Packaging materials for tube containers and tube containers

Abstract

To provide a packaging material for a tube container and the tube container that are resistant for scratch even if the outer and inner surfaces of the tube container are rubbed during transportation or molding at high speed, and that maintain the appearance.SOLUTION: A packaging material 10 for a tube container comprises a first sealant layer 2 arranged in order from an outer surface to an inner surface, a printing base material layer 3A, and a second sealant layer 5. The first sealant layer 2 and / or the second sealant layer 5 have / has resin and wear-resistant particles contained in the resin. The wear-resistant particles contain ultra-high molecular weight polyethylene particulates.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to packaging materials for tube containers and tube containers. [Background technology]

[0002] Conventionally, tube containers are known to have a first sealant layer, a base layer, and a second sealant layer, which are sequentially stacked from the outside to the inside. The base layer also has printing applied to its inner surface.

[0003] By the way, when transporting tube containers, multiple tube containers are placed inside a cardboard box, and each cardboard box is transported separately.

[0004] However, during transport of the tube containers, friction between the containers could cause scratches on the outer surface (first sealant layer side), resulting in deterioration of the tube container's appearance. Additionally, during high-speed molding of the tube containers, friction between the tube container's inner surface (second sealant layer side) and the molding machine could cause scratches on the inner surface. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2005-178851 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] This invention was made with these points in mind, and aims to provide a packaging material for tube containers and a tube container that is resistant to scratches even when the outer or inner surface of the tube container is rubbed during transport or high-speed molding, and that maintains its appearance. [Means for solving the problem]

[0007] That is, the present invention provides a packaging material for a tube container, comprising a first sealant layer, a printing base material layer, and a second sealant layer, which are arranged in order from the outer surface toward the inner surface. The first and / or second sealant layer has a resin and wear-resistant particles contained in the resin, and the wear-resistant particles include ultra-high molecular weight polyethylene fine particles.

[0008] In addition, the present invention provides a tube container comprising a cylindrical body portion in which opposing ends of the above-described packaging material for a tube container are overlapped and joined to each other, and a head member joined to one end of the cylindrical body portion.

Advantages of the Invention

[0009] According to the present invention, even if tube containers rub against each other during transportation or at the time of high-speed molding, the tube containers are less likely to be damaged, and thus it is possible to provide a packaging material for a tube container and a tube container having an excellent appearance.

Brief Description of the Drawings

[0010] [Figure 1] (a) is a side cross-sectional view showing a laminated sheet of a packaging material for a tube container according to the first embodiment, (b) is a side cross-sectional view showing a laminated sheet of a packaging material for a tube container according to the second embodiment, (c) is a side cross-sectional view showing a laminated sheet of a packaging material for a tube container according to the third embodiment, (d) is a side cross-sectional view showing a laminated sheet of a packaging material for a tube container according to the fourth embodiment, (e) is a side cross-sectional view showing a laminated sheet of a packaging material for a tube container according to the fifth embodiment, and (f) is a side cross-sectional view showing a laminated sheet of a packaging material for a tube container according to the sixth embodiment. [Figure 2] Figure 2 is a diagram showing a method for manufacturing a tube container. [Figure 3] Figure 3 is a diagram showing a method for manufacturing a tube container. [Figure 4] Figure 4 is a side cross-sectional view showing a packaging product including a tube container. [Figure 5] Figure 5 is a diagram showing a method for manufacturing a tube container.

Embodiments for Carrying Out the Invention

[0011] The packaging material for tube containers and tube containers according to embodiments of the present invention will be described in more detail below with reference to drawings and other figures.

[0012] First, a tube container 20 created using the tube container packaging material 10 according to the present invention will be described with reference to Figures 2 through 4.

[0013] The tube container 20 comprises a cylindrical body 21 containing the tube container packaging material 10, and a shoulder portion 13 and a mouth portion 14 formed by applying resin to the cylindrical body 21 by compression molding. A cap 16 is attached to the mouth portion 14 of the tube container 20.

[0014] A tube container 20 having such a configuration is obtained through the following manufacturing process.

[0015] First, as shown in Figure 2, a cylindrical body 21 is manufactured by using the tube container packaging material 10 according to the present invention, overlapping a pair of bonding ends (hereinafter also referred to as both ends) 11, 11' of the tube container packaging material 10, and heat-sealing the outer and inner surfaces of the overlapping portion to form a heat-sealed portion 12. Next, as shown in Figure 3, the cylindrical body 21 is placed in a mold (not shown), and a shoulder portion 13 and a mouth portion 14 are formed at one opening 21A of the cylindrical body 21 by a conventional method such as compression molding. In this way, the shoulder portion 13 and the mouth portion 14 are integrally molded at one opening 21A of the cylindrical body 21 to produce a tube container 20. Then a cap 16 is attached to the mouth portion 14 of the tube container 20.

[0016] Next, as shown in Figure 4, an appropriate amount of contents 17, such as toothpaste or other items, is filled into the other opening 21B of the cylindrical body 21 of the tube container 20. After that, the other opening 21B is welded to form a bottom seal 18, and a packaged product 20A is obtained, which includes the tube container 20 filled with contents 17.

[0017] Next, the packaging material 10 for the tube container 20, which is used to manufacture the tube container 20, will be described with reference to Figures 1(a) to 1(f).

[0018] First, with reference to Figure 1(a), the packaging material 10 for the tube container 20 will be described. The packaging material 10 for the tube container of the first embodiment of the present invention consists of a laminated sheet having a first sealant layer 2 arranged sequentially from the outer surface to the inner surface, a printing substrate layer 3A having a printed portion 3a consisting of a substrate layer 3 and printing ink, and a second sealant layer 5, as shown in Figure 1(a). The first sealant layer 2 and / or the second sealant layer 5 have a resin and abrasion-resistant particles contained in this resin.

[0019] Furthermore, the first sealant layer 2 and the printing substrate layer 3A are joined by an adhesive layer 8, and the printing substrate layer 3A and the second sealant layer 5 are joined by an adhesive layer 8.

[0020] A second embodiment of the present invention will be described with reference to Figure 1(b). In the second embodiment shown in Figure 1(b), a gas barrier layer 4 is attached to the printed substrate layer 3A of the tube container packaging material 10 by dry lamination, and a second sealant layer 5 is attached to this gas barrier layer 4 by dry lamination. In the second embodiment shown in Figure 1(b), the other configurations are the same as in the first embodiment shown in Figures 1(a), 2 to 4. In the second embodiment shown in Figure 1(b), the same parts as in the first embodiment shown in Figures 1(a), 2 to 4 are denoted by the same reference numerals, and detailed descriptions are omitted.

[0021] A third embodiment of the present invention will be described with reference to Figure 1(c). In the third embodiment shown in Figure 1(c), the first sealant layer 2 is composed of a three-layer co-extruded laminated sheet consisting of a first resin layer 2a, a second resin layer 2b, and a third resin layer 2c. The first resin layer 2a contains the abrasion-resistant particles. In the third embodiment shown in Figure 1(c), the other components are the same as those in the first embodiment shown in Figures 1(a) and 2 to 4. In the third embodiment shown in Figure 1(c), the same parts as those in the first embodiment shown in Figures 1(a) and 2 to 4 are denoted by the same reference numerals, and detailed descriptions are omitted.

