Laminate tube container and packaging article

Abstract

To provide a laminate tube container capable of improving quality and appearance even if a recycled resin is contained in at least one of a cap and a cap mounting part, and a packaged article.SOLUTION: A laminated tube container comprising a body portion obtained using a laminate comprising a first sealant layer, a substrate, and a second sealant layer in this order, a cap attachment portion provided on the body portion and having a mouth portion, and a cap to be attached to the mouth portion, wherein at least one of the cap and the cap attachment portion is composed of a polyolefin resin molded body containing a recycled resin, and the recycled resin is a chemically recycled resin.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to laminated tube containers and packaging articles. [Background technology]

[0002] Laminated tube containers are known as packaging containers suitable for packaging toothpaste and the like. For example, the laminated tube container described in Patent Document 1 below is known as such a laminated tube container. Patent Document 1 below describes a laminated tube container comprising a container body and a cap, the container body comprising a cylindrical body portion whose lower end is closed and a cap attachment portion provided on the body portion, the cap attachment portion having a truncated cone-shaped shoulder portion connected to the upper end of the cylindrical container body portion and a mouth portion connected to the shoulder portion, and the cap being attached to the mouth portion, wherein the shoulder portion and the mouth portion are made of a polymer having a density of 0.880 to 0.925 g / cm 3 polymerized using a single-site catalyst. 3 Laminated tube containers are known that are molded using ethylene-α-olefin copolymers as the molding material. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 10-249966 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, from the viewpoint of environmental consideration, there has been a demand for the use of recycled materials in order to reduce the amount of petroleum materials used, reduce waste, and make effective use of resources. Therefore, it is considered to use recycled resin as the resin for laminated tube containers. In this case, it is desirable to use recycled resin for the cap of the laminated tube container, which does not come into direct contact with the contents, or for the cap attachment portion, which comes into contact with the contents for a relatively short period of time.

[0005] However, if the recycled resin is a so-called material recycled resin, impurities or foreign matter such as gels or aggregates may appear on the surface of the cap or cap attachment part of the laminated tube container. Furthermore, if the recycled resin is a material recycled resin, the cap or cap attachment part tends to turn yellow or darker in color, which may make the cap or cap attachment part appear less hygienic. Therefore, it is believed that there is room for improvement in the appearance of laminated tube containers. Furthermore, thermal degradation of the recycled resin in the cap or cap attachment portion may result in the generation of odorous components. Furthermore, the inclusion of a large amount of foreign matter from the recycled resin during molding of the cap or cap attachment portion may impair kneading in the injection screw, potentially increasing the amount of carbonized material in the cap or cap attachment portion. Furthermore, the presence of unmelted material in the cap or cap attachment portion may cause poor fitting, potentially resulting in leakage of the contents from the cap or cap attachment portion. Furthermore, if a large sink mark originating from the core of a foreign matter occurs during injection molding of the cap or cap attachment portion, it may impair the weldability of the cap attachment portion. For these reasons, laminated tube containers are considered to have room for improvement in terms of quality.

[0006] An object of the present disclosure is to provide a laminated tube container and a packaging article that can improve quality and appearance even when recycled resin is contained in at least one of the cap and the cap attachment portion. [Means for solving the problem]

[0007] One aspect of the present disclosure provides a laminated tube container comprising a body obtained using a laminate having a first sealant layer, a substrate, and a second sealant layer in this order, a cap attachment portion provided on the body and having a mouth, and a cap attached to the mouth, wherein at least one of the cap and the cap attachment portion is made of a polyolefin resin molded product containing recycled resin, and the recycled resin is a chemically recycled resin. According to the laminated tube container, even if recycled resin is contained in at least one of the cap and the cap attachment portion, the quality and appearance can be improved. More specifically, in the laminated tube container, at least one of the cap and cap attachment part is made of a polyolefin resin molded product containing recycled resin, and the recycled resin is chemically recycled resin. Chemically recycled resin is produced by first depolymerizing discarded resin through a process appropriate for the material's characteristics, such as monomerization via gasification or oil-refined naphtha, or by depolymerization to monomerize the resin. Therefore, chemically recycled resin is less likely to be contaminated with impurities or foreign matter such as gels or aggregates, compared to material recycled resin, which is a resin made by cleaning, crushing, and then heating and melting recovered resin products such as used packaging materials to recycle them into raw materials. This reduces the appearance of foreign matter such as gels or aggregates on the surface of the cap or cap attachment part. Furthermore, because the recycled resin is chemically recycled resin, the cap or cap attachment part is less likely to yellow or turn dark. Therefore, the appearance of a laminated tube container can be improved even if the cap or cap attachment part contains recycled resin. Furthermore, unlike material recycled resins, chemically recycled resins are not subject to heat treatments such as melting after the recycling process, making them less susceptible to thermal degradation and odorous emissions. Furthermore, because at least one of the cap and cap attachment part is made of a polyolefin resin molded body containing recycled resin, and the recycled resin is chemically recycled, contaminants originating from the material recycled resin are not introduced during molding of the cap or cap attachment part, preventing impediments to kneading in the injection screw and reducing the buildup of carbonized material in the cap or cap attachment part. Furthermore, unmelted material is prevented from being present in the cap or cap attachment part, reducing attachment failures and reducing leakage of contents from the gap between the cap and the opening of the cap attachment part. Furthermore, contaminants originating from the material recycled resin are not introduced during molding of the cap or cap attachment part, reducing the likelihood of large sink marks originating from the core of the contaminants during injection molding of the cap or cap attachment part.Therefore, the quality of the laminated tube container can be improved even if recycled resin is contained in at least one of the cap and the cap attachment portion.

[0008] The proportion of chemically recycled resin in the laminated tube container is preferably 10% or more, more preferably 20% or more, even more preferably 25% or more, and particularly preferably 30% or more, where the unit of recycled resin proportion is mass% or volume%. If the proportion of chemically recycled resin in the laminated tube container is 10% or more, the environmental load can be reduced.

[0009] In the laminated tube container, the recycled resin may include post-consumer recycled resin (PCR). PCR can reduce the cost of laminated tube containers because it can be sold in large quantities on the market. The recycled resin may be a combination of PCR and post-industrial recycled resin (PIR).

[0010] At least one of the cap attachment portion and the cap may be colored.

[0011] In the laminated tube container, the laminate may further include a second substrate between the first sealant layer and the substrate and / or between the second sealant layer and the substrate. In this case, the base material is reinforced by the second base material, and therefore the strength of the body portion can be further improved.

[0012] In the laminated tube container, the laminate may further include a gas barrier layer at least one between the first sealant layer and the substrate and between the second sealant layer and the substrate. In this case, the gas barrier properties of the body are further improved, and therefore, when contents are placed in a laminated tube container obtained by fabricating a body using the laminate and attaching a cap attachment part and a cap, deterioration of the contents due to gases such as oxygen can be effectively suppressed.

