Barrier laminate and packaging container equipped with said barrier laminate

Abstract

To provide a barrier laminate which is provided with a multi-layer base material having excellent interlayer adhesiveness to a vapor deposition film and has high gas barrier properties.SOLUTION: A barrier laminate of the present invention is provided with a multi-layer base material, a vapor deposition film and a sealant layer, in which the multi-layer base material undergoes a stretching treatment, the multi-layer base material is provided with at least a polypropylene resin layer and a surface resin layer, the surface resin layer comprises a resin material having a melting point of 180°C or higher, and the vapor deposition film is composed of an inorganic oxide.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a barrier laminate and a packaging container provided with the barrier laminate. [Background technology]

[0002] Conventionally, films made of polyesters such as polyethylene terephthalate (hereinafter also referred to as polyester films) have been used as substrates for constituting laminates used in the production of packaging containers because they have excellent mechanical properties, chemical stability, heat resistance, and transparency, as well as being inexpensive.

[0003] Depending on the contents to be filled into the packaging container, the packaging container may be required to have high gas barrier properties such as oxygen barrier property and water vapor barrier property, and in order to meet this requirement, it is common to form a vapor-deposited film containing alumina, silica, etc. on the surface of a polyester film (Patent Document 1).

[0004] Recently, there has been a search for resin materials to replace polyester films, and the application of polyolefin films, particularly polypropylene films, to substrates has been investigated. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-053223 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors were considering using a stretched polypropylene film (hereinafter also referred to as a stretched polypropylene film) instead of a conventional polyester film substrate, and discovered a new problem: even when a vapor-deposited film was formed on the surface of the stretched polypropylene film, satisfactory gas barrier properties could not be obtained.

[0007] As a result of further investigations, the present inventors discovered that, in packaging containers using a barrier laminate in which a vapor-deposited film is provided on the stretched polypropylene film, a unique phenomenon not observed in conventional barrier laminates using polyester film substrates occurs, namely, delamination occurs between the stretched polypropylene film and the vapor-deposited film, and they came to the realization that this phenomenon causes insufficient gas barrier properties.

[0008] The inventors then discovered that by providing a surface resin layer containing a resin material having a melting point of 180°C or higher on the surface of a stretched polypropylene film, the adhesion of the vapor-deposited film formed on the surface resin layer is improved and the gas barrier properties are also improved.

[0009] The inventors also discovered that providing a coating layer containing a resin material having a polar group on the surface of a stretched polypropylene film improves the adhesion of the vapor-deposited film formed on the coating layer and also improves the gas barrier properties.

[0010] The present invention was made based on this finding, and the problem to be solved by the present invention is to provide a barrier laminate having high gas barrier properties and including a multilayer substrate that exhibits excellent interlayer adhesion with a vapor-deposited film.

[0011] Another problem to be solved by the present invention is to provide a packaging container comprising the barrier laminate. [Means for solving the problem]

[0012] In a first aspect, the barrier laminate of the present invention comprises a multilayer substrate, a vapor-deposited film, and a sealant layer, The multilayer substrate has been subjected to a stretching treatment, Furthermore, the multilayer substrate comprises at least a polypropylene resin layer and a surface resin layer, the surface resin layer contains a resin material with a melting point of 180°C or higher, The vapor-deposited film is characterized by being made of an inorganic oxide.

[0013] In one embodiment, the polypropylene resin layer and the sealant layer are made of the same material, which is polypropylene.

[0014] In one embodiment, the melting point of the resin material is 265° C. or less.

[0015] In one embodiment, the difference between the melting point of the resin material and the melting point of the polypropylene contained in the polypropylene resin layer is 20 to 80°C.

[0016] In one embodiment, the resin material has a polar group.

[0017] In one embodiment, the resin material is one or more resin materials selected from ethylene vinyl alcohol copolymer, polyvinyl alcohol, nylon 6, nylon 6,6, MXD nylon, and amorphous nylon.

[0018] In one embodiment, the resin material is a polyamide.

[0019] In one embodiment, the resin material is ethylene vinyl alcohol.

[0020] In one embodiment, the ratio of the thickness of the surface resin layer to the total thickness of the multilayer substrate is 1% or more and 10% or less.

[0021] In one embodiment, the multilayer substrate is a co-extruded film.

[0022] In a second embodiment, the barrier laminate of the present invention comprises a multilayer substrate, a vapor-deposited film, and a sealant layer, The multilayer substrate includes at least a polypropylene resin layer and a surface coating layer, the polypropylene resin layer has been subjected to a stretching treatment, the surface coating layer contains a resin material having a polar group, The vapor-deposited film is characterized by being made of an inorganic oxide.

[0023] In one embodiment, the polypropylene resin layer and the sealant layer are made of the same material, which is polypropylene.

[0024] In one embodiment, the ratio of the thickness of the surface coating layer to the total thickness of the multilayer substrate is 0.08% or more and 20% or less.

[0025] In one embodiment, the thickness of the surface coating layer is 0.02 μm or more and 10 μm or less.

[0026] In one embodiment, the resin material is one or more resin materials selected from ethylene vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyester, polyethyleneimine, hydroxyl group-containing (meth)acrylic resin, nylon 6, nylon 6,6, MXD nylon, amorphous nylon, and polyurethane.

[0027] In one embodiment, the surface coating layer is a layer formed using a water-based emulsion or a solvent-based emulsion.

[0028] In one embodiment, the barrier laminate of the present invention further comprises a barrier coat layer between the multilayer substrate and the vapor-deposited film.

[0029] In one embodiment, the barrier laminate of the present invention is used for packaging container applications.

[0030] The packaging container of the present invention is characterized by comprising the above-mentioned barrier laminate. [Effects of the Invention]

[0031] According to the present invention, it is possible to produce a packaging container having high laminate strength and including a multilayer substrate that has excellent interlayer adhesion with a vapor-deposited film, and it is also possible to provide a barrier laminate that has high gas barrier properties. Furthermore, according to the present invention, it is possible to provide a packaging container comprising the barrier laminate. [Brief explanation of the drawings]

[0032] [Figure 1] 1 is a schematic cross-sectional view showing one embodiment of a barrier laminate of the present invention. [Figure 2] 1 is a schematic cross-sectional view showing one embodiment of a barrier laminate of the present invention. [Figure 3] 1 is a schematic cross-sectional view showing one embodiment of a barrier laminate of the present invention. [Figure 4] 1 is a schematic cross-sectional view showing one embodiment of a barrier laminate of the present invention. [Figure 5] FIG. 1 is a schematic cross-sectional view showing one embodiment of a vapor deposition apparatus. [Figure 6] FIG. 1 is a schematic cross-sectional view showing one embodiment of a vapor deposition apparatus. [Figure 7] FIG. 10 is a schematic cross-sectional view showing another embodiment of a vapor deposition apparatus. [Figure 8] 1 is a schematic cross-sectional view showing one embodiment of a barrier laminate of the present invention. [Figure 9] 1 is a schematic cross-sectional view showing one embodiment of a barrier laminate of the present invention. [Figure 10] 1 is a front view showing an embodiment of a packaging container of the present invention. [Figure 11] 1 is a perspective view showing one embodiment of a packaging container of the present invention. [Figure 12] FIG. 2 is a schematic diagram showing an example of a method for measuring laminate strength. [Figure 13] FIG. 2 is a schematic diagram showing an example of a method for measuring laminate strength. [Figure 14] FIG. 10 is a graph showing the change in tensile stress relative to the distance between a pair of grippers that pull the substrate side and the sealant layer side to measure the laminate strength. DETAILED DESCRIPTION OF THE INVENTION

[0033] (Barrier laminate according to the first embodiment) As shown in FIG. 1, the barrier laminate 10 of the present invention comprises a multilayer substrate 11, a vapor-deposited film 12, and a sealant layer 13, and the multilayer substrate 11 comprises at least a polypropylene resin layer 14 and a surface resin layer 15. In one embodiment, the barrier laminate 10 of the present invention further comprises a barrier coat layer 16 between the vapor-deposited film 12 and the sealant layer 13, as shown in FIG. In one embodiment, the multilayer substrate 11 includes an adhesive resin layer 17 between the polypropylene resin layer 14 and the surface resin layer 15, as shown in FIG. 4, the barrier laminate 10 includes a multilayer substrate 11, a vapor-deposited film 12, a barrier coat layer 16 provided on the vapor-deposited film 12, and a sealant layer 13. The multilayer substrate 11 includes a polypropylene resin layer 14, an adhesive resin layer 17, and a surface resin layer 15, and the adhesive resin layer 17 is provided between the polypropylene resin layer 14 and the surface resin layer 15. In one embodiment, the barrier laminate of the present invention comprises an adhesive layer (not shown) between the vapor-deposited film and the sealant layer. In one embodiment, the barrier laminate of the present invention comprises an intermediate layer between the vapor-deposited film and the sealant layer.

[0034] The haze value of the barrier laminate is preferably 20% or less, and more preferably 5% or less, which can improve the transparency of the barrier laminate. In this specification, the haze value of the barrier laminate is measured in accordance with JIS K 7105:1981 using a haze meter (Murakami Color Research Laboratory Co., Ltd.).

[0035] In the barrier laminate of the first aspect, the lamination strength between the multilayer substrate and the vapor-deposited film over a width of 15 mm is preferably 3 N or more, more preferably 4 N or more, and even more preferably 5.5 N or more. The upper limit of the lamination strength of the barrier laminate of the first aspect may be 20 N or less. The method for measuring the laminate strength of the barrier laminate will be explained in the examples below.

[0036] Conventionally, laminates in which a substrate and a sealant layer are made of different resin materials have been used to manufacture packaging containers. However, since it is difficult to separate the substrate and the sealant layer after collecting used packaging containers, they are not actively recycled. By forming the substrate and the sealant layer from the same material, there is no need to separate the substrate and the sealant layer, and the recycling suitability can be improved. By constructing the sealant layer from the same material as the polypropylene resin layer of the base material, i.e., polypropylene, there is no need to separate the packaging container into layers after collection, thereby improving its recyclability.

[0037] When the sealant layer is made of polypropylene, the content of polypropylene relative to the total amount of resin materials contained in the barrier laminate of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, thereby further improving the recyclability of packaging containers produced using the barrier laminate of the present invention.

