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 and suppression of degradation in design quality.SOLUTION: A laminate 10 comprises a wear-resistant varnish layer 21, a first printing layer 15a, a wear-resistant resin layer 22, an outer sealant layer 11, and an inner sealant layer 12. A material forming a second inner layer 12b of the inner sealant layer 12 has a density different from densities of materials forming a first inner layer 12a and a third inner layer 12c of the inner sealant layer 12. The density of the inner sealant layer 12 is 0.92 g / m3 or more and 0.93 g / m3 or less. A static friction coefficient of an outer surface 101 with respect to metal is 0.25 or less, and a dynamic friction coefficient thereof is 0.20 or less. A static friction coefficient of an inner surface 102 with respect to metal is 0.40 or less, and a dynamic friction coefficient thereof is 0.35 or less.SELECTED DRAWING: Figure 2

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] Recently, there has been a demand for reducing the amount of resin used in order to reduce environmental impact. Furthermore, tube containers may rub against each other during transportation, causing scratches on the outer surface of the tube container, which can deteriorate the appearance of the tube container. This reduces the design quality of the tube container. Therefore, there is a demand for ways to prevent this deterioration in the design quality of tube containers.

[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 and suppress deterioration in design. [Means for solving the problem]

[0006] The embodiments of the present disclosure relate to the following [1] to [8].

[0007] [1] The product comprises an abrasion-resistant varnish layer, a print layer, an abrasion-resistant resin layer, an outer sealant 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 is as follows: the static coefficient of friction of said outer surface against metal is 0.25 or less; the coefficient of dynamic friction of said outer surface against metal is 0.20 or less; The coefficient of static friction of the inner surface against metal is 0.40 or less; A laminate in which the coefficient of dynamic friction of the inner surface against metal is 0.35 or less.

[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 substrate layer provided between the outer sealant layer and the inner sealant layer.

[0010] [4] The laminate according to [3], further comprising a barrier layer provided between the base material layer and the inner sealant layer.

[0011] [5] The laminate according to any one of [1] to [4], wherein the abrasion-resistant varnish layer contains an ultraviolet-curable resin.

[0012] [6] The laminate according to any one of [1] to [5], wherein the abrasion-resistant resin layer contains linear low-density polyethylene.

[0013] [7] In a tube container, [1] to [6], and a body tube formed by overlapping and joining opposing edges of the laminate according to any one of [1] to [6]. a head member joined to one end of the body tube.

[0014] [8] In a tube container with a cap, [7] The tube container according to [7], a cap attached to the head member. [Effects of the Invention]

[0015] According to the present disclosure, it is possible to reduce the amount of resin used in a tube container and to prevent a decrease in design. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 is a partial vertical cross-sectional view showing a tube container with a cap according to this embodiment. [Figure 2] FIG. 2 is a cross-sectional view showing an example of the layer structure of the laminate according to this 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]FIG. 7 is a cross-sectional view showing an example of the layer structure of the laminate according to Comparative Example 1. As shown in FIG. [Figure 8] 8(a) to 8(c) are diagrams illustrating a test for evaluating the bondability of a shoulder portion according to an embodiment. [Figure 9] FIG. 9 is a table showing densities and inner sealant layer thicknesses according to examples. [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 rubbing 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 the biomass content of the inner sealant layer, according to an example. DETAILED DESCRIPTION OF THE INVENTION

[0017] 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.

[0018] (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.

[0019] (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.

[0020] 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.

[0021] 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.

[0022] 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).

[0023] (Laminate) Next, the layer structure of the laminate 10 will be described. Fig. 2 shows an example of the layer structure of the laminate 10 constituting the body tube 41. As shown in Fig. 2, the laminate 10 includes an abrasion-resistant varnish layer 21, a printed layer 15, an abrasion-resistant resin layer 22, an outer sealant layer 11, and an inner sealant layer 12, which are arranged in this order from the outer surface 101 to the inner surface 102. The laminate 10 may further include a substrate layer 13 provided between the outer sealant layer 11 and the inner sealant layer 12. The laminate 10 may further include a barrier layer 16 provided between the substrate layer 13 and the inner sealant layer 12.