[0013] Yet another aspect of the present disclosure provides a packaged article including the laminated tube container described above and a content contained in the laminated tube container. The packaging article includes a laminated tube container, and the quality and appearance of the laminated tube container can be improved even if recycled resin is contained in at least one of the cap and the cap attachment part. Therefore, the quality and appearance of the packaging article can be improved even if recycled resin is contained in at least one of the cap and the cap attachment part. [Effects of the Invention]

[0014] According to the present disclosure, a laminated tube container and a packaged article are provided that can improve quality and appearance even when recycled resin is contained in at least one of the cap and the cap attachment portion. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a packaging article according to the present disclosure. [Figure 2] FIG. 2 is a cross-sectional view showing one embodiment of a laminate that forms the body of the laminate tube container of FIG. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, an embodiment of the packaging article of the present disclosure will be described in detail. In the drawings, the same or corresponding parts are designated by the same reference numerals, and duplicated explanations will be omitted. Fig. 1 is a cross-sectional view showing one embodiment of the packaging article of the present disclosure, and Fig. 2 is a cross-sectional view showing one embodiment of a laminate that forms the body of the laminated tube container of Fig. 1.

[0017] The packaged article 500 shown in FIG. 1 includes a laminated tube container 400 and a content C contained in the laminated tube container 400. The laminated tube container 400 includes a body 300, a cap attachment part 310 provided on the body 300 and having a mouth 311, and a cap 320 attached to the mouth 311. At least one of the cap attachment part 310 and the cap 320 is made of a polyolefin resin molded product containing recycled resin, and the recycled resin is a chemically recycled resin. The body 300 is obtained using the laminate 100. As shown in FIG. 2, the laminate 100 includes a first sealant layer 40, a substrate 10, and a second sealant layer 30. The laminate 100 may further include a second substrate 20 between the substrate 10 and the second sealant layer 30 (see FIG. 2). The laminate 100 may include a second substrate 20 between the first sealant layer 40 and the substrate 10, or may include a second substrate 20 between the first sealant layer 40 and the substrate 10, and between the substrate 10 and the second sealant layer 30. The laminate 100 may further include a printed layer 50 .

[0018] The packaged article 500 includes a laminated tube container 400, and the quality and appearance of the laminated tube container 400 can be improved even if recycled resin is contained in at least one of the cap attachment portion 310 and the cap 320. Therefore, the quality and appearance of the packaged article 500 can be improved even if recycled resin is contained in at least the cap 320 or the cap attachment portion 310.

[0019] The body part 300, the cap attachment part 310, the cap 320 and the contents C will be described in detail below.

[0020] <<Body>> The body portion 300 is obtained using a laminate 100 including a first sealant layer 40, a substrate 10, and a second sealant layer 30. Specifically, the body portion 300 is obtained by rolling the laminate 100, for example with the first sealant layer 40 facing outward, forming a first sealed portion 301 with parts of the laminate 100 overlapping each other to form a cylindrical body, and heat-sealing the end of the cylindrical body to form a second sealed portion 302.

[0021] <Base material> The substrate 10 contains a resin. Examples of such resins include polyolefin resins, polyester resins, and polyamide resins. Among them, polyester resins are preferred from the viewpoint of mechanical strength.

[0022] Examples of polyolefin resins include polyethylene and polypropylene.

[0023] Polyethylene is a resin containing ethylene as a structural unit. Examples of polyethylene include ethylene homopolymers and copolymers of ethylene with other monomers. The proportion of ethylene in polyethylene is, for example, 80 mol % or more. Examples of other monomers include α-olefins, vinyl acetate, and acrylic esters. The α-olefin may be an olefin having a carbon number in the range of 3 to 20. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene. Examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, etc. These may be used alone or in combination of two or more.

[0024] Polypropylene is a resin containing propylene as a structural unit, but may not contain ethylene as a structural unit, and may be a copolymer of propylene alone or with ethylene or various α-olefins. Examples of polypropylene include homopolypropylene, block polypropylene, and random polypropylene.

[0025] Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Of the above resins, polyester resins are preferred from the viewpoint of ensuring strength, and polyethylene terephthalate is preferred from the viewpoint of ease of availability.

[0026] Examples of polyamide resins include nylon 6, nylon 6,6, a copolymer of nylon 6 and nylon 6,6, nylon 9T, nylon 10, polymetaxylylene adipamide (MXD6), nylon 11, nylon 12, and the like.

[0027] The resin may be a non-recycled resin, a recycled resin, or a mixture thereof.

[0028] The non-recycled resin may be a petroleum-derived resin obtained using petroleum-derived raw material monomers, a biomass-derived resin obtained using biomass-derived raw material monomers, or a mixture thereof, but from the viewpoint of reducing the environmental load, a biomass-derived resin is preferred.

[0029] When the resin contains recycled resin, the substrate 10 does not come into direct contact with the contents C, and therefore the recycled resin may be either material recycled resin or chemical recycled resin. When the contents C are placed in the laminated tube container 400, the contents C come into contact with the body 300 of the container body for a long period of time. However, when the recycled resin contains chemical recycled resin, chemical recycled resin is more hygienic than material recycled resin, and foreign matter is prevented from being mixed into the contents C. Furthermore, when the recycled resin is material recycled resin, costs and energy consumption in the recycling process can be reduced.

[0030] The recycled resin may include a material recycled resin, but the material recycled resin is preferably material recycled polyethylene terephthalate. Currently, collection and recycling schemes for material recycled polyethylene terephthalate have been established, and the supply is relatively stable. Therefore, if the recycled resin contained in the substrate 10 includes material recycled polyethylene terephthalate among all recycled resins, a more stable supply of the laminate 100 is possible. Furthermore, since recycling processes for material recycled polyethylene terephthalate are well established, it is more hygienic than material recycled resins other than material recycled polyethylene terephthalate. However, from the viewpoint of hygiene, chemically recycled polyethylene terephthalate is more preferable than material recycled polyethylene terephthalate.

[0031] The recycled resin may be post-consumer recycled resin (PCR), post-industrial recycled resin (PIR), or a mixture thereof, but is preferably PCR. PCR can be secured in large quantities on the market, so if the recycled resin is PCR, the cost of the laminate 100 can be reduced and the laminate 100 can be supplied more stably.

[0032] Furthermore, the substrate 10 may be composed of a single layer or a laminate of multiple layers. When the substrate 10 is composed of a laminate of multiple layers and contains a recycled resin, it is sufficient that at least one layer of the substrate 10 contains a recycled resin. Furthermore, the substrate 10 may be a layer formed by co-extrusion of a layer made of ethylene-vinyl alcohol copolymer or a layer made of polyamide, optionally with an adhesive resin, and then stretching the resulting film. Examples include a three-type five-layer substrate made of recycled resin / adhesive resin / ethylene-vinyl alcohol copolymer / adhesive resin / recycled resin, a three-type three-layer substrate made of recycled resin / adhesive resin / ethylene-vinyl alcohol copolymer, and a multi-type multilayer substrate made of petroleum-derived (natural) resin / recycled resin / petroleum-derived (natural) resin, etc. In the multilayer substrate 10, materials of the same type may have different specific gravities depending on their functions.

[0033] The substrate 10 may further contain additives such as fillers, antistatic agents, plasticizers, lubricants, light-shielding pigments, and antioxidants, as needed. When the substrate 10 contains a light-shielding pigment, the substrate 10 can function as a light-shielding layer.

[0034] The substrate 10 may be an unstretched film or a stretched film. The stretched film may be a uniaxially stretched film or a biaxially stretched film. When the substrate 10 is a uniaxially stretched film, the tear resistance and heat resistance of the laminate 100 can be improved. When the substrate 10 is a biaxially stretched film, the mechanical strength and dimensional stability of the laminate 100 can be improved.