[0038] Each layer of the barrier laminate of the present invention will be described below.

[0039] (Multilayer base material) The multilayer substrate includes at least a polypropylene resin layer and a surface resin layer, and may further include an adhesive resin layer between the polypropylene resin layer and the surface resin layer.

[0040] The multilayer substrate is subjected to a stretching treatment, and the stretching treatment may be uniaxial stretching or biaxial stretching. The stretching ratio of the multilayer base material in the machine direction (MD direction) and transverse direction (TD direction) is preferably 2 to 15 times, and more preferably 5 to 13 times. By stretching the multilayer substrate at a ratio of 2 or more, the strength and heat resistance of the multilayer substrate can be further improved, and the printability of the multilayer substrate can also be improved. From the viewpoint of the breaking limit of the multilayer substrate, the stretching ratio is preferably 15 times or less. Furthermore, when the polypropylene resin layer of the multilayer substrate is made heat-sealable to form a packaging container (e.g., a tube) that is produced by sealing an envelope, the stretching ratio is preferably 2 to 10 times, and more preferably 2.5 to 7 times.

[0041] In one embodiment, the multilayer substrate is preferably stretched so that the tensile strength in the machine direction (MD) is greater than the tensile strength in the transverse direction (TD). By adopting such a structure, it is possible to impart high ease of tearing in one direction to the packaging container produced from the barrier laminate of the present invention. The tensile strength of the multilayer substrate in the machine direction (MD) is preferably at least 1.05 times, more preferably at least 1.10 times, and even more preferably at least 1.2 times, greater than the tensile strength in the transverse direction (TD). The tensile strength in the machine direction (MD direction) can be, for example, 200 MPa or more and 300 MPa or less. In this specification, the tensile strength is measured in accordance with JIS K7127: 1999. As a measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used. The test specimen can be a rectangular film cut from the multilayer substrate, 15 mm wide and 150 mm long. The distance between the pair of chucks holding the test specimen is 100 mm at the start of the measurement, and the tensile speed is 300 mm / min. In this application, unless otherwise specified, the environment during tensile strength measurement is a temperature of 23°C and a relative humidity of 50%.

[0042] The surface resin layer of the multilayer substrate may be subjected to a surface treatment, which can improve adhesion to adjacent layers. The surface treatment method is not particularly limited, and examples thereof include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, and glow discharge treatment, as well as chemical treatments such as oxidation treatment using chemicals.

[0043] (Polypropylene resin layer) The polypropylene resin layer is made of polypropylene and may have a single-layer structure or a multi-layer structure. By providing the multilayer substrate with a layer made of polypropylene, it is possible to improve the oil resistance of a packaging container produced using the multilayer substrate.

[0044] The polypropylene contained in the polypropylene resin layer may be any of a homopolymer, a random copolymer, and a block copolymer. A polypropylene homopolymer is a polymer of only propylene, a polypropylene random copolymer is a random copolymer of propylene and an α-olefin other than propylene (e.g., ethylene, butene-1, 4-methyl-1-pentene, etc.), and a polypropylene block copolymer is a copolymer having a polymer block made of propylene and a polymer block made of the above-mentioned α-olefin other than propylene. Among these polypropylenes, it is preferable to use a homopolymer or a random copolymer from the viewpoint of transparency. When emphasis is placed on the rigidity and heat resistance of the packaging bag, it is preferable to use a homopolymer, and when emphasis is placed on impact resistance, it is preferable to use a random copolymer. It is also possible to use biomass-derived polypropylene or mechanically or chemically recycled polypropylene.

[0045] The polypropylene content in the polypropylene resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0046] The polypropylene resin layer may contain a heat seal modifier, which can improve the heat sealability of the polypropylene resin layer and make it easier to produce a packaging container by sealing it with an envelope. The heat seal modifier is not particularly limited as long as it has excellent compatibility with the polypropylene constituting the heat seal layer, and examples thereof include olefin copolymers. Furthermore, a conventionally known heat sealing agent may be applied to the surface of the polypropylene resin layer and then dried.

[0047] As long as the properties of the present invention are not impaired, the polypropylene resin layer may contain a resin material other than polypropylene, such as polyolefins such as polyethylene, (meth)acrylic resins, vinyl resins, cellulose resins, polyamide resins, polyesters, and ionomer resins. Furthermore, the polypropylene resin layer may contain additives, such as crosslinking agents, antioxidants, antiblocking agents, slip agents, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins, as long as the additives do not impair the properties of the present invention.

[0048] The thickness of the polypropylene resin layer is preferably 10 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less. By making the thickness of the polypropylene resin layer 10 μm or more, the strength and heat resistance of the multilayer substrate can be further improved. Furthermore, by setting the thickness of the polypropylene resin layer to 50 μm or less, the film-forming properties and processability of the multilayer substrate can be further improved.

[0049] The polypropylene resin layer may have a printed layer on its surface, and the image formed on the printed layer is not particularly limited, and may be a letter, a pattern, a symbol, or a combination thereof. The printing layer on the substrate can be formed using ink derived from biomass, which further reduces the environmental impact. The method for forming the printed layer is not particularly limited, and examples thereof include conventionally known printing methods such as gravure printing, offset printing, and flexographic printing.

[0050] (Surface resin layer) The multilayer substrate has a surface protective layer on a polypropylene resin layer, the surface protective layer containing a resin material having a melting point of 180°C or higher (hereinafter also referred to as a high-melting-point resin material), and a vapor-deposited film with high adhesion can be formed on the surface resin layer, thereby improving gas barrier properties. Furthermore, as will be described later, packaging containers produced using a barrier laminate having such a surface resin layer have high laminate strength.

[0051] The melting point of the high-melting-point resin material is more preferably 185°C or higher, even more preferably 190°C or higher, and particularly preferably 205°C or higher. By setting the melting point of the high-melting-point resin material to 185°C or higher, the adhesiveness of the vapor-deposited film can be further improved, the gas barrier properties can be further improved, and the laminate strength of the packaging container can be further improved. From the viewpoint of film-forming properties of the multilayer substrate, the melting point of the high-melting-point resin material is preferably 265°C or lower, more preferably 260°C or lower, and even more preferably 250°C or lower. In this specification, the melting point can be measured in accordance with JIS K7121:2012 (Method for measuring transition temperature of plastics). Specifically, the melting point can be determined by measuring a DSC curve using a differential scanning calorimetry (DSC) device at a temperature rise rate of 10°C / min.

[0052] The difference between the melting point of the high-melting-point resin material contained in the multilayer base material and the melting point of the polypropylene contained in the polypropylene resin layer is preferably 20 to 80°C, more preferably 20 to 60°C. By ensuring that the difference in melting point between the high-melting-point resin material contained in the multilayer substrate and the polypropylene contained in the polypropylene resin layer is 20°C or more, the adhesion of the vapor-deposited film can be further improved, the gas barrier properties can be further improved, and the laminate strength of the packaging container can be further improved. Furthermore, by making the difference between the melting point of the high-melting-point resin material contained in the multilayer substrate and the melting point of the polypropylene contained in the polypropylene resin layer 80°C or less, the film-forming properties of the multilayer substrate can be further improved.

[0053] The high-melting-point resin material preferably has a polar group. In the present invention, the polar group refers to a group containing one or more heteroatoms, and examples thereof include an ester group, an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, a carbonyl group, a carboxylic anhydride group, a sulfone group, a thiol group, and a halogen group. Among these, from the viewpoint of the gas barrier properties and laminate strength of the packaging container, hydroxyl groups, ester groups, amino groups, amide groups, carboxyl groups and carbonyl groups are preferred, and amide groups are more preferred.

[0054] The high-melting point resin material can be used without any particular limitation as long as it has a melting point of 180°C or higher, and examples thereof include vinyl resin, polyamide, polyimide, polyester, (meth)acrylic resin, cellulose resin, polyolefin resin, and ionomer resin.

[0055] In the present invention, resin materials having a melting point of 180° C. or higher and having a polar group are particularly preferred, and polyamides such as ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyester, nylon 6, nylon 6,6, MXD nylon, and amorphous nylon are preferred. By using such a resin material, the adhesion of the vapor-deposited film formed on the surface resin layer can be significantly improved, and the gas barrier properties thereof can be effectively improved.

[0056] In one embodiment, the high-melting-point resin material is more preferably an ethylene-vinyl alcohol copolymer. By using an ethylene-vinyl alcohol copolymer as the high-melting-point resin material, it is possible to suppress a decrease in the gas barrier properties even when the barrier laminate is bent.

[0057] In one embodiment, the high-melting-point resin material is preferably polyamide. By using polyamide as the high-melting-point resin material, it is possible to suppress a decrease in gas barrier properties even when the barrier laminate is bent, and also to suppress a decrease in gas barrier properties even when heating is performed, such as heat sealing, when producing a packaged product using the barrier laminate. It is more preferable that the high-melting-point resin material be nylon 6.

[0058] The content of the high-melting-point resin material in the surface resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0059] The surface resin layer may contain a resin material other than the high-melting-point resin material as long as the characteristics of the present invention are not impaired. Furthermore, the surface resin layer may contain additives, such as crosslinking agents, antioxidants, antiblocking agents, slip agents, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins, as long as the additives do not impair the properties of the present invention.

[0060] The ratio of the thickness of the surface resin layer to the total thickness of the multilayer base material is preferably 1% or more and 10% or less, and more preferably 1% or more and 5% or less. By making the ratio of the thickness of the surface resin layer to the total thickness of the multilayer substrate 1% or more, the adhesion of the vapor-deposited film can be further improved, the gas barrier properties can be further improved, and the laminate strength of the packaging container can be further improved. Furthermore, by setting the ratio of the thickness of the surface resin layer to the total thickness of the multilayer substrate to 10% or less, the film-forming properties and processability of the multilayer substrate can be further improved. Furthermore, as will be described later, the recyclability of packaging containers produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0061] The thickness of the surface resin layer is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 4 μm or less. By making the thickness of the surface resin layer 0.1 μm or more, the adhesion of the vapor-deposited film can be further improved, the gas barrier properties can be further improved, and the laminate strength of the packaging container can be further improved. Furthermore, by setting the thickness of the surface resin layer to 5 μm or less, the film-forming property and processability of the multilayer substrate can be further improved, and as will be described later, the recyclability of packaging containers produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0062] (adhesive resin layer) In one embodiment, the multilayer substrate may include an adhesive resin layer between the polypropylene resin layer and the surface resin layer, thereby improving adhesion between these layers.