[0022] A fourth embodiment of the present invention will be described with reference to Figure 1(d). In the fourth embodiment shown in Figure 1(d), a gas barrier layer 4 is attached to the printed substrate layer 3A of the tube container packaging material 10 of the third embodiment by dry lamination, and a second sealant layer 5 is attached to this gas barrier layer 4 by dry lamination. In the fourth embodiment shown in Figure 1(d), the other configurations are the same as in the first embodiment shown in Figures 1(a) to (c) and Figures 2 to 4. In the fourth embodiment shown in Figure 1(d), the same reference numerals are used for parts that are the same as those in the embodiments shown in Figures 1(a) to (c) and Figures 2 to 4, and a detailed description is omitted.

[0023] A fifth embodiment of the present invention will be described with reference to Figure 1(e). In the fifth embodiment shown in Figure 1(e), the second sealant layer 5 of the second embodiment is composed of a three-layer co-extruded laminated sheet consisting of a first resin layer 5a (inner surface side), a second resin layer 5b, and a third resin layer 5c. The first resin layer 5a of the second sealant layer 5 contains the wear-resistant particles. In the fifth embodiment shown in Figure 1(e), the other configurations are the same as those in the embodiments shown in Figures 1(b), 2 to 4. In the fifth embodiment shown in Figure 1(e), the same parts as those in the first embodiment shown in Figures 1(a) to (b) and 2 to 4 are denoted by the same reference numerals, and detailed descriptions are omitted.

[0024] A sixth embodiment of the present invention will be described with reference to Figure 1(f). In the sixth embodiment shown in Figure 1(f), the second sealant layer 5 of the fourth embodiment is composed of a three-layer co-extruded laminated sheet consisting of a first resin layer 5a (inner surface side), a second resin layer 5b, and a third resin layer 5c. The first resin layer 5a of the second sealant layer 5 contains the wear-resistant particles. In the sixth embodiment shown in Figure 1(f), the other configurations are the same as those in the embodiments shown in Figures 1(d), 2 to 4. In the sixth embodiment shown in Figure 1(f), the same reference numerals are used for parts that are the same as those in the first embodiment shown in Figures 1(a) to 1(d) and 2 to 4, and a detailed description is omitted.

[0025] In this specification, "outer surface" and "inner surface" refer to the "outer surface" and "inner surface" when a tube container 20 is manufactured using the tube container packaging material 10. Figures 1 through 3 above illustrate an example of the tube container packaging material according to the present invention, and the present invention is not limited thereto.

[0026] Next, we will describe the materials of each component that make up the packaging material 10 for the tube container.

[0027] The first sealant layer 2 and the second sealant layer 5 may contain, for example, polyethylene (PE). Specifically, the first sealant layer 2 and the second sealant layer 5 may be made from the following materials.

[0028] The first sealant layer 2 and the second sealant layer 5 can be made of materials that can melt and fuse with each other by heat. For example, one or more resins can be used, such as low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene, polypropylene (PP), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene, or polyolefin resins modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc., as well as polyvinyl acetate resins, polyester resins, polystyrene resins, and other resins.

[0029] The first sealant layer 2 or the second sealant layer 5 is preferably made of polyethylene resin. Here, high-density polyethylene (HDPE) is used, and has a density of 0.945 g / cm³. 3 The above polyethylenes can be used, and as medium-density polyethylene (MDPE), the density is 0.930 g / cm³. 3 More than 0.942g / cm 3 Polyethylene with a density of less than 0.910 g / cm³ can be used, and as low-density polyethylene (LDPE), a density of 0.910 g / cm³ can be used. 3 More than 0.930g / cm 3 Polyethylene with a density of less than 0.910 g / cm³ can be used, and as linear low-density polyethylene (LLDPE), a density of 0.910 g / cm³ can be used. 3 More than 0.930g / cm 3 Polyethylene with a density of less than 0.910 g / cm³ can be used, and ultra-low density polyethylene has a density of 0.910 g / cm³. 3Polyethylene of a certain density or less can be used. Using low-density polyethylene (LDPE) can improve film-forming properties. Using medium-density polyethylene (MDPE) can improve scratch resistance. Furthermore, using linear low-density polyethylene (LLDPE) can improve the toughness of the film. Note that the polyethylene resin may also be biomass-derived resin.

[0030] In this invention, theoretically, if all ethylene derived from biomass is used as the raw material for polyethylene, the biomass-derived ethylene concentration will be 100%, and the biomass content of the biomass-derived polyolefin will be 100%. Furthermore, the biomass-derived ethylene concentration in fossil fuel-derived polyethylene produced solely from fossil fuel-derived raw materials will be 0%, and the biomass content of the fossil fuel-derived polyethylene will be 0%.

[0031] In the above-mentioned biomass-derived polyethylene film, it is preferable that the biomass content is between 5% and 95%. By setting the biomass content to 5% or more, the reduction of environmental impact can be improved. By setting the biomass content to 95% or less, the rigidity of the resin film can be improved.

[0032] 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 materials. The plant materials are not particularly limited, and conventionally known plants can be used. Examples include corn, sugarcane, beets, and manioc.

[0033] Furthermore, the above-mentioned LLDPE is a copolymer obtained by copolymerizing ethylene and α-olefins having 3 to 20 carbon atoms at low temperature and low pressure using a single-site catalyst such as a metallocene catalyst or a multi-site catalyst such as a Ziegler-Natta catalyst. Specific examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, and 1-dodecene. Copolymerization methods include low-pressure methods, slurry methods, solution methods, and gas-phase methods for polymerization of ethylene and α-olefins.

[0034] The LLDPE of this embodiment has 3 to 25 short-chain branches per 1000 carbon atoms, but is distinguished from LDPE by not having long-chain branches exceeding approximately 20 carbon atoms. Typically, in LLDPE, ethylene-derived structural units account for approximately 99.9 to 90 mol%, and α-olefin-derived structural units account for approximately 0.1 to 10 mol%.

[0035] In this embodiment, the first sealant layer 2 and the second sealant layer 5 mainly consist of, for example, one or more of the above-mentioned resins, and further contain abrasion-resistant particles in these resins.

[0036] Furthermore, the first sealant layer 2 and the second sealant layer 5 may be single layers, but they may also consist of multiple layers. The multiple layers are not limited to the three layers shown in Figures 1(c) to (f), but may consist of two or more layers, or even four or more layers.

[0037] The content of abrasion-resistant particles in the resin that forms the base material of the first sealant layer 2 and the second sealant layer 5 is preferably in the range of 0.1% by mass or more and 6.0% by mass or less, more preferably in the range of 0.2% by mass or more and 5.0% by mass or less, and even more preferably in the range of 1.0% by mass or more and 5.0% by mass or less. By setting the content of abrasion-resistant particles in the resin that forms the base material of the first sealant layer 2 to 0.1% by mass or more, the first sealant layer 2 can have excellent abrasion resistance. If it exceeds 6.0% by mass, it becomes difficult to uniformly add abrasion-resistant particles.