[0035] When an adhesive layer is provided on the surface of the substrate 10, various pretreatments such as corona treatment, plasma treatment, ozone treatment, and flame treatment may be performed on the surface on the adhesive layer side in order to enhance adhesion to the adhesive layer, or a coating layer such as an easy-adhesion layer may be provided.

[0036] The thickness of the substrate 10 is not particularly limited and is, for example, 10 μm or more and 100 μm or less. From the viewpoint of obtaining excellent heat resistance, impact resistance, and gas barrier properties, the thickness of the substrate 10 is preferably 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, or 40 μm or more. Furthermore, from the viewpoint of reducing materials to reduce environmental impact, the thickness of the substrate 10 is preferably 60 μm or less, or 50 μm or less.

[0037] <First sealant layer> The first sealant layer 40 is a layer that is bonded to the second sealant layer 30 when manufacturing the cylindrical body portion 300 by overlapping parts of the laminate 100 and applying heat and pressure, and contains a resin.

[0038] Examples of such resins include polyolefin resins and polyester resins. Polyolefin resins are suitable for use in terms of sealing suitability, etc., while polyester resins are preferred in terms of low content adsorption and flavor barrier properties.

[0039] Examples of polyolefin resins include polyethylene and polypropylene.

[0040] Polyethylene is a resin containing ethylene as a structural unit. Examples of polyethylene include ethylene homopolymers and copolymers of ethylene with other monomers. The proportion of ethylene in polyethylene is, for example, 80 mol % or more. Examples of other monomers include α-olefins, vinyl acetate, and acrylic esters. The α-olefin may be an olefin having a carbon number in the range of 3 to 20. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene. Examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, etc. These may be used alone or in combination of two or more.

[0041] Polypropylene is a resin containing propylene as a structural unit, but may not contain ethylene as a structural unit, and may be a copolymer of propylene alone or with ethylene or various α-olefins. Examples of polypropylene include homopolypropylene, block polypropylene, and random polypropylene.

[0042] Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Of the above resins, polyester resins are preferred from the viewpoint of ensuring strength, and polyethylene terephthalate is preferred from the viewpoint of ease of availability.

[0043] The resin may be a non-recycled resin, a recycled resin, or a mixture thereof.

[0044] The non-recycled resin may be a petroleum-derived resin obtained using petroleum-derived raw material monomers, a biomass-derived resin obtained using biomass-derived raw material monomers, or a mixture thereof, but from the viewpoint of reducing the environmental load, a biomass-derived resin is preferred.

[0045] When the resin contains a recycled resin, the recycled resin may be a material recycled resin or a chemical recycled resin. When the contents C are contained in the laminated tube container 400, the contents C are in contact with the container body 330 for a long period of time. However, when the second recycled resin contains a chemical recycled resin, the chemical recycled resin is more hygienic than the material recycled resin, and the contamination of the contents C with foreign matter is suppressed. Furthermore, when the recycled resin is a material recycled resin, the cost and the amount of energy used in the recycling process can be reduced.

[0046] The recycled resin may be post-consumer recycled resin (PCR), post-industrial recycled resin (PIR), or a mixture thereof, but is preferably PCR. PCR can be secured in large quantities on the market, so if the recycled resin is PCR, the cost of the laminate 100 can be reduced and the laminate 100 can be supplied more stably.

[0047] The first sealant layer 40 preferably has a melting point lower than that of the substrate 10. In this case, when the laminate 100 is heat-sealed, it is possible to heat-seal the first sealant layer 40 while suppressing melting of the substrate 10. Furthermore, by heating the laminate 100, the substrate 10 and the first sealant layer 40 or the second sealant layer 30 can be easily separated, and material recycling can be easily performed for each of the substrate 10 and the first sealant layer 40 or the second sealant layer 30.

[0048] The first sealant layer 40 may further contain additives such as a flame retardant, a slip agent, an antiblocking agent, an antioxidant, a light stabilizer, a tackifier, an antistatic agent, and a light-shielding pigment, as required. When the first sealant layer 40 contains a light-blocking pigment, the first sealant layer 40 can function as a light-blocking layer.

[0049] The first sealant layer 40 may be a single layer or a laminate of multiple layers. When the first sealant layer 40 is composed of a single layer, the first sealant layer 40 may be a recycled resin film or a non-recycled resin film. As the recycled resin film, a film containing a chemically recycled resin as the recycled resin is preferable because it is excellent in terms of hygiene and quality. When the first sealant layer 40 has three layers, the layers may be composed of a first outer layer, a middle layer, and a second outer layer. Here, the first outer layer and the second outer layer may be made of a non-recycled resin film, and the intermediate layer may be made of a recycled resin film. The first sealant layer 40 may also be colored white or the like. For example, a white sealant containing a titanium oxide-based white pigment can be used. The first sealant layer 40 is not limited to a white sealant, and may contain a pigment other than the white pigment to form a sealant layer of a different color.

[0050] The thickness of the first sealant layer 40 is not particularly limited and may be adjusted appropriately depending on the application of the laminate 100. The thickness of the first sealant layer 40 may be, for example, 10 μm or more, 25 μm or more, 30 μm or more, 40 μm or more, or 50 μm or more. The thickness of the first sealant layer 40 may also be 200 μm or less, 150 μm or less, 100 μm or less, 80 μm or less, 70 μm or less, or 60 μm or less.

[0051] <Second sealant layer> The second sealant layer 30 is a layer that is bonded to the first sealant layer 40 when manufacturing the cylindrical body portion 300 by overlapping parts of the laminate 100 and applying heat and pressure, and contains a resin.

[0052] Examples of such resins include polyolefin resins and polyester resins. Polyolefin resins are suitable for use in terms of sealing suitability, etc., while polyester resins are preferred in terms of low content adsorption and flavor barrier properties.

[0053] Examples of polyolefin resins include polyethylene and polypropylene.

[0054] Polyethylene is a resin containing ethylene as a structural unit. Examples of polyethylene include ethylene homopolymers and copolymers of ethylene with other monomers. The proportion of ethylene in polyethylene is, for example, 80 mol % or more. Examples of other monomers include α-olefins, vinyl acetate, and acrylic esters. The α-olefin may be an olefin having a carbon number in the range of 3 to 20. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene. Examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, etc. These may be used alone or in combination of two or more.

[0055] Polypropylene is a resin containing propylene as a structural unit, but may not contain ethylene as a structural unit, and may be a copolymer of propylene alone or with ethylene or various α-olefins. Examples of polypropylene include homopolypropylene, block polypropylene, and random polypropylene.

[0056] Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Of the above resins, polyester resins are preferred from the viewpoint of ensuring strength, and polyethylene terephthalate is preferred from the viewpoint of ease of availability.

[0057] The resin may be a non-recycled resin, a recycled resin, or a mixture thereof.

[0058] The non-recycled resin may be a petroleum-derived resin obtained using petroleum-derived raw material monomers, a biomass-derived resin obtained using biomass-derived raw material monomers, or a mixture thereof, but from the viewpoint of reducing the environmental load, a biomass-derived resin is preferred.

