Laminate, tube container, and tube container with cap

Abstract

To provide a laminate, a tube container, and a tube container with a cap that enable reduction in resin usage.SOLUTION: Provided is a laminate 10 comprising, in order from an outer surface 101 toward an inner surface 102, an outer sealant layer 11, a base layer 13, and an inner sealant layer 12, the outer sealant layer 11 comprising, in order from the outer surface 101 toward the inner surface 102, a first outer layer 11a, a second outer layer 11b, and a third outer layer 11c, wherein a material forming the second outer layer 11b has a density different from densities of materials forming the first outer layer 11a and the third outer layer 11c, and wherein the density of the outer sealant layer 11 is 0.92 g / m3 or more and 0.93 g / m3 or less.SELECTED DRAWING: Figure 2A

Description

[Technical Field]

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

[0002] Conventionally, laminated tube containers have been known as tube containers (see, for example, Patent Document 1). Patent Document 1 discloses a tube container in which the body forming the storage space for the contents has a laminated structure made of multiple materials, and the laminated structure comprises a barrier layer having a metal foil and a highly reflective layer provided on the outside of the barrier layer and having a metal vapor deposition film formed on at least one surface of a base material. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-19493 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, there has been a demand to reduce the amount of resin used in order to reduce the environmental impact.

[0005] The present disclosure has been made in consideration of these points, and aims to provide a laminate, a tube container, and a tube container with a cap that can reduce the amount of resin used. [Means for solving the problem]

[0006] The embodiments of the present disclosure relate to the following [1] to

[11] .

[0007] [1] The sealant layer includes an outer sealant layer, a base layer, and an inner sealant layer, which are arranged in this order from the outer surface to the inner surface, The outer sealant layer has a first outer layer, a second outer layer, and a third outer layer arranged in this order from the outer surface to the inner surface, the density of the material constituting the second outer layer is different from the density of the material constituting the first outer layer and the density of the material constituting the third outer layer; The density of the outer sealant layer is 0.92 g / m 3 More than 0.93g / m 3 The laminate is as follows:

[0008] [2] The laminate according to [1], wherein the inner sealant layer contains a biomass-derived resin.

[0009] [3] The laminate according to [1] or [2], further comprising a barrier layer provided between the base material layer and the inner sealant layer.

[0010] [4] The laminate according to any one of [1] to [3], wherein all layers contain a biomass-derived resin.

[0011] [5] The coefficient of static friction of the inner surface against metal is 0.40 or less; The laminate according to any one of [1] to [4], wherein the coefficient of dynamic friction of the inner surface against metal is 0.35 or less.

[0012] [6] The loop stiffness in the first direction is 900 mN or greater; The laminate according to any one of [1] to [5], wherein the loop stiffness in a second direction perpendicular to the first direction is 1100 mN or more.

[0013] [7] The laminate according to any one of [1] to [6], which has a biomass ratio of 10% or more and 50% or less.

[0014] [8] The inner sealant layer has a first inner layer, a second inner layer, and a third inner layer arranged in this order from the outer surface to the inner surface, the density of the material constituting the second inner layer is different from the density of the material constituting the first inner layer and the density of the material constituting the third inner layer; The density of the inner sealant layer is 0.92 g / m 3 More than 0.93g / m 3 The laminate according to any one of [1] to [7] below.

[0015] [9] The sealant layer includes an outer sealant layer, a base layer, and an inner sealant layer, which are arranged in this order from the outer surface to the inner surface, The inner sealant layer has a first inner layer, a second inner layer, and a third inner layer arranged in this order from the outer surface to the inner surface, the density of the material constituting the second inner layer is different from the density of the material constituting the first inner layer and the density of the material constituting the third inner layer; The density of the inner sealant layer is 0.92 g / m 3 More than 0.93g / m 3 The laminate is as follows:

[0016]

[10] In a tube container, [1] to [9], and a body tube in which opposing edges of the laminate according to any one of [1] to [9] are overlapped and joined to each other; a head member joined to one end of the body tube.

[0017]

[11] In a tube container with a cap,

[10] The tube container according to

[10] , a cap attached to the head member. [Effects of the Invention]

[0018] According to the present disclosure, the amount of resin used in the tube container can be reduced. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a partial vertical cross-sectional view showing a tube container with a cap according to this embodiment. [Figure 2A] FIG. 2A is a cross-sectional view showing an example of the layer structure of the laminate according to this embodiment. [Figure 2B] FIG. 2B is a cross-sectional view showing an example of the layer structure of the laminate according to this embodiment. [Figure 2C] FIG. 2C is a cross-sectional view showing an example of the layer structure of the laminate according to the present embodiment. [Figure 2D] FIG. 2D is a cross-sectional view showing an example of the layer structure of the laminate according to this embodiment. [Figure 2E] FIG. 2E is a cross-sectional view showing an example of the layer structure of the laminate according to the present embodiment. [Figure 2F] FIG. 2F is a cross-sectional view showing an example of the layer structure of the laminate according to the present embodiment. [Figure 3] 3(a) and 3(b) are schematic diagrams showing a method for manufacturing a tube container with a cap according to this embodiment. [Figure 4] FIG. 4 is a perspective view showing a method for manufacturing a capped tube container according to this embodiment. [Figure 5] 5(a) and 5(b) are cross-sectional views showing a method for manufacturing a capped tube container according to this embodiment. [Figure 6] FIG. 6 is a cross-sectional view showing a method for manufacturing a capped tube container according to this embodiment. [Figure 7] 7(a) to 7(c) are diagrams illustrating a test for evaluating the bondability between the body tube and the head member according to the embodiment. [Figure 8] FIG. 8 is a table showing densities according to an example. [Figure 9] FIG. 9 is a table showing densities according to an example. [Figure 10]FIG. 10 is a table showing the results of the static friction coefficient measurement test, the dynamic friction coefficient measurement test, and the loop stiffness measurement test according to the examples. [Figure 11] FIG. 11 is a table showing the results of evaluation of the bondability at the body seal portion and the bondability between the body tube and the head member according to the examples. [Figure 12] FIG. 12 is a table showing biomass degrees according to an example. DETAILED DESCRIPTION OF THE INVENTION

[0020] An embodiment will be described below with reference to the drawings. FIGS. 1 to 6 are diagrams illustrating one embodiment. The following figures are schematic diagrams. Therefore, the size and shape of each part are appropriately exaggerated for ease of understanding. Furthermore, appropriate modifications can be made without departing from the technical concept. In the following figures, identical parts are denoted by the same reference numerals, and some detailed descriptions may be omitted. Furthermore, the numerical values, such as dimensions, and material names of each component described in this specification are examples of an embodiment, and are not limited to these and may be selected and used as appropriate. In this specification, terms specifying shapes or geometric conditions, such as parallel, orthogonal, and perpendicular, are interpreted not only strictly but also to include substantially the same state.

[0021] (Tube container with cap) As shown in FIG. 1, a capped tube container 40A according to this embodiment includes a tube container 40 and a cap 49 attached to a head member 43 of the tube container 40, which will be described later.

[0022] (Tube container) The tube container 40 includes a body tube 41, which is a laminated tube, and a head member 43 joined to one end 42 of the body tube 41. The body tube 41 has a generally cylindrical shape overall. The body tube 41 is made of a laminate 10, which is a packaging material for tube containers. In this case, the body tube 41 may be configured so that the outer surface of the packaging material for tube containers (i.e., the outer surface 101 of the laminate 10, which will be described later) faces away from the contents, and the inner surface (i.e., the inner surface 102 of the laminate 10, which will be described later) faces the contents.