[0038] As the wear-resistant particles contained in the resins of the first sealant layer 2 and the second sealant layer 5, ultra-high molecular weight polyethylene fine particles are included.

[0039] The ultra-high molecular weight polyethylene of the present embodiment has an intrinsic viscosity-average molecular weight of 10×10 4 ~1000×10 4 This means that. It is preferable that the surface of the ultra-high molecular weight polyethylene fine particles is at least composed of ultra-high molecular weight polyethylene having a melt flow rate (MFR) of 1.6 g / 10 minutes or more. By having a melt flow rate of 1.6 g / 10 minutes or more, excellent wear resistance can be achieved. Also, from the viewpoint of productivity, it is preferably 3.0 g / 10 minutes or less.

[0040] It is preferable that the ultra-high molecular weight polyethylene fine particles of the present embodiment have a polyethylene content in the range of 50% by mass or more and 99% by mass or less, and more preferably in the range of 60% by mass or more and 95% by mass or less. When the polyethylene content is within the above range, it is excellent in terms of wear resistance.

[0041] The average particle diameter of the ultra-high molecular weight polyethylene fine particles of the present embodiment is not particularly limited, but from the viewpoint of moldability, it is preferably 1 μm to 20 μm, and more preferably 5 μm to 15 μm. When within the above range, when adjusting the resin composition, it has excellent handleability and can be uniformly added to the resin. Note that the average particle diameter of the ultra-high molecular weight polyethylene fine particles is the particle diameter at which the cumulative weight becomes 50%, that is, the median diameter.

[0042] For the first sealant layer 2, additives such as wear-resistant particles are added to the resin serving as the base material to prepare a resin composition, and then, using the resin composition prepared above, for example, a film or sheet can be formed using a T-die method, an inflation method, or other molding methods.

[0043] Furthermore, the materials used for the first sealant layer 2 and the second sealant layer 5 may optionally contain, for example, an antiblocking agent, a lubricant (such as a fatty acid amide), an antistatic agent, a flame retardant, an inorganic or organic filler, etc.

[0044] In this embodiment, the thickness of the first sealant layer 2 and the second sealant layer 5 is preferably 10 μm or more and 300 μm or less, and more preferably 30 μm or more and 250 μm or less.

[0045] The first sealant layer 2 and the second sealant layer 5 may be multilayered rather than single-layered. In the case of a multilayered configuration, it is preferable that at least the surface layer contains the wear-resistant particles.

[0046] In the first sealant layer 2 and the second sealant 5, the thickness of the surface layer (first resin layer) is 5 to 50% of the total thickness of each sealant layer, more preferably 10 to 30%. If the total thickness of the first resin layer is less than 5% of the total thickness, sufficient abrasion resistance will be difficult to obtain. Conversely, if it is thicker than 50%, there is a risk that the flexibility of the film and the lamination strength with the substrate, etc., cannot be ensured.

[0047] The first resin layer (surface layer) is preferably, for example, 2.5 to 50 μm thick in the case of the first sealant layer. The second resin layer is preferably, for example, 5 to 100 μm thick. The third resin layer is preferably, for example, 2.5 to 50 μm thick. In the case of the second sealant layer, the first resin layer (surface layer) is preferably, for example, 2.5 to 75 μm thick. The second resin layer is preferably, for example, 5 to 150 μm thick. The third resin layer is also preferably, for example, 2.5 to 150 μm thick. As a result, the first sealant layer 2 and the second sealant layer 5 of this embodiment can possess excellent abrasion resistance, flexibility, film formation stability, and heat sealability.

[0048] Furthermore, the base material layer 3 can be any material that has strength, toughness, and heat resistance, serving as the basic material for the tube container.

[0049] As materials constituting the base layer 3, for example, films or sheets of polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polyacetal resin, fluororesin, and other tough resins can be used.

[0050] Among the above, polyester resins, particularly polyethylene terephthalate (PET) resins, are preferred for forming the printed portion 3a. Here, polyethylene terephthalate resins refer to pure polyethylene terephthalate resins and various modified polyethylene terephthalate resins.

[0051] Furthermore, the base layer 3 can be any of the following: an unstretched film, or a stretched film stretched uniaxially or biaxially. In particular, in this embodiment, a biaxially oriented polyester resin film is preferred because it is superior in terms of forming the printed portion 3a.

[0052] In this embodiment, the thickness of the base layer 3 is preferably 10 μm or more and 25 μm or less.

[0053] Furthermore, the printed section 3a is a layer for forming patterns and designs on the body of the tube container.

[0054] The printed section 3a can be formed on the substrate layer 3 described above by printing methods such as gravure printing, letterpress printing, screen printing, transfer printing, flexographic printing, and inkjet printing.

[0055] There are no particular restrictions on the design; examples include letters, shapes, symbols, patterns, etc.

[0056] It is preferable that the printed portion 3a is formed on one or both sides of the base material layer 3, rather than on the outermost surface, so that damage to the pattern layer can be prevented by external impacts.

[0057] As the printing section 3a, an ink composition can be used that is prepared by mainly using one or more types of ordinary ink vehicles, optionally adding one or more of the following additives as needed: plasticizers, stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, and other additives, and further adding colorants such as dyes and pigments, and thoroughly mixing with a solvent, 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, ethylcellulose, chlorinated rubber, cyclized rubber, and others. One or more of these can be used in combination.

[0058] Furthermore, ink adhesion can be improved by performing surface treatments such as primer treatment or corona treatment on the substrate layer 3 before printing.

[0059] Examples of primer layer materials include non-curing or curing primer coating agents such as chlorinated polypropylene, ethyl vinyl acetate, styrene maleic acid, isocyanate, polyolefin, organic titanate, polyethyleneimine, polybutadiene, polyester, and acrylic.

[0060] The above-mentioned primer layer can be formed by coating using methods such as roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, drying the coating film to remove solvents and diluents, and then performing aging treatments as needed.

[0061] The gas barrier layer 4 is a layer designed to suppress the permeation of oxygen, water vapor, and other gases.

[0062] The gas barrier layer 4 may have a vapor-deposited layer. The vapor-deposited layer is preferably a layer consisting of one or more types selected from the group consisting of an aluminum vapor-deposited film, an aluminum oxide vapor-deposited film, and a silicon oxide vapor-deposited film.

[0063] As a method for forming a vapor-deposited layer, a vapor-deposited layer can be formed on a substrate film using a metal or inorganic oxide as a raw material, for example, by physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, ion plating, or cluster ion beam deposition, or by chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermochemical vapor deposition, or photochemical vapor deposition.

[0064] To explain in more detail, in the PVD method described above, for example, a winding type deposition machine is used, and the resin film coming out of the unwinding roll is placed into the deposition chamber in a vacuum chamber, where the deposition source heated in the crucible is evaporated, and if necessary, oxygen is blown out from the oxygen outlet, a deposition layer is formed on the resin film on the cooled coating drum via a mask, and then the resin film with the deposition layer formed on it is wound onto a winding roll, thereby producing a resin film having a deposition layer according to the present invention.

