

[0120] The stretched multilayer substrate of the first embodiment includes a high-density polyethylene layer and a medium-density polyethylene layer in this order in the thickness direction. The surface resin layer of the stretched substrate is a high-density polyethylene layer, which can improve, for example, the strength and heat resistance of the stretched substrate. The stretched substrate includes a medium-density polyethylene layer, which can improve, for example, the stretchability of the laminate before stretching.

[0121] The stretched multilayer substrate of the second embodiment includes a high density polyethylene layer, a medium density polyethylene layer, and a high density polyethylene layer in this order in the thickness direction. This configuration can improve the strength and heat resistance of the stretched substrate, suppress curling in the stretched substrate, and improve the stretchability of the pre-stretched laminate, for example.

[0122] The stretched multilayer substrate of the third embodiment includes a high-density polyethylene layer, a medium-density polyethylene layer, a low-density polyethylene layer, a linear low-density polyethylene layer or an ultra-low-density polyethylene layer (for the sake of simplicity, these three layers are collectively referred to as "low-density polyethylene layer, etc."), a medium-density polyethylene layer, and a high-density polyethylene layer, in this order in the thickness direction. By adopting such a configuration, for example, the stretchability of the laminate before stretching can be improved, the strength and heat resistance of the stretched substrate can be improved, and the occurrence of curling in the stretched substrate can be suppressed.

[0123] Other embodiments of the stretched multilayer substrate include a stretched substrate having, in the thickness direction, a high density polyethylene layer, a high density polyethylene layer, a blend layer of medium density polyethylene and high density polyethylene, a high density polyethylene layer, and a high density polyethylene layer, in that order; and a stretched substrate having, in the thickness direction, a medium density polyethylene layer, a high density polyethylene layer, a linear low density polyethylene layer, a high density polyethylene layer, and a medium density polyethylene layer, in that order.

[0124] Further, an example of a stretched substrate includes a high-density polyethylene layer, a blend layer of high-density polyethylene and medium-density polyethylene, a low-density polyethylene layer, a blend layer of high-density polyethylene and medium-density polyethylene, and a high-density polyethylene layer, in this order in the thickness direction.

[0125] The stretched multilayer substrate of the fourth embodiment includes a medium density polyethylene layer, a high density polyethylene layer, a blend layer of medium density polyethylene and high density polyethylene, a high density polyethylene layer, and a medium density polyethylene layer, in this order in the thickness direction. By adopting such a configuration, for example, the printability, strength, and heat resistance of the stretched substrate can be improved, and the stretchability of the pre-stretched laminate can be improved.

[0126] The stretched multilayer substrate of the fifth embodiment includes, in the thickness direction, a medium density polyethylene layer, a medium density polyethylene layer, a blend layer of medium density polyethylene and linear low density polyethylene, a medium density polyethylene layer, and a medium density polyethylene layer in this order. By adopting such a configuration, for example, the printability, strength, and heat resistance of the stretched substrate can be improved, and the stretchability of the pre-stretched laminate can be improved.

[0127] The stretched multilayer substrate of the sixth embodiment includes, in the thickness direction, a blend layer of medium density polyethylene and high density polyethylene, a blend layer of medium density polyethylene and linear low density polyethylene, a linear low density polyethylene layer, a blend layer of medium density polyethylene and linear low density polyethylene, and a blend layer of medium density polyethylene and high density polyethylene in this order. By adopting such a configuration, for example, the printability, strength and heat resistance of the stretched substrate can be improved, and the stretchability of the pre-stretched laminate can be improved.

[0128] The stretched multilayer substrate of the seventh embodiment includes, in the thickness direction, a blend layer of high density polyethylene and medium density polyethylene, a medium density polyethylene layer, a blend layer of linear low density polyethylene and medium density polyethylene, a medium density polyethylene layer, and a blend layer of high density polyethylene and medium density polyethylene in this order. By adopting such a configuration, for example, the printability, strength, and heat resistance of the stretched substrate can be improved, and the stretchability of the pre-stretched laminate can be improved.

[0129] The stretched multilayer substrate of the eighth embodiment includes a first layer containing medium density polyethylene and high density polyethylene, a second layer containing high density polyethylene, a third layer containing linear low density polyethylene, a fourth layer containing high density polyethylene, and a fifth layer containing medium density polyethylene and high density polyethylene, in this order in the thickness direction. The second layer and the fourth layer may each independently further contain low density polyethylene. This can further improve the balance of the heat resistance, rigidity, and processability of the stretched substrate. The third layer may further contain low density polyethylene.

[0130] The thickness of each of the second layer and the fourth layer may be independently 0.5 μm to 15 μm, 1 μm to 10 μm, or 1 μm to 8 μm. This can further improve the heat resistance of the stretched substrate. The thickness of the third layer may be 1 μm to 50 μm, 2 μm to 40 μm, or 5 μm to 30 μm. This can further improve the balance of heat resistance, rigidity, and stretchability.

[0131] In the stretched multi-layered substrates of the fourth to eighth embodiments, the thickness of each of the two surface resin layers may be independently 0.5 μm or more and 10 μm or less, 1 μm or more and 8 μm or less, or 1 μm or more and 5 μm or less. This can, for example, improve the heat resistance and printability of the stretched substrate. In the stretched multi-layered substrates of the fourth to eighth embodiments, the thickness of each of the two surface resin layers is preferably smaller than the total thickness of the three inner layers (multi-layered intermediate layer). The ratio of the thickness of each of the two surface resin layers to the total thickness of the multi-layered intermediate layer (surface resin layer / multi-layered intermediate layer) can be 0.05 or more and 0.8 or less, 0.1 or more and 0.7 or less, or 0.1 or more and 0.4 or less. This can, for example, improve the rigidity, strength, and heat resistance of the stretched substrate.

[0132] At least one layer selected from each layer constituting the stretched multilayer base material may contain a slip agent. This can improve the processability of the stretched base material, for example. For example, in the stretched multilayer base material of the eighth embodiment described above, the third layer may contain a slip agent, and all of the first to fifth layers may contain a slip agent. Examples of slip agents include amide-based lubricants, fatty acid esters such as glycerin fatty acid esters, hydrocarbon waxes, higher fatty acid waxes, metal soaps, hydrophilic silicones, silicone-modified (meth)acrylic resins, silicone-modified epoxy resins, silicone-modified polyethers, silicone-modified polyesters, block-type silicone (meth)acrylic copolymers, polyglycerol-modified silicones, and paraffins. Among the slip agents, amide-based lubricants are preferred. Examples of the amide-based lubricants include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides. Among these, unsaturated fatty acid amides are preferred, and erucic acid amide is more preferred.

[0133] In the stretched multilayer substrate, the content of the slip agent in the layer containing the slip agent may be, for example, from 0.01% to 3% by mass, or from 0.03% to 1% by mass, which can further improve the processability of the stretched substrate.

[0134] The stretched substrate can be produced, for example, by forming a film of polyethylene or a polyethylene composition by the inflation method or the T-die method, and stretching the film. The stretched multi-layer substrate can be produced, for example, by forming a laminate of a plurality of polyethylenes or polyethylene compositions by the inflation method or the T-die method, and stretching the resulting laminate. The stretching treatment can improve the transparency, rigidity, strength, and heat resistance of the polyethylene layer, and the stretched substrate can be suitably used, for example, as a substrate for packaging materials. Stretching can also be performed in an inflation film-forming machine.

[0135] In one embodiment, the stretched multi-layer substrate is a coextruded resin film, and each layer constituting the stretched multi-layer substrate is a coextruded resin layer. The coextruded resin film can be produced by film formation using, for example, an inflation method or a T-die method.

[0136] In one embodiment, the stretched multilayer base material is obtained by stretching a laminate (precursor) having a multilayer structure. Specifically, the resin materials constituting each layer are co-extruded into a tube shape to form a film, and the laminate can be manufactured. Alternatively, the resin materials constituting each layer are co-extruded into a tube shape, and then the opposing layers are pressed together with a rubber roll or the like to manufacture the laminate. By manufacturing the laminate by such a method, the number of defective products can be significantly reduced, and production efficiency can be improved.

[0137] <Print layer> The laminate of the present disclosure may include a printed layer. The printed layer includes an image. Examples of images include characters, figures, symbols, patterns, and combinations thereof. Images may include text information such as product names, names of contents in packaging containers, manufacturers, and raw material names. Images may be solid colors (so-called solid images).

[0138] The print layer may be formed using a print layer composition, such as a thermoplastic resin composition, a thermosetting resin composition, or an energy ray curable resin composition, each of which contains a colorant. Specifically, the print layer contains a resin component, such as a thermoplastic resin, a cured product of a thermosetting resin, or a cured product of an energy ray curable resin, and a colorant.

[0139] Examples of the colorant include pigments such as inorganic pigments 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 the pigment include titanium oxide, zinc oxide, carbon black, iron oxide, yellow iron, ultramarine blue, metallic pigments, pearl pigments, and fluorescent pigments. The print layer may be a high brightness layer having a high metallic luster.