[0023] The body tube 41 has a body seal portion 44 formed by joining together pieces of tube container packaging material. This body seal portion 44 is formed along the longitudinal direction of the body tube 41. Such a body tube 41 may be obtained, for example, by rolling a tube container packaging material into a cylindrical shape, overlapping opposing edge portions of the tube container packaging material, and joining them together by, for example, heat sealing.

[0024] The body tube 41 also has a bottom seal 45 where the tube container packaging materials are joined together. This bottom seal 45 is a part where the tube container packaging materials are joined together near an opening 41B (see FIGS. 4 and 6) formed at the other end 46 of the body tube 41 after an appropriate amount of content C has been filled through the opening.

[0025] 1 again, the head member 43 has a shoulder portion 47 and a mouth portion 48. A cap 49 is attached to the mouth portion 48. The head member 43 is molded by, for example, compression molding. The head member 43 is made of, for example, a resin material such as high-density polyethylene (HDPE).

[0026] (Laminate) Next, the layer structure of the laminate 10 will be described. Figures 2A to 2F show an example of the layer structure of the laminate 10 that constitutes the body tube 41. As shown in Figures 2A to 2F, the laminate 10 includes an outer sealant layer 11, a base layer 13, and an inner sealant layer 12, which are arranged in this order from the outer surface 101 to the inner surface 102. Furthermore, as shown in Figures 2D to 2F, the laminate 10 may further include a barrier layer 16 provided between the base layer 13 and the inner sealant layer 12.

[0027] 2A, the laminate 10 includes, in this order, an outer sealant layer 11, a first adhesive layer 14a, a substrate layer 13, a printed layer 15, a second adhesive layer 14b, and an inner sealant layer 12. Of these, the outer sealant layer 11 has multiple layers. In the illustrated example, the outer sealant layer 11 has a first outer layer 11a, a second outer layer 11b, and a third outer layer 11c, which are arranged in this order from the outer surface 101 to the inner surface 102. The inner sealant layer 12 has multiple layers. In the illustrated example, the inner sealant layer 12 has a first inner layer 12a, a second inner layer 12b, and a third inner layer 12c, which are arranged in this order from the outer surface 101 to the inner surface 102. In this case, the first outer layer 11a of the outer sealant layer 11 forms the outer surface 101 of the laminate 10 (the outer surface of the body tube 41), and the third inner layer 12c of the inner sealant layer 12 forms the inner surface 102 of the laminate 10 (the inner surface of the body tube 41). Note that, as shown in FIGS. 2B and 2C , one of the outer sealant layer 11 and the inner sealant layer 12 may be a single layer. Specifically, as shown in Figure 2B, the outer sealant layer 11 may have multiple layers, and the inner sealant layer 12 may be a single layer. Alternatively, as shown in Figure 2C, the outer sealant layer 11 may be a single layer, and the inner sealant layer 12 may have multiple layers. Although not shown, when the outer sealant layer 11 has multiple layers, the outer sealant layer 11 may be made of four or more layers. Similarly, when the inner sealant layer 12 has multiple layers, the inner sealant layer 12 may be made of four or more layers.

[0028] 2D , the laminate 10 includes, in this order, an outer sealant layer 11, a first adhesive layer 14a, a substrate layer 13, a printed layer 15, a second adhesive layer 14b, a barrier layer 16, an intermediate layer 17, a third adhesive layer 14c, and an inner sealant layer 12. Among these, the outer sealant layer 11 includes multiple layers. In the illustrated example, the outer sealant layer 11 includes a first outer layer 11a, a second outer layer 11b, and a third outer layer 11c, which are arranged in this order from the outer surface 101 to the inner surface 102. The inner sealant layer 12 includes multiple layers. In the illustrated example, the inner sealant layer 12 includes a first inner layer 12a, a second inner layer 12b, and a third inner layer 12c, which are arranged in this order from the outer surface 101 to the inner surface 102. In this case, the first outer layer 11a of the outer sealant layer 11 forms the outer surface 101 of the laminate 10 (the outer surface of the body tube 41), and the third inner layer 12c of the inner sealant layer 12 forms the inner surface 102 of the laminate 10 (the inner surface of the body tube 41). As shown in FIGS. 2E and 2F , one of the outer sealant layer 11 and the inner sealant layer 12 may be a single layer. Specifically, as shown in FIG. 2E , the outer sealant layer 11 may have multiple layers, and the inner sealant layer 12 may be a single layer. Alternatively, as shown in FIG. 2F , the outer sealant layer 11 may be a single layer, and the inner sealant layer 12 may have multiple layers. Although not shown, when the outer sealant layer 11 has multiple layers, the outer sealant layer 11 may be composed of four or more layers. Similarly, when the inner sealant layer 12 has multiple layers, the inner sealant layer 12 may be composed of four or more layers.

[0029] Each layer of the laminate 10 will now be described.

[0030] <Outer sealant layer> The outer sealant layer 11 is a layer for bonding the laminates 10 together, and the material constituting the outer sealant layer 11 may be any material that melts and fuses when heated.

[0031] <<First Configuration>> As shown in Fig. 2A etc., the outer sealant layer 11 according to the first configuration has a plurality of layers. In the examples shown in Fig. 2A, 2B, 2D and 2E, as described above, the outer sealant layer 11 has a first outer layer 11a, a second outer layer 11b and a third outer layer 11c.

[0032] In this case, the first outer layer 11a, the second outer layer 11b, and the third outer layer 11c can be, for example, a low-density polyethylene (LDPE) film, a medium-density polyethylene (MDPE) film, a high-density polyethylene (HDPE) film, a linear low-density polyethylene (LLDPE) film, a polypropylene film, an acid-modified polyolefin resin film in which a polyolefin resin such as polyethylene or polypropylene is modified with acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, or other unsaturated carboxylic acid, a polyvinyl acetate resin film, a polyester resin film, a polystyrene resin film, or a film made of one or more other resins such as polyacrylonitrile, saturated polyester, or polyvinyl alcohol.

[0033] Here, low density polyethylene has a density of 910 kg / m 3 More than 930kg / m 3 Medium density polyethylene has a density of 930 kg / m 3 More than 942kg / m 3 Furthermore, high density polyethylene has a density of 942 kg / m 3 The above polyethylenes are available. Low-density polyethylene is obtained by polymerizing ethylene at a high pressure, for example, from 1,000 to less than 2,000 atmospheres. Medium-density polyethylene and high-density polyethylene are obtained by polymerizing ethylene at a medium or low pressure, for example, from 1 to less than 1,000 atmospheres.

[0034] It should be noted that medium-density polyethylene and high-density polyethylene may partially contain a copolymer of ethylene and an α-olefin. Even when ethylene is polymerized under medium or low pressure, medium-density or low-density polyethylene can be produced if a copolymer of ethylene and an α-olefin is contained. The linear low-density polyethylene described above is such a polyethylene. Linear low-density polyethylene is obtained by copolymerizing an α-olefin with a linear polymer obtained by polymerizing ethylene under medium or low pressure to introduce short-chain branches. Examples of α-olefins include 1-butene (C4), 1-hexene (C6), 4-methylpentene (C6), and 1-octene (C8). The density of linear low-density polyethylene is, for example, 915 kg / m 3 More than 945kg / m 3 The following is the result.