[0065] On the other hand, in the above-described CVD method, a mixed gas consisting of, for example, an organosilicon compound as a monomer gas, oxygen gas, and an inert gas supplied from a vapor deposition raw material volatilization supply device is introduced onto the resin film surface unwound from an unwinding roll placed in the vapor deposition chamber, and on the circumferential surface of the electrode drum, thereby producing a resin film in which a silicon oxide vapor deposition layer is formed by plasma. Furthermore, in the present invention, the resin film having such an inorganic oxide vapor deposition layer prevents the permeation of oxygen gas or water vapor from the contents of the tube container 20, and functions as a barrier layer against them.

[0066] In the above, the thickness of the vapor-deposited layer is preferably 5 to 300 nm, more preferably 10 to 200 nm, and even more preferably 10 to 100 nm, in order to obtain sufficient barrier properties. More specifically, in the PVD method described above, the thickness of the vapor-deposited layer made of aluminum oxide is preferably 20 to 100 nm, and more preferably around 30 to 50 nm. Furthermore, in the above-described CVD method, the thickness of the silicon dioxide deposition layer is preferably 5 to 50 nm, and more preferably 10 to 30 nm. In general, for vapor-deposited layers made of metal oxides and inorganic oxides, if the thickness of the vapor-deposited layer exceeds 200 nm, cracks and other defects are more likely to occur in the layer, which reduces its barrier properties and also increases material costs, making it undesirable. Furthermore, if the thickness is less than 10 nm, it becomes difficult to achieve oxygen barrier properties, which is also undesirable.

[0067] In this embodiment, the gas barrier layer 4 may include a barrier coat layer below or above the vapor-deposited layer. This improves the oxygen barrier and water vapor barrier properties of the contents of the tube container. If the resin film includes a vapor-deposited film, the barrier coating layer may be provided on or below the vapor-deposited film.

[0068] In this embodiment, the barrier coat layer includes ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, polyamides such as nylon 6, nylon 6,6 and polymethaxylylene adipamide (MXD6), polyester, polyurethane, and barrier resins such as (meth)acrylic resin. Among these, polyvinyl alcohol is preferred from the viewpoint of oil barrier, oxygen barrier, and water vapor barrier properties of the contents of the tube container 20. Furthermore, when the vapor-deposited film is composed of an inorganic oxide, the occurrence of cracks in the vapor-deposited film can be effectively prevented by incorporating polyvinyl alcohol into the barrier coat layer.

[0069] The barrier resin content in the barrier coat layer is preferably 50% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 90% by mass or less. By setting the barrier resin content in the barrier coat layer to 50% by mass or more, the oxygen barrier properties and water vapor barrier properties can be further improved.

[0070] The thickness of the barrier coat layer is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less. By making the barrier coating layer 0.01 μm or thicker, the oxygen barrier and water vapor barrier properties of the contents of the tube container can be further improved.

[0071] A barrier coating layer can be formed by dissolving or dispersing the above-mentioned material in water or a suitable solvent, applying it, and drying it. Alternatively, a barrier coating layer can also be formed by applying and drying a commercially available barrier coating agent.

[0072] In another embodiment, the barrier coating layer is a barrier coating film comprising at least one resin composition, such as a hydrolyzed metal alkoxide or a hydrolyzed condensate of a metal alkoxide, obtained by polycondensation of a mixture of a metal alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel catalyst, water, and an organic solvent. When the gas barrier layer 4 comprises a vapor-deposited film made of an inorganic oxide, the occurrence of cracks in the vapor-deposited film can be effectively prevented by providing the barrier coat layer of the above form adjacent to the vapor-deposited film.

[0073] In one embodiment, the metal alkoxide is represented by the following general formula. R 1 n M(OR 2 ) m (However, in the formula, R 1 , R 2(Each represents an organic group with 1 to 8 carbon atoms, M represents a metal atom, n represents a non-negative integer, m represents a non-negative integer, and n+m represents the valence of M.)

[0074] Examples of metal atoms M that can be used include silicon, zirconium, titanium, and aluminum. Also, R 1 and R 2 Examples of organic groups represented by include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, and i-butyl groups.

[0075] Examples of metal alkoxides that satisfy the above general formula include tetramethoxysilane (Si(OCH3)4), tetraethoxysilane (mass%) Si(OC2H5)4), tetrapropoxysilane (Si(OC3H7)4), and tetrabutoxysilane (Si(OC4H9)4).

[0076] Furthermore, it is preferable to use a silane coupling agent together with the above-mentioned metal alkoxide. As silane coupling agents, known organic reactive group-containing organoalkoxysilanes can be used, but organoalkoxysilanes having an epoxy group are particularly preferred. Examples of organoalkoxysilanes having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0077] Two or more of the above-mentioned silane coupling agents may be used, and it is preferable to use the silane coupling agent in an amount of about 1 to 20 parts by mass per 100 parts by mass of the total amount of the above-mentioned alkoxides.

[0078] As water-soluble polymers, polyvinyl alcohol and ethylene-vinyl alcohol copolymers are preferred, and from the viewpoint of oil barrier properties, oxygen barrier properties, water vapor barrier properties, water resistance, and weather resistance of the contents, it is preferable to use these in combination.

[0079] The water-soluble polymer content in the barrier coating film is preferably 5 parts by mass or more and 500 parts by mass or less per 100 parts by mass of metal alkoxide. By setting the water-soluble polymer content in the barrier coating film to 5 parts by mass or more per 100 parts by mass of metal alkoxide, the oil barrier, oxygen barrier, and water vapor barrier properties of the contents of the tube container can be further improved. Furthermore, by setting the water-soluble polymer content in the barrier coating film to 500 parts by mass or less per 100 parts by mass of metal alkoxide, the film-forming properties of the barrier coating film can be improved.

[0080] The thickness of the barrier coating film is preferably 0.01 μm to 100 μm, and more preferably 0.1 μm to 50 μm. This further improves the oxygen barrier and water vapor barrier properties of the contents of the tube container 20. By setting the thickness of the barrier coating film to 0.01 μm or more, the oxygen barrier and water vapor barrier properties of the contents of the tube container can be improved. Furthermore, when it is provided adjacent to a vapor-deposited film composed of inorganic oxides, it can prevent the occurrence of cracks in the vapor-deposited film.

[0081] A barrier coating film can be formed by applying a composition containing the above-mentioned materials using conventionally known methods such as roll coating (including gravure roll coaters), spray coating, dipping, brushing, bar coating, or applicators, and then polycondensing the composition by a sol-gel method. Suitable catalysts for the sol-gel process include acids or amine compounds. Suitable amine compounds include tertiary amines that are substantially insoluble in water and soluble in organic solvents, such as N,N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine. Among these, N,N-dimethylbenzylamine is preferred. The sol-gel catalyst is preferably used in an amount of 0.01 parts by mass or more and 1.0 part by mass or less per 100 parts by mass of metal alkoxide, and more preferably in an amount of 0.03 parts by mass or more and 0.3 parts by mass or less. The catalytic effect can be improved by using 0.01 parts by mass or more of the sol-gel catalyst per 100 parts by mass of metal alkoxide. Furthermore, by using 1.0 part by mass or less of the sol-gel catalyst per 100 parts by mass of metal alkoxide, the thickness of the formed barrier coating film can be made uniform.