[0140] The content of the resin component in the printed layer may be 10% by mass or more, 30% by mass or more, 50% by mass or more, and 99% by mass or less, 97% by mass or less, or 95% by mass or less. The content of the colorant 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.

[0141] The printing layer composition may contain an organic solvent and / or water from the viewpoint of improving the coating properties, etc. 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.

[0142] The printing layer may be provided, for example, on at least one of the surfaces of the second heat seal layer and the substrate. For example, the laminate of the present disclosure may include a printing substrate between the second heat seal layer and the barrier resin layer, specifically between the second heat seal layer and the barrier film. The printing substrate includes a substrate (first substrate) containing polyethylene as a main component, and a printing layer provided on at least one of the surfaces of the substrate. The printing layer of the printing substrate may be provided on the surface of the substrate facing the second heat seal layer, or may be provided on the surface of the substrate facing the first heat seal layer. The printing layer of the printing substrate is preferably provided on the surface of the substrate facing the second heat seal layer.

[0143] In addition, the laminate of the present disclosure may have a printed layer on one surface (second surface 2S) of the second heat seal layer, or may have a printed layer on the other surface of the second heat seal layer facing the barrier resin layer. When a printed layer is provided on the surface of the second heat seal layer, it is preferably provided on the other surface facing the barrier resin layer.

[0144] The thickness of the printed layer is preferably 0.01 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more, with the upper limit being 30 μm or less, preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

[0145] Examples of printing methods for the printing layer include letterpress printing, flexographic printing, gravure printing, offset printing, screen printing, inkjet printing, and thermal transfer printing. When the printing layer is formed by letterpress printing or flexographic printing, it is preferable to use an energy ray curable resin composition, and it is more preferable to use an ultraviolet ray curable resin composition. The printing layer may contain, for example, a sublimation dye. The printing layer of this embodiment can be formed, for example, by sublimation transfer printing using a thermal transfer sheet.

[0146] When the laminate of the present disclosure is viewed in plan, it is preferable that no printed layer is formed in the area corresponding to the planned area for heat sealing to form the body of the tube container body. "Viewed in plan" refers to viewing the laminate from the normal direction of the second surface of the laminate. In addition to suppressing the end surface exposure of the barrier resin layer at the joint as described above, such a printed layer configuration can suppress delamination starting from the printed layer at the joint (the tube attachment location).

[0147] <Anchor coat layer> The laminate of the present disclosure may further include an anchor coat layer between the print layer and the extruded resin layer. Such a laminate has, for example, excellent interlayer adhesion. The anchor coat layer is formed, for example, from an anchor coat agent.

[0148] Examples of the anchor coating agent include polyurethane-based, polyolefin-based, polyethyleneimine-based, or epoxy resin-based anchor coating agents. In one embodiment, the anchor coating agent is a two-liquid curing resin, and is composed of, for example, a polyol as a main agent and a polyisocyanate as a curing agent. Examples of the polyol include polyether polyol, polyester polyol, and (meth)acrylic polyol. Examples of the polyisocyanate include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenylene polyisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate. In one embodiment, the anchor coating layer is composed of polyurethane obtained by the reaction of a polyol with a polyisocyanate. Specific examples of the polyurethane include polyether polyurethane, polyester polyurethane, and poly(meth)acrylic polyurethane.

[0149] The anchor coat layer can be formed, for example, by applying an anchor coat agent to the printing substrate. The anchor coat agent can be applied by a coating method such as roll coating, gravure roll coating, or kiss coating, or by a printing method.

[0150] The thickness of the anchor coat layer is preferably 0.01 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more, and is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less.

[0151] Specifically, in the laminate 1 shown in Figures 3 and 4, the thickness of the anchor coat layer is preferably 0.05 μm or more, more preferably 0.1 μm or more, even more preferably 0.2 μm or more, and preferably 3.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less.

[0152] <Adhesive layer> The laminate of the present disclosure may have an adhesive layer (extruded resin layer) between any of the 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 can improve the interlayer adhesion strength in the laminate, and therefore, for example, can suppress delamination in the laminate and tube container. Specifically, in the laminate 1 shown in FIG. 3, it is preferable to provide an adhesive layer between the second heat seal layer 20 and the printing substrate 40, between the printing substrate 40 and the barrier film 30, and between the barrier film 30 and the first heat seal layer 10. In addition, in the laminate 1 shown in FIG. 4, it is preferable to provide an adhesive layer between the second heat seal layer 20 and the printing substrate 40, between the printing substrate 40 and the barrier film 30, between the barrier film 30 and the substrate 50, and between the substrate 50 and the first heat seal layer 10.

[0153] The adhesive layer is not particularly limited, but from the viewpoint of mono-material, an extruded resin layer containing polyethylene as a main component is preferable. A laminate including an extruded resin layer has a high polyethylene content and is excellent in recyclability.

[0154] Examples of the polyethylene contained in the extruded resin layer include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, and very low density polyethylene. Among these, from the viewpoint of interlayer adhesion, low density polyethylene, linear low density polyethylene, and very low density polyethylene are preferred, and low density polyethylene is more preferred.

[0155] From the viewpoints of film-forming and processability, the melt flow rate (MFR) of the polyethylene contained in the extruded resin 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, and is preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, even more preferably 20 g / 10 min or less. Specifically, in the laminate 1 shown in Figures 3 and 4, the melt flow rate (MFR) of the polyethylene contained in the extruded resin layer is, from the viewpoints of film-forming ability and processability, preferably 0.1 g / 10 min or more, more preferably 0.2 g / 10 min or more, even more preferably 3 g / 10 min or more, and preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, even more preferably 20 g / 10 min or less. 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.

[0156] From the viewpoint of a balance between heat resistance and adhesiveness, the melting point (Tm) of the polyethylene contained in the extruded resin layer is preferably 100° C. or higher, and preferably 140° C. or lower, more preferably 130° C. or lower, and further preferably 120° C. or lower. The Tm of the polyethylene is the melting peak temperature obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121:2012.

[0157] The extruded resin layer may contain biomass polyethylene. The extruded resin layer may contain recycled polyethylene. The extruded resin layer may contain the above-mentioned additives.

[0158] The content of polyethylene in the extruded resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. With such a constitution, for example, adhesiveness and recyclability can be improved.

[0159] The thickness of the extruded resin layer is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more, and is 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, the interlayer adhesion can be further improved. When the thickness is 40 μm or less, the production cost of the laminate can be reduced and the productivity can be improved.

[0160] The extruded resin layer may be formed, for example, by melt-extruding a resin composition containing at least polyethylene onto a target film, at a melting temperature of, for example, preferably 280° C. or higher, more preferably 290° C. or higher, and preferably 340° C. or lower, more preferably 335° C. or lower.

[0161] [Tube container body] The tube container body of the present disclosure includes the above-described laminate. The tube container body of the present disclosure will be described below with reference to the drawings. Fig. 6 is a diagram showing a simplified configuration of a tube container 100, and Fig. 7 is a cross-sectional view taken along line AA in Fig. 6. As shown in Fig. 6, the tube container body 101 includes a head 102 and a body 103, and the body 103 is made of the laminate of the present disclosure.

[0162] <Head> The head 102 includes a shoulder 104 connected to one end of the body 103, and a spout 105 connected to the shoulder 104. In one embodiment, the spout 105 includes threads 107 for threading a cap 106 thereon.

[0163] In one embodiment, the head is formed of a resin composition containing polyethylene. This can improve 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 very low-density polyethylene. Among these, high-density polyethylene is preferred from the viewpoints of shape retention and moldability.

[0164] The resin composition may contain at least one selected from biomass polyethylene and recycled polyethylene. The resin composition may contain the additives.

[0165] The head portion can be manufactured by a conventional method, for example, by compression molding or injection molding, and can be joined to the body portion.

[0166] When the tube container body is manufactured using a compression molding method, the body may be attached to a male mold having a convex portion on the top, the male mold and the female mold are placed opposite each other, a molten resin composition is supplied into the male and female molds, and the head is formed by compression molding, and the head is joined to one opening of the body, thereby manufacturing a tube container body having a head and a body.

[0167] When the tube container body is manufactured using an injection molding method, the body may be attached to a male mold having a convex portion on the top, the male mold and the female mold are opposed to each other, a molten resin composition is supplied from a gate, and the head is formed by injection molding, and the head is joined to one opening of the body, thereby manufacturing a tube container body having a head and a body.

[0168] <Torso> In the tube container body 101 of the present disclosure, the body 103 is connected to a shoulder 104 of the head 102. The body 103 includes a joint 108 formed, for example, by overlapping the laminate of the present disclosure at one end so that the surface on the first heat seal layer side of the laminate at the other end is in contact with the surface on the second heat seal layer side of the laminate, rolling the laminate into a tubular shape (e.g., cylindrical shape), and heat sealing the overlapped portion. The body 103 includes a bottom joint 109 formed, for example, by heat sealing the opening of the laminate rolled into a cylindrical shape.

