Barrier laminate, and packaging container having the barrier laminate

Abstract

To provide a barrier laminate which has a multilayer base material excellent in adhesion between a vapor-deposited film and a layer, and high gas barrier property.SOLUTION: A barrier laminate includes a multilayer base material having a vapor-deposited film, and a sealant layer, wherein the multilayer base material includes at least a polypropylene resin layer and a surface coat layer, the polypropylene resin layer is subjected to drawing treatment, the surface coat layer contains a resin material having a polar group, the vapor-deposited film is composed of an inorganic oxide, the vapor-deposited film is provided on the surface coat layer, a barrier coat layer is provided on a surface opposite to a surface where the surface coat layer of the vapor-deposited film is provided, the barrier coat layer is a gas barrier coating film containing metal alkoxide and a water-soluble polymer (excluding gas barrier coating film further containing inorganic layer laminar compound), and laminate strength between the multilayer base material and the vapor-deposited film is 3 N or more in the width of 15 mm.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a barrier laminate and a packaging container including the barrier laminate.

Background Art

[0002] Conventionally, a film made of polyester such as polyethylene terephthalate (hereinafter also referred to as a polyester film) has excellent mechanical properties, chemical stability, heat resistance, and transparency, and is inexpensive. Therefore, it is used as a base material constituting a laminate used for manufacturing a packaging container.

[0003] Depending on the contents filled in the packaging container, the packaging container is required to have gas barrier properties such as high oxygen barrier properties and water vapor barrier properties. In order to meet this requirement, it is widely practiced to form a vapor deposition film containing alumina, silica, or the like on the surface of the polyester film (Patent Document 1).

[0004] By the way, in recent years, a search for a resin material to replace the polyester film has been conducted, and the application to a base material of a polyolefin film, particularly a polypropylene film, has been studied.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The inventors of the present invention were considering using a stretched film of polypropylene (hereinafter also referred to as a stretched polypropylene film) instead of the conventional polyester film base material. However, they found a new problem that even if a vapor deposition film is formed on the surface of the stretched polypropylene film, satisfactory gas barrier properties cannot be obtained.

[0007] Then, as the inventors further investigated, they found that in a packaging container using a barrier laminate in which a vapor deposition film was provided on the stretched polypropylene film, there was a peculiar phenomenon not seen in conventional barrier laminates using a polyester film substrate, namely, delamination occurred between the stretched polypropylene film and the vapor deposition film, and they obtained the knowledge that this phenomenon rendered the gas barrier property insufficient.

[0008] And the inventors obtained the knowledge that by providing a surface resin layer containing a resin material having a melting point of 180°C or higher on the surface of the stretched polypropylene film, the adhesion of the vapor deposition film formed on the surface resin layer was improved and the gas barrier property was also enhanced.

[0009] Also, the inventors obtained the knowledge that by providing a coat layer containing a resin material having a polar group on the surface of the stretched polypropylene film, the adhesion of the vapor deposition film formed on the coat layer was improved and the gas barrier property was also enhanced.

[0010] The present invention has been made based on such knowledge, and the problem to be solved is to provide a barrier laminate having a multilayer base material excellent in adhesion between layers with a vapor deposition film and having a high gas barrier property.

[0011] Also, the problem to be solved by the present invention is to provide a packaging container including the barrier laminate.

Means for Solving the Problem

[0012] The barrier laminate of the present invention includes a multilayer base material having a vapor deposition film and a sealant layer. The multilayer base material includes at least a polypropylene resin layer and a surface coat layer. The polypropylene resin layer has been subjected to a stretching treatment. And the surface coat layer contains a resin material having a polar group. The vapor deposition film is composed of an inorganic oxide. The vapor deposition film is provided on the surface coat layer, and a barrier coat layer is provided on the surface of the vapor deposition film opposite to the surface on which the surface coat layer is provided, wherein the barrier coat layer is a gas barrier coating film containing a metal alkoxide and a water-soluble polymer (excluding a gas barrier coating film further containing an inorganic layered compound), and the laminate strength between the multilayer base material and the vapor deposition film is 3 N or more in a width of 15 mm.

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

[0014] In one embodiment, the ratio of the thickness of the surface coat layer to the total thickness of the multilayer base material is 0.08% or more and 20% or less.

[0015] In one embodiment, the thickness of the surface coat layer is 0.02 μm or more and 10 μm or less.

[0016] 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.

[0017] In one embodiment, the surface coat layer is a layer formed using an aqueous emulsion or a solvent-based emulsion.

[0018] In one embodiment, the barrier laminate of the present invention is used for packaging container applications.

[0019] The packaging container of the present invention is characterized by comprising the above-described barrier laminate.

Advantages of the Invention

[0020] According to the present invention, it is possible to produce a packaging container having a high laminate strength, provided with a multilayer substrate excellent in adhesion between layers with a vapor deposition film, and to provide a barrier laminate having a high gas barrier property. Further, according to the present invention, it is possible to provide a packaging container including the barrier laminate.