[0082] The above composition may further contain an acid. The acid is used as a catalyst for the sol-gel process, mainly as a catalyst for the hydrolysis of alkoxides and silane coupling agents. As acids, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, as well as organic acids such as acetic acid and tartaric acid, can be used. The amount of acid used is preferably 0.001 moles or more and 0.05 moles or less relative to the total molar amount of the alkoxide and the alkoxide portion (e.g., silicate portion) of the silane coupling agent. The catalytic effect can be improved by using an amount of acid equal to 0.001 moles or more relative to the total molar amount of the alkoxide component (e.g., silicate portion) of the alkoxide and silane coupling agent. Furthermore, by limiting the amount of alkoxide (e.g., silicate portion) of the alkoxide and silane coupling agent to 0.05 moles or less relative to the total molar amount, the thickness of the formed gas barrier coating can be made uniform.

[0083] Furthermore, the above composition preferably contains water in a proportion of 0.1 moles to 100 moles, more preferably 0.8 moles to 2 moles, per mole of the total molar amount of alkoxide. By setting the water content to 0.1 moles or more per mole of the total molar amount of alkoxide, the oil barrier properties, oxygen barrier properties, and water vapor barrier properties of the contents of the tube container 20 of the present invention can be improved. Furthermore, by ensuring that the water content is 100 moles or more per mole of the total molar amount of alkoxide, the hydrolysis reaction can be carried out rapidly.

[0084] Furthermore, the above composition may contain an organic solvent. Examples of organic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butanol.

[0085] The following describes one embodiment of a method for forming a barrier coating film. First, a composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel catalyst, water, an organic solvent, and, if necessary, a silane coupling agent. A polycondensation reaction gradually proceeds within the composition. Next, the composition is applied to the substrate using the conventionally known method described above and dried. This drying further promotes the polycondensation reaction between the alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains one), forming a layer of composite polymer. Finally, a gas barrier coating film can be formed by heating the above composition at a temperature of 20 to 250°C, preferably 50 to 220°C, for 1 second to 10 minutes.

[0086] The same material as the substrate layer 3 described above can be used as the substrate layer supporting the above-mentioned vapor-deposited thin film.

[0087] Furthermore, the adhesive layer 8 is a layer for bonding the first sealant layer 2, the printing substrate layer 3A, the gas barrier layer 4, the second sealant layer 5, and so on. This adhesive layer 8 can be appropriately selected depending on the resin that makes up the layers to be bonded.

[0088] As the adhesive layer 8, for example, anchor coating agents such as isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, and organotitanium-based, or anchor coating agents and laminating adhesives such as polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, and other laminating adhesives can be used as desired.

[0089] Furthermore, suitable materials for the adhesive layer 8 include, for example, polyethylene, polypropylene, linear low-density polyethylene, ethylene-vinyl alcohol, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, ionomer, maleic anhydride-modified polyolefin resin, and the like.

[0090] In this embodiment, the thickness of the adhesive layer 8 is preferably 3 μm or more and 60 μm or less.

[0091] Furthermore, the lamination of the first sealant layer 2, the printing substrate layer 3A, the gas barrier layer 4, the second sealant layer 5, etc., can be carried out by, for example, wet lamination, dry lamination, solvent-free dry lamination, extrusion lamination, T-die co-extrusion molding, co-extrusion lamination, inflation lamination, or any other arbitrary method. In addition, when performing the lamination described above, if necessary, pre-treatments such as corona treatment or ozone treatment can be applied to the film.

[0092] Furthermore, the tube container packaging material 10 may have an intermediate layer between the gas barrier layer 4 and the second sealant layer 5, if necessary. The intermediate layer is provided to adjust the thickness of the laminated sheet of the tube container packaging material 10. Olefin resin can be used for the intermediate 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 intermediate layer. The thickness of the intermediate layer is preferably, for example, 50 μm to 200 μm.

[0093] Next, the head member 40 of the tube container 20 will be described.

[0094] The head member 40 has a mouth portion 14 and a shoulder portion 13 provided below the mouth portion 14.

[0095] Of these, the mouth portion 14 has a threaded portion that is screwed onto the cap 16.

[0096] Furthermore, the shoulder portion 13 has a shape in which the diameter gradually increases from the mouth portion 14 side toward the torso portion 21 side. The horizontal cross-section of this shoulder portion 13 is circular.

[0097] Furthermore, the head member 40 is made from a resin material such as high-density polyethylene (HDPE). In addition to high-density polyethylene as described above, the head member 40 of the tube container 20 can also be made from an ethylene-α·olefin copolymer polymerized using a metallocene catalyst.

[0098] Next, the cylindrical body portion 21 will be described. The body portion 21 of the tube container 20 shown in Figure 4 has a generally cylindrical shape. This cylindrical body portion 21 is made of laminated packaging material 10 for tube containers (see Figures 1 to 3), which is rolled into a cylindrical shape, and the opposing ends are overlapped and joined together, for example, by heat sealing. Therefore, the body portion 21 has a heat-sealed portion 12 along its longitudinal direction, where the laminated sheets are joined together.

[0099] The thickness of the body portion 21 is preferably, for example, 220 μm or more and 400 μm or less. By having a body portion thickness of 220 μm or more, the body portion of the tube container 20 can maintain a predetermined strength. This allows the body portion to maintain its self-supporting and shape-retaining properties when the tube container 20 is placed upside down. Furthermore, by having a body portion thickness of 400 μm or less, the manufacturing cost of the packaging material 10 for the tube container can be reduced, and moldability can be ensured when the head member is formed by compression molding.

[0100] Examples of heat sealing (welding) methods used when manufacturing the cylindrical body 21 of the tube container 20 include bar sealing, rotary roll sealing, belt sealing, impulse sealing, high-frequency sealing, ultrasonic sealing, and flame sealing.

[0101] Furthermore, in this embodiment, the joining of the head member 40 and the cylindrical body 21 of the tube container 20 is performed by heat welding when the head member 40 is formed by compression molding. However, it is not limited to this, and the joining of the head member and the cylindrical body of the tube container 20 may also be performed by injection molding.

[0102] Next, with reference to Figure 5, a method for manufacturing the tube container 20 described above using the compression molding method will be explained.

[0103] As shown in Figure 5(a), the cylindrical body (body 21) is inserted into the mandrel 72, and a mold 71 for compression molding the head member 40 is attached to one end of the mandrel 72. That is, the pre-formed cylindrical body (body 21) is inserted into the mandrel 72, whose tip is the core for compression molding the head member 40, and is then advanced into the cavity of the mold 71 for molding the head member 40 to a predetermined position.