[0024] 2, the laminate 10 includes, in this order, an abrasion-resistant varnish layer 21, a first printed layer (printed layer) 15a, an abrasion-resistant resin layer 22, an outer sealant layer 11, a first adhesive layer 14a, a substrate layer 13, a second printed layer 15b, 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 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 abrasion-resistant varnish layer 21 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). Although not shown, the inner sealant layer 12 may be made up of four or more layers.

[0025] Each layer of the laminate 10 will now be described.

[0026] <Abrasion-resistant varnish layer> The abrasion-resistant varnish layer 21 is a layer for protecting the first printed layer 15a while improving the abrasion resistance of the laminate 10. The abrasion-resistant varnish layer 21 may contain a UV-curable resin, which makes it easy to adjust the glossiness (gloss or matte). In addition to UV-curable resin, the material constituting the abrasion-resistant varnish layer 21 may also be, for example, OP varnish. The abrasion-resistant varnish layer 21 may be formed, for example, by digital printing such as inkjet printing, gravure printing, flexographic printing, letterpress printing, or application using a coater.

[0027] As described above, the abrasion-resistant varnish layer 21 constitutes the outer surface 101 of the laminate 10. In this embodiment, the static friction coefficient of the outer surface 101 against metal is 0.25 or less. The dynamic friction coefficient of the outer surface 101 against metal is 0.20 or less. This prevents scratches on the outer surfaces of the body tubes 41 even when the body tubes 41 rub against each other when filling the contents or when multiple tube containers 40 are packed in cardboard boxes or the like for shipping and storage.

[0028] The static and dynamic friction coefficients of the outer surface 101 against metal may be adjusted by selecting the material used for the abrasion-resistant varnish layer 21, as described below. The static and dynamic friction coefficients of the outer surface 101 against metal can be measured by the following static and dynamic friction coefficient measurement tests.

[0029] <<<Static friction coefficient measurement test / Dynamic friction coefficient measurement test>>> The static and dynamic coefficients of friction are measured according to JIS K 7125:1999. Specifically, the static and dynamic coefficients of friction are measured according to JIS K 7125:1999, Section 8.2, "Measurement of Films in Contact with Metals or Other Materials." A measurement device, such as the TR-2 manufactured by Toyo Seiki Seisakusho Co., Ltd., may be used. First, the measurement device and the laminate are stabilized in an environment of 26°C. The laminate is then cut into 80mm x 200mm 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 abrasion-resistant varnish layer 21 facing the mating material, and a sliding piece is placed on top of it. The sliding piece weighs 200g. The test piece and the sliding piece are then brought into close contact with each other 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 divided by the normal force of the sliding piece (1.96 N) to calculate the static friction coefficient and kinetic friction coefficient. The kinetic friction coefficient is calculated from the average value over the first 30 mm after the start of the relative shear movement between the test piece and the mating material, ignoring the peak static friction force. The load cell is directly connected to the sliding piece. Three test pieces are prepared, and the static friction coefficient and kinetic friction coefficient are measured for each test piece. The average values ​​of the three test pieces for the surface static friction coefficient and kinetic friction coefficient, respectively, are taken as the static friction coefficient and kinetic friction coefficient of the laminate 10.

[0030] <Print layer> The first printed layer 15a and the second printed layer 15b are layers on which a pattern or the like is printed, and are layers for improving the design of the laminate 10. The first printed layer 15a and the second printed layer 15b can be an ink composition obtained by adjusting the ink composition by adding one or more of ordinary ink vehicles as the main component, if necessary, optionally adding one or more of plasticizers, stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, and other additives, 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.

[0031] <Abrasion-resistant resin layer> The abrasion-resistant resin layer 22 is a layer for improving the abrasion resistance of the laminate 10 while also improving the bonding strength with the inner sealant layer 12. The abrasion-resistant resin layer 22 may contain linear low-density polyethylene. This makes it possible to more effectively improve the bonding strength with the inner sealant layer 12 containing linear low-density polyethylene. Note that the material constituting the abrasion-resistant resin layer 22 may be, for example, low-density polyethylene in addition to linear low-density polyethylene.

[0032] In addition, the first printed layer 15a is formed on the wear-resistant resin layer 22. For this reason, the wear-resistant resin layer 22 is preferably an extruded resin layer. Extruded resin layers have good compatibility with ink compositions. For this reason, when the wear-resistant resin layer 22 is an extruded resin layer, it becomes easier to form the first printed layer 15a on the wear-resistant resin layer 22.