[0059] When the resin contains a recycled resin, the recycled resin may be a material recycled resin or a chemical recycled resin. When the contents C are contained in the laminated tube container 400, the contents C are in contact with the container body 330 for a long period of time. However, when the second recycled resin contains a chemical recycled resin, the chemical recycled resin is more hygienic than the material recycled resin, and the contamination of the contents C with foreign matter is suppressed. Furthermore, when the recycled resin is a material recycled resin, the cost and the amount of energy used in the recycling process can be reduced.

[0060] The recycled resin may be post-consumer recycled resin (PCR), post-industrial recycled resin (PIR), or a mixture thereof, but is preferably PCR. PCR can be secured in large quantities on the market, so if the recycled resin is PCR, the cost of the laminate 100 can be reduced and the laminate 100 can be supplied more stably.

[0061] The second sealant layer 30 preferably has a melting point lower than that of the substrate 10. In this case, when the laminate 100 is heat-sealed, it is possible to heat-seal the second sealant layer 30 while suppressing melting of the substrate 10. Furthermore, by heating the laminate 100, the substrate 10 and the second sealant layer 30 can be easily separated, and material recycling of each of the substrate 10 and the second sealant layer 30 can be easily performed.

[0062] The second sealant layer 30 may further contain additives such as a flame retardant, a slip agent, an antiblocking agent, an antioxidant, a light stabilizer, a tackifier, an antistatic agent, and a light-shielding pigment, as required. When the second sealant layer 30 contains a light-blocking pigment, the second sealant layer 30 can function as a light-blocking layer.

[0063] The material that makes up the second sealant layer 30 may be the same as or different from the material that makes up the first sealant layer 40 .

[0064] The second sealant layer 30 may be a single layer or a laminate of multiple layers. When the second sealant layer 30 is composed of a single layer, the second sealant layer 30 may be a recycled resin film or a non-recycled resin film. As the recycled resin film, a film containing a chemically recycled resin as the recycled resin is preferable because it is excellent in terms of hygiene and quality. When the second sealant layer 30 has three layers, the layers may be composed of a first outer layer, a middle layer, and a second outer layer. Here, the first outer layer and the second outer layer may be made of a non-recycled resin film, and the intermediate layer may be made of a recycled resin film. The second sealant layer 30 may also be colored white or the like. For example, a white sealant containing a titanium oxide-based white pigment can be used. The second sealant layer 30 is not limited to a white sealant, and may contain a pigment other than the white pigment to form a sealant layer of a different color.

[0065] The thickness of the second sealant layer 30 is not particularly limited and may be adjusted appropriately depending on the application of the laminate 100. The thickness of the second sealant layer 30 may be, for example, 10 μm or more, 25 μm or more, 30 μm or more, 40 μm or more, or 50 μm or more. The thickness of the second sealant layer 30 may also be 250 μm or less, 200 μm or less, 150 μm or less, 100 μm or less, 80 μm or less, 70 μm or less, or 60 μm or less.

[0066] <Second base material> The second substrate 20 is a substrate that reinforces the substrate 10, and can further improve the strength of the laminate 100. The second substrate 20 may be provided on the inner side (the second sealant layer 30 side) of the substrate 10, as shown in Fig. 2, or on the outer side (the side opposite to the second sealant layer 30). The second substrate 20 may also be provided on both sides of the substrate 10. The second substrate 20 includes a resin. Examples of such resins include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin resins such as polyethylene, polypropylene, and cyclic olefin copolymers COC and COP, polyamide resins such as polystyrene and nylon 66, and engineering plastics such as polycarbonate resin, polyacrylonitrile resin, and polyimide resin. Resins having mechanical strength and dimensional stability are preferred. The resin is processed into a film and used as a film substrate, which may be an unstretched film or a stretched film.

[0067] The second substrate 20 may be formed of a single layer or a laminate of multiple layers. When the second substrate 20 is configured as a single layer, the second substrate 20 may be a recycled resin film, or may be a non-recycled resin film such as a petroleum-derived resin or a biomass-derived resin. When the second substrate 20 is composed of a laminate of multiple layers, all layers may be recycled resin films, all layers may be non-recycled resin films, or some layers may be non-recycled resin films and the rest may be recycled resin films. When the plurality of layers is three layers, the plurality of layers may be composed of a first outer layer, a middle layer, and a second outer layer. The first and second outer layers may be made of non-recycled resin films, and the intermediate layer may be made of recycled resin film. In this case, the possibility that impurities or foreign matter such as gels or aggregates will migrate from the second substrate 20 through the second sealant layer 30 to the contents due to heating during retort or boiling of the laminated tube container can be further reduced. Therefore, the laminate 100 can be used safely to package contents such as food. The second substrate 20 may be a co-extruded resin film of polypropylene (PP) and ethylene vinyl alcohol resin (EVOH) (PP / EVOH), a co-extruded resin film of polyethylene and EVOH (PE / EVOH), or a co-extruded resin film of multiple layers and EVOH. Here, an example of the multiple layers is a three-layer polypropylene film (PP / PP / PP).

[0068] The thickness of the second substrate 20 is not particularly limited and is adjusted appropriately depending on the application of the laminated tube container 400. The thickness of the second substrate 20 may be, for example, 10 μm or more, 25 μm or more, 30 μm or more, 40 μm or more, or 50 μm or more. The thickness of the second substrate 20 may also be 100 μm or less, 80 μm or less, 70 μm or less, or 60 μm or less.

[0069] <Adhesive layer> Examples of the adhesive layer include an adhesive layer formed using an adhesive agent and an adhesive layer containing an adhesive resin (hereinafter also referred to as an "adhesive resin layer").

[0070] Examples of adhesives include known adhesives such as urethane adhesives, polyester adhesives, polyamide adhesives, epoxy adhesives, and isocyanate adhesives.

[0071] The adhesive may or may not contain a biomass-derived component, but preferably contains a biomass-derived component from the viewpoint of reducing the environmental impact. Specific examples of biomass-derived components include the "DIC Dry BM Series" manufactured by DIC Corporation and the "ECOAD Series" manufactured by Toyo Ink Co., Ltd. The adhesive may be a gas barrier adhesive that exhibits gas barrier properties after curing. By using a gas barrier adhesive, the adhesive layer has gas barrier properties, and therefore the gas barrier properties of the laminate 100 can be improved. Gas barrier adhesives include epoxy adhesives and polyester / polyurethane adhesives. A specific example of a gas barrier adhesive is " Examples include "Maxive" manufactured by DIC Corporation and "Paslim" manufactured by DIC Corporation.

[0072] The adhesive may be an adhesive containing an organic solvent or an adhesive containing no organic solvent, but from the viewpoint of reducing the environmental load, an adhesive containing no organic solvent (solvent-free adhesive) is preferred.

[0073] The adhesive resin layer may be an extruded or non-extruded resin layer. The adhesive resin is a heat-sealable adhesive thermoplastic resin that can be melted and fused by heat, and examples thereof include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, methylpentene polymer, and acid-modified polyolefin resins obtained by modifying polyolefin resins such as polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like.

[0074] The thickness of the adhesive layer is not particularly limited and may be, for example, 1 μm or more. By making the thickness of the adhesive layer 1 μm or more, sufficient adhesive strength can be obtained. The thickness of the adhesive layer may be 2 μm or more. The thickness of the adhesive layer may be 50 μm or less, 5 μm or less, or 3 μm or less.