Brief Description of the Drawings

[0021]

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Mode for Carrying Out the Invention

[0022] (Barrier laminate in the first aspect) As shown in FIG. 1, the barrier laminate 10 of the present invention includes a multilayer base material 11, a vapor deposition film 12, and a sealant layer 13, and the multilayer base material 11 includes at least a polypropylene resin layer 14 and a surface resin layer 15. In one embodiment, as shown in FIG. 2, the barrier laminate 10 of the present invention further includes a barrier coat layer 16 between the vapor deposition film 12 and the sealant layer 13. In one embodiment, as shown in FIG. 3, the multilayer base material 11 includes an adhesive resin layer 17 between the polypropylene resin layer 14 and the surface resin layer 15. In one embodiment, as shown in FIG. 4, the barrier laminate 10 includes a multilayer base material 11, a vapor deposition film 12, a barrier coat layer 16 provided on the vapor deposition film 12, and a sealant layer 13. The multilayer base material 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 includes an adhesive layer (not shown) between the vapor deposition film and the sealant layer. In one embodiment, the barrier laminate of the present invention includes an intermediate layer between the vapor deposition film and the sealant layer.

[0023] The haze value of the barrier laminate is preferably 20% or less, and more preferably 5% or less. Thereby, the transparency of the barrier laminate can be improved. In this specification, the haze value of the barrier laminate is measured by a haze meter (Murakami Color Technology Laboratory Co., Ltd.) in accordance with JIS K 7105:1981.

[0024] In the barrier laminate according to the first aspect, the lamination strength between the multilayer substrate and the vapor deposition film is preferably 3 N or more, more preferably 4 N or more, and even more preferably 5.5 N or more in a width of 15 mm. The upper limit of the lamination strength of the barrier laminate according to the first aspect may be 20 N or less. The method for measuring the lamination strength of the barrier laminate will be described in the examples described later.

[0025] Conventionally, a laminate in which a substrate and a sealant layer are made of different resin materials has been used for manufacturing packaging containers. However, after collecting used packaging containers, it is difficult to separate the substrate and the sealant layer, so there is a current situation where it is not actively recycled. By configuring the substrate and the sealant layer with the same material, it is not necessary to separate the substrate and the sealant layer, and the recyclability can be improved. By configuring the sealant layer with the same material as the polypropylene resin layer provided in the substrate, that is, polypropylene, it is not necessary to separate the recovered packaging container layer by layer, and the recyclability can be improved.

[0026] When the sealant layer is made of polypropylene, the content of polypropylene in 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, the recyclability of the packaging container manufactured using the barrier laminate of the present invention can be further improved.

[0027] Hereinafter, each layer included in the barrier laminate of the present invention will be described.

[0028] (Multilayer substrate) The multilayer substrate includes at least a polypropylene resin layer and a surface resin layer. Further, the multilayer substrate may include an adhesive resin layer between the polypropylene resin layer and the surface resin layer.

[0029] The multilayer substrate has been subjected to a stretching treatment, and the stretching treatment may be uniaxial stretching or biaxial stretching. The stretching ratios in the longitudinal direction (MD direction) and the transverse direction (TD direction) of the multilayer substrate are 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 multilayer substrate can be further improved. Also, the printability on the multilayer substrate can be improved. Also, from the viewpoint of the breaking limit of the multilayer substrate, the stretching ratio is preferably 15 times or less. Further, when the polypropylene resin layer provided in the multilayer substrate is given heat sealability to form a packaging container (for example, a tube, etc.) produced by envelope pasting, the stretching ratio is preferably 2 times or more and 10 times or less, and more preferably 2.5 times or more and 7 times or less.

[0030] In one embodiment, it is preferable to perform a stretching treatment so that the tensile strength in the longitudinal direction (MD direction) of the multilayer substrate is greater than the tensile strength in the transverse direction (TD direction). With such a configuration, high tear ease in one direction can be imparted to the packaging container produced from the barrier laminate of the present invention. The tensile strength in the longitudinal direction (MD direction) of the multilayer substrate is preferably 1.05 times or more greater than the tensile strength in the transverse direction (TD direction), more preferably 1.10 times or more greater, and still more preferably 1.2 times or more greater. The tensile strength in the longitudinal 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 the measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used. As the test piece, a rectangular film with a width of 15 mm and a length of 150 mm cut out from a multilayer substrate can be used. The interval at the start of measurement between a pair of chucks holding the test piece is 100 mm, and the tensile speed is 300 mm / min. In the present application, unless otherwise specified, the environment during the measurement of the tensile strength is a temperature of 23°C and a relative humidity of 50%.

[0031] In addition, the surface resin layer provided in the multilayer substrate may be subjected to a surface treatment. Thereby, the adhesion with an adjacent layer can be improved. The method of the surface treatment 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, glow discharge treatment, and chemical treatments such as oxidation treatment using chemical agents.

[0032] (Polypropylene resin layer) The polypropylene resin layer may be composed of polypropylene and may have a single-layer structure or a multilayer structure. By providing a layer composed of polypropylene in the multilayer substrate, it becomes possible to improve the oil resistance of the packaging container produced using the multilayer substrate.