[0033] In this embodiment, the thickness of the wear-resistant resin layer 22 is preferably 10 μm or more and 60 μm or less.

[0034] <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.

[0035] In this case, the outer sealant layer 11 may 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 obtained by modifying a polyolefin resin such as polyethylene or polypropylene 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.

[0036] 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 3The 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.

[0037] 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.

[0038] The outer sealant layer 11 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 raw material monomer may contain fossil fuel-derived ethylene or an α-olefin monomer such as butylene, hexene, or octene.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] In this embodiment, the thickness of the outer sealant layer 11 is preferably 50 μm or more and 250 μm or less.

[0043] <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.

[0044] 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.

[0045] 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.

[0046] <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.

[0047] As shown in Figure 2, the inner sealant layer 12 has multiple layers. In the example shown in Figure 2, 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.

[0048] In the inner sealant layer 12, the first inner layer 12a, the second inner layer 12b, and the third inner layer 12c can be made of the same materials as those used for the outer sealant layer 11. 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] The coefficient of dynamic friction of the inner surface 102 with respect to 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 sealant layer 80 (described later). Furthermore, since scratches on the inner sealant layer 12 can be prevented, the bonding strength between the inner sealant layer 12 and the outer sealant layer 11 (the abrasion-resistant resin layer 22) can be improved. Furthermore, since 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 sealant layer 80 (described later) and the like.

[0054] 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 static and dynamic friction coefficients of the inner surface 102 against metal can be measured by the static and dynamic friction coefficient measurement tests described above. During measurement, the test piece is placed on the counter material with the inner sealant layer 12 facing the counter material, and a sliding piece is placed on top of it.

[0055] In this embodiment, the thickness of the inner sealant layer 12 is preferably 50 μm or more and 250 μm or less.

[0056] <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.

[0057] 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.

[0058] 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.

[0059] In this embodiment, the thickness of the adhesive layer is preferably 3 μm or more and 60 μm or less.

[0060] The outer sealant layer 11, the base layer 13, the inner sealant layer 12, etc. may be laminated together by any method, such as wet lamination, dry lamination, solventless dry lamination, extrusion lamination, T-die coextrusion molding, coextrusion lamination, inflation, or any other method. When laminating as described above, the film may be subjected to pretreatment such as corona treatment or ozone treatment, if necessary.

[0061] <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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] The barrier layer 16 may also be a transparent vapor-deposited layer that can be formed by a conventionally known method. When the barrier layer 16 is a transparent vapor-deposited layer, the laminate 10 can be made transparent. In this case, the barrier layer 16 may be a transparent vapor-deposited layer made of a vapor-deposited layer of an inorganic oxide.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] <Other layers> Other layers, such as a concealing layer, may also be provided. The concealing layer is a layer that prevents color changes or variations in the colors of the layers from affecting the color of the pattern, etc., of the first printed layer 15a. An olefin resin may be used for the concealing layer. More specifically, it is preferable to use a polyethylene film such as low-density polyethylene, linear low-density polyethylene, or medium-density polyethylene 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.

[0071] 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.

[0072] (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.

[0073] First, the laminate 10 shown in FIG. 2 is prepared.

[0074] Next, a tube container 40 is manufactured from the obtained laminate 10.

[0075] 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).

[0076] 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. 2, etc.) provided on the outer surface 101 side of the laminate 10 and the inner sealant layer 12 (see FIG. 2, etc.) provided on the inner surface 102 side are melted and joined, forming a body seal portion 44.

[0077] 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.

[0078] Next, the above-mentioned tube container 40 is manufactured by compression molding.

[0079] 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.

[0080] 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)).

[0081] 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.

[0082] 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.

[0083] As described above, according to this embodiment, the laminate 10 includes the abrasion-resistant varnish layer 21, the first printed layer 15a, the abrasion-resistant resin layer 22, the outer sealant layer 11, and the inner sealant layer 12, which are arranged in this order from the outer surface 101 to the inner surface 102. The inner sealant layer 12 includes the first inner layer 12a, the second inner layer 12b, and the third inner layer 12c, which are 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. This allows the density of the entire inner sealant layer 12 to 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.

[0084] 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.