[0063] The adhesive resin layer can be formed by using an adhesive resin such as polyether, polyester, silicone resin, epoxy resin, polyurethane, vinyl resin, phenolic resin, polyolefin, or acid-modified polyolefin. Of the above, and as will be described later, from the viewpoint of the recyclability of packaging containers produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene, polyolefins and acid-modified products thereof are preferred, and polypropylene and acid-modified products thereof are particularly preferred. As the adhesive polypropylene, commercially available products can be used, for example, the Admer series manufactured by Mitsui Chemicals, Inc.

[0064] The thickness of the adhesive resin layer is not particularly limited, but can be, for example, 1 μm or more and 15 μm or less. By making the thickness of the adhesive resin layer 1 μm or more, the adhesion between the polypropylene resin layer and the surface resin layer can be further improved. By making the thickness of the adhesive layer 15 μm or less, the processability of the multilayer substrate can be improved.

[0065] In one embodiment, the multilayer substrate is a co-extruded film, which can be produced by forming a laminated film using a T-die method, an inflation method, or the like, and then stretching the laminated film. By forming the film by the inflation method, the laminated film can be stretched at the same time.

[0066] (evaporated film) The barrier laminate of the present invention has a vapor-deposited film composed of an inorganic oxide on a surface resin layer. This improves the gas barrier properties of the barrier laminate, specifically the oxygen barrier properties and water vapor barrier properties. Furthermore, it also reduces the weight loss of contents filled in a packaging container made using the barrier laminate of the present invention.

[0067] Examples of inorganic oxides include aluminum oxide (alumina), silicon oxide (silica), magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, and silicon carbide oxide (carbon-containing silicon oxide). Among the above, silica, silicon carbide oxide and alumina are preferred. Furthermore, silica is particularly preferable because it does not require aging treatment after forming the vapor-deposited film. In one embodiment, the inorganic oxide is more preferably carbon-containing silicon oxide, since this can prevent a decrease in gas barrier properties even when the barrier laminate is bent.

[0068] The thickness of the vapor-deposited film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and even more preferably 10 nm or more and 40 nm or less. By making the thickness of the vapor-deposited film 1 nm or more, the oxygen barrier property and water vapor barrier property of the barrier laminate can be further improved. Furthermore, by setting the thickness of the vapor-deposited film to 150 nm or less, it is possible to prevent the occurrence of cracks in the vapor-deposited film, and as will be described later, it is possible to improve the recyclability of packaging containers produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene.

[0069] The vapor deposition film can be formed by a conventionally known method, for example, physical vapor deposition methods (PVD methods) such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition methods (CVD methods) such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0070] The vapor-deposited film may be a single layer formed by a single vapor deposition process, or may be a multilayer formed by multiple vapor deposition processes. In the case of a multilayer film, each layer may be made of the same material or different materials. Furthermore, each layer may be formed by the same method or different methods.

[0071] A plasma-assisted vacuum film-forming apparatus can be used as an apparatus for forming a vapor-deposited film by the PVD method. An embodiment of a method for forming a vapor-deposited film using a plasma-assisted vacuum film-forming apparatus will be described below. In one embodiment, as shown in Figures 5 and 6, the vacuum film formation apparatus includes a vacuum vessel A, an unwinding section B, a film formation drum C, a winding section D, a transport roll E, an evaporation source F, a reaction gas supply section G, an adhesion-proof box H, an evaporation material I, and a plasma gun J. 5 is a schematic cross-sectional view of the vacuum film-forming apparatus in the XZ plane direction, and FIG. 6 is a schematic cross-sectional view of the vacuum film-forming apparatus in the XY plane direction. As shown in Fig. 5, a barrier laminate 10 wound around a film-forming drum C is placed in the upper part of a vacuum container A with its surface resin layer facing downward, and an electrically grounded deposition-protective box H is placed below the film-forming drum C in the vacuum container A. An evaporation source F is placed on the bottom of the deposition-protective box H. The film-forming drum C is placed in the vacuum container A so that the surface resin layer of the multilayer substrate 11 wound around the film-forming drum C is positioned opposite the top surface of the evaporation source F with a certain gap between them. Further, transport rolls E are arranged between the unwinding section B and the film-forming drum C, and between the film-forming drum C and the winding section D. The vacuum vessel is connected to a vacuum pump (not shown). The evaporation source F is for holding the evaporation material I and is equipped with a heating device (not shown). The reactive gas supply unit G is a portion that supplies a reactive gas (oxygen, nitrogen, helium, argon, a mixed gas of these, etc.) that reacts with the evaporated deposition material. The vapor deposition material I is heated and evaporated from the evaporation source F and irradiated onto the surface resin layer of the multilayer substrate 11, and at the same time, plasma is also irradiated from the plasma gun J onto the surface resin layer, forming a vapor deposition film. Details of this formation method are disclosed in Japanese Patent Application Laid-Open No. 2011-214089.

[0072] The plasma generating device used in plasma chemical vapor deposition can be a device that generates high-frequency plasma, pulsed wave plasma, microwave plasma, or the like. A device having two or more film formation chambers can also be used. It is preferable that the device is equipped with a vacuum pump so that each film formation chamber can be maintained under vacuum. The vacuum level in each deposition chamber was 1×10 to 1×10 -6 Pa is preferred. An embodiment of a method for forming a vapor-deposited film using a plasma generating device will be described below. First, the multilayer substrate is sent into the film-forming chamber and transported onto the cooling electrode drum at a predetermined speed via an auxiliary roll. Next, a mixed gas composition containing a film-forming monomer gas containing an inorganic oxide, oxygen gas, an inert gas, etc. is supplied from the gas supply device into the film-forming chamber, and plasma is generated on the surface resin layer by glow discharge, which is then irradiated to form a vapor-deposited film containing an inorganic oxide on the surface resin layer. Details of this formation method are disclosed in Japanese Patent Application Laid-Open No. 2012-076292.

[0073] FIG. 7 is a schematic diagram showing the configuration of a plasma chemical vapor deposition apparatus used in the CVD method.

[0074] In one embodiment, as shown in FIG. 7, a plasma enhanced chemical vapor deposition apparatus unwinds a multilayer substrate 11 from a winding section B1 located within a vacuum vessel A1. The multilayer substrate 11 is then transported at a predetermined speed onto the circumferential surface of a cooling electrode drum C1 via a transport roll E1. Oxygen, nitrogen, helium, argon, and a mixture thereof are supplied from a reactive gas supply G1, and a film-forming monomer gas and the like are supplied from a raw material gas supply I1. A vapor deposition mixed gas composition consisting of these components is adjusted and introduced into the vacuum vessel A1 through a raw material supply nozzle H1. A glow discharge plasma F1 is then generated on the surface resin layer of the multilayer substrate 11 transported onto the circumferential surface of the cooling electrode drum C1, and this plasma is irradiated to form a vapor deposition film. A predetermined power is applied to the cooling electrode drum C1 from a power source K1 located outside the vacuum vessel A1, and a magnet J1 is placed near the cooling electrode drum C1 to promote plasma generation. Next, after forming the vapor-deposited film, the multilayer substrate 11 is wound up at a predetermined winding speed by a transport roll E1 onto a winding section D1. In the drawing, L1 represents a vacuum pump.

[0075] As an apparatus used in the method for forming a vapor-deposited film, a continuous vapor-deposited film-forming apparatus equipped with a plasma pretreatment chamber and a film-forming chamber can be used. An embodiment of a method for forming a vapor-deposited film using the apparatus will be described below. First, in the plasma pretreatment chamber, plasma is irradiated onto the surface resin layer of the multilayer substrate from a plasma supply nozzle, and then, in the film formation chamber, a vapor deposition film is formed on the plasma-treated surface resin layer. Details of this formation method are disclosed in International Publication WO2019 / 087960.

[0076] The surface of the deposited film is preferably subjected to the above-mentioned surface treatment, which can improve adhesion to adjacent layers.

[0077] In the barrier laminate of the present invention, the vapor-deposited film is preferably a vapor-deposited film formed by a CVD method, and more preferably a carbon-containing silicon oxide vapor-deposited film formed by a CVD method, which can prevent a decrease in gas barrier properties even when the barrier laminate is bent.

[0078] The carbon-containing silicon oxide vapor-deposited film contains silicon, oxygen, and carbon. In the carbon-containing silicon oxide vapor-deposited film, the carbon content C is preferably 3% or more and 50% or less, more preferably 5% or more and 40% or less, and even more preferably 10% or more and 35% or less, relative to the total of the three elements silicon, oxygen, and carbon (100%). By setting the carbon content C in the carbon-containing silicon oxide vapor-deposited film within the above range, it is possible to prevent the gas barrier properties from decreasing even when the barrier laminate is bent. In this specification, the ratio of each element is based on moles.

[0079] In one embodiment of the carbon-containing silicon oxide vapor-deposited film, the silicon content Si is preferably 1% to 45%, more preferably 3% to 38%, and even more preferably 8% to 33%, relative to 100% of the total of the three elements silicon, oxygen, and carbon. The oxygen content O is preferably 10% to 70%, more preferably 20% to 65%, and even more preferably 25% to 60%, relative to 100% of the total of the three elements silicon, oxygen, and carbon. By setting the silicon ratio Si and oxygen ratio O in the carbon-containing silicon oxide vapor-deposited film within the above ranges, the degradation of the gas barrier properties can be further suppressed even when the barrier laminate is bent.

[0080] In one embodiment of the carbon-containing silicon oxide vapor-deposited film, the oxygen ratio O is preferably higher than the carbon ratio C, and the silicon ratio Si is preferably lower than the carbon ratio C. The oxygen ratio O is preferably higher than the silicon ratio Si, that is, the ratios preferably decrease in the order of ratio O, ratio C, and ratio Si. This makes it possible to further suppress deterioration in gas barrier properties even when the barrier laminate is bent.