[0033] The polypropylene contained in the polypropylene resin layer may be any of a homopolymer, a random copolymer, and a block copolymer. The polypropylene homopolymer is a polymer of only propylene, the polypropylene random copolymer is a random copolymer of propylene and other α-olefins other than propylene (for example, ethylene, butene-1, 4-methyl-1-pentene, etc.), and the polypropylene block copolymer is a copolymer having a polymer block composed of propylene and a polymer block composed of other α-olefins other than the above-mentioned propylene. Among these polypropylenes, from the viewpoint of transparency, it is preferable to use a homopolymer or a random copolymer. When emphasizing the rigidity and heat resistance of the packaging bag, it is preferable to use a homopolymer, and when emphasizing impact resistance or the like, it is preferable to use a random copolymer. Also, polypropylene derived from biomass or polypropylene that has been mechanically recycled or chemically recycled can be used.

[0034] The content of polypropylene 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.

[0035] The polypropylene resin layer can contain a heat-seal modifier. Thereby, the heat-sealability of the polypropylene resin layer can be improved, and a packaging container by envelope sticking can be produced more easily. 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. Further, a conventionally known heat-sealant may be applied and dried on the surface of the polypropylene resin layer.

[0036] Within a range not impairing the characteristics of the present invention, the polypropylene resin layer may contain a resin material other than polypropylene, and examples thereof include polyolefins such as polyethylene, (meth)acrylic resins, vinyl resins, cellulose resins, polyamide resins, polyesters, and ionomer resins. Also, within a range not impairing the characteristics of the present invention, the polypropylene resin layer can contain additives, such as crosslinking agents, antioxidants, antiblocking agents, slip agents, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0037] 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 setting the thickness of the polypropylene resin layer to 10 μm or more, the strength and heat resistance of the multilayer substrate can be further improved. Also, by setting the thickness of the polypropylene resin layer to 50 μm or less, the film-forming property and processing suitability of the multilayer substrate can be further improved.

[0038] The polypropylene resin layer may have a printing layer on its surface. The image formed on the printing layer is not particularly limited, and characters, patterns, symbols, and combinations thereof are represented. The formation of the printing layer on the substrate can be performed using biomass-derived ink. Thereby, the environmental load can be further reduced. The method for forming the printing layer is not particularly limited, and examples thereof include conventionally known printing methods such as gravure printing, offset printing, and flexographic printing.

[0039] (Surface resin layer) The multilayer substrate includes a surface protection 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) on the polypropylene resin layer, and a vapor deposition film having high adhesion can be formed on the surface resin layer, thereby improving the gas barrier property. Also, as described later, the packaging container produced using the barrier laminate including the surface resin layer has high laminate strength.

[0040] The melting point of the high melting point resin material is more preferably 185°C or higher, further 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 adhesion of the vapor deposition film can be further improved, and the gas barrier property can be further improved. Also, the laminate strength of the packaging container can be further improved. From the perspective of the film-forming property 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 (Test Method for Measuring the Transition Temperature of Plastics). Specifically, using a differential scanning calorimetry (DSC) apparatus, a DSC curve can be measured at a heating rate of 10 °C / min to obtain the melting point.

[0041] 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 is preferably 20 to 80 °C, and more preferably 20 to 60 °C. When 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 is 20 °C or more, the adhesion of the vapor deposition film can be further improved, and the gas barrier property can be further improved. Also, the laminate strength of the packaging container can be further improved. In addition, when 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 is 80 °C or lower, the film-forming property of the multilayer substrate can be further improved.

[0042] 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 viewpoints of the gas barrier property and laminate strength of the packaging container, a hydroxyl group, an ester group, an amino group, an amide group, a carboxyl group, and a carbonyl group are preferable, and an amide group is more preferable.

[0043] The high melting point resin material can be used without particular limitation as long as its melting point is 180°C or higher. For example, vinyl resins, polyamides, polyimides, polyesters, (meth)acrylic resins, cellulose resins, polyolefin resins, ionomer resins, etc. can be mentioned.

[0044] In the present invention, a resin material having a melting point of 180°C or higher and having a polar group is particularly preferred, and polyamides such as ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyester, nylon 6, nylon 6,6, MXD nylon, amorphous nylon, etc. are preferred. By using such a resin material, the adhesion of the vapor deposition film formed on the surface resin layer can be significantly improved, and its gas barrier property can be effectively enhanced.

[0045] 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 property even when the barrier laminate is bent.

[0046] 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 the gas barrier property even when the barrier laminate is bent, and it is also possible to suppress a decrease in the gas barrier property even when heating such as heat sealing is performed when producing a packaging product using the barrier laminate. The high melting point resin material is more preferably nylon 6.

[0047] 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.

[0048] Within a range that does not impair the characteristics of the present invention, the surface resin layer may contain a resin material other than the high melting point resin material. Also, within a range that does not impair the characteristics of the present invention, the surface resin layer can contain additives, for example, crosslinking agents, antioxidants, antiblocking agents, slip agents, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0049] The ratio of the thickness of the surface resin layer to the total thickness of the multilayer substrate is preferably 1% or more and 10% or less, and more preferably 1% or more and 5% or less. By setting the ratio of the thickness of the surface resin layer to the total thickness of the multilayer substrate to 1% or more, the adhesion of the vapor deposition film can be further improved, and the gas barrier property can be further improved. Also, the lamination strength of the packaging container can be further improved. Also, 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 property and processing suitability of the multilayer substrate can be further improved. Also, as will be described later, the recyclability of a packaging container produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0050] 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 setting the thickness of the surface resin layer to 0.1 μm or more, the adhesion of the vapor deposition film can be further improved, and the gas barrier property can be further improved. Also, the lamination strength of the packaging container can be further improved. Also, by setting the thickness of the surface resin layer to 5 μm or less, the film-forming property and processing suitability of the multilayer substrate can be further improved. Also, as will be described later, the recyclability of a packaging container produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0051] (Adhesive resin layer) In one embodiment, the multilayer substrate can include an adhesive resin layer between a polypropylene resin layer and a surface resin layer, thereby improving the adhesion between these layers.