[0035] The outer sealant layer 11 (first outer layer 11a, second outer layer 11b, and third outer layer 11c) may contain a biomass-derived resin. For example, when the outer sealant layer 11 contains polyethylene or polypropylene, the polyethylene may be biomass polyethylene, and the polypropylene may be biomass polypropylene. When the outer sealant layer 11 contains a biomass-derived resin, the amount of fossil fuel used can be reduced, and the environmental impact of the laminate 10 can be reduced. Biomass polyethylene is a monomer polymer containing biomass-derived ethylene. Since biomass-derived ethylene is used as the raw material monomer, the polymerized polyolefin is biomass-derived. The content of biomass-derived ethylene in the raw material monomer does not need to be 100% by mass, and is, for example, preferably 50% or more, more preferably 80% or more. The feedstock monomers may include ethylene derived from fossil fuels, and may also include α-olefin monomers such as butylene, hexene, and octene.

[0036] For example, biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use biomass-derived fermented ethanol obtained from plant raw materials. The plant raw material is not particularly limited, and conventionally known plants can be used. Conventionally known plants include, for example, corn, sugarcane, beet, and manioc.

[0037] In the present embodiment, the heat-sealable film can be prepared, for example, by preparing a resin composition using one or more of the above-mentioned resins as the main component, optionally adding desired additives thereto, and then using the resin composition prepared above, for example, by a T-die method, an inflation method, or other molding method to form a film or sheet.

[0038] The material for the outer sealant layer 11 may contain, for example, an antiblocking agent, a lubricant (fatty acid amide, etc.), a flame retardant, an inorganic or organic filler, or the like.

[0039] In this embodiment, the density of the material constituting the second outer layer 11b may be different from the density of the material constituting the first outer layer 11a and the density of the material constituting the third outer layer 11c. For example, the density of the material constituting the second outer layer 11b may be higher than the density of the material constituting the first outer layer 11a and the density of the material constituting the third outer layer 11c. In this case, by increasing the density of the material constituting the second outer layer 11b, the density of the entire outer sealant layer 11 can be increased while maintaining the meltability of the first outer layer 11a. This increases the stiffness of the entire laminate 10. Furthermore, the density of the material constituting the second outer layer 11b may be lower than the density of the material constituting the first outer layer 11a and the density of the material constituting the third outer layer 11c. In this case, for example, if the second outer layer 11b contains a biomass-derived resin, the biomass-derived resin can be sandwiched between the high-density first outer layer 11a and the third outer layer 11c. This prevents the biomass-derived resin from leaching out.

[0040] The density of the outer sealant layer 11 is 0.92 g / m 3 More than 0.93g / m 3 The density of the outer sealant layer 11 may be 0.92 g / m or less. 3 As a result, the adhesive strength between the outer sealant layer 11 and the inner sealant layer 12 can be increased when forming the body seal portion 44. This makes it possible to prevent the outer sealant layer 11 and the inner sealant layer 12 from peeling off in the body seal portion 44. In addition, when the density of the outer sealant layer 11 is 0.93 g / m 3 or less, productivity of the tube container 40 can be improved. That is, when the density of the outer sealant layer 11 is increased, the melting point of the outer sealant layer 11 tends to be higher. Therefore, when the density of the outer sealant layer 11 is increased, the sealing temperature when forming the body seal portion 44 may become higher. In contrast, when the density of the outer sealant layer 11 is 0.93 g / m or less, 3 By satisfying the above condition, it is possible to prevent the sealing temperature from becoming too high when forming the body seal portion 44. As a result, the productivity of the tube container 40 can be improved.

[0041] In this embodiment, the thickness of the outer sealant layer 11 is preferably 50 μm or more and 250 μm or less.

[0042] <<Second Configuration>> 2C and 2F, the outer sealant layer 11 according to the second configuration is a single layer. The outer sealant layer 11 according to the second configuration may be made of the same materials as the first outer layer 11a, the second outer layer 11b, and the third outer layer 11c of the outer sealant layer 11 according to the first configuration.

[0043] The other configurations of the outer sealant layer 11 according to the second configuration are the same as those of the outer sealant layer 11 according to the first configuration, and therefore detailed explanations thereof will be omitted here.

[0044] <Base layer and intermediate layer> The substrate layer 13 and intermediate layer 17 (hereinafter also simply referred to as the substrate layer 13, etc.) are layers that support, for example, the outer sealant layer 11 and the inner sealant layer 12 and increase the strength of the entire laminate 10. Materials that can be used to form the substrate layer 13, etc. include, for example, films or sheets of polyester resins, polyamide resins, polyaramid resins, polyolefin resins, polycarbonate resins, polyacetal resins, fluorine-based resins, and other tough resins. Examples of polyolefin resins that can be used include films of extruded low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene.

[0045] The resin film or sheet may be an unstretched film, a uniaxially or biaxially stretched film, etc. Among these, a biaxially stretched polyester resin film is preferred in the present embodiment because of its excellent printability.

[0046] In this embodiment, the thickness of each of the base layer 13 and the like is preferably 10 μm or more and 25 μm or less.

[0047] <Inner sealant layer> The inner sealant layer 12 is a layer for bonding the laminates 10 together, and the material constituting the inner sealant layer 12 may be any material that melts and fuses when heated.

[0048] <<First Configuration>> As shown in Fig. 2A etc., the inner sealant layer 12 according to the first configuration has multiple layers. In the examples shown in Fig. 2A, 2C, 2D and 2F, as described above, the inner sealant layer 12 has a first inner layer 12a, a second inner layer 12b and a third inner layer 12c.

[0049] In the inner sealant layer 12 according to the first configuration, the first inner layer 12a, the second inner layer 12b, and the third inner layer 12c may be made of the same materials as the first outer layer 11a, the second outer layer 11b, and the third outer layer 11c of the outer sealant layer 11 according to the first configuration. For example, the inner sealant layer 12 (the first inner layer 12a, the second inner layer 12b, and the third inner layer 12c) may contain a biomass-derived resin. In this case, for example, when the inner sealant layer 12 contains polyethylene or polypropylene, the polyethylene may be biomass polyethylene, and the polypropylene may be biomass polypropylene.

[0050] When the inner sealant layer 12 contains a biomass-derived resin, the environmental impact of the tubular container 40 can be reduced while suppressing poor appearance of the tubular container 40. Specifically, the surface of a layer containing a biomass-derived resin is more likely to develop fisheye-like appearance defects compared to the surface of a layer not containing a biomass-derived resin. These fisheyes can occur, for example, when a portion of the resin does not completely melt and remains as clumps. In contrast, the inner sealant layer 12 of the tubular container 40 is not a layer visible from the outside. Therefore, even if fisheyes develop on the surface of the inner sealant layer 12, they do not adversely affect the appearance of the tubular container 40. As a result, when the inner sealant layer 12 contains a biomass-derived resin, the environmental impact of the tubular container 40 can be reduced while suppressing poor appearance of the tubular container 40.