[0169] Examples of the heat sealing method include conventionally known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, ultrasonic sealing and flame sealing.

[0170] For example, the laminate of the present disclosure may be rolled into a cylindrical shape by overlapping the first heat seal layer side surface of one end of the laminate with the second heat seal layer side surface of the other end, and heat sealing the overlapped portion to produce a cylindrical body. From the viewpoint of heat sealability, it is preferable that one overlapped end 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 are melted and joined to form a joint.

[0171] In the above embodiment, the joint is formed by overlapping, but it is also possible to butt the same surfaces of both ends of the laminate together and heat seal the first heat seal layers together to join them.

[0172] [Tube container] The tube container of the present disclosure will be described below with reference to the drawings. As shown in Fig. 6, the tube container 100 of the present disclosure includes a tube container body 101 and a cap 106 attached to a head portion 102.

[0173] <Tube container body> The tube container body has been described above, so a description thereof will be omitted here.

[0174] <Cap> The cap is detachably attached to the extraction port of the head, and plays a role in closing the extraction port. In one embodiment, the cap is formed of a resin composition containing a thermoplastic resin. Examples of the thermoplastic resin include polyolefins such as polyethylene and polypropylene, polyesters, cellulose resins, and vinyl resins. From the viewpoint of recyclability, polyethylene is particularly preferred. Examples of the polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and very low-density polyethylene. Among these, high-density polyethylene is preferred from the viewpoint of shape retention and openability.

[0175] The resin composition may contain at least one selected from biomass polyethylene and recycled polyethylene. The resin composition may contain the additives.

[0176] The cap may be a screw type having a groove on the inner surface of the cap so as to screw into the threads 107 of the extraction port 105, as shown in FIG. 6, or it may be a plug type which fits into the extraction port 105 by plugging it.

[0177] [Mechanism of action] 3, the laminate 1 of the present disclosure is a four-layer laminate film including, in this order, a first heat seal layer 10, a barrier film 30 including a barrier resin layer 32, a printing substrate 40 including a substrate (first substrate) 42, and a second heat seal layer 10, and since the first heat seal layer 10, the barrier film 30, the printing substrate 40, and the second heat seal layer each contain polyethylene as a main component, the laminate 1 of the present disclosure has excellent recyclability. This allows the laminate 1 of the present disclosure to reduce the environmental load. Furthermore, the laminate 1 of the present disclosure has excellent concealing properties because at least one of the substrate (first substrate) 42 and the first heat seal layer 10 is a polyethylene film having a total light transmittance of 10% or more and 40% or less. As a result, when the laminate 1 of the present disclosure is used as a tube container body, it can protect contents that are sensitive to direct sunlight.

[0178] As shown in Fig. 4, the laminate 1 of the present disclosure is a five-layer laminate film including, in this order, a first heat seal layer 10, a substrate (second substrate) 50, a barrier film 30 including a barrier resin layer 32, a printing substrate 40 including a substrate (first substrate) 42, and a second heat seal layer 10, and since the first heat seal layer 10, the substrate 50, the barrier film 30, the printing substrate 40, and the second heat seal layer each contain polyethylene as a main component, the laminate 1 of the present disclosure has excellent recyclability. This allows the laminate 1 of the present disclosure to reduce the environmental load. Furthermore, the laminate 1 of the present disclosure has excellent concealing properties because at least the substrate (second substrate) 50 is a polyethylene film having a total light transmittance of 10% or more and 40% or less. As a result, when the laminate 1 of the present disclosure is used as a tube container body, it can protect contents that are sensitive to direct sunlight.

[0179] Incidentally, as shown in Fig. 3 and Fig. 4, the laminate 1 of the present disclosure may have a first heat seal layer 10 containing a white pigment. When a tube container body (e.g., reference numeral 101 in Fig. 6) is manufactured using the laminate 1 having such a configuration, the first heat seal layer 10 may come into contact with a metal part such as a roller of a manufacturing device, and the white pigment may be exposed to the inside of the tube container body on the surface layer (first surface layer 1S) of the first heat seal layer 10. When the white pigment is exposed on the surface layer of the first heat seal layer 10, the white pigment may come into contact with the contents in the tube container, causing deterioration of the contents (e.g., the taste of toothpaste may change, etc.).

[0180] Therefore, as shown in Figures 3 and 4, the laminate 1 of the present disclosure is preferably configured such that the first heat seal layer 10 does not contain a white pigment. With such a configuration, when a tube container body is manufactured using the laminate 1 of the present disclosure, there is no risk of the white pigment being exposed on the surface layer (first surface layer 1S) of the first heat seal layer 10 due to contact between a metal part such as a roller of a manufacturing device and the first heat seal layer 10. This makes it possible to prevent the contents in the tube container from coming into contact with the white pigment and deteriorating the contents (for example, changing the taste of toothpaste, etc.).

[0181] 4, the laminate 1 of the present disclosure includes a substrate (second substrate) 50 between the first heat seal layer 10 and the barrier film 30 including the barrier resin layer 32, and therefore the thickness of the polyethylene layer from the barrier resin layer 32 to the first heat seal layer 10 can be increased. By manufacturing a tube container body using a laminate 1 that satisfies the required relationship in thickness, the layer containing polyethylene as a main component can adequately cover the end face of the barrier resin layer at the joint (tube attachment portion) on the inner surface of the barrel of the tube container body. This makes it possible to suppress the occurrence of delamination.

[0182] The present disclosure also relates to, for example, the following

[0101] to

[0122] .

[0101] A laminate comprising at least a first heat seal layer, a barrier resin layer, and a second heat seal layer in this order, wherein the first heat seal layer contains polyethylene as a main component, the second heat seal layer contains polyethylene as a main component, and the barrier resin layer contains a gas barrier resin as a main component, the laminate has a first surface and a second surface opposite to the first surface, the first heat seal layer constitutes the first surface, the second heat seal layer constitutes the second surface, and a total thickness (T in ) the thickness (T b1 ) to the ratio (T in / T b1 ) is 8.0 or more, and the content of polyethylene in the entire laminate is 90 mass% or more.

[0102] The laminate described in

[0101] , wherein the barrier resin layer contains an ethylene-vinyl alcohol copolymer as a main component.

[0103] The laminate described in

[0101] or

[0102] , comprising 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.

[0104] The laminate described in

[0103] , wherein the thickness of the barrier film is 20 μm or more and 100 μm or less.

[0105] The total thickness (T in ) is 120 μm or more and 250 μm or less.

[0106] The total thickness (T out ) the thickness (T b2 ) to the ratio (T out / T b2 ) is 6.0 or more and 14.0 or less.

[0107] The total thickness (T out ) is 100 μm or more and 220 μm or less.

[0108] A laminate described in any one of

[0101] to

[0107] , wherein the laminate further comprises a printed 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 printed substrate comprising a substrate containing polyethylene as a main component and a printed layer provided on at least one surface of the substrate.

[0109] The laminate described in

[0108] , comprising, in this order, the barrier resin layer, a substrate in the printing substrate, a printing layer in the printing substrate, and the second heat seal layer.

[0110] A laminate described in

[0108] or

[0109] , wherein the substrate in the printing substrate is a stretched film containing at least one selected from medium density polyethylene and high density polyethylene.

[0111] A laminate for forming the body of a tube container body, 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, the laminate described in any one of

[0101] to

[0110] .

[0112] The laminate described in

[0111] above, further comprising a printed 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 printed substrate comprising a substrate containing polyethylene as a main component and a printed layer provided on at least one surface of the substrate, and the printed layer is not formed in an area of ​​the printed substrate corresponding to the planned area for heat sealing to form the barrel of the tube container body.

[0113] The laminate described in

[0111] or

[0112] , comprising, in this 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 containing polyethylene as a main component, and a printing substrate having a printing layer, optionally an extruded polyethylene layer, and the second heat seal layer.

[0114] The laminate described in

[0113] above, wherein the first heat seal layer contains a white pigment.

[0115] A laminate described in

[0113] or

[0114] , wherein the first heat seal layer is a polyethylene film having a total light transmittance (measured in accordance with JIS K7375:2008) of 5% or more and 40% or less.

[0116] A laminate described in any one of

[0111] to

[0115] above, comprising, in this order from the inner surface, the first heat seal layer, an optional extruded polyethylene layer, a substrate containing polyethylene as a main component, an optional extruded polyethylene layer, a barrier film comprising the barrier resin layer, an optional extruded polyethylene layer, a substrate containing polyethylene as a main component, and a printing substrate comprising a printing layer, an optional extruded polyethylene layer, and the second heat seal layer.

[0117] The laminate described in

[0116] , wherein at least one selected from the first heat seal layer and the substrate containing polyethylene as a main component contains a white pigment.

[0118] A laminate described in

[0116] or

[0117] , 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 (measured in accordance with JIS K7375:2008) of 5% or more and 40% or less.

[0119] A tube container body having a head and a body, wherein the head has a shoulder portion connected to one end of the body and an extraction port portion connected to the shoulder portion, and the body is formed from a laminate described in any one of

[0101] to

[0118] .