[0052] 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, and acid-modified polyolefin. Among the above, and as will be described later, from the perspective of the recyclability of a packaging container produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene, polyolefin and its acid-modified product are preferable, and polypropylene and its acid-modified product are particularly preferable. As the adhesive polypropylene, commercially available products can be used. For example, the Admer series manufactured by Mitsui Chemicals, Inc. can be used.

[0053] 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 setting the thickness of the adhesive resin layer to 1 μm or more, the adhesion between the polypropylene resin layer and the surface resin layer can be further improved. By setting the thickness of the adhesive layer to 15 μm or less, the processability of the multilayer substrate can be improved.

[0054] In one embodiment, the multilayer substrate is a coextrusion film and can be produced by film formation using the T-die method or the inflation method, etc., and then stretching after forming a laminated film. By forming a film by the inflation method, stretching of the laminated film can be performed simultaneously.

[0055] (Vapor deposition film) The barrier laminate of the present invention includes a vapor deposition film composed of an inorganic oxide on a surface resin layer. Thereby, the gas barrier property of the barrier laminate, specifically, the oxygen barrier property and the water vapor barrier property can be improved. Further, a decrease in the mass of the contents filled in a packaging container produced using the barrier laminate of the present invention can be suppressed.

[0056] Examples of the inorganic oxide include aluminum oxide (alumina), silicon oxide (silica), magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, silicon carbide oxide (carbon-containing silicon oxide), and the like. Among those described above, silica, silicon carbide oxide, and alumina are preferable. Further, since an aging treatment after the formation of the vapor deposition film is not required, silica is particularly preferable. In one embodiment, from the viewpoint that the decrease in the gas barrier property can be suppressed even when the barrier laminate is bent, the inorganic oxide is more preferably carbon-containing silicon oxide.

[0057] Further, the thickness of the vapor deposition 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 setting the thickness of the vapor deposition film to 1 nm or more, the oxygen barrier property and the water vapor barrier property of the barrier laminate can be further improved. Further, by setting the thickness of the vapor deposition film to 150 nm or less, the generation of cracks in the vapor deposition film can be prevented. Furthermore, as described later, the recyclability of a packaging container produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0058] The formation of the vapor deposition film can be carried out using a conventionally known method. For example, physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum evaporation method, sputtering method and ion plating method, and chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as plasma chemical vapor deposition method, thermal chemical vapor deposition method and photo-chemical vapor deposition method can be mentioned.

[0059] The vapor deposition film may be a single layer formed by a single vapor deposition process or a multi-layer formed by a plurality of vapor deposition processes. In the case of a multi-layer, each layer may be made of the same material or different materials. Also, each layer may be formed by the same method or different methods.

[0060] As an apparatus used for the method of forming a vapor deposition film by the PVD method, a vacuum film forming apparatus with plasma assist can be used. An embodiment of the method for forming a vapor deposition film using a vacuum film forming apparatus with plasma assist will be described below. In one embodiment, as shown in FIGS. 5 and 6, the vacuum film forming apparatus includes a vacuum chamber A, an unwinding section B, a film forming drum C, a winding section D, a conveying roll E, an evaporation source F, a reaction gas supply section G, a deposition prevention box H, a vapor deposition material I, and a plasma gun J. Note that FIG. 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, inside the upper part of the vacuum chamber A, the barrier laminate 10 wound around the film forming drum C is arranged with its surface resin layer facing downward, and below the film forming drum C inside the vacuum chamber A, a deposition prevention box H electrically grounded is arranged. The evaporation source F is arranged on the bottom surface of the deposition prevention box H. The film forming drum C is arranged inside the vacuum chamber A such that the surface resin layer of the multi-layer base material 11 wound around the film forming drum C is positioned at a position facing the upper surface of the evaporation source F with a certain interval therebetween. Also, conveying 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 chamber is connected to a vacuum pump (not shown). The evaporation source F is for holding the vapor deposition material I and includes a heating device (not shown). The reaction gas supply part G is a part for supplying a reaction gas (such as oxygen, nitrogen, helium, argon, and a mixed gas thereof) that reacts with the evaporated vapor deposition material. The vapor deposition material I heated and evaporated from the evaporation source F is irradiated onto the surface resin layer of the multilayer substrate, and at the same time, plasma is irradiated from the plasma gun J toward the surface resin layer, and a vapor deposition film is formed. Details of this formation method are disclosed in Japanese Patent Laid-Open No. 2011-214089.