[0051] In this embodiment, the density of the material constituting the second inner layer 12b may be different from the density of the material constituting the first inner layer 12a and the density of the material constituting the third inner layer 12c. For example, the density of the material constituting the second inner layer 12b may be higher than the density of the material constituting the first inner layer 12a and the density of the material constituting the third inner layer 12c. In this case, by increasing the density of the material constituting the second inner layer 12b, the density of the entire inner sealant layer 12 can be increased while maintaining the meltability of the third inner layer 12c. This increases the stiffness of the entire laminate 10. Furthermore, the density of the material constituting the second inner layer 12b may be lower than the density of the material constituting the first inner layer 12a and the density of the material constituting the third inner layer 12c. In this case, for example, if the second inner layer 12b contains a biomass-derived resin, the biomass-derived resin can be sandwiched between the high-density first inner layer 12a and the third inner layer 12c. This prevents the biomass-derived resin from leaching out.

[0052] The density of the inner sealant layer 12 is 0.92 g / m 3 More than 0.93g / m 3 The density of the inner sealant layer 12 may be 0.92 g / m or less. 3 As a result, the adhesive strength between the outer sealant layer 11 and the inner sealant layer 12 can be increased when forming the body seal portion 44. This makes it possible to prevent the outer sealant layer 11 and the inner sealant layer 12 from peeling off in the body seal portion 44. In addition, when the density of the inner sealant layer 12 is 0.93 g / m 3 or less, productivity of the tube container 40 can be improved. That is, when the density of the inner sealant layer 12 is increased, the melting point of the inner sealant layer 12 tends to be higher. Therefore, when the density of the inner sealant layer 12 is increased, the sealing temperature when forming the body seal portion 44 may become higher. In contrast, when the density of the inner sealant layer 12 is 0.93 g / m or less, 3 By satisfying the above condition, it is possible to prevent the sealing temperature from becoming too high when forming the body seal portion 44. As a result, the productivity of the tube container 40 can be improved.

[0053] Other configurations of the inner sealant layer 12 according to the first configuration are the same as those of the outer sealant layer 11 according to the first configuration, and therefore detailed description thereof will be omitted here.

[0054] <<Second Configuration>> 2B and 2E, the inner sealant layer 12 according to the second configuration is a single layer. The inner sealant layer 12 according to the second configuration may be made of the same materials as the first outer layer 11a, the second outer layer 11b, and the third outer layer 11c of the outer sealant layer 11 according to the first configuration.

[0055] Other configurations of the inner sealant layer 12 according to the second configuration are the same as those of the inner sealant layer 12 according to the first configuration, and therefore detailed explanations will be omitted here.

[0056] As described above, the inner sealant layer 12 constitutes the inner surface 102 of the laminate 10. In this embodiment, the static friction coefficient of the inner surface 102 against metal is 0.40 or less. This makes it possible to prevent scratches on the inner sealant layer 12 even if the transportation of the laminate 10 is stopped during the production of the body tube 41.

[0057] The coefficient of dynamic friction of the inner surface 102 against metal is 0.35 or less. This makes it possible to prevent scratches from occurring on the inner sealant layer 12 when wrapping the laminate 10 around the inner seal member 80 (described later). Furthermore, because scratches on the inner sealant layer 12 can be prevented, foreign matter (e.g., precipitated pigments) caused by scratches on the inner sealant layer 12 can be prevented from adhering to the inner seal member 80 (described later) and the like.

[0058] The static and dynamic friction coefficients of the inner surface 102 against metal may be adjusted by selecting the resin material used for the inner sealant layer 12, as described below, or by applying varnish or the like to the inner sealant layer 12. The dynamic friction coefficient of the inner surface 102 against metal can be measured by the following static and dynamic friction coefficient measurement tests.

[0059] <<<Static friction coefficient measurement test / Dynamic friction coefficient measurement test>>> The static and dynamic friction coefficients are measured by a method in accordance with JIS K 7125: 1999. Specifically, the static and dynamic friction coefficients are measured in accordance with JIS K 7125: 1999, section 8.2 "Measurement of films in contact with metals or other materials." The measuring device may be a TR-2 manufactured by Toyo Seiki Seisakusho, Ltd. First, the measuring device and the laminate are stabilized in an environment of 26°C. The laminate is then cut into 80 mm x 200 mm test pieces using a specified mold. A mating material is also prepared to contact the cut-out test piece. In this case, the mating material is made of metal, such as stainless steel. Next, the test piece is placed on the mating material with the inner sealant layer 12 facing the mating material, and a sliding piece is placed on top of it. The sliding piece weighs 200 g. The test piece and the sliding piece are then brought into close contact to prevent slippage. Next, the sliding piece is pulled at a speed of 100 mm / min, and the static friction force (N) and kinetic friction force (N) between the test piece and the mating material are measured. The static friction force and kinetic friction force are then divided by the normal force of the sliding piece (1.96 N) to calculate the static and kinetic friction coefficients. The coefficient of kinetic friction is determined from the average value for the first 30 mm after the start of the relative shear movement between the test piece and the mating material, ignoring the peak of the static friction force. The load cell is directly connected to the sliding piece. Three test pieces are prepared, and the static and kinetic friction coefficients are measured for each test piece. The average values ​​of the three test pieces for the surface static and kinetic friction coefficients are then used as the static and kinetic friction coefficients of the laminate 10.

[0060] In this embodiment, the thickness of the inner sealant layer 12 is preferably 50 μm or more and 250 μm or less.

[0061] <Adhesive layer> The adhesive layers, such as the first adhesive layer 14a, the second adhesive layer 14b, and the third adhesive layer 14c, are layers for bonding together the outer sealant layer 11, the base material layer 13, the inner sealant layer 12, etc. The material used for these adhesive layers can be appropriately selected depending on the resin that constitutes the layers to be bonded.

[0062] As the adhesive layer, for example, anchor coating agents such as isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, and organic titanium-based, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, and other laminating adhesives can be used as desired.

[0063] Furthermore, for example, polyethylene, polypropylene, linear low-density polyethylene, ethylene-vinyl alcohol, ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer, ionomer, maleic anhydride-modified polyolefin resin, etc. can be suitably used as the adhesive layer.

[0064] In this embodiment, the thickness of the adhesive layer is preferably 3 μm or more and 60 μm or less.

[0065] Furthermore, the outer sealant layer 11, the base material layer 13, the inner sealant layer 12, etc. can be laminated to one another by, for example, wet lamination, dry lamination, solventless dry lamination, extrusion lamination, T-die coextrusion molding, coextrusion lamination, inflation molding, or any other method. When carrying out the above-mentioned lamination, if necessary, the film may be subjected to a pretreatment such as corona treatment or ozone treatment. <Print layer> The printed layer 15 is a layer on which a picture or the like is printed, and is a layer for improving the design of the laminate 10. The printed layer 15 may be an ink composition obtained by adjusting the ink composition by adding one or more of ordinary ink vehicles as the main component, optionally adding one or more of plasticizers, stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, and other additives as needed, and further adding a colorant such as a dye or pigment, and thoroughly kneading the mixture with a solvent, a diluent, etc. Examples of such ink vehicles include linseed oil, tung oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin-modified resin, shellac, alkyd resin, phenolic resin, maleic acid resin, natural resin, hydrocarbon resin, polyvinyl chloride resin, polyacetic acid resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin, melamine resin, aminoalkyd resin, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, and others, and one or more of these can be used in combination. The printing method may be gravure printing, letterpress printing, screen printing, transfer printing, flexographic printing, or other printing methods.