[0120] A tube container body as described in

[0119] , wherein the head is formed from a resin composition containing polyethylene.

[0121] A tube container comprising a tube container body described in

[0119] or

[0120] and a cap.

[0122] A tube container as described in

[0121] , wherein the cap is formed from a resin composition containing polyethylene. EXAMPLES

[0183] The laminate of the present disclosure will be described more specifically below with reference to examples, but the laminate of the present disclosure is not limited to the following examples.

[0184] [Polyethylene base material] The following polyethylene substrates were used: 25μm thick oriented substrate, uniaxially oriented high density polyethylene substrate 1 (Tokyo Ink, Hibron SMKQW, milky white grade) · Unstretched base material with a thickness of 40 μm, unstretched polyethylene base material 2 (Idemitsu Unitech, HS-862CX3)

[0185] [EVOH-containing polyethylene film] The following EVOH-containing polyethylene films were used: Barrier film 1: Linear low-density polyethylene (Dow Chemical, DOWLEX2045G, density 0.920g / cm 3), adhesive resin (Mitsui Chemicals, Admer NF557), and ethylene-vinyl alcohol copolymer (Kuraray, EVAL H171B, density 1.17 g / cm 3 , ethylene content 38 mol%), adhesive resin (Mitsui Chemicals, Admer NF557), linear low-density polyethylene (Dow Chemical, DOWLEX2045G, density 0.920 g / cm 3 ) were co-extruded by an inflation method to obtain a 75 μm-thick EVOH-containing polyethylene film. In the film, the thickness of the ethylene-vinyl alcohol copolymer layer was about 20% of the total film thickness, and the thickness of the linear low-density polyethylene layer was about 40%. Barrier film 2: Thickness 80 μm (Tamapoly, Multitron ZEX101)

[0186] [Polyethylene film] The following polyethylene films were used: -Antistatic agent-containing polyethylene film 1 (polyethylene (density: 0.920 g / cm) with a thickness of 50 μm or 80 μm 3 , MFR: 1.9g / 10min) and antistatic agent mixture) 50μm thick polyethylene film containing antistatic agent 2 (polyethylene (density: 0.931g / cm 3 , MFR: 2.1g / 10min) and antistatic agent mixture) Polyethylene film 3 (polyethylene (density: 0.920 g / cm 3 , MFR: 1.9g / 10min) and a mixture of white pigments to form a film, milky type, total light transmittance: about 20%) 50μm thick polyethylene film 4 (polyethylene (density: 0.931g / cm 3 , MFR: 2.1g / 10min and a mixture of white pigments are used to form a film, milky type, total light transmittance: approx. 20%) 50μm thick polyethylene film 5 (Aicello, L100N)

[0187] [Example 1] A uniaxially oriented high density polyethylene substrate 1 having a thickness of 25 μm was used as the substrate. A urethane-based gravure ink (NEW-LP Super, manufactured by Toyo Ink) was applied onto the substrate by gravure printing and dried to form a printed layer having a thickness of 1 μm. In this manner, a printed substrate was obtained.

[0188] Each layer was laminated using an extrusion laminator. Specifically, a high-pressure low-density polyethylene (Nippon Polyethylene, Novatec LD LC602A, density: 0.919 g / cm) melted at 335°C was applied to the barrier film 1. 3 A 30-μm-thick extruded resin layer was formed by extruding a LDPE (melting point: 107°C, MFR: 8.2 g / 10 min) and a 100-μm-thick milky white polyethylene film 3 was laminated onto the extruded resin layer. Next, a high-pressure low-density polyethylene (Nippon Polyethylene, Novatec LD LC602A, density: 0.919 g / cm) melted at 335°C was applied to the opposite side of the barrier film 1. 3 , melting point: 107°C, MFR: 8.2g / 10min, LDPE) was extruded to form an extruded resin layer with a thickness of 20μm, and a uniaxially oriented high density polyethylene substrate 1 with a thickness of 25μm was laminated to the opposite side of the printed surface. Further, high pressure low density polyethylene (Nippon Polyethylene, Novatec LD LC602A, density: 0.919g / cm) melted at 335°C was used. 3 LDPE) (melting point: 107° C., MFR: 8.2 g / 10 min) was extruded to bond two antistatic agent-containing polyethylene films 1 having thicknesses of 20 μm and 80 μm. In this manner, a laminate was obtained.

[0189] The laminate comprises, in order, (outermost layer) an antistatic agent-containing polyethylene film 1 (80 μm), an extruded resin layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented high-density polyethylene substrate 1, an extruded resin layer (20 μm), a barrier film 1 (75 μm), an extruded resin layer (30 μm), and a milky polyethylene film 3 (100 μm) (innermost layer).

[0190] [Example 2] A laminate was obtained in the same manner as in Example 1, except that the uniaxially oriented high-density polyethylene substrate 1 was changed to an unoriented polyethylene substrate 2 and the printing position was changed.

[0191] The laminate comprises, in order, (outermost layer) antistatic agent-containing polyethylene film 1 (80 μm), extruded resin layer (20 μm), unstretched high-density polyethylene substrate 2 (40 μm), printed layer (1 μm), anchor coat layer (1 μm), extruded resin layer (20 μm), barrier film 1 (75 μm), extruded resin layer (30 μm), and milky polyethylene film 3 (100 μm) (innermost layer).

[0192] [Example 3] A laminate was obtained in the same manner as in Example 1, except that a polyethylene film 5 having a thickness of 50 μm was laminated under the barrier film 1 and the polyethylene film 3 having a thickness of 50 μm.

[0193] The laminate comprises, in order, (outermost layer) antistatic agent-containing polyethylene film 1 (50 μm), extruded resin layer (20 μm), anchor coat layer (1 μm), printed layer (1 μm), uniaxially oriented high-density polyethylene substrate 1 (25 μm), extruded resin layer (20 μm), barrier film 1 (75 μm), extruded resin layer (20 μm), polyethylene film 3 (50 μm), extruded resin layer (30 μm), and polyethylene film 5 (50 μm) (innermost layer).

[0194] [Example 4] A laminate was obtained in the same manner as in Example 3, except that the uniaxially oriented high-density polyethylene substrate 1 was changed to an unoriented polyethylene substrate 2 and the printing position was changed.

[0195] The laminate comprises, in order, (outermost layer) antistatic agent-containing polyethylene film 1 (50 μm), extruded resin layer (20 μm), unstretched polyethylene base material 2 (40 μm), printed layer (1 μm), anchor coat layer (1 μm), extruded resin layer (20 μm), barrier film 1 (75 μm), polyethylene film 3 (50 μm), extruded resin layer (30 μm), and polyethylene film 5 (50 μm) (innermost layer).

[0196] [Example 5] A laminate was obtained in the same manner as in Example 2, except that the outermost layer was an antistatic agent-containing polyethylene film 2 having a thickness of 50 μm, and the innermost layer was a polyethylene film 4 having a thickness of 50 μm.

[0197] The laminate comprises, in order, (outermost layer) an antistatic agent-containing polyethylene film 2 (50 μm), an extruded resin layer (20 μm), an anchor coat layer (1 μm), a printed layer (1 μm), a uniaxially oriented high-density polyethylene substrate 1 (25 μm), an extruded resin layer (20 μm), a barrier film 1 (75 μm), an extruded resin layer (20 μm), a polyethylene film 4 (50 μm), an extruded resin layer (30 μm), and a polyethylene film 4 (50 μm) (innermost layer).

[0198] [Example 6] A laminate was obtained in the same manner as in Example 5, except that the uniaxially oriented high-density polyethylene substrate 1 was changed to an unoriented polyethylene substrate 2 and the printing position was changed.

[0199] The laminate comprises, in order, (outermost layer) an antistatic agent-containing polyethylene film 2 (50 μm), an extruded resin layer (20 μm), an unstretched polyethylene base material 2 (40 μm), a printed layer (1 μm), an anchor coat layer (1 μm), an extruded resin layer (20 μm), a barrier film 1 (75 μm), an extruded resin layer (20 μm), a polyethylene film 4 (50 μm), an extruded resin layer (30 μm), and a polyethylene film 4 (50 μm) (innermost layer).

[0200] [Example 7] Each layer was laminated using an extrusion laminator. Specifically, a high-pressure low-density polyethylene (Nippon Polyethylene, Novatec LD LC602A, density: 0.919 g / cm) melted at 335°C was applied to the barrier film 1. 3LDPE (melting point: 107°C, MFR: 8.2g / 10min) was extruded to form an extruded resin layer of 30μm thickness, and a milky white polyethylene film 3 of 100μm thickness was laminated on the extruded resin layer. Next, high-pressure low-density polyethylene (same as above) melted at 335°C was extruded on the opposite side of the barrier film 1 to form an extruded resin layer of 20μm thickness, and a uniaxially oriented high-density polyethylene film 1 of 25μm thickness was laminated on a uniaxially oriented high-density polyethylene substrate 1 of 25μm thickness as a substrate, and high-pressure low-density polyethylene (same as above) melted at 335°C was extruded to laminate an extruded resin layer of 20μm thickness and a polyethylene film 1 of 80μm thickness. Then, the laminate was subjected to flexographic printing and varnishing. As described above, a laminate was obtained.