[0075] <Print layer> The printing layer 50 is a layer that displays characters, pictures, etc., and can be formed using ink. The printing layer 50 is provided between layers. When the printing layer 50 is provided between layers, the printing layer 50 may be provided between the first substrate 10 and the first sealant layer 40, or may be provided between the first substrate 10 and the second sealant layer 30. When the printing layer 50 is provided between the first substrate 10 and the first sealant layer 40 or the second sealant layer 30, the printing layer 50 is protected by the first substrate 10 and the first sealant layer 40 or the second sealant layer 30, thereby preventing deterioration of the printing layer 50. Furthermore, when the laminate 100 includes a second substrate 20, the printing layer 50 may be provided on the second substrate 20. Here, the printing layer 50 may be provided between the first substrate 10 and the second substrate 20, or may be provided between the second substrate 20 and the second sealant layer 30.

[0076] As the ink, for example, inks obtained by adding various pigments, plasticizers, drying agents, stabilizers, etc. to a binder resin such as urethane resin, acrylic resin, nitrocellulose resin, or rubber can be used.

[0077] The ink may be either a water-based ink or an oil-based ink, but is preferably a water-based ink. A water-based ink uses water or alcohol as a solvent, which can further reduce the environmental impact. In particular, when the adhesive is a solventless adhesive, using a water-based ink as the ink can significantly reduce the environmental impact. Furthermore, the ink may or may not be a biomass ink, but from the perspective of reducing the environmental impact, a biomass ink is preferred. Here, biomass ink refers to an ink containing components obtained from biological resources (biomass), such as cotton, pulp, rice bran, vegetable oil, and angiosperm seeds. The ink may be recycled ink, which is made by collecting and recycling used ink, or may be non-recycled ink, but recycled ink is preferred from the viewpoint of environmental impact.

[0078] Furthermore, an easily recyclable ink can also be used as the ink. By using an easily recyclable ink, it becomes possible to easily recycle the laminated tube container 400 including the laminate 100 after disposal. Specifically, an example of an easily recyclable ink is "SunSpectro Solvawash" manufactured by DIC Corporation.

[0079] <Gas barrier layer> 1, the laminate 100 may include a gas barrier layer 60. The gas barrier layer 60 may be provided on at least one surface of the first substrate 10. Alternatively, the gas barrier layer 60 may be provided on at least one surface of the second substrate 20. The gas barrier layer 60 is a layer that improves the gas barrier properties of the laminate 100, and has barrier properties against gases such as water vapor or oxygen.

[0080] The gas barrier layer 60 may be, for example, a vapor deposition layer such as a metal vapor deposition layer or an inorganic compound vapor deposition layer. Metals include aluminum and silicon. Inorganic compounds include aluminum oxide and silicon oxide (silica). When the gas barrier layer 60 is a vapor-deposited layer of a metal such as aluminum, the gas barrier layer 60 can function as a light-shielding layer. In addition, when the gas barrier layer 60 has a vapor deposition layer, the gas barrier layer 60 may further have an anchor coat layer between the first substrate 10 or the second substrate 20 and the vapor deposition layer in order to improve adhesion between the first substrate 10 or the second substrate 20 and the vapor deposition layer.

[0081] The gas barrier layer 60 may further include an overcoat layer on the vapor deposition layer. The overcoat layer may be a coating layer obtained using a composition containing a water-soluble polymer and silicon alkoxide, or a coating layer made of a resin such as urethane.

[0082] In the first sealed portion 301 of the body portion 300, the second sealant layer 30 and the first sealant layer 40 of the laminate 100 may be directly bonded by heat sealing, or may be bonded to each other with an adhesive.

[0083] <<Cap mounting part>> The cap attachment portion 310 includes a cylindrical mouth portion 311 through which the contents C pass, and a shoulder portion 312 connecting the mouth portion 311 and the body portion 300. The outer circumferential surface of the mouth portion 311 may have a thread portion (for example, a spiral convex portion) for attaching the cap 320. The cap attachment portion 310 is made of a polyolefin resin molded body containing polyolefin resin.

[0084] Examples of polyolefin resins include polyethylene and polypropylene, with polyethylene being preferred.

[0085] Polyethylene is a resin containing ethylene as a structural unit. Examples of polyethylene include ethylene homopolymers and copolymers of ethylene with other monomers. The proportion of ethylene in polyethylene is, for example, 80 mol % or more. Examples of other monomers include α-olefins, vinyl acetate, and acrylic esters. The α-olefin may be an olefin having a carbon number in the range of 3 to 20. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene. Examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, etc. These may be used alone or in combination of two or more.

[0086] Polypropylene is a resin containing propylene as a structural unit, but may not contain ethylene as a structural unit, and may be a copolymer of propylene alone or with ethylene or various α-olefins. Examples of polypropylene include homopolypropylene, block polypropylene, and random polypropylene.

[0087] The polyolefin resin may be a non-recycled resin, a recycled resin (second recycled resin), or a mixture thereof, but contains recycled resin when the polyolefin resin molded body constituting the cap 320 does not contain recycled resin. The polyolefin resin may contain recycled resin even when the polyolefin resin molded body constituting the cap attachment portion 310 does not contain recycled resin.

[0088] The non-recycled resin may be a petroleum-derived resin obtained using petroleum-derived raw material monomers, a biomass-derived resin obtained using biomass-derived raw material monomers, or a mixture thereof, but from the viewpoint of reducing the environmental load, a biomass-derived resin is preferred.

[0089] When the polyolefin resin contains a recycled resin and the cap 320 contains a recycled resin, the recycled resin in the cap attachment portion 310 may or may not be the same as the recycled resin contained in the cap 320, but from the viewpoint of a stable supply of the laminated tube container 400, it is preferable that they are different.

[0090] The proportion of recycled resin in the cap attachment portion 310 is not particularly limited, but is, for example, 10% or more, 20% or more, 30% or more, 40% or more, or 50% or more. The percentage of recycled resin in the cap attachment portion 310 may be 100% or less, 80% or less, or 60% or less. The above percentages are expressed in units of volume % or mass %.

[0091] <<Cap>> Cap 320 is attached to mouth 312 of cap attachment part 310. When mouth 311 has a spiral convex portion on its outer circumferential surface, cap 320 may have a spiral concave portion on its inner circumferential surface. Furthermore, cap 320 may further have an inner ring on its bottom surface to prevent the contents from leaking from mouth 311. The cap 320 is made of a polyolefin resin molded body containing a polyolefin resin.

[0092] Examples of polyolefin resins include polyethylene and polypropylene, with polyethylene being preferred.

[0093] Polyethylene is a resin containing ethylene as a structural unit. Examples of polyethylene include ethylene homopolymers and copolymers of ethylene with other monomers. The proportion of ethylene in polyethylene is, for example, 80 mol % or more. Examples of other monomers include α-olefins, vinyl acetate, and acrylic esters. The α-olefin may be an olefin having a carbon number in the range of 3 to 20. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene. Examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, etc. These may be used alone or in combination of two or more.

[0094] Polypropylene is a resin containing propylene as a structural unit, but may not contain ethylene as a structural unit, and may be a copolymer of propylene alone or with ethylene or various α-olefins. Examples of polypropylene include homopolypropylene, block polypropylene, and random polypropylene.