[0104] Next, the head member 40 is compression molded by supplying molten resin from the resin supply device into the mold 71. In this case, by inserting the opening 21A at one end of the body 21 into the mold 71, the head member 40 is molded and at the same time the cylindrical body 21 is integrally fused to the head member 40. After that, the integrated head member 40 and body 21 are removed from the mold 71 and mandrel 72 to obtain a tube container 20 as shown in Figure 5(b).

[0105] Furthermore, when manufacturing a tube container with a cap, the cap 16 is prepared in parallel with the production of the tube container 20. In this case, the cap 16 is manufactured by injection molding using, for example, an injection molding machine (not shown). Then, by screwing the cap 16 onto the opening of the head member 40 of the tube container 20, the tube container with a cap shown in Figure 3 is obtained.

[0106] Furthermore, in the present invention, the contents to be filled and packaged can be filled into the opening at the lower end of the tube container 20 manufactured above before it is completed, and then the opening can be heat-sealed to form a bottom welded portion, thereby manufacturing the tube packaging (packaged product) 20A shown in Figure 4.

[0107] Examples of contents to be filled and packaged include toothpaste, cosmetics, glue, mustard paste, wasabi paste, cream, paint, ointment, pharmaceuticals, and others. [Examples]

[0108] Next, a specific example of the above embodiment will be described.

[0109] (Example 1) First, the resin composition constituting the first resin layer 2a of the first sealant layer 2 is linear low-density polyethylene (Prime Polymer Co., Ltd., product name "Evolu (registered trademark) SP2320", density 0.920 g / cm³). 3, 95.0% by mass) and ultra-high molecular weight polyethylene fine particles as abrasion-resistant particles {PM-200 (molecular weight 180 × 10) contained in the masterbatch LDPM1005C manufactured by Mitsui Chemicals Fine Co., Ltd. 4 A resin composition was prepared by thoroughly kneading 5.0% by mass of a substance with a melting point of 136°C, a viscosity of 10-15 dl / g, and an average particle size of 10 μm. Next, the resin constituting the second resin layer 2b and the third resin layer 2c of the first sealant layer 2 is linear low-density polyethylene (Prime Polymer Co., Ltd., product name "Evolu (registered trademark) SP2320", density 0.920 g / cm³). 3 I prepared ). Using the resin and resin composition prepared above, a first sealant layer 2 (thickness 130 μm) was manufactured by a three-layer co-extrusion film formation method using the inflation method, having a layer structure of first resin layer 2a (26 μm) / second resin layer 2b (78 μm) / second resin layer 2c (26 μm). In the description of laminated sheets in this specification, " / " indicates that the layers to the left and right of it are laminated and integrated.

[0110] On the other hand, a biaxially oriented polyethylene terephthalate film (12 μm thick) with corona discharge treatment on both sides was prepared as the base material layer 3. Next, using gravure printing, desired patterns, characters, and other printing information were printed on this corona discharge-treated surface using cyan, magenta, yellow, and black inks to form a printed area 3a. As a result, a printed base material layer 3A having the printed area 3a was manufactured.

[0111] Next, a dry laminating adhesive (RU-80 / H-5, manufactured by Rock Paint Co., Ltd.) was applied to the side of the biaxially oriented polyethylene terephthalate film opposite to the printing surface of the printed portion 3a, using the third resin layer surface of the first sealant layer 2 as the adhesive layer 8. Furthermore, a linear low-density polyethylene film (a film produced by the inflation method using Evolu® SP2320, manufactured by Prime Polymer Co., Ltd.) (180 μm) was applied as the second sealant layer 5 on the side of the printing surface of the biaxially oriented polyethylene terephthalate film using a roll-coating method with a polyurethane-based adhesive for dry lamination (main component: polyester resin, curing agent: aliphatic polyisocyanate, a two-component curing type urethane adhesive) at a rate of 4 g / m². 2 After coating and drying, the material was dry-laminated to obtain a raw material for tube container packaging 10. The layer structure is as follows.

[0112] First sealant layer 2: LLDPE layer (first resin layer 2a / second resin layer 2b / third resin layer 2c) (130 μm) / Adhesive layer 8: DL adhesive / Substrate layer 3: PET layer (12 μm) / Printed area 3a / Adhesive layer 8: DL adhesive / Second sealant layer 5: LLDPE layer (180 μm)

[0113] Using the tube container packaging material 10 obtained above, one side portion was overlapped with the other side portion using a mandrel to form a cylindrical shape, and the back layer and surface layer of the laminated sheet at the overlapping portion were welded by a heat welding method to obtain a cylindrical molded body.

[0114] Subsequently, a tube container according to Example 1 of the present invention was obtained by integrally molding a head member 40 onto this tubular molded body using a compression molding method. High-density polyethylene (HDPE) was used as the material for the head member 40.

[0115] In parallel with the production of the tube container 20, a polypropylene cap 16 was manufactured by injection molding. The resulting cap 16 was then screwed onto the opening 14 of the head member 40 of the tube container to create a tube container with a cap.

[0116] Because this capped tube container has abrasion-resistant particles on the outer surface of the tube container packaging material 10, even if the tube containers 20 rub against each other, the outer surface of the tube containers 20 will not be scratched, and the appearance of the tube containers can be maintained.

[0117] (Example 2) The resin composition constituting the first resin layer 2a of the first sealant layer 2 is linear low-density polyethylene film (product name "Uz3520L" manufactured by Prime Polymer Co., Ltd., density 0.931 g / cm³). 3 Except for the change made to ), a tube container packaging material 10 was obtained in the same manner as in Example 1, and a tube container 20 was manufactured. The layer structure of the tube container packaging material 10 is as follows.

[0118] First sealant layer 2: LLDPE layer (first resin layer 2a / second resin layer 2b / third resin layer 2c) (130 μm) / Adhesive layer 8: DL adhesive / Substrate layer 3: PET layer (12 μm) / Printed area 3a / Adhesive layer 8: DL adhesive / Second sealant layer 5: LLDPE layer (180 μm)

[0119] (Example 3) The resin composition constituting the first resin layer of the first sealant layer 2 is linear low-density polyethylene film (product name "Uz3520L" manufactured by Prime Polymer Co., Ltd., density 0.931 g / cm³). 3 )93.0% by mass, and ultra-high molecular weight polyethylene fine particles as abrasion-resistant particles {PM-200 (molecular weight 180 × 10) contained in the masterbatch LDPM1005C 4 A resin composition was prepared by thoroughly kneading 5.0% by mass of a material (melting point 136°C, average particle size 10 μm) and 2.0% by mass of a slip agent (product name "M425" manufactured by Ube Maruzen Polyethylene Co., Ltd.). Except for the above changes, a tube container packaging material 10 was obtained in the same manner as in Example 1, and a tube container 20 was made. The layer structure of the tube container packaging material 10 is as follows.