[0201] The laminate comprises, in order, (outermost layer) varnish, printed layer (1 μm), anchor coat layer (1 μm), polyethylene film 1 (80 μm), extruded resin layer (20 μm), uniaxially oriented high-density polyethylene substrate 1 (25 μm), extruded resin layer (20 μm), barrier film 1 (75 μm), extruded resin layer (30 μm), and polyethylene film 3 (100 μm) (innermost layer).

[0202] [Example 8] A laminate was obtained in the same manner as in Example 7, except that the uniaxially oriented high-density polyethylene substrate 1 was changed to the unoriented polyethylene substrate 2.

[0203] The laminate comprises, in order, (outermost layer) varnish, a printing layer (1 μm), an anchor coat layer (1 μm), a polyethylene film 1 (80 μm), an extruded resin layer (20 μm), an unstretched polyethylene substrate 2 (40 μm), an extruded resin layer (20 μm), a barrier film 1 (75 μm), an extruded resin layer (30 μm), and a polyethylene film 3 (100 μm) (innermost layer).

[0204] [Example 9] A laminate was obtained in the same manner as in Example 7, except that the thickness of the extruded resin layer between the barrier film 1 and the polyethylene film 3 was changed to 20 μm, the thickness of the polyethylene film 3 was changed to 50 μm, and a polyethylene film 5 having a thickness of 50 μm was laminated under the polyethylene film 3 via an extruded resin layer having a thickness of 30 μm.

[0205] The laminate comprises, in order, (outermost layer) varnish, printed layer (1 μm), anchor coat layer (1 μm), polyethylene film 1 (80 μm), extruded resin layer (20 μm), uniaxially oriented high-density polyethylene substrate 1 (25 μm), extruded resin layer (20 μm), barrier film 1 (75 μm), extruded resin layer (20 μm), polyethylene film 3 (50 μm), extruded resin layer (30 μm), and polyethylene film 5 (50 μm) (innermost layer).

[0206] [Example 10] A laminate was obtained in the same manner as in Example 9, except that the uniaxially oriented high-density polyethylene substrate 1 was changed to the unoriented polyethylene substrate 2.

[0207] The laminate comprises, in order, (outermost layer) varnish, printed layer (1 μm), anchor coat layer (1 μm), polyethylene film 1 (80 μm), extruded resin layer (20 μm), unstretched polyethylene base material 2 (40 μm), extruded resin layer (20 μm), barrier film 1 (75 μm), extruded resin layer (320 μm), polyethylene film 3 (50 μm), extruded resin layer (30 μm), and polyethylene film 5 (50 μm) (innermost layer).

[0208] [Example 11] A laminate was obtained in the same manner as in Example 9, except that the outermost layer was changed from polyethylene film 1 to polyethylene film 2 having a thickness of 50 μm, the innermost layer was changed from polyethylene film 5 to polyethylene film 4 having a thickness of 50 μm, and the polyethylene film 3 between the barrier film 1 and polyethylene film 5 was changed to polyethylene film 4 having a thickness of 50 μm.

[0209] The laminate comprises, in order, (outermost layer) varnish, printed layer (1 μm), anchor coat layer (1 μm), polyethylene film 2 (50 μm), extruded resin layer (20 μm), uniaxially oriented high-density polyethylene substrate 1 (25 μm), extruded resin layer (20 μm), barrier film 1 (75 μm), extruded resin layer (20 μm), polyethylene film 4 (50 μm), extruded resin layer (30 μm), and polyethylene film 4 (50 μm) (innermost layer).

[0210] [Example 12] A laminate was obtained in the same manner as in Example 11, except that the uniaxially oriented high-density polyethylene substrate 1 was changed to the unoriented polyethylene substrate 2.

[0211] The laminate comprises, in order, (outermost layer) varnish, printed layer (1 μm), anchor coat layer (1 μm), polyethylene film 2 (50 μm), extruded resin layer (20 μm), unstretched polyethylene base material 2 (40 μm), extruded resin layer (20 μm), barrier film 1 (75 μm), extruded resin layer (20 μm), polyethylene film 4 (50 μm), extruded resin layer (30 μm), and polyethylene film 4 (50 μm) (innermost layer).

[0212] [Comparative Example 1] The substrate was a vapor-deposited film (IB-PET-WUB, Dai Nippon Printing Co., Ltd.) in which a vapor-deposited film was formed on a 12 μm-thick biaxially oriented polyethylene terephthalate film. A urethane-based gravure ink (NEW-LP Super, Toyo Ink Co., Ltd.) was applied by gravure printing onto the vapor-deposited film of the substrate, and dried to form a 1 μm-thick printed layer. In this way, a printed substrate was obtained.

[0213] Using a tandem dry laminator, each layer was laminated on the printing substrate. Specifically, a urethane-based two-component curing adhesive (made by Rock Paint, solvent-based adhesive, main agent: RU-004, curing agent: H-1) was applied to the printing layer-forming surface of the printing substrate, dried to form an adhesive layer with a thickness of 3.0 μm, and a polyethylene film 4 (milky white type) with a thickness of 130 μm was laminated on this adhesive layer. Next, the above-mentioned urethane-based two-component curing adhesive (main agent: RU-004, curing agent: H-1) was applied to the surface opposite to the printing layer-forming surface of the printing substrate, dried to form an adhesive layer with a thickness of 3.0 μm, and a polyethylene film 3 containing an antistatic agent with a thickness of 130 μm was laminated on this adhesive layer. In this manner, a laminate was obtained.

[0214] The laminate comprises, in order, an antistatic agent-containing polyethylene film 3 (130 μm) (outermost layer), an adhesive layer (3.0 μm), a vapor-deposited film (IB-PET-WUB, 12 μm), a printed layer (1 μm), an adhesive layer (3.0 μm), and a polyethylene film 4 (milky type, 130 μm) (innermost layer).

[0215] [Preparation of tube containers] The laminates obtained in the Examples and Comparative Examples were processed into individual laminate pieces having a width of 120.0 mm using a bobbin cutter, and both ends in the width direction were overlapped so that the overlap width was about 1.2 mm, and then the overlapped ends were heat sealed to obtain a cylindrical raw roll with a tube pasted on it. The obtained raw roll was cut in the length direction to 144.6 mm to produce a cylindrical body that would become the body of a tube container. The cylindrical body was attached to a mandrel for forming a tube container, and a head consisting of a truncated cone-shaped shoulder and a cylindrical extraction port connected to it was attached to one end of the cylindrical body using high-density polyethylene (Suntec J345, manufactured by Asahi Kasei, density 0.956 g / cm 3) was used for compression molding to produce a tube container body as shown in FIG. 7. The spout part at the head of the obtained tube container body had an inner diameter of 8.0 mm, and a screw thread was provided on the side of the spout part. The outer diameter of the shoulder part was 50 mm. Next, the high density polyethylene was injected into a die for forming a cap and molded to produce a cap. In this manner, a tube container was obtained.

[0216] [Physical property evaluation] <Evaluation of tube container physical properties (seal strength and lamination strength)> (Side seam strength) The body of the tube container was cut into a strip of 15 mm width in a direction perpendicular to the side seam (the part where the tube was attached) to obtain a test piece. In accordance with JIS K6854-2, the test piece was pulled at a test speed of 300 mm / min using a tensile tester (STA-1150, manufactured by Orientec Co., Ltd.) to measure the strength at which the test piece broke (side seam strength). The tube container was filled with 100 g of NONIO (manufactured by Lion Co., Ltd.) and stored at 40°C dry for one month. The physical properties (seal strength) of the tube container after storing the contents were measured. The measurement results are shown in Table 1 below.

[0217] (Shoulder adhesion strength) The two adhesion points between the body and shoulder of the tube container, the tube attachment point and its 180° opposite point, were cut into strips with a width of 15 mm toward the bottom to obtain test pieces. The test pieces were pulled at a test speed of 300 mm / min using a tensile tester (STA-1150, manufactured by Orientec Co., Ltd.) to measure the peel strength when the body was peeled off from the shoulder. The measurement results are shown in Table 1 below.

[0218] (Laminate strength) The laminate strength under the barrier was measured for the test pieces prepared for the side seam strength measurement. The average laminate strength was measured at a tensile speed of 50 mm / min. The measurement results are shown in Table 1 below. The initial laminate strength of 2.0 N or more was considered to be acceptable. The tube container was filled with 100 g of NONIO (manufactured by Lion) and stored at 40°C dry for one month. The physical properties (lamination strength) of the tube container after storage of the contents were measured. The laminate strength was measured under the barrier layer in all cases. The measurement results are shown in Table 1 below.