[0061] As the plasma generation device used in the plasma chemical vapor deposition method, a device for generating high-frequency plasma, pulse wave plasma, microwave plasma, etc. can be used. Also, a device having two or more film formation chambers may be used. It is preferable that the device includes a vacuum pump and can maintain each film formation chamber in a vacuum. The degree of vacuum in each film formation chamber is preferably 1×10~1×10 -6 Pa. An embodiment of the method for forming a vapor deposition film using a plasma generation device will be described below. First, the multilayer substrate is sent into the film formation chamber and conveyed onto the cooling / electrode drum at a predetermined speed via an auxiliary roll. Next, a mixed gas composition containing a film formation monomer gas containing an inorganic oxide, oxygen gas, an inert gas, etc. is supplied from the gas supply device into the film formation chamber, plasma is generated by glow discharge on the surface resin layer, irradiated, and a vapor deposition film containing an inorganic oxide is formed on the surface resin layer. Details of this formation method are disclosed in Japanese Patent Laid-Open No. 2012-076292.

[0062] Figure 7 is a schematic configuration diagram showing a plasma chemical vapor deposition device used in the CVD method.

[0063] In one embodiment, as shown in FIG. 7, a plasma chemical vapor deposition apparatus unwinds a multilayer substrate 11 from a unwinding section B1 disposed in a vacuum chamber A1, and further conveys the multilayer substrate 11 at a predetermined speed onto the circumferential surface of a cooling / electrode drum C1 via a conveying roll E1. Oxygen, nitrogen, helium, argon, and a mixed gas thereof are supplied from G1 for reaction gas supply, and a monomer gas for film formation and the like are supplied from a raw material gas supply section I1. While adjusting the vapor deposition mixed gas composition composed of these, the vapor deposition mixed gas composition is introduced into the vacuum chamber A1 through a raw material supply nozzle H1, and on the surface resin layer of the multilayer substrate 11 conveyed onto the circumferential surface of the above-mentioned cooling / electrode drum C1, plasma is generated by a glow discharge plasma F1 and irradiated to form a vapor deposition film. At that time, the cooling / electrode drum C1 is applied with a predetermined power from a power source K1 disposed outside the vacuum chamber A1, and a magnet J1 is disposed near the cooling / electrode drum C1 to promote the generation of plasma. Next, after the multilayer substrate 11 forms a vapor deposition film, it is wound up by a winding section D1 via a conveying roll E1 at a predetermined winding speed. In the figure, L1 represents a vacuum pump.

[0064] As an apparatus used for the method of forming a vapor deposition film, a continuous vapor deposition film forming apparatus including a plasma pretreatment chamber and a film forming chamber can be used. An embodiment of the method of forming a vapor deposition film using this apparatus is described below. First, in the plasma pretreatment chamber, the surface resin layer of the multilayer substrate is irradiated with plasma from a plasma supply nozzle. Next, in the film forming chamber, a vapor deposition film is formed on the plasma-treated surface resin layer. Details of this forming method are disclosed in the pamphlet of International Publication WO2019 / 087960.

[0065] It is preferable that the surface of the vapor deposition film is subjected to the above surface treatment. Thereby, the adhesion with an adjacent layer can be improved.

[0066] In the barrier laminate of the present invention, the vapor deposition film is preferably a vapor deposition film formed by CVD method, and more preferably a carbon-containing silicon oxide vapor deposition film formed by CVD method. Thereby, even when the barrier laminate is bent, a decrease in gas barrier property can be suppressed.

[0067] The carbon-containing silicon oxide vapor deposition film contains silicon, oxygen, and carbon. In the carbon-containing silicon oxide vapor deposition film, the ratio C of carbon 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 with respect to 100% in total of the three elements of silicon, oxygen, and carbon. In the carbon-containing silicon oxide vapor deposition film, by setting the ratio C of carbon within the above range, even when the barrier laminate is bent, a decrease in gas barrier property can be suppressed. In the present specification, the ratio of each element is on a molar basis.

[0068] In one embodiment of the carbon-containing silicon oxide vapor deposition film, the ratio Si of silicon is preferably 1% or more and 45% or less, more preferably 3% or more and 38% or less, and even more preferably 8% or more and 33% or less with respect to 100% in total of the three elements of silicon, oxygen, and carbon. The ratio O of oxygen is preferably 10% or more and 70% or less, more preferably 20% or more and 65% or less, and even more preferably 25% or more and 60% or less with respect to 100% in total of the three elements of silicon, oxygen, and carbon. In the carbon-containing silicon oxide vapor deposition film, by setting the ratio Si of silicon and the ratio O of oxygen within the above ranges, even when the barrier laminate is bent, a decrease in gas barrier property can be more suppressed.

[0069] In one embodiment of the carbon-containing silicon oxide vapor deposition film, the ratio O of oxygen is preferably higher than the ratio C of carbon, and the ratio Si of silicon is preferably lower than the ratio C of carbon. The ratio O of oxygen is preferably higher than the ratio Si of silicon, that is, it is preferable that each ratio decreases in the order of ratio O, ratio C, and ratio Si. Thereby, even when the barrier laminate is bent, a decrease in gas barrier property can be more suppressed.