[0095] The polyolefin resin may be a non-recycled resin, a recycled resin, or a mixture thereof, but it contains recycled resin when the polyolefin resin molded body constituting the cap attachment portion 310 does not contain recycled resin. The polyolefin resin may contain recycled resin even when the polyolefin resin molded body constituting the cap attachment portion 310 does not contain recycled resin.

[0096] The non-recycled resin may be a petroleum-derived resin obtained using petroleum-derived raw material monomers, a biomass-derived resin obtained using biomass-derived raw material monomers, or a mixture thereof, but from the viewpoint of reducing the environmental load, a biomass-derived resin is preferred.

[0097] When the polyolefin resin contains a recycled resin and the cap attachment portion 310 contains a recycled resin, the recycled resin in the cap 320 may or may not be the same as the recycled resin contained in the cap attachment portion 310, but from the viewpoint of a stable supply of the laminated tube container 400, it is preferable that they are different.

[0098] The proportion of recycled resin in cap 320 is not particularly limited, but may be, for example, 10% or more, 20% or more, 30% or more, 40% or more, or 50% or more. The percentage of recycled resin in the cap attachment portion 310 may be 100% or less, 80% or less, or 60% or less. The above percentages are expressed in units of volume % or mass %.

[0099] <<Contents>> The content C is not particularly limited and may be appropriately selected depending on the application of the laminated tube container 400. The content C is not particularly limited, and examples of the content C include toothpaste, cosmetics, glue, mustard greens, wasabi paste, cream, butter, margarine, and other seasonings, paints, ointments, and medicines.

[0100] (A) Percentage of recycled resin In the laminated tube container 400, the proportion of chemically recycled resin is preferably 10% or more. In addition, if the cap 320, the substrate 10, the second substrate 20, the first sealant layer 40 or the second sealant layer 30 is a mixture of chemically recycled resin and non-recycled resin such as petroleum-derived resin or biomass-derived resin, the mass of the recycled resin in each of the cap 320, the substrate 10, the second substrate 20, the first sealant layer 40 or the second sealant layer 30 is calculated according to the mass ratio of the chemically recycled resin to the non-recycled resin, and the proportion (%) of chemically recycled resin in the laminated tube container 400 is calculated.

[0101] The chemically recycled resin may be a post-consumer recycled resin (PCR), a post-industrial recycled resin (PIR), or a mixture thereof, but preferably includes PCR. PCR is available in large quantities on the market, so if the chemically recycled resin is PCR, the cost of the laminated tube container 400 can be reduced.

[0102] (B) Odor components In a total ion chromatogram obtained by performing mass analysis using purge-and-trap gas chromatography-mass spectrometry on the cap 320 and the cap attachment portion 310 of the laminated tube container 400, when the ratio of the peak area of ​​nonanal as an indicator of odor components to the sum of the peak area values ​​of all aliphatic hydrocarbon components is defined as R1 (%) and the ratio of the peak area of ​​decanal to the sum of the peak area values ​​of all aliphatic hydrocarbon components is defined as R2 (%), R1 is preferably less than 1.5%, more preferably 1.0% or less, and particularly preferably 0.5% or less. Furthermore, R2 is preferably less than 3.5%, more preferably 2.5% or less, and particularly preferably 1.5% or less. It is preferable that R1 is less than 1.5% and R2 is less than 3.5%, in which case thermal degradation is suppressed as a whole in the laminated tube container 400, and the quality of the laminated tube container 400 can be further improved. Specifically, the mass analysis is carried out by cutting out a 1.0 gram sample from the portion of the cap 320 and cap attachment portion 310 of the laminated tube container 400 that contains recycled resin, placing this sample in a 20 mL vial together with an odor component collector, and heating it at 60°C for 1 hour to adsorb the volatile components from the sample onto the collector, and then analyzing the volatile components in the collector using a purge-and-trap gas chromatograph mass analyzer.

[0103] <Manufacturing method of packaging article> Next, an example of a method for manufacturing a packaged article 500 using the laminate 100 will be described.

[0104] First, the body portion laminate 100 is prepared. Then, the body portion laminate 100 is rolled up with the first sealant layer 40 on the outside, and parts are overlapped. The first sealant layer 40 and the second sealant layer 30 are heat-sealed to form a first sealed portion 301, forming a cylindrical body. One end of the cylindrical body is then heat-sealed to form a second sealed portion 302, thereby producing the body portion 300. Next, the material constituting the cap attachment portion 310 is melted and molded to obtain the molten cap attachment portion 310. At this time, the cap attachment portion 310 is molded to have a mouth portion 311 and a shoulder portion 312, and a thread portion (e.g., a spiral convex portion) for attaching the cap 320 is formed on the outer periphery of the mouth portion 311. Then, the end of the body portion 300 is brought into contact with the shoulder portion 312 of the molten cap attachment portion 310, and the cap attachment portion 310 and the body portion 300 are joined and integrated to obtain the container body.

[0105] Meanwhile, the material constituting cap 320 is melted and molded to prepare cap 320. At this time, if a threaded portion (e.g., a spiral convex portion) is formed on the outer periphery of mouth portion 312, cap 320 may have a threaded portion (e.g., a spiral concave portion) formed on the inside thereof that engages with the threaded portion (e.g., the spiral convex portion) of cap attachment portion 310. Then, the contents C are filled into the container body through the mouth 311. Thereafter, the cap 320 is attached to the mouth 311. In this manner, a packaged article 500 including the laminated tube container 400 and the contents C can be manufactured.

[0106] The outline of the present disclosure is as follows. [1] A laminated tube container comprising a body obtained by using a laminate having a first sealant layer, a substrate, and a second sealant layer in this order, a cap attachment part provided on the body and having a mouth, and a cap attached to the mouth, At least one of the cap and the cap attachment portion is made of a polyolefin resin molded body containing recycled resin, A laminated tube container, wherein the recycled resin is a chemical recycled resin. [2] The laminated tube container according to [1], wherein the proportion of chemically recycled resin in the laminated tube container is 10% or more. [3] The laminated tube container according to [2], wherein the proportion of chemically recycled resin in the laminated tube container is 20% or more. [4] The laminated tube container according to any one of [1] to [3], wherein the recycled resin includes post-consumer recycled resin. [5] The laminated tube container according to any one of [1] to [4], wherein at least one of the cap and the cap attachment portion is colored. [6] A laminated tube container according to any one of [1] to [5], wherein the laminate further comprises a second substrate at least either between the first sealant layer and the substrate or between the second sealant layer and the substrate. [7] A laminated tube container according to any one of [1] to [6], wherein the laminate further comprises a gas barrier layer at least either between the first sealant layer and the substrate or between the second sealant layer and the substrate. [8] A laminated tube container according to any one of [1] to [7], and a content contained in the laminated tube container. [Example]