[0219] <Total light transmittance evaluation> The total light transmittance of the laminates obtained in the examples and comparative examples was measured using a haze meter (Haze / Transmittance Meter HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K7375:2008. The measurement was performed on three laminates, and the average value of the obtained values ​​was calculated. The results are shown in Table 1 below.

[0220] <Mono-material> The polyethylene content (mono-material ratio) was calculated from the specific gravity of the material constituting each layer of the laminate obtained in the examples and comparative examples and the thickness of each layer. The results are shown in Table 1 below. Furthermore, the laminates obtained in the examples and comparative examples were judged to be mono-material in accordance with the CEFLEX guidelines. Compliance with the CEFLEX guidelines was evaluated as "Good", and non-compliance was evaluated as "Poor".

[0221] [Table 1]

[0222] The laminate of the present disclosure will be described in more detail below using test examples, but the laminate of the present disclosure is not limited to the following test examples. In the following description, polyethylene is also referred to as "PE", linear low density polyethylene is also referred to as "LLDPE", high density polyethylene is also referred to as "HDPE", low density polyethylene is also referred to as "LDPE", ethylene-vinyl alcohol copolymer is also referred to as "EVOH", polyethylene terephthalate is also referred to as "PET", polyethylene film is also referred to as "PEF", barrier film is also referred to as "BF", and extruded polyethylene layer is also referred to as "EC-PE".

[0223] [Film used] The films used in the test examples and reference examples are described below. ·Uniaxially oriented HDPE film Tokyo Ink, Hibron SMKQW, HDPE, thickness 25μm Biaxially oriented PET film Toyobo, E5200, thickness 12μm Aluminum-deposited biaxially stretched PET film Toray Film Processing, BR-PET1312, thickness 12μm ·Transparent vapor-deposited biaxially stretched PET film A film in which a silica vapor deposition layer is formed on one surface of a 12 μm-thick PET film by the CVD method. Polyethylene film Aicello, Suzulon L-100N, LLDPE, Thickness 30μm, 50μm or 80μm Polyethylene film A Thickness: 50 μm or 80 μm, polyethylene (density: 0.931 g / cm 3 , MFR: 2.1g / 10min) was formed into a film Polyethylene film B Thickness: 180 μm, polyethylene (density: 0.920 g / cm 3 , MFR: 1.9g / 10min) was formed into a film Milky white polyethylene film A Thickness: 130μm, 100μm, 80μm or 50μm, polyethylene (density: 0.920g / cm 3 A film obtained by forming a film from a mixture of 94% by mass of acrylic resin (MFR: 1.9 g / 10 min) and 6% by mass of white pigment (titanium oxide pigment). Milky white polyethylene film B Thickness: 80 μm, polyethylene (density: 0.924 g / cm 3 A film obtained by forming a mixture of 85% by mass of acrylic resin (MFR: 2.0 g / 10 min) and 15% by mass of white pigment (titanium oxide pigment) ·Antistatic agent-containing polyethylene film A Thickness: 110μm, 80μm, 50μm or 30μm, polyethylene (density: 0.920g / cm 3 A film obtained by forming a mixture of 98% by mass of acrylic resin (MFR: 1.9 g / 10 min) and 2% by mass of an antistatic agent into a film. Antistatic agent-containing polyethylene film B Thickness: 50 μm or 30 μm, polyethylene (density: 0.930 g / cm 3 A film obtained by forming a mixture of 98.5% by mass of acrylic resin (MFR: 2.1 g / 10 min) 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 / cm 3 A film obtained by forming a mixture of 98% by mass of acrylic resin (MFR: 1.9 g / 10 min) and 2% by mass of an antistatic agent into a film. ·EVOH-based barrier film LLDPE (Dow Chemical, DOWLEX2045G, density: 0.920g / cm 3 ), adhesive resin (Mitsui Chemicals, Admer NF557), and EVOH (Kuraray, Eval H171B, density: 1.17 g / cm 3 , ethylene content: 38 mol%), adhesive resin (Mitsui Chemicals, Admer NF557), LLDPE (Dow Chemical, DOWLEX2045G, density: 0.920 g / cm 3 ) was co-extruded by the inflation method to form a five-layer barrier film. The barrier film had a total thickness of about 75 μm, comprising a 30 μm-thick LLDPE layer, an adhesive resin layer, a 15 μm-thick EVOH layer, an adhesive resin layer, and a 30 μm-thick LLDPE layer, in that order.

[0224] [Test Example 1-1] A urethane-based gravure ink (manufactured by Toyo Ink) was applied by gravure printing to one surface of a uniaxially stretched HDPE film (Hybron SMKQW) having a thickness of 25 μm as a substrate, and dried to form a printed layer having a thickness of 1 μm. In this way, a printed substrate was obtained. However, in the width direction (direction perpendicular to the flow direction of the original roll) of the laminate piece obtained by the processing described later, a printed layer was not formed in the area corresponding to the 4.0 mm region at one end and the 2.0 mm region at the other end (the area to be attached to the cylinder).

[0225] The lamination process was carried out by the single extrusion lamination method as follows: LDPE (Nippon Polyethylene, Novatec LD LC602A, MFR: 8.2 g / 10 min, density: 0.919 g / cm) was applied to one surface of the EVOH barrier film. 3 C.) was melt-extruded at 330.degree. C. to form an extruded polyethylene layer having a thickness of 30 .mu.m, and a milky white polyethylene film A having a thickness of 100 .mu.m was laminated via this extruded polyethylene layer.

[0226] The lamination process was carried out by the tandem extrusion lamination method as follows. LDPE (LC602A) was melt-extruded at 330°C onto the other surface of the EVOH-based barrier film to form an extruded polyethylene layer with a thickness of 20 μm, and the non-printed surface of the printed substrate was bonded to the extruded polyethylene layer surface. An anchor coating agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed substrate surface on which the printed substrate was formed and dried to form an anchor coating layer with a thickness of 1 μm. LDPE (LC602A) was melt-extruded at 330°C onto the surface of the anchor coating layer to form an extruded polyethylene layer with a thickness of 20 μm, and an antistatic agent-containing polyethylene film A with a thickness of 80 μm was bonded via the extruded polyethylene layer.

[0227] In this manner, a laminate was obtained. The laminate comprises, in this order, (outermost layer) antistatic agent-containing polyethylene film (80 μm, second heat seal layer), extruded polyethylene layer (20 μm), anchor coat layer (1 μm), printed layer (1 μm), uniaxially oriented HDPE film (25 μm), extruded polyethylene layer (20 μm), EVOH-based barrier film (75 μm), extruded polyethylene layer (30 μm) and milky white polyethylene film (100 μm, first heat seal layer) (innermost layer). The numbers in parentheses indicate thickness.

[0228] [Test Examples 1-2 to 1-4] Laminates were prepared in the same manner as in Test Example 1, except that the antistatic agent-containing polyethylene film in the outermost layer and / or the milky white polyethylene film in the innermost layer were changed as shown in Table 2. [Test Example 1-5] A laminate was produced in the same manner as in Test Example 1-1, except that a printed layer was also formed in the area to be attached to the cylinder.

[0229] [Test Example 2-1] A urethane-based gravure ink (manufactured by Toyo Ink) was applied by gravure printing to one surface of a uniaxially oriented HDPE film (Hybron SMKQW) having a thickness of 25 μm as a substrate, and dried to form a printed layer having a thickness of 1 μm. In this way, a printed substrate was obtained. However, no printed layer was formed on the area to be attached to the cylinder.

[0230] The lamination process was carried out by the tandem extrusion lamination method as follows. LDPE (LC602A) was melt-extruded at 330°C onto one surface of the EVOH barrier film to form an extruded polyethylene layer with a thickness of 20 μm, and a milky polyethylene film A with a thickness of 50 μm was laminated via this extruded polyethylene layer. LDPE (LC602A) was melt-extruded at 330°C onto the surface of the laminated milky polyethylene film to form an extruded polyethylene layer with a thickness of 30 μm, and a polyethylene film (Suzulon L-100N) with a thickness of 50 μm was laminated via this extruded polyethylene layer.

[0231] The lamination process was carried out by the tandem extrusion lamination method as follows. LDPE (LC602A) was melt-extruded at 330°C onto the other surface of the EVOH-based barrier film to form an extruded polyethylene layer with a thickness of 20 μm, and the non-printed surface of the printed substrate was bonded to the extruded polyethylene layer surface. An anchor coating agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed substrate surface on which the printed layer was formed and dried to form an anchor coating layer with a thickness of 1 μm. LDPE (LC602A) was melt-extruded at 330°C onto the surface of the anchor coating layer to form an extruded polyethylene layer with a thickness of 20 μm, and an antistatic agent-containing polyethylene film A with a thickness of 50 μm was bonded via the extruded polyethylene layer.