[0081] The proportions C, Si, and O in the carbon-containing silicon oxide vapor-deposited film can be measured by narrow scan analysis using X-ray photoelectron spectroscopy (XPS) under the following measurement conditions. (Measurement conditions) Equipment used: "ESCA-3400" (manufactured by Kratos) [1] Spectral collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν=1253.6eV) X-ray output: 150W (10kV 15mA) X-ray scanning area (measurement area): approx. 6 mm diameter Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV) Emission current: 20 (mA) Etching range: 10mmφ Ion sputtering time: 30 seconds, and the spectrum was collected.

[0082] (sealant layer) In one embodiment, the sealant layer comprises a resin material that can be fused to one another by heat. Resin materials that can be fused together by heat include, for example, polyolefins such as polyethylene, polypropylene, polybutene, methylpentene polymers, and cyclic olefin copolymers. Specific examples include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ethylene-α-olefin copolymers polymerized using metallocene catalysts, and ethylene-propylene copolymers such as random or block copolymers of ethylene and propylene. Furthermore, examples of resin materials that can be fused to each other by heat include ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ionomer resins, heat-sealable ethylene-vinyl alcohol resins, acid-modified polyolefins obtained by modifying polyolefins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid, polyesters such as polyethylene terephthalate (PET), polyvinyl acetate resins, poly(meth)acrylic resins, and polyvinyl chloride resins.

[0083] Conventionally, laminates in which a substrate and a sealant layer are made of different resin materials have been used to manufacture packaging containers. However, since it is difficult to separate the substrate and the sealant layer after collecting used packaging containers, they are not actively recycled. By forming the substrate and the sealant layer from the same material, it is not necessary to separate the substrate and the sealant layer, and the recyclability of the laminate can be improved. That is, from the viewpoint of the recyclability of the packaging container produced using the laminate, it is preferable that the sealant layer be formed from polypropylene, among the above-mentioned resin materials. Furthermore, by forming the sealant layer from polypropylene, the oil resistance of the packaging container produced using the barrier laminate can be improved.

[0084] The sealant layer may contain the above-mentioned heat seal modifier and additives as long as the properties of the present invention are not impaired.

[0085] The sealant layer may have a single-layer structure or a multi-layer structure.

[0086] The thickness of the sealant layer is preferably 15 μm or more and 100 μm or less, and more preferably 20 μm or more and 70 μm or less. By making the thickness of the sealant layer 15 μm or more, the laminate strength of the packaging container provided with the barrier laminate of the present invention can be further improved. Furthermore, by making the thickness of the sealant layer 100 μm or less, the processability of the barrier laminate of the present invention can be further improved.

[0087] The sealant layer may be formed by laminating a heat-sealable stretched or unstretched film with a conventionally known adhesive, or by applying and drying a heat-sealing agent.

[0088] (barrier coat layer) The barrier laminate of the present invention may further include a barrier coat layer between the vapor-deposited film and the sealant layer, thereby improving the oxygen barrier property and water vapor barrier property of the barrier laminate.

[0089] In one embodiment, the barrier coat layer contains a gas barrier resin such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyacrylonitrile, polyamides such as nylon 6, nylon 6,6, and polymetaxylylene adipamide (MXD6), polyester, polyurethane, and (meth)acrylic resin. Among these, polyvinyl alcohol is preferred from the viewpoint of oxygen barrier property and water vapor barrier property. Furthermore, by including polyvinyl alcohol in the barrier coat layer, the occurrence of cracks in the vapor-deposited film can be effectively prevented.

[0090] The content of the gas barrier resin 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 making the content of the gas barrier resin in the barrier coat layer 50% by mass or more, it is possible to further improve the oxygen barrier property and water vapor barrier property.

[0091] The barrier coat layer may contain the above-mentioned additives to the extent that the properties of the present invention are not impaired.

[0092] 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 thickness of the barrier coat layer 0.01 μm or more, the oxygen barrier property and water vapor barrier property of the barrier laminate can be further improved. By making the thickness of the barrier coat layer 10 μm or less, the processability of the barrier laminate can be improved. Furthermore, the recyclability of packaging containers produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0093] The barrier coat layer can be formed by dissolving or dispersing the gas barrier resin in water or an appropriate solvent, applying the solution, and drying. Alternatively, the barrier coat layer can be formed by applying a commercially available barrier coating agent and drying it.

[0094] In another embodiment, the barrier coat layer is a gas barrier coating film containing at least one resin composition such as a hydrolyzate of a metal alkoxide or a hydrolyzed condensate of a metal alkoxide obtained by polycondensing 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, an organic solvent, etc. By providing such a barrier coating layer on the vapor-deposited film, it is possible to effectively prevent cracks from occurring in the vapor-deposited film.

[0095] In one embodiment, the metal alkoxide is represented by the following general formula: R 1 n M(OR 2 ) m (wherein, R 1 , R 2 each represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M.

[0096] As the metal atom M, for example, silicon, zirconium, titanium, aluminum, etc. can be used. Also, R 1 and R 2 Examples of the organic group represented by the formula (I) include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group.

[0097] Examples of metal alkoxides that satisfy the above general formula include tetramethoxysilane (Si(OCH3)4), tetraethoxysilane (Si(OC2H5)4), tetrapropoxysilane (Si(OC3H7)4), and tetrabutoxysilane (Si(OC4H9)4).

[0098] It is also preferable to use a silane coupling agent together with the metal alkoxide. As the silane coupling agent, known organoalkoxysilanes containing organic reactive groups can be used, but organoalkoxysilanes having epoxy groups are particularly preferred. Examples of organoalkoxysilanes having epoxy groups include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0099] Two or more of the above silane coupling agents may be used, and the silane coupling agent is preferably used in an amount of about 1 to 20 parts by mass per 100 parts by mass of the total amount of the metal alkoxides.

[0100] As the water-soluble polymer, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are preferred, and from the viewpoints of oxygen barrier property, water vapor barrier property, water resistance and weather resistance, it is preferred to use these in combination.

[0101] The content of the water-soluble polymer in the gas barrier coating film is preferably 5 parts by mass or more and 500 parts by mass or less per 100 parts by mass of the metal alkoxide. By adjusting the content of the water-soluble polymer in the gas barrier coating film to 5 parts by mass or more per 100 parts by mass of the metal alkoxide, the oxygen barrier property and water vapor barrier property of the barrier laminate can be further improved. Also, by adjusting the content of the water-soluble polymer in the gas barrier coating film to 500 parts by mass or less per 100 parts by mass of the metal alkoxide, the film formability of the gas barrier coating film can be improved.

[0102] In the gas barrier coating film, the ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) is preferably 4.5 or less, more preferably 1.0 or more and 4.5 or less, and even more preferably 1.7 or more and 3.5 or less, by mass. By setting the ratio of metal alkoxide to water-soluble polymer to 4.5 or less, it is possible to prevent the gas barrier properties from decreasing even when the barrier laminate is bent. By setting the ratio of metal alkoxide to water-soluble polymer to be 1.0 or more, deterioration of gas barrier properties can be suppressed even when heating is performed, such as heat sealing, when producing a packaged product using the barrier laminate. The above ratio is a solid content ratio.

[0103] The surface of the gas barrier coating film preferably has a ratio of silicon atoms to carbon atoms (Si / C) measured by X-ray photoelectron spectroscopy (XPS) of 1.60 or less, more preferably 0.50 or more and 1.60 or less, and even more preferably 0.90 or more and 1.35 or less. By setting the ratio of silicon atoms to carbon atoms to 1.60 or less, it is possible to prevent the gas barrier properties from decreasing even when the barrier laminate is bent. By setting the ratio of silicon atoms to carbon atoms to be 0.50 or more, deterioration of gas barrier properties can be suppressed even when heating is performed, such as heat sealing, when a packaged product is produced using the barrier laminate. The above range of the ratio of silicon atoms to carbon atoms can be achieved by appropriately adjusting the ratio of metal alkoxide to water-soluble polymer. In this specification, the ratio of silicon atoms to carbon atoms is based on moles.

[0104] The ratio of silicon atoms to carbon atoms by X-ray photoelectron spectroscopy (XPS) can be measured by narrow scan analysis under the following measurement conditions. (Measurement conditions) Equipment used: "ESCA-3400" (manufactured by Kratos) [1] Spectral collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν=1253.6eV) X-ray output: 150W (10kV 15mA) X-ray scanning area (measurement area): approx. 6 mm diameter Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV) Emission current: 20 (mA) Etching range: 10mmφ Ion sputtering time: 30 seconds + 30 seconds + 60 seconds (total 120 seconds) and spectrum was collected.

[0105] The thickness of the gas barrier coating film is preferably from 0.01 μm to 100 μm, and more preferably from 0.1 μm to 50 μm, which allows for improved oxygen barrier properties and water vapor barrier properties while maintaining recyclability. By making the thickness of the gas barrier coating film 0.01 μm or more, the oxygen barrier property and water vapor barrier property of the barrier laminate can be improved, and the occurrence of cracks in the vapor-deposited film can be prevented. By setting the thickness of the gas barrier coating film to 100 μm or less, the recyclability of packaging containers produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0106] The gas barrier coating film can be formed by applying a composition containing the above-mentioned materials by a conventionally known means such as roll coating using a gravure roll coater or the like, spray coating, spin coating, dipping, brush coating, bar coating, or applicator coating, and then polycondensing the composition by a sol-gel method. The sol-gel catalyst is preferably an acid or an amine compound. As the amine compound, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is preferred, such as N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. Among these, N,N-dimethylbenzylamine is preferred. The sol-gel catalyst is preferably used in the range of 0.01 to 1.0 part by mass, more preferably 0.03 to 0.3 part by mass, per 100 parts by mass of the metal alkoxide. By using a sol-gel catalyst in an amount of 0.01 part by mass or more per 100 parts by mass of metal alkoxide, the catalytic effect can be improved, and by using a sol-gel catalyst in an amount of 1.0 part by mass or less per 100 parts by mass of metal alkoxide, the thickness of the gas barrier coating film formed can be made uniform.