[0070] In the silicon oxide vapor deposition film containing carbon, the ratios C, Si, and O can be measured by narrow scan analysis under the following measurement conditions using X-ray photoelectron spectroscopy (XPS). (Measurement conditions) Equipment used: "ESCA-3400" (manufactured by Kratos) [1] Spectrum acquisition conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV) X-ray output: 150 W (10 kV·15 mA) X-ray scanning area (measurement region): approximately 6 mm φ Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV) Emission current: 20 (mA) etch range: 10 mm φ Ion sputtering is performed for 30 seconds, and the spectrum is acquired

[0071] (Sealant layer) In one embodiment, the sealant layer includes a resin material that can be fused to each other by heat. Examples of the resin material that can be fused to each other by heat include polyolefins such as polyethylene, polypropylene, polybutene, methylpentene polymer, and cyclic olefin copolymer. Specifically, low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), ethylene-α-olefin copolymer polymerized using a metallocene catalyst, and ethylene-propylene copolymer such as random or block copolymer of ethylene and propylene can be mentioned. In addition, 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 resin, heat-sealable ethylene-vinyl alcohol resin, acid-modified polyolefin obtained by modifying polyolefin 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-based resins, poly(meth)acrylic-based resins, polyvinyl chloride-based resins, and the like.

[0072] Conventionally, a laminate in which a base material and a sealant layer are made of different resin materials has been used for manufacturing packaging containers. However, after collecting used packaging containers, it is difficult to separate the base material and the sealant layer, so there is a current situation where they are not actively recycled. By configuring the base material and the sealant layer with the same material, there is no need to separate the base material and the sealant layer, and the recyclability can be improved. That is, among the above-described resin materials, from the viewpoint of the recyclability of packaging containers manufactured using a laminate, the sealant layer is preferably composed of polypropylene. In addition, by configuring the sealant layer with polypropylene, the oil resistance of packaging containers manufactured using a barrier laminate can be improved.

[0073] Within a range that does not impair the characteristics of the present invention, the sealant layer can contain the above heat-seal modifier and additives.

[0074] The sealant layer may have a single-layer structure or a multilayer structure.

[0075] 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 setting the thickness of the sealant layer to 15 μm or more, the laminating strength of the packaging container provided with the barrier laminate of the present invention can be further improved. Also, by setting the thickness of the sealant layer to 100 μm or less, the processability of the barrier laminate of the present invention can be further improved.

[0076] The sealant layer may be formed by laminating a stretched or unstretched film having heat sealability via a conventionally known adhesive, or may be formed by applying and drying a heat sealant.

[0077] (Barrier coat layer) The barrier laminate of the present invention can further include a barrier coat layer between the vapor deposition film and the sealant layer. Thereby, the oxygen barrier property and the water vapor barrier property of the barrier laminate can be improved.

[0078] In one embodiment, the barrier coat layer includes gas barrier resins such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyacrylonitrile, nylon 6, nylon 6,6, and polymetaxylylene adipamide (MXD6), polyesters, polyurethanes, and (meth)acrylic resins. Among these, polyvinyl alcohol is preferable from the viewpoints of oxygen barrier property and water vapor barrier property. Further, by containing polyvinyl alcohol in the barrier coat layer, the occurrence of cracks in the vapor deposition film can be effectively prevented.

[0079] 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 setting the content of the gas barrier resin in the barrier coat layer to 50% by mass or more, the oxygen barrier property and the water vapor barrier property can be further improved.

[0080] The barrier coat layer can contain the above additives as long as the characteristics of the present invention are not impaired.

[0081] 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 setting the thickness of the barrier coat layer to 0.01 μm or more, the oxygen barrier property and water vapor barrier property of the barrier laminate can be further improved. By setting the thickness of the barrier coat layer to 10 μm or less, the processability of the barrier laminate can be improved. Further, the recyclability of a packaging container produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0082] The barrier coat layer can be formed by dissolving or dispersing the above gas barrier resin in water or a suitable solvent, applying it, and drying it. Further, the barrier coat layer can also be formed by applying and drying a commercially available barrier coating agent.

[0083] 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 hydrolytic 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 method catalyst, water, an organic solvent, etc. By providing such a barrier coat layer on the vapor deposition film, the occurrence of cracks in the vapor deposition film can be effectively prevented.

[0084] In one embodiment, the metal alkoxide is represented by the following general formula. R 1 n M(OR 2 ) m (However, in the formula, R 1 、R 2Each 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.)

[0085] 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 include alkyl groups such as methyl group, ethyl group, n - propyl group, i - propyl group, n - butyl group and i - butyl group.

[0086] Examples of the metal alkoxide satisfying the above general formula include tetramethoxysilane (Si(OCH3)4), tetraethoxysilane (Si(OC2H5)4), tetrapropoxysilane (Si(OC3H7)4), tetrabutoxysilane (Si(OC4H9)4), etc.

[0087] Also, it is preferable to use a silane coupling agent together with the above metal alkoxide. As the silane coupling agent, known organoalkoxysilanes containing organic reactive groups can be used, and in particular, organoalkoxysilanes having an epoxy group are preferable. Examples of the organoalkoxysilane having an epoxy group include γ - glycidoxypropyltrimethoxysilane, γ - glycidoxypropylmethyldiethoxysilane, and β - (3,4 - epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0088] Two or more kinds of the above silane coupling agents may be used, and the silane coupling agent is preferably used in the range of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the above metal alkoxide.