[0232] In this manner, a laminate was obtained. The laminate comprises, in order, (outermost layer) antistatic agent-containing polyethylene film (50 μm, second heat seal layer), extruded polyethylene layer (20 μm), anchor coat layer (1 μm), printed layer (1 μm), uniaxially oriented HDPE film (25 μm), extruded polyethylene layer (20 μm), EVOH-based barrier film (75 μm), extruded polyethylene layer (20 μm), milky polyethylene film (50 μm), extruded polyethylene layer (30 μm), and polyethylene film (50 μm, first heat seal layer) (innermost layer).

[0233] [Test Examples 2-2 to 2-3] A laminate was prepared in the same manner as in Test Example 2-1, except that the antistatic agent-containing polyethylene film of the outermost layer and / or the polyethylene film of the innermost layer were changed as shown in Table 2.

[0234] [Test Example 2-4] A laminate was produced in the same manner as in Test Example 2-1, except that a printed layer was also formed in the area to be attached to the cylinder.

[0235] [Test Example 3-1] A urethane-based gravure ink (manufactured by Toyo Ink) was applied by gravure printing to one surface of a uniaxially oriented HDPE film (Hybron SMKQW) having a thickness of 25 μm as a substrate, and dried to form a printed layer having a thickness of 1 μm. In this way, a printed substrate was obtained. However, no printed layer was formed on the area to be attached to the cylinder.

[0236] The lamination process was carried out by the tandem extrusion lamination method as follows. LDPE (LC602A) was melt-extruded at 330°C onto one surface of the EVOH-based barrier film to form an extruded polyethylene layer with a thickness of 20 μm, and a milky polyethylene film A with a thickness of 50 μm was laminated via this extruded polyethylene layer. LDPE (LC602A) was melt-extruded at 330°C onto the surface of the laminated milky polyethylene film to form an extruded polyethylene layer with a thickness of 30 μm, and a polyethylene film A with a thickness of 50 μm was laminated via this extruded polyethylene layer.

[0237] The lamination process was carried out by the tandem extrusion lamination method as follows. LDPE (LC602A) was melt-extruded at 330°C onto the other surface of the EVOH-based barrier film to form an extruded polyethylene layer with a thickness of 20 μm, and the non-printed surface of the printed substrate was bonded to the extruded polyethylene layer surface. An anchor coating agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed substrate surface on which the printed substrate was formed and dried to form an anchor coating layer with a thickness of 1 μm. LDPE (LC602A) was melt-extruded at 330°C onto the surface of the anchor coating layer to form an extruded polyethylene layer with a thickness of 20 μm, and an antistatic agent-containing polyethylene film B with a thickness of 50 μm was bonded via the extruded polyethylene layer.

[0238] In this manner, a laminate was obtained. The laminate comprises, in order, (outermost layer) antistatic agent-containing polyethylene film (50 μm, second heat seal layer), extruded polyethylene layer (20 μm), anchor coat layer (1 μm), printed layer (1 μm), uniaxially oriented HDPE film (25 μm), extruded polyethylene layer (20 μm), EVOH-based barrier film (75 μm), extruded polyethylene layer (20 μm), milky polyethylene film (50 μm), extruded polyethylene layer (30 μm), and polyethylene film (50 μm, first heat seal layer) (innermost layer).

[0239] [Test Examples 3-2 to 2-3] A laminate was prepared in the same manner as in Test Example 3-1, except that the antistatic agent-containing polyethylene film of the outermost layer and / or the polyethylene film of the innermost layer were changed as shown in Table 2. [Test Example 3-4] A laminate was produced in the same manner as in Test Example 3-1, except that a printed layer was also formed in the area to be attached to the cylinder.

[0240] [Reference example 1-1] A urethane-based gravure ink (manufactured by Toyo Ink) was applied by gravure printing to one surface of a uniaxially oriented HDPE film (Hybron SMKQW) having a thickness of 25 μm as a substrate, and dried to form a printed layer having a thickness of 1 μm. In this way, a printed substrate was obtained. However, no printed layer was formed on the area to be attached to the cylinder.

[0241] The lamination process was carried out by the tandem extrusion lamination method as follows. LDPE (LC602A) was melt-extruded at 330°C onto one surface of a 50 μm-thick milky polyethylene film A to form an extruded polyethylene layer of 20 μm thickness, and an EVOH-based barrier film was laminated via this extruded polyethylene layer. LDPE (LC602A) was melt-extruded at 330°C onto the surface of the laminated EVOH-based barrier film to form an extruded polyethylene layer of 30 μm thickness, and a 50 μm-thick polyethylene film (Suzulon L-100N) was laminated via this extruded polyethylene layer.

[0242] The lamination process was carried out by the tandem extrusion lamination method as follows. LDPE (LC602A) was melt-extruded at 330°C onto the other surface of the milky polyethylene film A to form an extruded polyethylene layer having a thickness of 20 μm, and the non-printed surface of the printed substrate was bonded to the extruded polyethylene layer surface. An anchor coating agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the printed substrate surface on which the printed substrate was formed and dried to form an anchor coating layer having a thickness of 1 μm. LDPE (LC602A) was melt-extruded at 330°C onto the surface of the anchor coating layer to form an extruded polyethylene layer having a thickness of 20 μm, and an antistatic agent-containing polyethylene film C having a thickness of 50 μm was bonded via the extruded polyethylene layer.

[0243] In this manner, a laminate was obtained. The laminate comprises, in order, (outermost layer) antistatic agent-containing polyethylene film (50 μm, second heat seal layer), extruded polyethylene layer (20 μm), anchor coat layer (1 μm), printed layer (1 μm), uniaxially oriented HDPE film (25 μm), extruded polyethylene layer (20 μm), milky polyethylene film (50 μm), extruded polyethylene layer (20 μm), EVOH-based barrier film (75 μm), extruded polyethylene layer (30 μm), and polyethylene film (50 μm, first heat seal layer) (innermost layer).

[0244] [Reference example 1-2~1-3] A laminate was produced in the same manner as in Reference Example 1-1, except that the antistatic agent-containing polyethylene film of the outermost layer and / or the polyethylene film of the innermost layer were changed as shown in Table 2.

[0245] [Reference example 1-4] A laminate was produced in the same manner as in Reference Example 1-1, except that a print layer was also formed in the area intended for tubular attachment.

[0246] [Reference example 2] A urethane-based gravure ink (manufactured by Toyo Ink Co., Ltd.) was applied by gravure printing to one surface of a 12 μm-thick biaxially oriented PET film (E5200) used as a substrate, and then dried to form a 1 μm-thick printed layer. In this way, a printing substrate was obtained.

[0247] The lamination process was carried out by the tandem dry lamination method as follows. A urethane-based two-component curing adhesive (manufactured by Rock Paint, base agent: RU-80, curing agent: H-5) was applied to the surface of the printed layer of the printing substrate and dried to form an adhesive layer with a thickness of 3 μm, and a 12 μm thick aluminum-deposited biaxially stretched PET film (BR-PET1312) was bonded through this adhesive layer. The above-mentioned urethane-based two-component curing adhesive was applied to the surface of the bonded aluminum-deposited PET film and dried to form an adhesive layer with a thickness of 3 μm, and a 180 μm thick polyethylene film B was bonded through this adhesive layer.

[0248] The lamination process was carried out by the single dry lamination method as follows: The above-mentioned urethane-based two-component curing adhesive was applied to the non-printed surface of the printing substrate and dried to form a 3 μm-thick adhesive layer, and a 130 μm-thick polyethylene film C containing an antistatic agent was bonded to the adhesive layer.

[0249] In this manner, a laminate was obtained. The laminate comprises, in order, (outermost layer) an antistatic agent-containing polyethylene film (130 μm, second heat seal layer), an adhesive layer (3 μm), a biaxially oriented PET film (12 μm), a printing layer (1 μm), an adhesive layer (3 μm), an aluminum-vapor-deposited biaxially oriented PET film (12 μm), an adhesive layer (3 μm) and a polyethylene film (180 μm, first heat seal layer) (innermost layer).

[0250] [Reference example 3] A urethane-based gravure ink (manufactured by Toyo Ink Co., Ltd.) was applied by gravure printing to one surface of a 12 μm-thick biaxially oriented PET film (E5200) used as a substrate, and then dried to form a 1 μm-thick printed layer. In this way, a printing substrate was obtained.

[0251] The lamination process was carried out by the single dry lamination method as follows: A urethane-based two-component curing adhesive (Mitsui Chemicals, base: XA-311, curing agent: A-3) was applied to one surface of an 80 μm-thick milky white polyethylene film B and dried to form a 3 μm-thick adhesive layer, and a 12 μm-thick transparent vapor-deposited biaxially stretched PET film was bonded through this adhesive layer.

[0252] The lamination process was carried out by the tandem extrusion lamination method as follows. 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 stretched PET film and dried to form an anchor coat layer with a thickness of 1 μm. An ethylene-methacrylic acid copolymer (Mitsui-Dow Polychemical, Nucrel N0908C) was melt-extruded at 290°C onto the surface of the anchor coat layer to form an extruded resin layer with a thickness of 25 μm, and an 80 μm-thick polyethylene film (Suzuron L-100N) was laminated through this extruded resin layer. LDPE (LC602A) was melt-extruded at 330°C onto the other surface of the milky white polyethylene film B to form an extruded polyethylene layer with a thickness of 25 μm, and the surface of the printing substrate on which the printing layer was formed was laminated to the surface of this extruded polyethylene layer.