[0066] <Barrier layer> The barrier layer 16 is a layer for preventing the transmission of oxygen gas, water vapor, etc. For the barrier layer 16, for example, a gas barrier material against oxygen gas, water vapor, etc., a light-shielding material against sunlight, etc., or a material that has aroma retention properties for the contents can be used.

[0067] The barrier layer 16 can be made of, for example, aluminum foil, tin, lead, copper, iron, nickel, or an alloy thereof, or a thin layer of a metal such as aluminum. When aluminum foil is used as the barrier layer 16, the thickness of the barrier layer 16 may be approximately 5 μm or more and 20 μm or less. By using aluminum foil as the barrier layer 16, the laminate 10 can be easily produced.

[0068] Furthermore, when a metal vapor deposition layer such as aluminum is used as the barrier layer 16, a vapor deposition thin film of a metal such as aluminum can be formed on the intermediate layer 17 using, for example, a physical vapor deposition method (PVD method) such as vacuum deposition, sputtering, ion plating, or cluster ion beam method.

[0069] When a metal vapor-deposited aluminum layer is used as the barrier layer 16, the thickness of the barrier layer 16 is usually preferably about 50 Å to 3000 Å, and particularly preferably about 100 Å to 2000 Å. The surface of the intermediate layer 17 supporting the vapor-deposited thin aluminum film may be coated in advance with, for example, a vapor deposition primer to improve adhesion of the vapor-deposited film, or other required pretreatment may be optionally performed.

[0070] The barrier layer 16 may also be a transparent vapor deposition layer that can be formed by a conventionally known method. The barrier layer 16 being a transparent vapor deposition layer can make the laminate 10 transparent. In this case, the barrier layer 16 may be a transparent vapor deposition layer made of an inorganic oxide vapor deposition layer.

[0071] The transparent vapor-deposited layer may be, for example, a vapor-deposited layer of an oxide of silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), etc. In particular, for tubular containers, it is preferable to provide a vapor-deposited layer of aluminum oxide or silicon oxide.

[0072] Inorganic oxides are expressed as, for example, SiO X , AlO X MO etc. X(wherein, M represents an inorganic element, and the value of X varies depending on the inorganic element.) The value of X can range from 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1.5 for magnesium (Mg), 0 to 1 for calcium (Ca), 0 to 1 for potassium (K), 0 to 0.5 for tin (Sn), 0 to 2 for sodium (Na), 0 to 0.5 for boron (B), 0 to 1.5 for titanium (Ti), 0 to 2 for lead (Pb), 0 to 2 for zirconium (Zr), and 0 to 1.5 for yttrium (Y). In the above, when X=0, it is a completely inorganic element (pure substance) and is not transparent, and the upper limit of the range of X is the value when it is completely oxidized. Silicon (Si) and aluminum (Al) are preferably used for packaging materials, with silicon (Si) having a value in the range of 1.0 to 2.0 and aluminum (Al) having a value in the range of 0.5 to 1.5.

[0073] The thickness of the transparent vapor-deposited layer varies depending on the type of inorganic oxide used, but is desirably selected from the range of, for example, 50 to 2000 Å, preferably 100 to 1000 Å. For example, in the case of a vapor-deposited layer of aluminum oxide or silicon oxide, the thickness is desirably 50 to 500 Å, more preferably 100 to 300 Å.

[0074] The transparent vapor deposition layer can be formed on the intermediate layer 17 using the following formation methods. Examples of methods for forming a vapor deposition layer include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition (CVD) methods such as plasma enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. Specifically, a vapor deposition layer can be formed on a forming roller using a roller-type vapor deposition layer forming device.

[0075] <Other layers> Other layers, such as a concealing layer, may be provided. The concealing layer is a layer for preventing changes or variations in color of each layer from affecting the color of the pattern, etc., of the printed layer 15. An olefin resin may be used for the concealing layer. More specifically, a polyethylene film such as low-density polyethylene, linear low-density polyethylene, or medium-density polyethylene is preferably used as the concealing layer. These polyethylene films may be colored, for example, like a milky white polyethylene film. The thickness of the concealing layer is preferably 50 μm or more and 200 μm or less.

[0076] In such a laminate 10, all layers may contain a biomass-derived resin, which can further reduce the environmental impact of the laminate 10.

[0077] The biomass degree of the laminate 10 may be 10% or more and 50% or less. When the biomass degree of the laminate 10 is 10% or more, the environmental impact of the laminate 10 can be further reduced. When the biomass degree of the laminate 10 is 50% or less, physical properties similar to those of a laminate made using only fossil fuel-derived resins can be obtained.

[0078] Furthermore, the loop stiffness in the first direction d1 may be 900 mN or more, and the loop stiffness in the second direction d2 perpendicular to the first direction d1 may be 1100 mN or more. The first direction d1 may be the longitudinal direction of the body tube 41 when the tube container 40 is manufactured. The second direction d2 may be the circumferential direction of the body tube 41 when the tube container 40 is manufactured. Here, the loop stiffness is a parameter that represents the stiffness of the body tube 41 (laminate 10).

[0079] When the first direction d1 is the longitudinal direction of the body tube 41, the self-standing ability of the tube container 40 can be improved by having the loop stiffness in the first direction d1 be 900 mN or more. Furthermore, when the second direction d2 is the circumferential direction of the body tube 41, the loop stiffness in the second direction d2 be 1100 mN or more, which can improve the restoring ability of the body tube 41 when the body tube 41 is crushed in the radial direction. This can improve the restoring ability of the body tube 41 after the contents are removed from the tube container 40. In particular, the restoring ability of the body tube 41 can be improved by having the loop stiffness in the second direction d2 be greater than the loop stiffness in the first direction d1.

[0080] When measuring the loop stiffness, first, a test piece is prepared by cutting the body tube 41 to a width of 15 mm and a length of 100 mm. At this time, two types of test pieces are prepared. That is, the test piece is cut out so that its longitudinal direction coincides with the longitudinal direction (first direction d1) of the body tube 41. Similarly, the test piece is cut out so that its longitudinal direction coincides with the circumferential direction (second direction d2) of the body tube 41. Next, both longitudinal ends of the test piece are clamped between a pair of chucks (not shown), and the chucks are brought close to each other to roll the test piece into a loop. At this time, the loop length is set to 70 mm. Next, the loop stiffness is measured by pressing the test piece with an indenter (not shown). When pressing the test piece with the indenter, the vertical distance between the chuck clamping the test piece and the indenter is set to 15 mm at the initial position. Then, the indenter is lowered from the initial position to press the test piece with the indenter. A Loop Stiffness Tester (registered trademark) manufactured by Toyo Seiki Seisaku-sho, Ltd. is used as the measuring device. The load range is set to 5000 mN, the compression speed is set to 3.3 mm / s, and the time for which the indenter presses the test piece is set to 5 seconds.

[0081] In the tube container 40 according to this embodiment, the body tube 41 and the head member 43 can be joined by thermal welding when the head member 43 is molded by compression molding, as will be described later. However, the joining is not limited to this, and the body tube 41 and the head member 43 may also be joined by injection molding.

[0082] (Method of manufacturing a tube container with a cap) Next, a method for manufacturing the capped tube container 40A will be described with reference to FIGS.