[0107] The composition may further contain an acid, which is used as a catalyst in the sol-gel process, mainly for the hydrolysis of metal alkoxides, silane coupling agents, and the like. Examples of acids that can be used include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid. The amount of acid used is preferably 0.001 mol or more and 0.05 mol or less based on the total molar amount of the metal alkoxide and the alkoxide portion (e.g., silicate portion) of the silane coupling agent. The catalytic effect can be improved by using an acid in an amount of 0.001 mole or more relative to the total molar amount of the metal alkoxide and the alkoxide portion (e.g., silicate portion) of the silane coupling agent.Furthermore, the thickness of the gas barrier coating film formed can be made uniform by using an acid in an amount of 0.05 mole or less relative to the total molar amount of the metal alkoxide and the alkoxide portion (e.g., silicate portion) of the silane coupling agent.

[0108] The composition preferably contains water in an amount of 0.1 to 100 moles, more preferably 0.8 to 2 moles, per mole of the total molar amount of the metal alkoxides. By adjusting the water content to 0.1 mol or more per mol of the total molar amount of metal alkoxides, the oxygen barrier property and water vapor barrier property of the barrier laminate of the present invention can be improved. Also, by adjusting the water content to 100 mol or less per mol of the total molar amount of alkoxides, the hydrolysis reaction can be carried out quickly.

[0109] The composition may also contain an organic solvent, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, or n-butanol.

[0110] An embodiment of the method for forming a gas barrier coating film will be described below. First, a composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel catalyst, water, an organic solvent, and optionally a silane coupling agent, etc. A polycondensation reaction gradually proceeds in the composition. Next, the composition is applied onto the vapor-deposited film by the above-mentioned conventionally known method and dried, which further promotes the polycondensation reaction of the metal alkoxide and the water-soluble polymer (and the silane coupling agent, if the composition contains one) to form a composite polymer layer. Finally, the composition is heated, for example, at a temperature of 20 to 250° C., preferably 50 to 220° C., for 1 second to 10 minutes, to form a gas barrier coating film.

[0111] The barrier coat layer may have a printed layer formed on its surface, and the method for forming the printed layer is as described above.

[0112] (Adhesive layer) The barrier laminate of the present invention includes an adhesive layer between the vapor-deposited film and the sealant layer.

[0113] The adhesive layer contains at least one adhesive, and the adhesive may be a one-component curing type, a two-component curing type, or a non-curing type. The adhesive may be a solvent-free adhesive or a solvent-based adhesive, but from the viewpoint of environmental load, a solvent-free adhesive is preferably used. Examples of solvent-free adhesives include polyether adhesives, polyester adhesives, silicone adhesives, epoxy adhesives, and urethane adhesives, and among these, two-component curing urethane adhesives can be preferably used. Examples of solvent-based adhesives include rubber-based adhesives, vinyl-based adhesives, silicone-based adhesives, epoxy-based adhesives, phenol-based adhesives, and olefin-based adhesives.

[0114] The thickness of the adhesive layer is not particularly limited, and can be, for example, 0.1 μm or more and 10 μm or less.

[0115] (middle class) In one embodiment, the barrier laminate of the present invention includes a middle layer between the vapor deposition layer and the sealant layer, which can provide stiffness to the barrier laminate of the present invention and improve its strength.

[0116] The intermediate layer contains a resin material, for example, polyolefin, vinyl resin, polyester, (meth)acrylic resin, cellulose resin, etc. Among these, polypropylene is particularly preferred from the viewpoint of the recyclability of the barrier laminate.

[0117] The intermediate layer may contain the above-mentioned additives to the extent that the properties of the present invention are not impaired.

[0118] The intermediate layer may have the above-mentioned vapor-deposited film or barrier coat layer on its surface.

[0119] The intermediate layer is preferably made of a resin film made of the above resin material, and from the viewpoint of strength, the resin film is preferably subjected to a stretching treatment. The stretching treatment may be uniaxial stretching or biaxial stretching.

[0120] The thickness of the intermediate layer is preferably 10 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less. By making the thickness of the intermediate layer 10 μm or more, the strength of the barrier laminate can be further improved. Furthermore, by making the thickness of the polypropylene resin layer 50 μm or less, the processability of the barrier laminate can be further improved.

[0121] The intermediate layer can be provided via the above-mentioned adhesive layer.

[0122] (Barrier laminate according to the second embodiment) As shown in FIG. 8, the barrier laminate 20 of the present invention comprises a multilayer substrate 21, a vapor-deposited film 22, and a sealant layer 23, and the multilayer substrate 21 comprises at least a polypropylene resin layer 24 and a surface coating layer 25. In one embodiment, the barrier laminate 20 of the present invention further comprises a barrier coat layer 26 on the vapor-deposited film 22, as shown in FIG. In one embodiment, the barrier laminate of the present invention comprises an adhesive layer (not shown) between the vapor-deposited film and the sealant layer. In one embodiment, the barrier laminate of the present invention comprises an intermediate layer between the vapor-deposited film and the sealant layer.

[0123] The haze value of the barrier laminate is preferably 20% or less, and more preferably 5% or less, which can improve the transparency of the barrier laminate.

[0124] In the barrier laminate of the second embodiment, the laminate strength between the multilayer substrate and the vapor-deposited film over a width of 15 mm is preferably 3 N or more, more preferably 4 N or more, and even more preferably 5.5 N or more. The upper limit of the laminate strength of the barrier laminate of the second embodiment may be 20 N or less. The method for measuring the laminate strength of the barrier laminate will be explained in the examples below.

[0125] As in the first embodiment, the sealant layer is preferably made of the same material as the polypropylene resin layer of the substrate, i.e., polypropylene, which can improve the recyclability of packaging containers made using the barrier laminate of the present invention.

[0126] When the sealant layer is made of polypropylene, the content of polypropylene relative to the total amount of resin materials contained in the barrier laminate of the present invention is preferably 80% by mass or more, more preferably 95% by mass or more, thereby further improving the recyclability of packaging containers produced using the barrier laminate of the present invention.

[0127] The multilayer substrate included in the barrier laminate of the present invention will be described below. Note that the layers included in the barrier laminate of the second embodiment other than the multilayer substrate are the same as those in the barrier laminate of the first embodiment, and therefore will not be described here.

[0128] (Multilayer base material) The multilayer substrate includes a polypropylene resin layer and a surface coating layer.

[0129] (Polypropylene resin layer) The polypropylene resin layer is made of polypropylene and may have a single-layer structure or a multi-layer structure. By providing the multilayer substrate with a layer made of polypropylene, it is possible to improve the oil resistance of a packaging container produced using the multilayer substrate.

[0130] The polypropylene resin layer is a film that has been subjected to a stretching treatment, and the stretching treatment may be uniaxial stretching or biaxial stretching. The stretching ratio in the machine direction (MD direction) and the transverse direction (TD direction) of the polypropylene resin layer is preferably 2 times or more and 15 times or less, and more preferably 5 times or more and 13 times or less. By setting the stretching ratio to 2 times or more, the strength and heat resistance of the polypropylene resin layer can be further improved, and the printability of the polypropylene resin layer can also be improved. From the viewpoint of the breaking limit of the polypropylene resin layer, the stretching ratio is preferably 15 times or less.

[0131] The polypropylene contained in the polypropylene resin layer may be any of a homopolymer, a random copolymer, and a block copolymer. A polypropylene homopolymer is a polymer of only propylene, a polypropylene random copolymer is a random copolymer of propylene and an α-olefin other than propylene (e.g., ethylene, butene-1, 4-methyl-1-pentene, etc.), and a polypropylene block copolymer is a copolymer having a polymer block made of propylene and a polymer block made of the above-mentioned α-olefin other than propylene. Among these polypropylenes, it is preferable to use a homopolymer or a random copolymer from the viewpoint of transparency. When emphasis is placed on the rigidity and heat resistance of the packaging bag, it is preferable to use a homopolymer, and when emphasis is placed on impact resistance, it is preferable to use a random copolymer. It is also possible to use biomass-derived polypropylene or mechanically or chemically recycled polypropylene.

[0132] The polypropylene content in the polypropylene resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0133] As long as the properties of the present invention are not impaired, the polypropylene resin layer may contain a resin material other than polypropylene, such as polyolefins such as polyethylene, (meth)acrylic resins, vinyl resins, cellulose resins, polyamide resins, polyesters, and ionomer resins. Furthermore, the polypropylene resin layer may contain additives, such as crosslinking agents, antioxidants, antiblocking agents, slip agents, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins, as long as the additives do not impair the properties of the present invention.

[0134] The thickness of the polypropylene resin layer is preferably 10 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less. By making the thickness of the polypropylene resin layer 10 μm or more, the strength and heat resistance of the multilayer substrate can be further improved. Furthermore, by setting the thickness of the polypropylene resin layer to 50 μm or less, the film-forming properties and processability of the multilayer substrate can be further improved.

[0135] The polypropylene resin layer may have a printed layer on its surface, and the image formed on the printed layer is not particularly limited, and may be a letter, a pattern, a symbol, or a combination thereof. From the viewpoint of environmental impact, it is preferable that the printing layer be formed on the substrate using ink derived from biomass. The method for forming the printed layer is not particularly limited, and examples thereof include conventionally known printing methods such as gravure printing, offset printing, flexographic printing, etc. Among these, flexographic printing is preferred from the viewpoint of environmental load.

[0136] The polypropylene resin layer may be subjected to a surface treatment, which can improve adhesion to the surface coating layer. The surface treatment method is not particularly limited, and examples thereof include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, and glow discharge treatment, as well as chemical treatments such as oxidation treatment using chemicals.

[0137] (surface coating layer) The multilayer substrate has a surface coating layer containing a resin material having a polar group on a polypropylene resin layer, and a vapor-deposited film with high adhesion can be formed on the surface coating layer, thereby improving gas barrier properties. Furthermore, as will be described later, packaging containers produced using a barrier laminate having a surface coating layer have high laminate strength.

[0138] The surface coating layer contains a resin material having a polar group. In the present invention, a polar group refers to a group containing one or more heteroatoms, and examples thereof include an ester group, an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, a carbonyl group, a carboxylic anhydride group, a sulfone group, a thiol group, and a halogen group. Among these, from the viewpoint of lamination properties of packaging containers, carboxyl groups, carbonyl groups, ester groups, hydroxyl groups and amino groups are preferred, and carboxyl groups and hydroxyl groups are more preferred.