[0120] First sealant layer 2 LLDPE layer (first resin layer / second resin layer / third resin layer) (130 μm) / Adhesive layer 8 DL adhesive / Substrate layer 3 PET layer (12 μm) / Printed section 3a / Adhesive layer 8 DL adhesive / Second sealant layer 5 LLDPE layer (180 μm)

[0121] (Example 4) Except for laminating a biaxially oriented polyethylene terephthalate film (product name "1310" manufactured by Toray Film Processing Co., Ltd.), which has an aluminum vapor-deposited layer formed as a gas barrier layer 4 on the inner surface side of the printing substrate layer 3A, via a two-component curing urethane adhesive (product name "RU-080 / H-5" manufactured by Rock Paint Co., Ltd.) (3 μm), a tube container packaging material 10 was obtained in the same manner as in Example 1, and a tube container 20 was manufactured. The layer structure of the tube container packaging material 10 is as follows.

[0122] 1st sealant layer 2 LLDPE layer (1st resin layer / 2nd resin layer / 3rd resin layer) (130 μm) / Adhesive layer 8 DL adhesive / Substrate layer 3 PET layer (12 μm) / Printed area 3a / Adhesive layer 8 DL adhesive / (Deposition surface) Gas barrier layer 4 Aluminum vapor-deposited PET layer (12 μm) / Adhesive layer 8 DL adhesive / 2nd sealant layer 5 LLDPE layer (180 μm)

[0123] (Example 5) The resin composition constituting the first resin layer 2a of the first sealant layer 2 is linear low-density polyethylene film (product name "Uz3520L" manufactured by Prime Polymer Co., Ltd., density 0.931 g / cm³). 3 )93.0% by mass, and ultra-high molecular weight polyethylene fine particles as abrasion-resistant particles {PM-200 (molecular weight 180 × 10) contained in the masterbatch LDPM1005C 4 A resin composition was prepared by thoroughly kneading 5.0% by mass of a material (melting point 136°C, average particle size 10 μm) and 2.0% by mass of a slip agent (product name "M425" manufactured by Ube Maruzen Polyethylene Co., Ltd.). Except for the above changes, a tube container packaging material 10 was obtained in the same manner as in Example 4, and a tube container 20 was made. The layer structure of the tube container packaging material 10 is as follows.

[0124] 1st sealant layer 2 LLDPE layer (1st resin layer / 2nd resin layer / 3rd resin layer) (130 μm) / Adhesive layer 8 DL adhesive / Substrate layer 3 PET layer (12 μm) / Printed area 3a / Adhesive layer 8 DL adhesive / (Deposition surface) Gas barrier layer 4 Aluminum vapor-deposited PET layer (12 μm) / Adhesive layer 8 DL adhesive / 2nd sealant layer 5 LLDPE layer (180 μm)

[0125] (Example 6) The resin composition constituting the first resin layer 5a of the second sealant layer 5 is linear low-density polyethylene (product name "Uz3520L" manufactured by Prime Polymer Co., Ltd., density 0.931 g / cm³). 3 )95.0% by mass) and ultra-high molecular weight polyethylene fine particles as abrasion-resistant particles {PM-200 (molecular weight 180 × 10) contained in the masterbatch LDPM1005C manufactured by Mitsui Chemicals Fine Co., Ltd. 4 A resin composition was prepared by thoroughly kneading 5.0% by mass of a material with a melting point of 136°C and an average particle size of 10 μm. Next, the resin constituting the second resin layer 5b and the third resin layer 5c of the second sealant layer 5 is linear low-density polyethylene (Prime Polymer Co., Ltd., product name "Evolu (registered trademark) SP2320", density 0.920 g / cm³). 3 I prepared ). Using the resin and resin composition prepared above, a second sealant layer 5 (thickness 180 μm) was manufactured by a three-layer co-extrusion film formation method using the inflation method, having a layer structure of first resin layer 5a (45 μm) / second resin layer 5b (90 μm) / second resin layer 5c (45 μm). Except for changing the second sealant layer 5, a tube container packaging material 10 was obtained in the same manner as in Example 1, and a tube container 20 was manufactured. The layer structure of the tube container packaging material 10 is as follows.

[0126] First sealant layer 2 LLDPE layer (first resin layer / second resin layer / third resin layer) (130 μm) / Adhesive layer 8 DL adhesive / Substrate layer 3 PET layer (12 μm) / Printed section 3a / Adhesive layer 8 DL adhesive / Second sealant layer 5 LLDPE layer (first resin layer / second resin layer / third resin layer) (180 μm)

[0127] (Example 7) The resin composition constituting the first sealant layer 2 is linear low-density polyethylene (product name "Evolu® SP2320" manufactured by Prime Polymer Co., Ltd., density 0.920 g / cm³). 3 95.0% by mass) and ultra-high molecular weight polyethylene fine particles as abrasion-resistant particles {PM-200 (molecular weight 180 × 10¹³) contained in the masterbatch LDPM1005C manufactured by Mitsui Chemicals Fine Co., Ltd. 4 A resin composition was prepared by thoroughly kneading 5.0% by mass of a material with a melting point of 136°C and an average particle size of 10 μm. Using the resin and resin composition prepared above, a single-layer first sealant layer 2 (thickness 130 μm) was manufactured by an extrusion film formation method using the inflation method.

[0128] On the other hand, the resin composition constituting the first resin layer 5a of the second sealant layer 5 is linear low-density polyethylene (product name "Evolu (registered trademark) SP2320" manufactured by Prime Polymer Co., Ltd., density 0.920 g / cm³). 3 95.0% by mass) and ultra-high molecular weight polyethylene fine particles as abrasion-resistant particles {PM-200 (molecular weight 180 × 10¹³) contained in the masterbatch LDPM1005C manufactured by Mitsui Chemicals Fine Co., Ltd. 4 A resin composition was prepared by thoroughly kneading 5.0% by mass of a material with a melting point of 136°C and an average particle size of 10 μm. Next, the resin constituting the second resin layer 5b and the third resin layer 5c of the second sealant layer 5 is linear low-density polyethylene (Prime Polymer Co., Ltd., product name "Evolu (registered trademark) SP2320", density 0.920 g / cm³). 3 I prepared ). Using the resin and resin composition prepared above, a second sealant layer 5 (thickness 180 μm) was manufactured by a three-layer co-extrusion film formation method using the inflation method, having a layer structure of a first resin layer 5a (40 μm) / second resin layer 5b (100 μm) / third resin layer 5c (40 μm). Except for changing the first and second sealant layers, a tube container packaging material 10 was obtained in the same manner as in Example 1, and a tube container 20 was manufactured. The layer structure of the tube container packaging material 10 is as follows.

[0129] 1st sealant layer 2 LLDPE layer (130 μm) / Adhesive layer 8 DL adhesive / Substrate layer 3 PET layer (12 μm) / Printed area 3a / Adhesive layer 8 DL adhesive / 2nd sealant layer 5 LLDPE layer (1st resin layer / 2nd resin layer / 3rd resin layer) (180 μm)

[0130] (Example 8) The resin composition constituting the second sealant layer 5 is linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., product name "Uz3520L", density 0.931 g / cm³). 3 )95.0% by mass) and ultra-high molecular weight polyethylene fine particles as abrasion-resistant particles {PM-200 (molecular weight 180 × 10) contained in the masterbatch LDPM1005C manufactured by Mitsui Chemicals Fine Co., Ltd. 4 A resin composition was prepared by thoroughly kneading 5.0% by mass of a material with a melting point of 136°C and an average particle size of 10 μm. Using the resin and resin composition prepared above, a single-layer second sealant layer 5 (180 μm thick) was manufactured by an extrusion film formation method using the inflation method. Except for changing the second sealant layer 5 from a multilayer to a single layer, a tube container packaging material 10 was obtained in the same manner as in Example 7, and a tube container 20 was manufactured. The layer structure of the tube container packaging material 10 is as follows.