[0089] As the water-soluble polymer, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are preferable, and from the viewpoints of oxygen barrier property, water vapor barrier property, water resistance and weather resistance, it is preferable to use them in combination.

[0090] 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 with respect to 100 parts by mass of the metal alkoxide. By setting the content of the water-soluble polymer in the gas barrier coating film to 5 parts by mass or more with respect to 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. Further, by setting the content of the water-soluble polymer in the gas barrier coating film to 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide, the film-forming property of the gas barrier coating film can be improved.

[0091] 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 on a mass basis, more preferably 1.0 or more and 4.5 or less, and further preferably 1.7 or more and 3.5 or less. By setting the ratio of the metal alkoxide to the water-soluble polymer to 4.5 or less, it is possible to suppress a decrease in the gas barrier property even when the barrier laminate is bent. By setting the ratio of the metal alkoxide to the water-soluble polymer to 1.0 or more, it is possible to suppress a decrease in the gas barrier property even when heating such as heat sealing is performed when producing a packaging product using the barrier laminate. Note that the above ratio is a solid content ratio.

[0092] 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 further 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 suppress a decrease in gas barrier properties even when the barrier laminate is bent. By setting the ratio of silicon atoms to carbon atoms to 0.50 or more, it is possible to suppress a decrease in gas barrier properties even when heating such as heat sealing is performed when manufacturing a packaging product 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 the metal alkoxide to the water-soluble polymer. In this specification, the ratio of silicon atoms to carbon atoms is based on a molar basis.

[0093] 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] Spectrum acquisition conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV) X-ray output: 150 W (10 kV·15 mA) X-ray scanning area (measurement region): approximately 6 mmφ Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV) Emission current: 20 (mA) etch range: 10 mmφ Ion sputtering is performed for 30 seconds + 30 seconds + 60 seconds (total 120 seconds), and the spectrum is acquired.

[0094] The thickness of the gas barrier coating film is preferably 0.01 μm or more and 100 μm or less, and more preferably 0.1 μm or more and 50 μm or less. Thereby, while maintaining recyclability, the oxygen barrier property and the water vapor barrier property can be further improved. By setting the thickness of the gas barrier coating film to 0.01 μm or more, the oxygen barrier property and water vapor barrier property of the barrier laminate can be improved. Further, the generation of cracks in the vapor deposition film can be prevented. By setting the thickness of the gas barrier coating film to 100 μm or less, the recyclability of a packaging container produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0095] The gas barrier coating film can be formed by applying a composition containing the above materials by a conventionally known means such as roll coating using a gravure roll coater, spray coating, spin coating, dipping, brush, bar code, applicator, etc., and subjecting the composition to polycondensation by the sol-gel method. As the sol-gel method catalyst, an acid or an amine-based compound is suitable. As the amine-based compound, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is suitable, and examples thereof include N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. Among these, N,N-dimethylbenzylamine is preferred. The sol-gel method catalyst is preferably used in the range of 0.01 part by mass or more and 1.0 part by mass or less per 100 parts by mass of the metal alkoxide, and more preferably in the range of 0.03 part by mass or more and 0.3 part by mass or less. By setting the usage amount of the sol-gel method catalyst to 0.01 part by mass or more per 100 parts by mass of the metal alkoxide, its catalytic effect can be improved. Further, by setting the usage amount of the sol-gel method catalyst to 1.0 part by mass or less per 100 parts by mass of the metal alkoxide, the thickness of the formed gas barrier coating film can be made uniform.

[0096] The above composition may further contain an acid. The acid is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of metal alkoxides, silane coupling agents, etc. As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid are used. The amount of the acid used is preferably 0.001 mol or more and 0.05 mol or less with respect to the total molar amount of the alkoxide moieties (for example, the silicate moiety) of the metal alkoxide and the silane coupling agent. By setting the amount of the acid used to 0.001 mol or more with respect to the total molar amount of the alkoxide moieties (for example, the silicate moiety) of the metal alkoxide and the silane coupling agent, the catalytic effect can be improved. Further, by setting the amount of the acid used to 0.05 mol or less with respect to the total molar amount of the alkoxide moieties (for example, the silicate moiety) of the metal alkoxide and the silane coupling agent, the thickness of the gas barrier coating film to be formed can be made uniform.

[0097] Further, the composition preferably contains water in a proportion of preferably 0.1 mol or more and 100 mol or less, more preferably 0.8 mol or more and 2 mol or less, per 1 mol of the total molar amount of the metal alkoxide. By setting the water content to 0.1 mol or more per 1 mol of the total molar amount of the metal alkoxide, the oxygen barrier property and the water vapor barrier property of the barrier laminate of the present invention can be improved. Further, by setting the water content to 100 mol or less per 1 mol of the total molar amount of the alkoxide, the hydrolysis reaction can be carried out promptly.

[0098] Further, the composition may contain an organic solvent. As the organic solvent, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used.