[0139] Preferred resin materials having a polar group include ethylene vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyester, polyethyleneimine, hydroxyl group-containing (meth)acrylic resin, polyamides such as nylon 6, nylon 6,6, MXD nylon and amorphous nylon, and polyurethane, with polyamides, hydroxyl group-containing (meth)acrylic resin, ethylene vinyl alcohol copolymer and polyvinyl alcohol being particularly preferred. In one embodiment, the resin material having a polar group is preferably a hydroxyl group-containing (meth)acrylic resin, since this can suppress deterioration of gas barrier properties even when heating, such as heat sealing, is performed when producing a packaged product using the barrier laminate. By using such a resin material, the adhesion of the vapor-deposited film formed on the surface coating layer can be significantly improved, and the gas barrier properties thereof can be effectively improved.

[0140] In the present invention, the surface coating layer can be formed using an aqueous emulsion or a solvent-based emulsion. Specific examples of aqueous emulsions include polyamide-based emulsions, polyethylene-based emulsions, and polyurethane-based emulsions, while specific examples of solvent-based emulsions include polyester-based emulsions.

[0141] The content of the resin material having a polar group in the surface coating layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0142] The surface coating layer may contain a resin material other than the resin material having a polar group, as long as the characteristics of the present invention are not impaired. Furthermore, the surface coating layer may contain additives, such as crosslinking agents, antioxidants, antiblocking agents, slip agents, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins, as long as the additives do not impair the properties of the present invention.

[0143] The ratio of the thickness of the surface coating layer to the total thickness of the multilayer substrate is preferably 0.08% or more and 20% or less, more preferably 0.2% or more and 20% or less, preferably 1% or more and 20% or less, and more preferably 3% or more and 10% or less. By setting the ratio of the thickness of the surface coating layer to the total thickness of the multilayer substrate to 0.08% or more, the adhesion of the vapor-deposited film can be further improved, the gas barrier properties can be further improved, and the laminate strength of the packaging container can be further improved. Furthermore, by setting the ratio of the thickness of the surface resin layer to the total thickness of the multilayer substrate to 20% or less, the processability of the multilayer substrate can be further improved. Furthermore, as will be described later, the recyclability of packaging containers produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0144] The thickness of the surface coating layer is preferably 0.02 μm or more and 10 μm or less, more preferably 0.05 μm or more and 10 μm or less, even more preferably 0.1 μm or more and 10 μm or less, and even more preferably 0.2 μm or more and 5 μm or less. By making the thickness of the surface coating layer 0.02 μm or more, the adhesion of the vapor-deposited film can be further improved, the gas barrier properties can be further improved, and the laminate strength of the packaging container can be further improved. Furthermore, by setting the thickness of the surface coating layer to 10 μm or less, the processability of the multilayer substrate can be further improved, and as will be described later, the recyclability of packaging containers produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0145] The multilayer substrate can be produced offline. Specifically, a resin composition containing polypropylene is formed into a film using a T-die method, an inflation method, or the like, and then stretched to form a resin film. A coating liquid for forming a coat is applied to the resin film, followed by drying. The multilayer substrate can also be produced in-line by forming a resin composition containing polypropylene into a film using a T-die method or an inflation method, etc., to form a resin film, stretching it in the machine direction (MD), applying a coating liquid for forming a coat onto the resin film, drying it, and then stretching it in the transverse direction (TD). Stretching in the transverse direction may be carried out first.

[0146] (packaging container) The packaging container of the present invention is characterized by comprising the above-mentioned barrier laminate. Examples of the packaging container include packaging products (packaging bags), lids, and laminate tubes.

[0147] Examples of packaging bags include various types of packaging bags such as a standing pouch type, a side seal type, a two-sided seal type, a three-sided seal type, a four-sided seal type, an envelope seal type, a palm seal type (pillow seal type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and a gusset type.

[0148] As shown in FIG. 10, the packaging container of the present invention is a packaging bag 30 made by bonding two barrier laminates together (the shaded areas are the heat-sealed areas). When the tensile strength of the multilayer substrate in the longitudinal direction (MD direction) is greater than the tensile strength in the transverse direction (TD direction), it is preferable to fabricate the packaging bag so that the longitudinal direction (MD direction) of the multilayer substrate corresponds to the transverse direction of the packaging bag 30, and the transverse direction (TD direction) of the multilayer substrate corresponds to the longitudinal direction of the packaging bag 30. This configuration makes it extremely easy to tear the packaging container in the transverse direction. The same applies to the packaging containers exemplified below.

[0149] The packaging container of the present invention is a stand-up pouch 40 as shown in FIG. Fig. 11 is a diagram showing a simplified example of the configuration of a stand-up pouch. As shown in Fig. 11, a stand-up pouch 40 is made up of a body portion (side sheets) 41 and a bottom portion (bottom sheet) 42. At least one of the side sheets 41 and the bottom sheet 42 of the standing pouch 40 is made of the barrier laminate of the present invention.

[0150] In one embodiment, the body 41 of the standing pouch 40 can be formed by bag manufacturing so that the sealant layer of the barrier laminate of the present invention is the innermost layer. In another embodiment, the side sheet 41 can be formed by preparing two barrier laminates of the present invention, overlapping them with their sealant layers facing each other, inserting two V-shaped laminates into both ends of the overlapped barrier laminate so that the sealant layers are on the outside, and heat-sealing the resulting laminate. This production method can produce a stand-up pouch having a body with side gussets.

[0151] In one embodiment, the bottom sheet 42 of the standing pouch 40 can be formed by inserting the barrier laminate of the present invention between pre-formed side sheets and heat-sealing them. More specifically, the bottom sheet 42 can be formed by folding the barrier laminate into a V-shape with the sealant layer facing outward, inserting it between pre-formed side sheets and heat-sealing them.

[0152] The packaging container may also be provided with easy-opening means 51 as shown in FIG. Examples of the easy-to-open means 51 include, as shown in FIG. 10, a notch portion 52 that serves as the starting point for tearing, and a half-cut line 53 formed by laser processing or a cutter as the path for tearing.

[0153] 11, the packaging container may be provided with a steam release mechanism 50. The steam release mechanism 50 is configured to connect the inside and outside of the packaging container when the steam pressure inside the packaging container reaches or exceeds a predetermined value, thereby allowing steam to escape and preventing steam from escaping from locations other than the steam release mechanism 50. The steam release mechanism 50 comprises a steam release seal portion 50a that protrudes from the side seal portion toward the inside of the packaging container, and a non-sealed portion 50b that is isolated from the content-accommodating portion by the steam release seal portion 50a. The non-sealed portion 50b is connected to the outside of the packaging container. When a packaging container filled with contents and having a heat-sealed opening is heated in a microwave oven or the like, the internal pressure increases and the steam-sealed portion 50a peels off. Steam passes through the peeled portion of the steam seal 50a and the non-sealed portion 50b and escapes to the outside of the packaging container.

[0154] Heat sealing can be performed by any known method, such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, or ultrasonic sealing.

[0155] The contents filled in the packaging container are not particularly limited, and may be liquid, powder, or gel. The contents may also be food or non-food. [Example]

[0156] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0157] Example 1-1 Polyamide (Ube Industries, Ltd., Polyamide 6, melting point: 220 ° C), adhesive resin (Mitsui Chemicals, Inc., Admer QF500, maleic anhydride modified polypropylene), and polypropylene (Japan Polypropylene, Novatec FL203D, melting point: 160 ° C) were co-extruded, and then stretched 5 times in the machine direction (MD direction) and 10 times in the transverse direction (TD direction) using a sequential biaxial stretching device. A 21 μm thick multilayer substrate was produced, comprising a surface resin layer (0.4 μm) made of polyamide, an adhesive resin layer (1 μm) made of adhesive resin, and a polypropylene resin layer (19.6 μm) made of polypropylene. The ratio of the thickness of the surface resin layer made of polyamide to the layer thickness of the multilayer substrate was 2%.

[0158] A carbon-containing silicon oxide vapor deposition film having a thickness of 12 nm was formed on the surface resin layer of the multilayer substrate prepared as described above using a low-temperature plasma chemical vapor deposition apparatus (CVD method) in a roll-to-roll manner while applying tension to the multilayer substrate. The vapor deposition film formation conditions were as follows: (Formation conditions) Hexamethyldisiloxane: oxygen gas: helium = 1:10:10 (unit: slm) Cooling and electrode drum power supply: 22kw Line speed: 100m / min

[0159] In the carbon-containing silicon oxide vapor-deposited film, the carbon percentage C, silicon percentage Si, and oxygen percentage O were 32.7%, 29.8%, and 37.5%, respectively, based on a total of 100% for the three elements silicon, oxygen, and carbon. The percentages of each element were measured by narrow scan analysis using X-ray photoelectron spectroscopy (XPS) under the following measurement conditions: (Measurement conditions) Equipment used: "ESCA-3400" (manufactured by Kratos) [1] Spectral collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν=1253.6eV) X-ray output: 150W (10kV 15mA) X-ray scanning area (measurement area): approx. 6 mm diameter Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV) Emission current: 20 (mA) Etching range: 10mmφ Ion sputtering time: 30 seconds, and the spectrum was collected.

[0160] 385 g of water, 67 g of isopropyl alcohol, and 9.1 g of 0.5 N hydrochloric acid were mixed to obtain a solution with a pH of 2.2. 175 g of tetraethoxysilane as a metal alkoxide and 9.2 g of glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed with this solution while cooling to 10°C, to obtain Solution A. Solution B was obtained by mixing 14.7 g of polyvinyl alcohol as a water-soluble polymer having a saponification degree of 99% or more and a polymerization degree of 2400, 324 g of water, and 17 g of isopropyl alcohol. Solution A and solution B were mixed in a mass ratio of 6.5:3.5 to obtain a barrier coating agent.

[0161] The barrier coating agent was spin-coated onto the vapor-deposited film formed on the multilayer substrate, and the resulting film was then heated in an oven at 80° C. for 60 seconds to form a barrier coating layer with a thickness of 300 nm.