[0107] The present disclosure will be explained in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0108] Example 1 A petroleum-derived biaxially stretched PET film (thickness 18 μm) was prepared as the substrate. An aluminum vapor deposition film (thickness 10 nm) was then formed on the surface of the substrate. An overcoat layer (thickness 300 nm) was then formed using a resin composition containing polyvinyl alcohol (PVA) and silicon alkoxide to obtain a structure. Furthermore, petroleum-derived linear low-density polyethylene (LLDPE) films (thickness: 50 μm) were prepared as the first sealant layer and the second sealant layer, respectively. Then, a dry laminating adhesive (urethane adhesive) was applied to the surface of the base material of the structure to form an adhesive layer with a thickness of 3 μm (dry film thickness), and one of the first sealant layers was attached to this adhesive layer. Next, a dry laminating adhesive (urethane adhesive) was applied onto the overcoat layer of the structure to form an adhesive layer with a thickness of 3 μm (dry film thickness), and a second sealant layer was attached to this adhesive layer. In this way, a laminate (first sealant layer / adhesive layer / substrate / vapor deposition layer / overcoat layer / adhesive layer / second sealant layer) was produced. From the above laminate, a rectangular laminate for the trunk portion measuring 9 cm x 16 cm was prepared. The obtained body laminate was then rolled up with the first sealant layer facing outward, and with both ends (short sides) of the laminate overlapping each other, the first sealant layer and the second sealant layer were heat-sealed at both ends using a heat seal bar to form a first sealed portion, resulting in a cylindrical body with a diameter (inner diameter) of 50.3 mm and a length of 9 cm. The seal width of the first sealed portion was 2 mm. One end of the cylindrical body was then heat-sealed using a heat seal bar to form a second sealed portion. The seal width of the second sealed portion was 8 mm. In this manner, the body was produced. The cap attachment portion was welded to the end of the body portion by compression molding using petroleum-derived high-density polyethylene (HDPE) so that it was integrated with the body portion. At this time, the cap attachment portion was formed to have a cylindrical mouth portion and a shoulder portion connecting the mouth portion and the body portion. The mouth portion had a spiral convex portion formed as a screw portion on its outer periphery. In this way, the container body was produced. On the other hand, we used used packaging materials to create caps made from a polyolefin resin molded body made from chemically recycled high-density polyethylene (PCRCR100%-HDPE). The caps had an inner ring formed on the bottom surface and a spiral recess on the inner circumferential surface. "PCRCR100%-HDPE" means that the proportion of post-consumer chemically recycled (PCRCR) resin in the cap is 100% by mass. The cap was then placed on the opening of the container body and rotated to attach it, thus completing the production of a laminated tube container. The proportion of chemically recycled (CR) resin in the obtained laminated tube container, the proportion of CR resin in the cap, and the proportion of CR resin in the cap attachment portion were as shown in Table 1.

[0109] Example 2 A laminated tube container was produced in the same manner as in Example 1, except that the substrate was changed from a petroleum-derived biaxially oriented PET film (thickness 18 μm) to a chemically recycled biaxially oriented PET film (thickness 18 μm). The proportion of chemically recycled (CR) resin in the obtained laminated tube container, the proportion of CR resin in the cap, and the proportion of CR resin in the cap attachment portion were as shown in Table 1.

[0110] Example 3 A laminated tube container was produced in the same manner as in Example 1, except that the material constituting the cap was changed from PCRCR100%-HDPE to petroleum-derived HDPE, and the material constituting the cap attachment portion was changed from petroleum-derived HDPE to PCRCR100%-HDPE. The proportion of chemically recycled (CR) resin in the obtained laminated tube container, the proportion of CR resin in the cap, and the proportion of CR resin in the cap attachment portion were as shown in Table 1.

[0111] Example 4 A laminated tube container was produced in the same manner as in Example 1, except that the substrate was changed from a petroleum-derived biaxially stretched PET film (thickness 18 μm) to a chemically recycled (CR) 50% OPP film (thickness 20 μm), and the first sealant layer was changed from a petroleum-derived LLDPE film (thickness 50 μm) to a petroleum-derived LDPE film (thickness 20 μm). Here, "CR 50% OPP film" means an OPP film in which 50 mass % of the film is recycled resin, and the recycled resin is chemically recycled resin. The proportion of chemically recycled (CR) resin in the obtained laminated tube container, the proportion of CR resin in the cap, and the proportion of CR resin in the cap attachment portion were as shown in Table 1.

[0112] Example 5 A laminated tube container was produced in the same manner as in Example 1, except that the material constituting the cap attachment part was changed from petroleum-derived HDPE to PCRCR100%-HDPE, and the sealant layer of the body laminate was changed from petroleum-derived LLDPE film to chemically recycled (CR) 25% LLDPE film. Here, "CR 25% LLDPE film" means an LLDPE film in which 25% by mass of the film is recycled resin, and the recycled resin is chemically recycled resin. The proportion of chemically recycled (CR) resin in the obtained laminated tube container, the proportion of CR resin in the cap, and the proportion of CR resin in the cap attachment portion were as shown in Table 1.

[0113] Example 6 A laminated tube container was produced in the same manner as in Example 1, except that the material constituting the cap attachment portion was changed from petroleum-derived HDPE to PCRCR100%-HDPE, the first and second sealant layers of the body laminate were changed from petroleum-derived LLDPE film to CR25% LLDPE film, and the base material of the body laminate was changed from petroleum-derived biaxially oriented PET film (thickness 18 μm) to CR50% biaxially oriented LDPE film (thickness 20 μm). Here, "CR25% LLDPE film" means an LLDPE film in which 25% by mass of the film is recycled resin and the recycled resin is chemically recycled resin, and "CR50% biaxially oriented LDPE film" means an LDPE film in which 50% by mass of the film is recycled resin and the recycled resin is chemically recycled resin. The proportion of chemically recycled (CR) resin in the obtained laminated tube container, the proportion of CR resin in the cap, and the proportion of CR resin in the cap attachment portion were as shown in Table 1.

[0114] (Comparative Example 1) A laminated tube container was produced in the same manner as in Example 1, except that the material constituting the cap was changed from PCRCR 100%-HDPE to material recycled (MR) 100%-HDPE. Note that "MR 100%-HDPE" means that the proportion of MR resin in the cap is 100% by mass. The proportion of chemically recycled (CR) resin in the obtained laminated tube container, the proportion of CR resin in the cap, and the proportion of CR resin in the cap attachment portion were as shown in Table 1.

[0115] <Evaluation> The laminated tube containers of the Examples and Comparative Examples prepared as described above were evaluated as follows: Evaluation 1 (emission of odorous components), Evaluation 2 (opening torque), Evaluation 3 (liquid leakage), and Evaluation 4 (foreign matter). Here, Evaluations 1 to 3 are evaluations related to quality, and Evaluation 4 is an evaluation related to appearance.