[0085] Furthermore, the coefficient of static friction of the outer surface 101 against metal is 0.25 or less, and the coefficient of dynamic friction of the outer surface 101 against metal is 0.20 or less. This prevents scratches on the outer surface of the body tube 41 even when the body tubes 41 rub against each other when filling the contents or when multiple tube containers 40 are packed in cardboard boxes or the like for shipping or storage.

[0086] Furthermore, the static friction coefficient of the inner surface 102 against metal is 0.40 or less, and the dynamic friction coefficient of the inner surface 102 against metal is 0.35 or less. This prevents scratches from occurring on the inner sealant layer 12. Furthermore, since scratches on the inner sealant layer 12 can be prevented, the bonding strength between the inner sealant layer 12 and the outer sealant layer 11 (the abrasion-resistant resin layer 22) can be improved. 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. Furthermore, since 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. [Example]

[0087] Next, a specific example of the above embodiment will be described.

[0088] Example 1 The laminate 10 shown in Fig. 2 was produced. First, a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name: EB522, thickness 12 µm) was prepared as the base layer 13. Next, a second printed layer 15b was formed on the polyethylene terephthalate film.

[0089] Furthermore, as the intermediate layer 17, a polyethylene terephthalate film (manufactured by Oike Kogyo Co., Ltd., trade name: Tetolite EXC-B, thickness 12 μm) provided with an aluminum vapor deposition layer (barrier layer 16) was prepared.

[0090] Furthermore, as the inner sealant layer 12, a polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: BCO LZ27N, average density: 0.927 g / cm 3 Both of these polyethylene films were three-layer films.

[0091] When producing a polyethylene film, first, 100 parts by mass of a 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 inner layer 12a. 3 A molten resin with a MFR of 2.1 g / 10 min and a biomass content of 0% was prepared.

[0092] The resin constituting the 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 The resin constituting the second inner layer 12b had an average density of 0.925 g / cm 3 , MFR: 1.0 g / 10 min, and biomass content of 87%. 3 It was.

[0093] Furthermore, the resin constituting the 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.

[0094] Next, these melts were co-extruded by inflation molding to produce a polyethylene film with a thickness ratio of 1:3:1 (first inner layer 12a: second inner layer 12b: 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%.

[0095] Next, the films for the base layer 13, the intermediate layer 17, and the inner sealant layer 12 were bonded together by dry lamination to produce an intermediate for the laminate 10. The layer structure of the obtained intermediate is as follows: PET / Mark / DL / ALM / PET / DL / PEF(PE / PE / PE) In the above, "PET" means polyethylene terephthalate film (same below). Also, "stamp" means printed layer (same below). Also, "DL" means adhesive layer made by dry lamination method using two-component curing adhesive (same below). Also, "ALM" means aluminum vapor deposition layer (same below). Also, "PEF" means polyethylene film (same below). Furthermore, "PE" means polyethylene (same below).

[0096] Next, as the outer sealant layer 11, a polyethylene film (manufactured by DNP Technopack Co., Ltd., trade name: SR-WN2, thickness 160 μm) was prepared.

[0097] Next, low-density polyethylene (manufactured by Japan Polyethylene Corporation, product name: LC600A) was extruded onto a polyethylene terephthalate film serving as the base layer 13 of the intermediate body to form an extruded polyethylene layer (first adhesive layer 14a) having a thickness of 25 μm. At this time, a polyethylene film serving as the outer sealant layer 11 was bonded via the extruded polyethylene layer (first adhesive layer 14a). Furthermore, low-density polyethylene (manufactured by Japan Polyethylene Corporation, product name: LC600A) was extruded onto the polyethylene film serving as the outer sealant layer 11 to form an abrasion-resistant resin layer 22 having a thickness of 25 μm.

[0098] Thereafter, a first printed layer 15a was formed on the abrasion-resistant resin layer 22 using a light-resistant ink (manufactured by Toyo Ink Co., Ltd., product name: FDFL MP). Furthermore, an abrasion-resistant varnish layer 21 was formed on the first printed layer 15a using a varnish (manufactured by Toyo Ink Co., Ltd., product name: FDFL AQF4). In this manner, a laminate 10 was produced. The layer structure of the obtained laminate 10 is as follows: Varnish / Mark / PE / PEF / PE / PET / Mark / DL / ALM / PET / DL / PEF(PE / PE / PE)

[0099] 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.