[0253] The lamination process was carried out by the single extrusion lamination method as follows. An anchor coat agent (Toyo Morton, EL-510 / CAT-RT80, dilution solvent: ethyl acetate) was applied to the non-printed surface of the printing substrate and dried to form an anchor coat layer with a thickness of 1 μm. LDPE (LC602A) was melt-extruded at 330°C onto the surface of the anchor coat layer to form an extruded polyethylene layer with a thickness of 25 μm, and an antistatic agent-containing polyethylene film A with a thickness of 80 μm was bonded via this extruded polyethylene layer.

[0254] In this manner, a laminate was obtained. The laminate comprises, in order, (outermost layer) antistatic agent-containing polyethylene film (80 μm, second heat seal layer), extruded polyethylene layer (25 μm), anchor coat layer (1 μm), biaxially oriented PET film (12 μm), printed layer (1 μm), extruded polyethylene layer (25 μm), milky polyethylene film (80 μm), adhesive layer (3 μm), transparent vapor-deposited biaxially oriented PET film (12 μm), anchor coat layer (1 μm), extruded resin layer (25 μm) and polyethylene film (80 μm, first heat seal layer) (innermost layer).

[0255] [Preparation of tube containers] The laminates obtained in the test examples and reference examples were processed into individual laminate pieces with a width of 120.0 mm using a bobbin cutter, and both ends in the width direction were overlapped so that the overlap width was about 1.2 mm, and then the overlapped ends were heat sealed under conditions of 0.1 MPa, 120°C, and 1.0 second to obtain a cylindrical raw roll with a tube pasted on it. The obtained raw roll was cut in the length direction to a length of 141.6 mm to produce a cylindrical body that would become the body of a tube container. The cylindrical body was attached to a mandrel for forming a tube container, and a head consisting of a truncated cone-shaped shoulder and a cylindrical extraction port connected to it was attached to one end of the cylindrical body by cutting the head into a high-density polyethylene (Suntec J345, manufactured by Asahi Kasei, density 0.956 g / cm 3) was used to form a tube container body as shown in Fig. 6 by compression molding. Next, the high density polyethylene was injected into a cap forming die and molded to form a cap. In this manner, a tube container was obtained.

[0256] 180g of Lux Super Rich Treatment (Unilever Japan) and 100g of Denter Spearmint (Lion) were filled into a tube container and stored at 50℃ in a dry place for one month. The physical properties of the tube container before and after storage were measured as follows.

[0257] [Side seam tensile test] The body of the tube container was cut into a 15 mm wide strip in the direction perpendicular to the side seam (the part where the tube was attached) (the TD direction of the laminate) to obtain a test piece. The test piece was pulled at a test speed of 300 mm / min using a tensile tester (STA-1150, manufactured by Orientec Co., Ltd.). When the side seam was pulled, no appearance defects such as peeling at the end face were recorded as "A", and when the side seam was pulled, appearance defects such as peeling at the end face were recorded as "B".

[0258] [Shoulder tensile test] The two adhesion points between the body and shoulder of the tube container, the side seam (the part where the tube is attached) and the opposite part at 180°, were cut into strips with a width of 15 mm in the bottom direction (MD direction of the laminate) to obtain test pieces. The test pieces were pulled at a test speed of 300 mm / min using a tensile tester (STA-1150, manufactured by Orientec Co., Ltd.). When the shoulder was pulled, there was no appearance defect such as peeling at the end face of the side seam, and when the shoulder was pulled, there was an appearance defect such as peeling at the end face of the side seam, the result was recorded as "A".

[0259] [Edge exposure] A 60 mm square test piece including the tube-attached portion of the body was cut out from the tube container. The vicinity of the tube-attached portion of the test piece was folded in a mountain shape along the tube-attached portion when viewed from the outer surface side of the body, and a crease was made by applying pressure. The cross section of the test piece in a direction perpendicular to the tube-attached portion (TD direction of the laminate) was photographed with a microscope to obtain an image, and the photographed image was visually inspected to confirm whether or not the barrier resin layer was exposed on the outer surface side of the tube-attached portion. In the same manner, a 60 mm square test piece including the tube-attached portion of the body was cut out from the tube container. The vicinity of the tube-attached portion of the test piece was folded in a valley shape along the tube-attached portion when viewed from the outer surface side of the body, and a crease was made by applying pressure. The cross section of the test piece in a direction perpendicular to the tube-attached portion of the test piece (TD direction of the laminate) was photographed with a microscope to obtain an image, and the photographed image was visually inspected to confirm whether or not the barrier resin layer was exposed on the inner surface side of the tube-attached portion. The case where the barrier resin layer was not exposed at the end face of the laminate at the tube attachment location was marked "A." The case where the barrier resin layer was exposed at the end face of the laminate at the tube attachment location was marked "B," and the case where it was difficult to cover the end face was marked "C."

[0260] [Mono-material] The polyethylene content (mono-material ratio) was calculated from the specific gravity of the material constituting each layer of the laminate obtained in the test example and the reference example and the thickness of each layer. The laminates obtained in the test example and the reference example were judged to be mono-material or not in accordance with the CEFLEX guidelines. Those that conformed to the CEFLEX guidelines were rated as "A", and those that did not conform were rated as "B".

[0261] [Total light transmittance] The total light transmittance was measured using a haze meter (Haze Meter HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K7375: 2008. The measurement was performed on three test pieces, and the average value of the obtained values ​​was calculated.

[0262] [Oxygen permeability and water vapor permeability measurement] Test pieces measuring 100 mm x 100 mm were cut out from the laminates obtained in the test examples and reference examples, and the oxygen permeability and water vapor permeability were measured. The oxygen permeability of the laminates measured in accordance with JIS K7126-2:2006 under an environment of temperature 23°C and humidity 90% RH was 1.0 cc / m 2 The water vapor permeability of the laminate measured in accordance with JIS K7129-2:2019 under an environment of a temperature of 40°C and a humidity of 90% was 2.0 g / m 2 ·days or less.

[0263] [Table 2]

[0264] [Table 3] [Explanation of symbols]

[0265] 1: Laminate 1S: First surface 2S: Second Surface 10: First heat seal layer (first resin layer) 20: Second heat seal layer (second resin 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 base material 42: Substrate (first substrate) 44: Printing layer 50: Substrate (second substrate) Ad: Adhesive layer (extruded resin layer) 100: Tube container 101: Tube container body 102:Head 103: Torso 104: Shoulder 105: Extraction outlet 106:キャップ 107:Screw 108: Joint 109: Bottom joint

Claims

1. The film comprises at least a first resin layer, a second film containing polyethylene as a main component, a barrier resin layer, a first film containing polyethylene as a main component, and a second resin layer, in this order; The first resin layer and the second resin layer each contain polyethylene as a main component, At least one of the second film and the first film is a polyethylene film containing a white pigment, The laminate, wherein the first resin layer does not contain the white pigment.

2. 2. The laminate according to claim 1, wherein the content of the white pigment in the polyethylene film containing the white pigment is 1% by mass or more and 50% by mass or less.

3. The laminate according to claim 1 , wherein the polyethylene film containing the white pigment has a total light transmittance of 10% or more and 40% or less.

4. 2. The laminate according to claim 1, further comprising an extruded resin layer between the first resin layer and the second film, between the second film and the barrier resin layer, between the barrier resin layer and the first film, and between the first film and the second resin layer.

5. The laminate according to claim 1 , wherein the barrier resin layer comprises ethylene vinyl alcohol.

6. The laminate according to claim 1 , further comprising a printed layer provided on at least one surface of the second resin layer or the first film.

7. 2. The laminate according to claim 1, wherein the first film is a uniaxially or biaxially oriented polyethylene film containing at least one selected from the group consisting of low density polyethylene, medium density polyethylene, and high density polyethylene.

8. The laminate according to claim 1 , wherein the first resin layer and the second resin layer each independently contain at least one selected from medium density polyethylene, low density polyethylene, and linear low density polyethylene.

9. The laminate according to claim 1 , wherein the content of polyethylene in the entire laminate is 90% by mass or more.

10. 2. The laminate according to claim 1, which is a laminate for forming a body of a tube container body, wherein the second resin layer is a sealant layer on an outer surface side of the body, and the first resin layer is a sealant layer on an inner surface side of the body.

11. A tube container body having a head and a body, The head portion includes a shoulder portion connected to one end of the body portion and a spout portion connected to the shoulder portion, and the body portion is constituted by the laminated body according to claim 1. Tube container body.

12. The tube container body according to claim 11, wherein the head portion is made of a resin composition containing polyethylene.

13. The tube container body according to claim 11, Cap and A tube container comprising:

14. The tube container according to claim 13, wherein the cap is made of a resin composition containing polyethylene.

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