[0083] First, for example, a laminate 10 shown in FIG. 2A is prepared.

[0084] Next, a tube container 40 is manufactured from the obtained laminate 10.

[0085] First, the laminate 10 is rolled and the opposing edges are joined together, for example, by heat sealing, to form a cylindrical tube 41. In this process, as shown in FIGS. 3(a)-(b), the laminate 10 is first wrapped around the outer surface of a cylindrical inner seal member 80, overlapping the opposing edges of the laminate 10. The laminate 10 is wrapped around the inner seal member 80 so that the inner sealant layer 12 of the laminate 10 faces the outer surface of the inner seal member 80. The inner seal member 80 may be made of metal, such as stainless steel. When overlapping the opposing edges of the laminate 10, the laminate 10 is transported downstream (to the left in FIGS. 3(a)-(b)) by a conveyor belt and guide rolls (not shown).

[0086] 3(b), an outer seal member 81 is pressed against the overlapping portion of the opposing edges of the laminate 10, and the overlapping portion of the opposing edges of the laminate 10 is sandwiched between the inner seal member 80 and the outer seal member 81. Next, the overlapping portion of the opposing edges of the laminate 10 is joined by heat sealing. In this case, the outer sealant layer 11 (see FIG. 2A, etc.) provided on the outer surface 101 side of the laminate 10 and the inner sealant layer 12 (see FIG. 2A, etc.) provided on the inner surface 102 side are melted and joined to form the body seal portion 44.

[0087] Thereafter, the joined laminate 10 is cut into individual body tubes 41. In this manner, the body tubes 41 are produced as shown in Fig. 4. At this time, the speed at which the body tubes 41 are produced may be about 300 tubes / min.

[0088] Next, the above-mentioned tube container 40 is manufactured by compression molding.

[0089] 5(a), the cylindrical laminate 10 (body tube 41) is wound around a mandrel 72, and a mold 71 for compression molding the head member 43 is attached to one end of the mandrel 72. That is, the laminate 10 (body tube 41), which has been molded into a cylindrical shape in advance, is inserted into the mandrel 72, whose tip serves as a core for compression molding the head member 43, and then advanced to a predetermined position into the cavity of the mold 71 for molding the head member 43.

[0090] Next, molten resin is supplied from a resin supply device (not shown) into the mold 71 to compression-mold the head member 43. In this case, one end 42 of the body tube 41 is inserted into the mold 71 to mold the head member 43, and at the same time, the body tube 41 is integrally fused to the head member 43. Thereafter, the integrated head member 43 and body tube 41 are removed from the mold 71 and mandrel 72 to obtain a tube container 40 including the body tube 41 and the head member 43 joined to one end 42 of the body tube 41 (see FIG. 5(b)).

[0091] When manufacturing the capped tube container 40A, the cap 49 is prepared in parallel with the production of the tube container 40. In this case, the cap 49 is produced by injection molding using, for example, an injection molding machine (not shown). The cap 49 is then screwed onto the opening of the head member 43 of the tube container 40, thereby obtaining the capped tube container 40A as shown in FIG.

[0092] Thereafter, an appropriate amount of contents C is filled into the body tube 41 through the opening 41B (see FIGS. 4 and 6). The opening 41B is then welded to form a bottom seal portion 45 (see FIG. 1). In this manner, a tube container 40A with a cap filled and packaged with the contents C is obtained.

[0093] As described above, according to this embodiment, the laminate 10 includes the outer sealant layer 11, the base layer 13, and the inner sealant layer 12, which are arranged in this order from the outer surface 101 to the inner surface 102. The outer sealant layer 11 includes the first outer layer 11a, the second outer layer 11b, and the third outer layer 11c, which are arranged in this order from the outer surface 101 to the inner surface 102. The density of the material constituting the second outer layer 11b is different from the density of the material constituting the first outer layer 11a and the density of the material constituting the third outer layer 11c. This allows the density of the entire outer sealant layer 11 to be increased while maintaining the meltability of the first outer layer 11a. This increases the stiffness of the entire laminate 10. As a result, the desired performance can be maintained even when the thickness of the outer sealant layer 11 is reduced. This allows the amount of resin used in the tube container 40 to be reduced.

[0094] The density of the outer sealant layer 11 is 0.92 g / m 3 More than 0.93g / m 3This prevents the outer sealant layer 11 and the inner sealant layer 12 from peeling off in the body seal portion 44. Furthermore, the sealing temperature can be prevented from becoming too high when forming the body seal portion 44, improving the productivity of the tube container 40. Therefore, even when the thickness of the outer sealant layer 11 is reduced, the desired performance can be maintained and the amount of resin used in the tube container 40 can be reduced. The fact that such effects can be obtained will be explained in the examples below.

[0095] Furthermore, according to this embodiment, the inner sealant layer 12 includes a first inner layer 12a, a second inner layer 12b, and a third inner layer 12c, arranged in this order from the outer surface 101 to the inner surface 102. The density of the material constituting the second inner layer 12b is different from the density of the material constituting the first inner layer 12a and the density of the material constituting the third inner layer 12c. Even in this case, the density of the entire inner sealant layer 12 can be increased while maintaining the meltability of the third inner layer 12c. This increases the stiffness of the entire laminate 10. As a result, the desired performance can be maintained even when the thickness of the inner sealant layer 12 is reduced. This allows the amount of resin used in the tube container 40 to be reduced.

[0096] The density of the inner sealant layer 12 is 0.92 g / m 3 More than 0.93g / m 3 This prevents the outer sealant layer 11 and the inner sealant layer 12 from peeling off in the body seal portion 44. Furthermore, the sealing temperature can be prevented from becoming too high when forming the body seal portion 44, improving the productivity of the tube container 40. Therefore, even if the thickness of the inner sealant layer 12 is reduced, the desired performance can be maintained and the amount of resin used in the tube container 40 can be reduced. The fact that such effects can be obtained will be explained in the examples below.

[0097] By making at least one of the outer sealant layer 11 and the inner sealant layer 12 multi-layered, as in the present embodiment, it is possible to expand the design variations compared to a single-layer structure. Furthermore, additives can be introduced into a specific layer of the multi-layer structure while maintaining performance, thereby improving defects such as uneven thickness. Furthermore, when the sealant layer is multi-layered, the overall density can be increased while maintaining performance as described above compared to a single-layer structure. This contributes to the thinning of the body tube 41.

[0098] Furthermore, by forming a multi-layer sealant layer, a layer containing a biomass-derived resin can be sandwiched between other layers within the sealant layer, which prevents the biomass-derived resin from being exposed from the body tube 41. [Example]

[0099] Next, a specific example of the above embodiment will be described.

[0100] Example 1 The laminate 10 shown in FIG. 2D was produced. First, a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name: E5200, thickness: 12 μm) was prepared as the base layer 13. Next, a printed layer 15 was formed on the polyethylene terephthalate film. The biomass content of the polyethylene terephthalate film was 20%. The biomass content of the ink forming the printed layer 15 was 10%.

[0101] Also, a polyethylene terephthalate film (manufactured by Oike Kogyo Co., Ltd., product name: Tetolite, thickness 12 μm) provided with an aluminum vapor deposition layer (barrier layer 16) was prepared as the intermediate layer 17. The biomass content of the polyethylene terephthalate film was 20%.