[0116] (1) Evaluation 1 (Odor component generation) First, the cap and cap attachment part of the laminated tube container were analyzed using purge-and-trap gas chromatography-mass spectrometry. Specifically, a 1.0 gram sample was cut from the part of the cap and cap attachment part of the laminated tube container that contained recycled resin. This sample was placed in a 20 mL vial together with an odor component collector and heated at 60°C for 1 hour to adsorb the volatile components from the sample onto the collector. The volatile components in the collector were then analyzed using a purge-and-trap gas chromatography-mass spectrometry system, and a total ion chromatogram was obtained. Next, in the total ion chromatogram obtained as described above, the ratio R1 of the peak area of ​​nonanal as an odor component index to the sum of the peak areas of all aliphatic hydrocarbon components, and the ratio R2 of the peak area of ​​decanal to the sum of the peak areas of all aliphatic hydrocarbon components were calculated. Note that, for Examples 5 and 6, the ratios R1 and R2 were calculated for both the cap and the cap attachment part, and the larger value was used. The results were evaluated based on the following criteria: (Evaluation criteria) ◎ R1 is less than 1.5% and R2 is less than 0.35% ○···R1 is less than 1.5% and R2 is 0.35% or more, or R1 is 1.5% or more and R2 is less than 0.35% × R1 is 1.5% or more and R2 is 0.35% or more

[0117] (2) Evaluation 2 (opening torque) The cap of a laminated tube container was tightened onto the opening of the cap attachment part using an automatic tightening machine at a specified tightening speed and tightening torque. After leaving the cap and the opening of the cap attachment part for three days to allow the fitting of the cap and the opening part to settle in, the cap was manually turned and opened using a torque measuring device with the opening part of the cap attachment part fixed, and the peak torque (unit: N·cm) at that time was measured as the opening torque. The following evaluation criteria were established according to the measured opening torque value, and the fitting condition of the cap was evaluated based on these evaluation criteria. The results are shown in Table 2. A "good" indicates that the cap fitting condition was good, and an "unsatisfactory" indicates that the cap fitting condition was poor. (Evaluation criteria) ○ Opening torque value is 10N·cm or more but less than 30N·cm × Opening torque is 30 N·cm or more

[0118] (3) Rating 3 (Leakage) The cap of the laminated tube container was tightened to the opening of the cap attachment section using an automatic tightening machine at a desired tightening speed and tightening torque. Then, with the cap facing downwards, the top of the laminated tube container was cut off, and commercially available Microcheck penetrant (red oil component) was poured into the opening. After leaving it at room temperature for 24 hours, the cap was turned and opened. Leakage was evaluated based on the following evaluation criteria. The results are shown in Table 2. "Good" indicates no leakage, and "Poor" indicates leakage. (Evaluation criteria) ○ Only the inside of the cap's inner ring is colored red × The inside and outside of the cap's inner ring are colored red

[0119] (4) Rating 4 (foreign matter) For caps made of recycled resin from laminated tube containers, an inspection light was irradiated onto the outer and inner surfaces of the cap using a visual inspection machine, the light reflected from the surface was detected by a camera, and the acquired image was binarized to check for the presence of colored foreign matter with a diameter of 0.3 mm or more. In this case, the inner surface of the cap was defined as the part within the range of the inspection light. For the cap attachment parts of laminated tube containers containing recycled resin, an appearance inspection machine was used to irradiate the outer surface of the cap attachment part for both the mouth and shoulder, the light reflected from the surface was detected by a camera, and the image obtained was then binarized to check for the presence of colored foreign matter of 0.3 mm or more in diameter. For the shoulder part, an interior inspection machine was used to irradiate the inner surface of the shoulder with an inspection light, the light reflected from the surface was detected by a camera, and the image obtained was then binarized to check for the presence of colored foreign matter of 0.3 mm or more in diameter. Plugs in which one or more colored foreign matter with a diameter of 0.3 mm or more was detected were marked with an "X", and plugs in which no colored foreign matter with a diameter of 0.3 mm or more was detected were marked with an "O". The results are shown in Table 2.

[0120] [Table 1] [Table 2]

[0121] From the results shown in Table 2, for Evaluation 1, the laminated tube containers of Examples 1 to 6, which used chemical recycled resin as the recycled resin for at least one of the cap and the cap attachment part, emitted less odorous components than the laminated tube container of Comparative Example 1, which used material recycled resin as the recycled resin for the cap.

[0122] Regarding Evaluation 2, in all of Examples 1 to 6, the opening torque was appropriately small, indicating a good fit between the cap and the opening of the cap attachment portion. In contrast, in Comparative Example 1, the opening torque was high, indicating a poor fit between the cap and the opening of the cap attachment portion. This result is thought to be due to the following reasons. In Comparative Example 1, protrusions caused by foreign matter derived from the recycled resin formed on the spiral convex portions on the inner surface of the cap and the outer surface of the opening of the cap attachment portion, which impeded the rotation of the cap when opening the cap, resulting in a high opening torque. In contrast, in Examples 1 to 6, the cap or cap attachment portion did not contain foreign matter derived from the recycled resin. Therefore, protrusions caused by foreign matter derived from the recycled resin did not form on the spiral convex portions on the inner surface of the cap and the outer surface of the opening of the cap attachment portion, which prevented the cap from rotating when opening the cap. This likely resulted in a moderate opening torque.

[0123] Regarding Evaluation 3, no liquid leakage occurred in any of Examples 1 to 6, whereas liquid leakage occurred in Comparative Example 1. This result is thought to be due to the following reasons. Specifically, in Comparative Example 1, it is thought that the liquid leakage occurred because a small gap was formed between the spiral recess on the inner circumferential surface of the cap and the spiral protrusion on the opening of the cap attachment part due to protrusions caused by foreign matter derived from the recycled resin at the opening of the cap attachment part or the inner ring of the cap. In contrast, in Examples 1 to 6, since the cap or cap attachment part did not contain foreign matter derived from the recycled resin, no protrusions caused by foreign matter derived from the recycled resin were formed at the opening of the cap attachment part or the inner ring of the cap, and therefore no gap was formed between the spiral recess on the inner circumferential surface of the cap and the spiral protrusion on the opening of the cap attachment part. This is thought to be why no liquid leakage occurred.

[0124] Regarding evaluation 4, the laminated tube container of the example, which used chemical recycled resin as the recycled resin for at least one of the cap and the cap attachment part, had no foreign matter and had a good appearance compared to the laminated tube container of comparison example 1, which used material recycled resin as the recycled resin for the cap.

[0125] From the above, it has been confirmed that the laminated tube container of the present disclosure can improve quality and appearance even if recycled resin is contained in at least one of the cap and the cap attachment portion. [Explanation of symbols]

[0126] 10...substrate, 20...second substrate, 30...second sealant layer, 40...first sealant layer, 50...printed layer, 60...gas barrier layer, 100...laminated body, 300...body portion, 310...cap attachment portion, 311...mouth portion, 320...cap, 400...laminated tube container, 500...packaged article, C...contents.

Claims

1. A laminated tube container comprising: a body portion obtained by using a laminate having a first sealant layer, a substrate, and a second sealant layer in this order; a cap attachment portion provided on the body portion and having a mouth portion; and a cap attached to the mouth portion, At least one of the cap and the cap attachment portion is made of a polyolefin resin molded body containing recycled resin, A laminated tube container, wherein the recycled resin is a chemical recycled resin.

2. 2. The laminated tube container according to claim 1, wherein the proportion of chemically recycled resin in the laminated tube container is 10% or more.

3. 3. The laminated tube container according to claim 2, wherein the proportion of chemically recycled resin in the laminated tube container is 20% or more.

4. 10. The laminated tube container of claim 1, wherein the recycled resin comprises post-consumer recycled resin.

5. 2. The laminated tube container according to claim 1, wherein at least one of the cap and the cap attachment portion is colored.

6. 2. The laminated tube container according to claim 1, wherein the laminate further comprises a second substrate between the first sealant layer and the substrate and / or between the second sealant layer and the substrate.

7. The laminated tube container according to claim 1 , wherein the laminate further comprises a gas barrier layer at least one between the first sealant layer and the substrate and between the second sealant layer and the substrate.

8. A laminated tube container according to any one of claims 1 to 7, and a content contained in the laminated tube container.

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