[0162] A 30 μm thick unstretched polypropylene film (CP S, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was dry laminated onto the barrier coat layer formed as above as a sealant layer via a polyurethane adhesive (Takelac A-969V / Takenate A-5 (blending ratio 3 / 1), manufactured by Mitsui Chemicals, Inc.), and the resulting mixture was left to stand at 40° C. for 24 hours to obtain a barrier laminate of the present invention. The thickness of the adhesive layer formed by the polyurethane adhesive was 1 μm. The polypropylene content in the barrier laminate was 94% by mass.

[0163] Example 1-2 A barrier laminate was produced in the same manner as in Example 1-1, except that the sealant layer was formed by applying a polypropylene heat seal material (Arrowbase DA1010N, manufactured by Unitika Ltd.) to the barrier coat layer and drying it. The thickness of the sealant layer was 3 μm. The polypropylene content in the barrier laminate was 95% by mass.

[0164] Examples 1-3 A barrier laminate was produced in the same manner as in Example 1-1, except that the sealant layer was changed to a 30 μm thick heat-sealable biaxially oriented polypropylene film (P6181, manufactured by Toyo Kaisha, Ltd.). The polypropylene content in the barrier laminate was 94% by mass.

[0165] Examples 1-4 On the barrier coating layer formed in Example 1-1, a biaxially oriented polypropylene film (P2171, manufactured by Toyo Kaisha, Ltd.) having a thickness of 30 μm was dry-laminated as an intermediate layer via a polyurethane adhesive (Takelac A-969V / Takenate A-5 (mixing ratio 3 / 1), manufactured by Mitsui Chemicals, Inc.). Next, a polypropylene heat seal material (Arrowbase DA1010N, manufactured by Unitika Ltd.) was applied to the biaxially oriented polypropylene film and dried to form a sealant layer with a thickness of 3 μm, thereby obtaining a barrier laminate of the present invention. The polypropylene content in the barrier laminate was 95% by mass.

[0166] Examples 1-5 A barrier laminate was produced in the same manner as in Example 1-1, except that the polyamide used in producing the multilayer substrate was changed to polyvinyl alcohol (Bhopal JC-33, manufactured by Nippon Acetic Acid Bhopal Co., Ltd., melting point: 200°C) and a surface resin layer was formed.

[0167] Example 2-1 A surface coating layer forming solution having the following composition was applied to the corona-treated surface of a 20 μm-thick biaxially oriented polypropylene film (ME-1, manufactured by Mitsui Chemicals Tohcello Co., Ltd.), one side of which had been corona-treated, and dried to form a 0.5 μm-thick surface coating layer, thereby producing a multilayer substrate. (Coating liquid composition for forming surface coating layer) Polyvinyl alcohol 5% by mass (Nippon Bi-Poval Co., Ltd., VC-10, polymerization degree 1000, saponification degree 99.3 mol% or more) ·Water 90% by mass Isopropanol (IPA) 5% by mass

[0168] A barrier laminate was produced in the same manner as in Example 1-1, except that the multilayer substrate produced in Example 1-1 was replaced with the multilayer substrate produced as described above. The polypropylene content in the barrier laminate was 96% by mass.

[0169] Example 2-2 A barrier laminate was produced in the same manner as in Example 2-1, except that the composition of the coating liquid for forming the surface coat layer was changed as follows. The polypropylene content in the barrier laminate was 96% by mass. (Coating liquid composition for forming surface coating layer) ·EVOH 75% by mass (Ebersolve #10, manufactured by Nippon Cima Co., Ltd.) ·Water 12.5% ​​by mass 1-propanol 12.5% ​​by mass

[0170] Comparative Example 1-1 The above polypropylene (Novatec FL203D, manufactured by Japan Polypropylene Corporation, melting point: 160°C) was extruded and then stretched 5 times in the machine direction (MD direction) and 10 times in the transverse direction (TD direction) using a sequential biaxial stretching device to produce a propylene film with a thickness of 20 μm. A barrier laminate was produced in the same manner as in Example 1-1, except that the multilayer substrate in Example 1-1 was changed to the polypropylene film produced as described above.

[0171] <<Gas barrier property evaluation>> The barrier laminates obtained in the above Examples and Comparative Examples were cut out to obtain test pieces. The test pieces were used to measure the oxygen permeability (cc / m 2 ·day·atm) and water vapor permeability (g / m 2 ·day) was measured by the following method, and the results are summarized in Table 1.

[0172] [Oxygen permeability] Using an oxygen permeability measuring device (OX-TRAN2 / 20 manufactured by MOCON), the test piece was set so that the multilayer substrate side was the oxygen supply side, and the oxygen permeability was measured in an environment of 23°C and a relative humidity of 90% RH in accordance with JIS K 7126. [Water vapor permeability] Using a water vapor permeability measuring device (MOCON, PERMATRAN-w 3 / 33), the test piece was set so that the multilayer substrate side was the water vapor supply side, and the water vapor permeability was measured in an environment of 40°C and a relative humidity of 90% RH in accordance with JIS K 7129.

[0173] <<Laminate strength test>> The barrier laminates obtained in the above Examples and Comparative Examples were cut into strips of 15 mm width, and the laminate strength (N / 15 mm) of each sample was measured using a tensile tester (Tensilon universal material testing machine, manufactured by Orientec Co., Ltd.) in accordance with JIS K6854-2, at a peel rate of 50 mm / min and a 90° peel angle (T-peel method). Specifically, a barrier laminate was cut out, and a strip-shaped test piece 70 was prepared by peeling the substrate side 71 from the sealant layer side 72 by 15 mm in the long-side direction, as shown in FIG. 12 . Then, as shown in FIG. 13 , the already peeled portions of the substrate side 71 and the sealant layer side 72 were each held with grips 73 of a measuring device. The grips 73 were pulled at a speed of 50 mm / min in opposite directions perpendicular to the plane of the portions where the substrate side 71 and the sealant layer side 72 were still laminated, and the average value of tensile stress in the stable region (see FIG. 14 ) was measured. The spacing S between the grips 73 at the start of pulling was 30 mm, and the spacing S between the grips 73 at the end of pulling was 60 mm. FIG. 14 shows the change in tensile stress with respect to the spacing S between the grips 73. As shown in FIG. 14 , the change in tensile stress with respect to the spacing S passes through a first region and then enters a second region (stable region) where the rate of change is smaller than that in the first region. The average value of the tensile stress in the stable region was measured for five test pieces 70, and the average value was used as the laminate strength. The measurement was performed in an environment of a temperature of 23°C and a relative humidity of 50%. The measurement results are summarized in Table 1.

[0174] [Table 1]

[0175] Example 3-1 A multilayer substrate was prepared in the same manner as in Example 1-1, and a vapor-deposited film was formed on the multilayer substrate.

[0176] A barrier coat layer was formed on the vapor-deposited film so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 5.1 on a mass basis.

[0177] The ratio of Si element to C element present on the surface of the barrier coat layer was measured. The measurement was performed by narrow scan analysis using X-ray photoelectron spectroscopy (XPS) under the following measurement conditions. In the following examples, the ratio of Si element to C element present on the surface of the barrier coat layer was measured in the same manner. (Measurement conditions) Equipment used: "ESCA-3400" (manufactured by Kratos) [1] Spectral collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν=1253.6eV) X-ray output: 150W (10kV 15mA) X-ray scanning area (measurement area): approx. 6 mm diameter Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV) Emission current: 20 (mA) Etching range: 10mmφ Ion sputtering time: 30 seconds + 30 seconds + 60 seconds (total 120 seconds) and spectrum was collected.

[0178] Next, a 60 μm thick unstretched polypropylene film (P1128, manufactured by Toyobo Co., Ltd.) was dry laminated onto the barrier coat layer using a two-component curing polyurethane adhesive to form a sealant layer, thereby obtaining a barrier laminate according to the first embodiment.

[0179] Example 3-2 A barrier laminate of the first embodiment was produced in the same manner as in Example 3-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 by mass.

[0180] Example 3-3 A barrier laminate of the first embodiment was produced in the same manner as in Example 3-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 by mass.

[0181] Examples 3-4 A barrier laminate of the first embodiment was produced in the same manner as in Example 3-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 by mass.

[0182] Examples 3-5 A barrier laminate of the first embodiment was produced in the same manner as in Example 3-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 by mass.

[0183] Examples 3-6 A barrier laminate according to the first embodiment was produced in the same manner as in Example 3-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 by mass.

[0184] Example 4-1 A barrier laminate of the first embodiment was produced in the same manner as in Example 3-1, except that the formation of the vapor-deposited film was changed as follows. Using a continuous vapor deposition film formation device that has a pretreatment section in which an actual oxygen plasma pretreatment device is placed and a film formation section separated from each other, in the pretreatment section, tension is applied to the multilayer substrate by roll-to-roll movement, and plasma is introduced from a plasma supply nozzle under the conditions described below to perform oxygen plasma pretreatment. In the film formation section, which is continuously transported, a 12 nm thick aluminum oxide (alumina) vapor deposition film is formed on the oxygen plasma-treated surface under the conditions described below using a reactive resistance heating method as the heating means for vacuum vapor deposition (PVD method). (Formation conditions) (Oxygen plasma pretreatment conditions) Plasma intensity: 200W·sec / m 2 Plasma formation gas ratio: oxygen:argon = 2:1 Voltage applied between pretreatment drum and plasma supply nozzle: 340V (Film formation conditions) Conveying speed: 400m / min Oxygen gas supply: 20,000 sccm

[0185] Example 4-2 A barrier laminate of the first embodiment was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 by mass.

[0186] Example 4-3 A barrier laminate of the first embodiment was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 by mass.

[0187] Example 4-4 A barrier laminate of the first embodiment was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 by mass.

[0188] Examples 4-5 A barrier laminate of the first embodiment was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 by mass.

[0189] Examples 4-6 A barrier laminate of the first embodiment was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 by mass.

[0190] Example 5-1 A barrier laminate of the first embodiment was produced in the same manner as in Example 3-1, except that the polyamide was changed to ethylene vinyl alcohol (Eval F171B, manufactured by Kuraray Co., Ltd., melting point: 183°C) and a surface resin layer was formed.

[0191] Example 5-2 A barrier laminate of the first embodiment was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 by mass.

[0192] Example 5-3 A barrier laminate of the first embodiment was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 by mass.