[0102] Furthermore, as the outer sealant layer 11, an antistatic agent-containing polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: BCO LZ27N AS), average density: 0.927 g / cm 3A polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: BCO LZ27N, average density: 0.927 g / cm) was prepared as the inner sealant layer 12. 3 Both of these polyethylene films were three-layer films.

[0103] When producing a polyethylene film, first, 100 parts by mass of fossil fuel-derived linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name: UZ3520L, density: 0.931 g / cm ) was used as the resin constituting the first outer layer 11a (first inner layer 12a). 3 A molten resin with a MFR of 2.1 g / 10 min and a biomass content of 0% was prepared.

[0104] The resin constituting the second outer layer 11b (second inner layer 12b) was 42 parts by mass of fossil fuel-derived linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name: Evolue SP4020, density: 0.937 g / cm 3 , MFR: 2.1 g / 10 min, biomass content: 0%), and 58 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem, product name: SLL-118, density: 0.916 g / cm 3 A resin was separately prepared by melting the above mixture, which had a MFR of 1.0 g / 10 min and a biomass content of 87%. The average density of the resin constituting the second outer layer 11b (second inner layer 12b) was 0.925 g / cm. 3 It was.

[0105] Furthermore, the resin constituting the third outer layer 11c (third inner layer 12c) was 100 parts by mass of fossil fuel-derived linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name: UZ3520L, density: 0.931 g / cm 3 A resin having a MFR of 2.1 g / 10 min and a biomass content of 0% was separately melted to prepare a resin.

[0106] Next, these melts were co-extruded by inflation molding to produce a polyethylene film with a thickness ratio of 1:3:1 (first outer layer 11a (first inner layer 12a): second outer layer 11b (second inner layer 12b): third outer layer 11c (third inner layer 12c)). The resin film had a thickness of 150 μm. The average density of the polyethylene film was 0.927 g / cm 3 The biomass content of the polyethylene film was 25%.

[0107] Next, the films for the outer sealant layer 11, the base material layer 13, the intermediate layer 17, and the inner sealant layer 12 were bonded together by dry lamination to produce a laminate 10. The biomass content of the adhesive layer obtained by dry lamination was 10%. The layer structure of the obtained laminate 10 is as follows: ASPEF(PE / PE / PE) / DL / PET / Mark / DL / ALVM / PET / DL / PEF(PE / PE / PE) In the above, "ASPEF" means polyethylene film containing antistatic agent (the same applies below). Also, "PE" means polyethylene (the same applies below). Also, "DL" means polyethylene. "PET" means a polyethylene terephthalate film (same below). "Ink" means a printed layer (same below). "ALVM" means an aluminum Furthermore, "PEF" means polyethylene film (hereinafter the same).

[0108] The resulting laminate 10 was used to produce a tube container 40 shown in Fig. 1. First, the laminate 10 was formed into a cylindrical shape to produce a body tube 41. After joining the laminate 10 with an inner seal member 80 and an outer seal member 81 by high frequency and heat sealing, the laminate 10 was cut into individual body tubes 41. The body tubes 41 were produced at a production rate of 300 tubes / min, and 250 tubes were produced for each sample, for a total of 750 body tubes 41.

[0109] Thereafter, each of these body tubes 41 was wound around a mandrel 82, and the head member 43 was integrally molded with the body tube 41 by compression molding to obtain the tube container 40. The head member 43 was made of high density polyethylene (HDPE).

[0110] In this way, a total of 750 tube containers 40 were produced.

[0111] Example 2 A laminate and a tube container were produced in the same manner as in Example 1, except that a polyethylene terephthalate film (manufactured by DNP Technopack Co., Ltd., product name: IB-PET-WBUB, thickness 12 μm) provided with a vapor-deposited silica layer (barrier layer 16) was used as the intermediate layer 17. The layer structure of the obtained laminate 10 is as follows. ASPEF(PE / PE / PE) / DL / PET / Mark / DL / Silica / PET / DL / PEF(PE / PE / PE) In the above, "silica" means a vapor-deposited layer of silica (the same applies hereinafter).

[0112] Example 3 A laminate and a tube container were produced in the same manner as in Example 1, except that a fossil fuel-derived linear low-density polyethylene was used as the resin constituting the second outer layer 11b (second inner layer 12b). The layer structure of the obtained laminate 10 is as follows. ASPEF(PE / PE / PE) / DL / PET / Mark / DL / ALVM / PET / DL / PEF(PE / PE / PE)

[0113] Example 4 A laminate and a tubular container were produced in the same manner as in Example 2, except that a fossil fuel-derived linear low-density polyethylene was used as the resin constituting the second outer layer 11b (second inner layer 12b). The layer structure of the obtained laminate 10 is as follows. ASPEF(PE / PE / PE) / DL / PET / Mark / DL / Silica / PET / DL / PEF(PE / PE / PE)

[0114] Example 5 The resin constituting the first outer layer 11a (first inner layer 12a) and the third outer layer 11c (third inner layer 12c) was fossil fuel-derived linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name: Evolue SP2020, density: 0.916 g / cm 3 The resin constituting the second outer layer 11b (second inner layer 12b) was a fossil fuel-derived linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name: Evolue SP2520, density: 0.925 g / cm 3 A laminate and a tube container were produced in the same manner as in Example 1, except that polyethylene film with an average density of 0.922 g / cm 3 was used. 3 The biomass content of the polyethylene film was 0%. The layer structure of the obtained laminate 10 is as follows. ASPEF(PE / PE / PE) / DL / PET / Mark / DL / ALVM / PET / DL / PEF(PE / PE / PE)

[0115] Example 6 The resin constituting the first outer layer 11a (first inner layer 12a) was a fossil fuel-derived linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name: Evolue SP4020, density: 0.937 g / cm 3 The resin constituting the second outer layer 11b (second inner layer 12b) was a biomass-derived linear low-density polyethylene (manufactured by Braskem, product name: SLL-118, density: 0.916 g / cm 3 The resin constituting the third outer layer 11c (third inner layer 12c) was a fossil fuel-derived linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name: Evolue SP2320, density: 0.920 g / cm 3A laminate and a tube container were produced in the same manner as in Example 2, except that polyethylene film with an average density of 0.921 g / cm 3 was used. 3 The biomass content of the polyethylene film was 50%. The layer structure of the obtained laminate 10 is as follows. ASPEF(PE / PE / PE) / DL / PET / Mark / DL / Silica / PET / DL / PEF(PE / PE / PE)

[0116] (Comparative Example 1) The intermediate layer was a polyethylene terephthalate film (manufactured by Toray Films Co., Ltd., product name: BR-PET1312, thickness: 12 μm) with an aluminum vapor deposition layer (barrier layer). The outer sealant layer was a polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: SR-WN2 AS) with an average density of 0.921 g / cm. 3 ) was used as the inner sealant layer, and polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: SR-WN2, average density: 0.920 g / cm 3 A laminate and a tube container were produced in the same manner as in Example 1, except that ) was used.

[0117] (Comparative Example 2) The intermediate layer was a polyethylene terephthalate film (manufactured by Toray Films Co., Ltd., product name: BR-PET1312, thickness 12 μm) with an aluminum vapor deposition layer (barrier layer). The outer sealant layer was a polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: MPR AS) with an average density of 0.923 g / cm. 3 The inner sealant layer was a polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: MP31, average density: 0.930 g / cm 3 A laminate and a tube container were produced in the same manner as in Example 1, except that a 180 μm thick sheet (100 μm thick) was used.