[0100] 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).

[0101] In this way, a total of 750 tube containers 40 were produced.

[0102] Example 2 A laminate and a tube container were produced in the same manner as in Example 1, except that a polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: SR-WN2, thickness 130 μm) was used as the outer sealant layer 11.

[0103] Example 3 A laminate and a tube container were produced in the same manner as in Example 1, except that linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., trade name: SP1070C) was used as the abrasion-resistant resin layer 22.

[0104] Example 4 A laminate and a tube container were produced in the same manner as in Example 3, except that a polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: SR-WN2, thickness 130 μm) was used as the outer sealant layer 11.

[0105] Example 5 The resin constituting the first inner layer 12a and the third inner layer 12c was a 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 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%.

[0106] Example 6 The resin constituting the first inner layer 12a and the third inner layer 12c was a 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 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 2, 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%.

[0107] Example 7 The resin constituting the 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 3The resin constituting the 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 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 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 0.921 g / cm 3 was used. 3 The biomass content of the polyethylene film was 50%.

[0108] Example 8 The resin constituting the 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 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 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 3 A 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%.

[0109] (Comparative Example 1) A laminate 100 shown in Fig. 7 was produced. This laminate includes, arranged in this order from the outer surface 111 to the inner surface 112, an outer sealant layer 110, a first adhesive layer 140a, a substrate layer 130, a printed layer 150, a second adhesive layer 140b, a barrier layer 160, an intermediate layer 170, a third adhesive layer 140c, and an inner sealant layer 120. Although not shown, each of the outer sealant layer 110 and the inner sealant layer 120 had multiple layers (three layers).

[0110] The outer sealant layer 110, first adhesive layer 140a, substrate layer 130, printed layer 150, second adhesive layer 140b, barrier layer 160, intermediate layer 170, third adhesive layer 140c and inner sealant layer 120 of the laminate 100 correspond to the outer sealant layer 11, first adhesive layer 14a, substrate layer 13, second printed layer 15b, second adhesive layer 14b, barrier layer 16, intermediate layer 17, third adhesive layer 14c and inner sealant layer 12 of the laminate 10, respectively.

[0111] When producing the laminate 100 according to Comparative Example 1, first, a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name: EB522, thickness 12 μm) was prepared as the base layer 130. Subsequently, a printed layer 150 was formed on the polyethylene terephthalate film.

[0112] Furthermore, as the intermediate layer 170, a polyethylene terephthalate film (manufactured by Oike Kogyo Co., Ltd., trade name: Tetolite EXC-B, thickness 12 μm) provided with an aluminum vapor deposition layer (barrier layer 160) was prepared.

[0113] 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 3 A polyethylene film (manufactured by DNP Technopack Co., Ltd., average density: 0.918 g / cm 3 ) was prepared as the inner sealant layer 12. 3Both of these polyethylene films were three-layer films. Of these, the polyethylene film serving as the inner sealant layer 12 had a density of 0.916 g / cm3 for the second inner layer. 3 , the density of the first inner layer and the third inner layer is 0.920 g / cm 3 As mentioned above, the layers (three layers) of the outer sealant layer 110 and the layers (three layers) of the inner sealant layer 120 are not shown in FIG.

[0114] 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 / ALM / PET / DL / PEF(PE / PE / PE) In the above, "ASPEF" means polyethylene film containing antistatic agent (the same applies below).

[0115] Furthermore, using the obtained laminate 100, a tube container was produced in the same manner as in Example 1.

[0116] (Comparative Example 2) A laminate and a tube container were produced in the same manner as in Comparative Example 1, except that a polyethylene film (manufactured by DNP Technopack Co., Ltd., product name: SR-WN2, thickness 180 μm) was used as the inner sealant layer 12.

[0117] <Static friction coefficient measurement test / Dynamic friction coefficient measurement test> The static and dynamic friction coefficients of the inner and outer 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 and kinetic friction forces 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 surface static and kinetic friction coefficients were used as the static and kinetic friction coefficients of the laminate.