[0131] First sealant layer 2: LLDPE layer (130 μm) / Adhesive layer 8: DL adhesive / Substrate layer 3: PET layer (12 μm) / Printed area 3a / Adhesive layer 8: DL adhesive / Second sealant layer 5: LLDPE layer (180 μm)

[0132] (Example 9) Except for preparing the resin composition by blending 97.0% by mass of linear low-density polyethylene and 3.0% by mass of ultra-high molecular weight polyethylene fine particles as abrasion-resistant particles, a tube container packaging material 10 was obtained in the same manner as in Example 1, and a tube container 20 was manufactured. The layer structure of the tube container packaging material 10 is as follows.

[0133] First sealant layer 2: LLDPE layer (first resin layer 2a / second resin layer 2b / third resin layer 2c) (130 μm) / Adhesive layer 8: DL adhesive / Substrate layer 3: PET layer (12 μm) / Printed area 3a / Adhesive layer 8: DL adhesive / Second sealant layer 5: LLDPE layer (180 μm)

[0134] It is also possible to combine the multiple components disclosed in the above embodiment as needed. Alternatively, some components may be removed from all the components shown in the above embodiment.

[0135] (Comparative Example 1) A laminated sheet of packaging material 10 for tube containers was obtained in the same manner as in Example 1, except that abrasion-resistant particles were not added to the resin constituting the first resin layer of the first sealant layer 2, and a tube container was manufactured.

[0136] (Comparative Example 2) A laminated sheet of packaging material 10 for tube containers was obtained in the same manner as in Example 2, except that abrasion-resistant particles were not added to the resin constituting the first resin layer of the first sealant layer 2, and a tube container was manufactured.

[0137] [Surface scratch resistance] The surface scratch resistance of the laminated sheets of the tube container packaging material 10 obtained in Examples 1-9 and Comparative Examples 1-2 was measured. For Examples 1-5 and 9, the surface on the first sealant side 2 was measured, and for Examples 6-8, the surface on the second sealant side 5 was measured. The results are shown in Tables 1 and 2. The measuring instrument used was a FR-2 manufactured by Suga Test Instruments Co., Ltd., and the JSPS friction test was performed in accordance with JIS L-0849. When performing the test, a strip-shaped (30 mm wide) laminated sheet of the tube container packaging material 10 was fixed to the lower test specimen stand, and a strip-shaped (30 mm wide) laminated sheet of the tube container packaging material 10 made of the same material was attached to the upper friction element. When performing the friction test between the laminated sheet of the tube container packaging material 10 and a metal plate, the metal plate was attached to the upper friction element and this friction element was slid. The metal plate used in this JSPS friction test was made of stainless steel with a smooth, mirror-like surface. A 200g weight was used. The JSPS friction test was repeated 100 and 300 times.

[0138] Furthermore, the scratch resistance was measured using the same material combination as the surface of the laminated sheet of the tube container packaging material 10, simulating friction between the first sealant layers 2 of the tubes during transport. In addition, the metal surface on the friction target surface is assumed to be in contact with metal parts such as guide components during the high-speed molding, filling, and packaging processes of the tube container.

[0139] <Evaluation Criteria> The number of scratches on the surface of the laminated sheet of the tube container packaging material 10 was counted visually. Samples with 21 or more scratches were marked as × (poor), samples with 1 to 20 scratches were marked as ○ (good), and samples with no scratches were marked as ◎ (best).

[0140] [Table 1]

[0141] [Table 2]

[0142] As shown in Tables 1 and 2, the laminated sheets of the tube container packaging material 10 in Examples 1 to 9 exhibited superior scratch resistance compared to Comparative Examples 1 and 2.

[0143] [Transportation Test] Tube containers made from the packaging materials described in Examples 1-9 and Comparative Examples 1-2 were prepared, and 80g of the treatment was filled into these tube containers.

[0144] Multiple tube containers containing various contents were placed inside a cardboard box, and a round-trip transport test was conducted over a distance of approximately 200 km. The presence or absence of damage to the outer surface of the containers was measured. The results are shown in Table 3.

[0145] <Evaluation Criteria> The number of scratches on the surface of the packaging material was counted. Containers with 20 or more scratches per tube were marked with a × (indicating a failure in the transport test), those with 10 to 20 scratches were marked with a △ (indicating a failure in the transport test), and those with fewer than 10 scratches were marked with a ○ (indicating a failure in the transport test).

[0146] [Table 3]

[0147] As shown in Table 3, the laminated sheets of the tube container packaging material 10 in Examples 1 to 9 were found to have fewer scratches during transport tests compared to Comparative Examples 1 and 2. [Explanation of Symbols]

[0148] 2. First sealant layer 2a 1st resin layer 2b 2nd resin layer 2c 3rd resin layer 3 Base material layer 3a Printing Department 3A Printing base material layer 4. Gas barrier layer 5. Second sealant layer 5a 1st resin layer 5b 2nd resin layer 5c 3rd resin layer 8 Adhesive layer 10 Packaging materials for tube containers 20 Tube containers 11,11' Pair of bonded ends 20 Tube containers 20A packaging products 21. Cylindrical body (body)

Claims

1. In packaging materials for tube containers, It comprises a first sealant layer, a printing substrate layer, and a second sealant layer, arranged sequentially from the outer surface to the inner surface. The first sealant layer and / or the second sealant layer comprises a resin and wear-resistant particles contained in the resin. The abrasion-resistant particles include ultra-high molecular weight polyethylene fine particles. The polyethylene content of the aforementioned ultra-high molecular weight polyethylene fine particles is 50% by mass or more and 99% by mass or less. The melt flow rate of the aforementioned ultra-high molecular weight polyethylene fine particles is 1.6 g / 10 min or more and 3.0 g / 10 min or less. The packaging material for the tube container has a thickness of 220 μm or more and 400 μm or less.

2. The abrasion-resistant particles are contained in the first sealant layer and / or the second sealant layer in an amount of 0.1% by mass or more and 6.0% by mass or less, according to claim 1, for packaging tube containers.

3. The packaging material for a tube container according to claim 1 or 2, wherein the first sealant layer and / or the second sealant layer comprises a polyethylene resin and the abrasion-resistant particles contained in the polyethylene resin.

4. The packaging material for a tube container according to any one of claims 1 to 3, wherein the first sealant layer and / or the second sealant layer consists of multiple layers and contains the abrasion-resistant particles in at least the surface layer.

5. A packaging material for a tube container according to any one of claims 1 to 4, further comprising a gas barrier layer.

6. A tube container comprising a cylindrical body formed by overlapping and joining opposing ends of a packaging material for a tube container according to any one of claims 1 to 5, and a head member joined to one end of the cylindrical body.

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