[0118] <Static friction coefficient measurement test / Dynamic friction coefficient measurement test> The static and dynamic friction coefficients of the inner surfaces of the laminates of Example 1 to Comparative Example 2 were measured. The static and dynamic friction coefficients were measured in accordance with JIS K 7125:1999, Section 8.2, "Measurement of Films in Contact with Metal or Other Materials." First, the measuring device and laminate 10 were stabilized at 26°C from each laminate. Then, the laminate was cut into 80 mm x 200 mm test pieces using a specified mold. A mating material was also prepared to contact the cut-out test pieces. The mating material was made of SUS304. Next, the test piece was placed on the mating material with the outer sealant layer facing the mating material, and a sliding piece was placed on top of it. For another test piece, the test piece was placed on the mating material with the inner sealant layer facing the mating material, and a sliding piece was placed on top of it. The total weight of the sliding pieces was 200 g. The test specimen and the sliding piece were then brought into close contact with each other to prevent slippage, and the sliding piece was pulled at a speed of 100 mm / min. The static friction force (N) and kinetic friction force (N) between the test specimen and the mating material were measured, and the static friction force and kinetic friction force were divided by the normal force of the sliding piece (1.96 N) to calculate the static and kinetic friction coefficients. The kinetic friction coefficient was calculated from the average value over the first 30 mm after the start of relative shear movement between the test specimen and the mating material, ignoring the peak static friction force. The load cell was directly connected to the sliding piece. Three test specimens were prepared, and the static and kinetic friction coefficients were measured for each specimen. The average values ​​of the three test specimens for the static and kinetic friction coefficients were used as the static and kinetic friction coefficients of the laminate.

[0119] <Loop stiffness measurement test> Furthermore, the loop stiffness was measured by first measuring the loop stiffness in the longitudinal direction of the body tube (the vertical direction (first direction) in Figure 1) and the loop stiffness in the circumferential direction of the body tube (the horizontal direction (second direction) in Figure 1).

[0120] First, a test specimen was prepared by cutting the body tube to a width of 15 mm and a length of 100 mm. Two types of test specimens were prepared. Specifically, the test specimens were cut so that the longitudinal direction of the test specimen coincided with the longitudinal direction (first direction d1) of the body tube. Similarly, the test specimens were cut so that the longitudinal direction of the test specimen coincided with the circumferential direction (second direction d2) of the body tube. Next, both longitudinal ends of the test specimen were clamped between a pair of chucks (not shown), and the chucks were brought close to each other to roll the test specimen into a loop. The loop length was set to 70 mm. Next, the loop stiffness was measured by pressing the test specimen with an indenter (not shown). When pressing the test specimen with the indenter, the vertical distance between the chuck clamping the test specimen and the indenter was 15 mm at the initial position. Then, the indenter was lowered from the initial position to press the test specimen with the indenter. The measuring device used was a Loop Stiffness Tester (registered trademark) manufactured by Toyo Seiki Seisakusho, Ltd. The load range was 5000 mN, the compression speed was 3.3 mm / s, and the time for the indenter to press the test piece was 5 seconds. The maximum load was taken as the loop stiffness.

[0121] <Evaluation of the joint strength of the body seal> Test pieces were obtained by cutting the body seal of the tube container into 15 mm wide strips with the longitudinal direction aligned with the circumferential direction of the body seal of the tube container. These test pieces were pulled at a test speed of 300 mm / min using a tensile tester (Orientec Co., Ltd., STA-1150). Three test pieces were prepared, and tests were performed on each test piece. The maximum load was taken as the bonding strength (N) of the body seal.

[0122] <Evaluation of the joint between the body tube and the head component> 7(a), a test piece S1 was prepared by cutting out a portion of the body tube 41 including the body seal portion 44 together with the head member 43 into a rectangle having a width of 15 mm and a length of 100 mm. When cutting out the body tube 41, the body tube 41 and the head member 43 were cut out so that the longitudinal direction of the test piece S1 was the up-and-down direction of the body tube 41 and the body seal portion 44 was located approximately in the center of the longitudinal direction of the test piece S1. Three test pieces S1 were prepared in this manner.

[0123] Furthermore, three test pieces S2 were prepared by cutting out a rectangular shape with a width of 15 mm and a length of 100 mm from a portion of the tube container 40 that was 180° rotationally symmetrical to the portion cut out of test piece S1 with respect to the central axis of the tube container 40, together with the head member 43. When cutting out the body tube 41, the body tube 41 and the head member 43 were cut out so that the longitudinal direction of test piece S2 was the up-down direction of the body tube 41. In this way, three test pieces S2 were produced.

[0124] Next, for these test pieces S1 and S2, the adhesive strength between the body tube 41 and the head member 43 was measured using a tensile tester (STA-1150, manufactured by Orientec Co., Ltd.).

[0125] During the measurement, first, as shown in Fig. 7(b), the body tube 41 and head member 43 of each test piece S1, S2 were partially peeled off. Next, as shown in Fig. 7(c), the peeled body tube 41 and head member 43 were each held with gripping tools 80 of a tensile tester, and the gripping tools 80 were moved in opposite directions to pull the test pieces S1, S2. The pulling speed for the test pieces S1, S2 was 300 mm / min. The maximum load was taken as the bonding strength (N) between the body tube and the head member.

[0126] The results are shown in Figures 8 to 12. Figures 8 and 9 are tables showing the densities of Example 1 to Comparative Example 2. Figure 10 is a table showing the results of the static friction coefficient measurement test, the dynamic friction coefficient measurement test, and the loop stiffness measurement test. Figure 11 is a table showing the results of the bondability evaluation of the body seal portion and the bondability evaluation between the body tube and the head member. Figure 12 is a table showing the biomass degree of Example 1 to Comparative Example 2.

[0127] 8 to 12, the tube containers according to Examples 1 to 6 were able to maintain the desired performance even when the thicknesses of the outer sealant layer and the inner sealant layer were made thinner than those of the tube containers according to Comparative Examples 1 and 2. Therefore, it was found that according to this embodiment, the amount of resin used in the tube container 40 can be reduced.

[0128] It is also possible to combine the multiple components disclosed in the above embodiments as needed, or to delete some of the components disclosed in the above embodiments. [Explanation of symbols]

[0129] 10 Laminate 11 Outer sealant layer 11a 1st outer layer 11b Second outer layer 11c 3rd outer layer 12 Inner sealant layer 12a 1st inner layer 12b 2nd inner layer 12c 3rd inner layer 13 Base material layer 16 Barrier Layer 40 tube containers 40A Tube with Cap 41 Body tube 42 one end 43 Head member 49 Cap 101 Exterior 102 Inside

Claims

[Claim 1] The sealant layer includes an outer sealant layer, a base layer, and an inner sealant layer, which are arranged in this order from the outer surface to the inner surface, The outer sealant layer has a first outer layer, a second outer layer, and a third outer layer arranged in this order from the outer surface to the inner surface, the density of the material constituting the second outer layer is different from the density of the material constituting the first outer layer and the density of the material constituting the third outer layer; The density of the outer sealant layer is 0.92 g / m ３ 0.93g / m or more ３ The laminate is as follows:

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