[0193] Example 5-4 A barrier laminate of the first embodiment was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 by mass.

[0194] Example 5-5 A barrier laminate of the first embodiment was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 by mass.

[0195] Examples 5-6 A barrier laminate of the first embodiment was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 by mass.

[0196] Example 6-1 A barrier laminate of the first embodiment was produced in the same manner as in Example 4-1, except that the polyamide was changed to ethylene vinyl alcohol (Eval F171B, manufactured by Kuraray Co., Ltd., melting point: 183°C) and a surface resin layer was formed.

[0197] Example 6-2 A barrier laminate of the first embodiment was produced in the same manner as in Example 6-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 by mass.

[0198] Example 6-3 A barrier laminate of the first embodiment was produced in the same manner as in Example 6-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 by mass.

[0199] Example 6-4 A barrier laminate of the first embodiment was produced in the same manner as in Example 6-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 by mass.

[0200] Examples 6-5 A barrier laminate of the first embodiment was produced in the same manner as in Example 6-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 by mass.

[0201] Example 6-6 A barrier laminate of the first embodiment was produced in the same manner as in Example 6-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 by mass.

[0202] Example 7-1 A coating liquid for forming a surface coating layer prepared as follows was applied to the corona-treated surface of the biaxially stretched polypropylene film of Example 2-1, and dried to form a surface coating layer with a thickness of 0.5 μm, thereby producing a multilayer substrate.

[0203] A hydroxyl group-containing (meth)acrylic resin (number average molecular weight 25,000, glass transition temperature 99°C, hydroxyl value 80 mg KOHL / g) was diluted with a mixed solvent of methyl ketone and ethyl acetate (mixing ratio 1:1) to a solids concentration of 10 mass % to prepare the base resin. An ethyl acetate solution containing tolylene diisocyanate (solid content 75% by mass) was added to the base resin as a curing agent to obtain a coating solution for forming a surface coating layer. The amount of the curing agent used was 10 parts by mass per 100 parts by mass of the base resin.

[0204] Next, a vapor-deposited film was formed in the same manner as in Example 2-1.

[0205] Next, a barrier coat layer was formed on the vapor-deposited film so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 5.1 on a mass basis.

[0206] Next, a 60 μm thick unstretched polypropylene film (P1128, manufactured by Toyobo Co., Ltd.) was dry laminated onto the barrier coat layer using a two-component curing polyurethane adhesive to form a sealant layer, thereby obtaining a barrier laminate according to the second embodiment.

[0207] Example 7-2 A barrier laminate of the second embodiment was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 by mass.

[0208] Example 7-3 A barrier laminate of the second embodiment was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 by mass.

[0209] Example 7-4 A barrier laminate of the second embodiment was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 by mass.

[0210] Example 7-5 A barrier laminate of the second embodiment was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 by mass.

[0211] Examples 7-6 A barrier laminate of the second embodiment was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 by mass.

[0212] Example 8-1 A third barrier laminate was produced in the same manner as in Example 7-1, except that the deposition film was formed as follows. A silicon oxide (silica) vapor deposition film with a thickness of 20 nm was formed on the surface coating layer using an induction heating vacuum deposition device equipped with a plasma gun, using a roll-to-roll method while applying tension to the multilayer substrate (PVD method).The vapor deposition film formation conditions were as follows: (Formation conditions) (Plasma irradiation conditions) Line speed: 30m / min ·Vacuum degree: 1.7×10 -2 Pa Output: 5.7kw Acceleration voltage: 151V Ar gas flow rate: 7.5 sccm (Film formation conditions) Deposition material: SiO Reactive gas: O2 Reaction gas flow rate: 100sccm

[0213] Example 8-2 A barrier laminate of the second embodiment was produced in the same manner as in Example 8-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 by mass.

[0214] Example 8-3 A barrier laminate of the second embodiment was produced in the same manner as in Example 8-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 by mass.

[0215] Example 8-4 A barrier laminate of the second embodiment was produced in the same manner as in Example 8-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 by mass.

[0216] Example 8-5 A barrier laminate of the second embodiment was produced in the same manner as in Example 8-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 by mass.

[0217] Examples 8-6 A barrier laminate of the second embodiment was produced in the same manner as in Example 8-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 by mass.

[0218] Example 9-1 A barrier laminate of the second embodiment was produced in the same manner as in Example 7-1, except that the formation of the vapor-deposited film was changed as follows.

[0219] Using a continuous vapor deposition film formation device that has a pretreatment section in which an actual oxygen plasma pretreatment device is placed and a film formation section separated from each other, in the pretreatment section, tension is applied to the multilayer substrate by roll-to-roll movement, and plasma is introduced from a plasma supply nozzle under the conditions described below to perform oxygen plasma pretreatment on the surface coating layer. In the film formation section, which is continuously transported, a 12 nm thick aluminum oxide (alumina) vapor deposition film is formed on the oxygen plasma treated surface under the conditions described below using a reactive resistance heating method as the heating means for vacuum vapor deposition (PVD method). (Formation conditions) (Oxygen plasma pretreatment conditions) Plasma intensity: 200W·sec / m 2 Plasma formation gas ratio: oxygen:argon = 2:1 Voltage applied between pretreatment drum and plasma supply nozzle: 340V (Film formation conditions) Conveying speed: 400m / min Oxygen gas supply: 20,000 sccm

[0220] Example 9-2 A barrier laminate of the second embodiment was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 by mass.

[0221] Example 9-3 A barrier laminate of the second embodiment was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 by mass.

[0222] Example 9-4 A barrier laminate of the second embodiment was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 by mass.

[0223] Example 9-5 A barrier laminate of the second embodiment was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed so that the solids ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 by mass.

[0224] Examples 9-6 A barrier laminate of the second embodiment was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 by mass.

[0225] <<Gas barrier property evaluation (after lamination)>> The barrier laminates obtained in Examples 3 to 9 were cut out to obtain test pieces. Using these test pieces, the oxygen permeability (cc / m 2 ·day·atm) and water vapor permeability (g / m 2 ·day) was measured. The results are summarized in Tables 2 to 8. In Tables 2 to 8, the units for oxygen permeability and vapor permeability are omitted.

[0226] <<Gas barrier property evaluation (after Gelboflex test)>> Cylindrical bags were produced using the barrier layers obtained in Examples 3 to 9. Using these bags, the Gelbo Flex test in accordance with ASTM F392 was repeated 10 times. Thereafter, a test piece was obtained by cutting out the barrier laminate from the bag. The test piece was used to measure the oxygen permeability (cc / m 2 ·day·atm) and water vapor permeability (g / m 2·day) was measured. The results are summarized in Tables 2 to 8. In Tables 2 to 8, the units for oxygen permeability and vapor permeability are omitted.

[0227] [Table 2]

[0228] [Table 3]

[0229] [Table 4]

[0230] [Table 5]

[0231] [Table 6]

[0232] [Table 7]

[0233] [Table 8] [Explanation of symbols]

[0234] 10: Barrier laminate, 11: Multilayer substrate, 12: Vapor deposition film, 13: Sealant layer, 14: Polypropylene resin layer, 15: Surface resin layer, 16: Barrier coat layer, 17: Adhesive resin layer, 20: Barrier laminate, 21: Multilayer substrate, 22: Vapor deposition film, 23: Sealant layer, 24: Polypropylene resin layer, 25: Surface coat layer, 26: Barrier coat layer, 30: Packaging bag, 40: Standing pouch, 41: Body (side sheet), 42: Bottom (bottom sheet), 51: Easy-opening means, 52: Notch portion, 53: Half-cut line, 60: Steam vent mechanism, 60a: Steam sealing part, 60b: non-sealing part, 70: test piece, 71: substrate side, 72: sealant layer side, 73: gripper, A: vacuum vessel, B: unwinding part, C: film-forming drum, D: winding part, E: transport roll, F: evaporation source, G: reactive gas supply part, H: deposition protection box, I: evaporation material, J: plasma gun, A1: vacuum vessel, B1: unwinding part, C1: cooling / electrode drum, D1: winding part, E1: transport roll, F1: glow discharge plasma, G1: reactive gas supply part, H1: raw material supply nozzle, I1: raw material gas supply part, J1: magnet, K1: power supply, L1: vacuum pump

Claims

1. A multilayer substrate having a vapor-deposited film, a barrier coat layer, and a sealant layer in this order, The multilayer substrate has been subjected to a biaxial stretching treatment, Furthermore, the multilayer substrate is a co-extruded film having at least a polypropylene resin layer, an adhesive resin layer, and a surface resin layer in this order, the surface resin layer contains a resin material having a melting point of 180°C or higher, the adhesive resin layer is an acid-modified polypropylene, the vapor-deposited film is made of an inorganic oxide, The vapor-deposited film is provided on the surface resin layer, A barrier laminate, characterized in that the barrier coat layer is provided on the surface of the vapor-deposited film opposite to the surface on which the surface resin layer is provided.

2. the polypropylene resin layer and the sealant layer are made of the same material; 2. The barrier laminate according to claim 1, wherein the same material is polypropylene.

3. 3. The barrier laminate according to claim 1, wherein the resin material has a melting point of 265°C or lower.

4. 4. The barrier laminate according to claim 1, wherein the difference between the melting point of the resin material and the melting point of the polypropylene contained in the polypropylene resin layer is 20 to 80°C.

5. The barrier laminate according to any one of claims 1 to 4, wherein the resin material has a polar group.

6. 6. The barrier laminate according to claim 1, wherein the resin material is one or more resin materials selected from the group consisting of ethylene-vinyl alcohol copolymer, polyvinyl alcohol, nylon 6, nylon 6,6, MXD nylon, and amorphous nylon.

7. The barrier laminate according to any one of claims 1 to 5, wherein the resin material is a polyamide.

8. The barrier laminate according to any one of claims 1 to 5, wherein the resin material is an ethylene-vinyl alcohol copolymer.

9. 9. The barrier laminate according to claim 1, wherein the ratio of the thickness of the surface resin layer to the total thickness of the multilayer base material is 1% or more and 10% or less.

10. The barrier laminate according to any one of claims 1 to 9, which is used for packaging container applications.

11. A packaging container comprising the barrier laminate according to any one of claims 1 to 10.

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