[0118] <Rubbing test (JSPS test)> Rubbing tests were performed on the laminates of Example 1 to Comparative Example 2, simulating the conditions during transportation. A measuring device, FR-2 manufactured by Suga Test Instruments Co., Ltd., was used, and measurements were performed to meet JIS-L-0849. First, a rectangular laminate (30 mm wide) was fixed to the lower test piece stand, and a rectangular laminate (30 mm wide) made of the same material was attached to the upper friction element. The metal plate used in the rubbing test was a stainless steel plate with a smooth surface. The weight of the weight was 200 g. The rubbing test was repeated 100 times, and the number of scratches on the surface of the laminate was visually counted. If the number of scratches on the surface of the laminate was less than 10, the test result was rated A (good). If the number of scratches on the surface of the laminate was 10 to less than 20, the test result was rated B (acceptable). If the number of scratches on the surface of the laminate was 20 or more, the test result was rated C (poor).

[0119] <Evaluation of the joint strength of the body seal> The bondability of the body seal portion was evaluated for the laminates of Example 1 to Comparative Example 2. At this time, the meltability of the body seal portion was confirmed for each laminate using an optical microscope manufactured by Keyence Corporation. When the interface between the laminates in the body seal portion was not visible and the laminates were completely melted, the test result was rated A (good). When the interface between the laminates in the body seal portion was slightly visible, the test result was rated B (fair).

[0120] <Evaluation of the joint between the body tube and the head component> 8(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. In this manner, three test pieces S1 were prepared.

[0121] 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.

[0122] 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.).

[0123] During the measurement, first, as shown in Fig. 8(b), the body tube 41 and head member 43 of each test piece S1, S2 were partially peeled off. Next, as shown in Fig. 8(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.

[0124] <Appearance evaluation> Appearance evaluation was performed on the tube containers according to Example 1 to Comparative Example 2. At this time, each tube container was filled with the contents, and a bottom seal was formed by ultrasonic sealing. Then, the appearance of the tube container after the bottom seal was formed was checked for peeling and tearing. If no peeling or tearing occurred, the test result was rated A (good). If no peeling or tearing occurred, the test result was rated A (good). If peeling or tearing occurred but did not pose a quality problem, the test result was rated B (acceptable). If peeling or tearing occurred and there was a quality problem, the test result was rated C (unacceptable).

[0125] The results are shown in Figures 9 to 12. Figure 9 is a table showing the density and thickness of the inner sealant layer for 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 rubbing test. Figure 11 is a table showing the results of the bondability evaluation of the body seal and the bondability evaluation between the body tube and the head member. Figure 12 is a table showing the biomass degree of the inner sealant layer for Example 1 to Comparative Example 2.

[0126] 9 to 12, the tube containers according to Examples 1 to 8 were able to maintain the desired performance even when the thickness of the inner sealant layer was thinner than 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.

[0127] 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]

[0128] 10 Laminate 11 Outer sealant layer 12 Inner sealant layer 12a 1st inner layer 12b 2nd inner layer 12c 3rd inner layer 13 Base material layer 15a Printing layer 16 Barrier Layer 21 Wear-resistant varnish layer 22 Abrasion-resistant resin layer 40 tube containers 40A Tube with Cap 41 Body tube 42 one end 43 Head member 49 Cap 101 Exterior 102 Inside

Claims

1. The product comprises an abrasion-resistant varnish layer, a print layer, an abrasion-resistant resin layer, an outer sealant 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 0.93g / m or more ３ is as follows: the coefficient of static friction of said outer surface against metal is 0.25 or less; the coefficient of dynamic friction of said outer surface against metal is 0.20 or less; The coefficient of static friction of the inner surface against metal is 0.40 or less; A laminate in which the coefficient of dynamic friction of the inner surface against metal is 0.35 or less.

2. The laminate of claim 1 , wherein the inner sealant layer comprises a biomass-derived resin.

3. The laminate of claim 1 further comprising a substrate layer disposed between the outer sealant layer and the inner sealant layer.

4. The laminate of claim 3 further comprising a barrier layer disposed between the substrate layer and the inner sealant layer.

5. The laminate of claim 1 , wherein the abrasion-resistant varnish layer comprises an ultraviolet-curable resin.

6. The laminate according to claim 1 , wherein the abrasion-resistant resin layer comprises linear low-density polyethylene.

7. In a tube container, a body tube formed by overlapping and joining opposing edge portions of the laminate according to any one of claims 1 to 6; a head member joined to one end of the body tube.

8. In a tube container with a cap, The tube container according to claim 7; a cap attached to the head member.

Images