[0099] Hereinafter, an embodiment of a method for forming a gas barrier coating film will be described below. First, a metal alkoxide, a water-soluble polymer, a sol-gel method catalyst, water, an organic solvent, and, if necessary, a silane coupling agent, etc. are mixed to prepare a composition. In the composition, a polycondensation reaction gradually proceeds. Next, the composition is applied and dried on the vapor deposition film by the above-described conventionally known method. By this drying, the polycondensation reaction of the metal alkoxide and the water-soluble polymer (and also the silane coupling agent if the composition contains a silane coupling agent) further proceeds, and a layer of the composite polymer is formed. Finally, the composition can be heated at a temperature of, for example, 20 to 250°C, preferably 50 to 220°C, for 1 second to 10 minutes to form a gas barrier coating film.

[0100] The barrier coat layer may have a printing layer formed on its surface. The method of forming the printing layer and the like are as described above.

[0101] (Adhesive layer) The gas barrier laminate of the present invention includes an adhesive layer between the vapor deposition film and the sealant layer.

[0102] The adhesive layer contains at least one adhesive, and any of one-component curable type, two-component curable type, or non-curable type adhesives may be used. Further, the adhesive may be a solventless adhesive or a solvent-based adhesive, but from the viewpoint of environmental load, a solventless adhesive can be preferably used. Examples of the solventless adhesive include polyether-based adhesives, polyester-based adhesives, silicone-based adhesives, epoxy-based adhesives, and urethane-based adhesives. Among these, a two-component curable urethane-based adhesive can be preferably used. Examples of the solvent-based adhesive include rubber-based adhesives, vinyl-based adhesives, silicone-based adhesives, epoxy-based adhesives, phenol-based adhesives, and olefin-based adhesives.

[0103] 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.

[0104] (Intermediate layer) In one embodiment, the barrier laminate of the present invention includes an intermediate layer between a vapor deposition layer and a sealant layer. Thereby, the barrier laminate of the present invention can have firmness and its strength can be improved.

[0105] The intermediate layer contains a resin material, and examples thereof include polyolefin, vinyl resin, polyester, (meth)acrylic resin, and cellulose resin. Among these, polypropylene is particularly preferable from the viewpoint of the recyclability of the barrier laminate.

[0106] The intermediate layer can contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

[0107] The intermediate layer may be provided with the above-mentioned vapor deposition film or barrier coat layer on its surface.

[0108] The intermediate layer is preferably composed of a resin film made of the above-mentioned 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.

[0109] 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 setting the thickness of the intermediate layer to 10 μm or more, the strength of the barrier laminate can be further improved. Also, by setting the thickness of the polypropylene resin layer to 50 μm or less, the processability of the barrier laminate can be further improved.

[0110] The intermediate layer can be provided via the above-mentioned adhesive layer.

[0111] (Barrier laminate in the second aspect) As shown in FIG. 8, the barrier laminate 20 of the present invention includes a multilayer base material 21, a vapor deposition film 22, and a sealant layer 23, and the multilayer base material 21 includes at least a polypropylene resin layer 24 and a surface coat layer 25. In one embodiment, as shown in FIG. 9, the barrier laminate 20 of the present invention further includes a barrier coat layer 26 on the vapor deposition film 22. In one embodiment, the barrier laminate of the present invention includes an adhesive layer (not shown) between the vapor deposition film and the sealant layer. In one embodiment, the barrier laminate of the present invention includes an intermediate layer between the vapor deposition film and the sealant layer.

[0112] The haze value of the barrier laminate is preferably 20% or less, and more preferably 5% or less. Thereby, the transparency of the barrier laminate can be improved.

[0113] In the barrier laminate in the second aspect, the laminate strength between the multilayer substrate and the vapor deposition film is preferably 3 N or more, more preferably 4 N or more, and still more preferably 5.5 N or more in a width of 15 mm. The upper limit of the laminate strength of the barrier laminate in the second aspect may be 20 N or less. The method for measuring the laminate strength of the barrier laminate will be described in the examples described later.

[0114] Similar to the first aspect, it is preferable that the sealant layer is made of the same material as the polypropylene resin layer provided on the substrate, that is, polypropylene. Thereby, the recyclability of the packaging container produced using the barrier laminate of the present invention can be improved.

[0115] When the sealant layer is made of polypropylene, the content of polypropylene with respect to the total amount of the resin material contained in the barrier laminate of the present invention is preferably 80% by mass or more, and more preferably 95% by mass or more. Thereby, the recyclability of the packaging container produced using the barrier laminate of the present invention can be further improved.

[0116] Hereinafter, the multilayer base material included in the barrier laminate of the present invention will be described. Note that, since the layers other than the multilayer base material included in the barrier laminate in the second aspect are the same as those in the barrier laminate in the first aspect, the description thereof is omitted here.

[0117] (Multilayer base material) The multilayer base material includes a polypropylene resin layer and a surface coat layer.

[0118] (Polypropylene resin layer) The polypropylene resin layer may be composed of polypropylene and may have a single-layer structure or a multilayer structure. By providing a layer composed of polypropylene in the multilayer base material, it becomes possible to improve the oil resistance of the packaging container produced using the multilayer base material.

[0119] The polypropylene resin layer is a film subjected to a stretching treatment, and the stretching treatment may be uniaxial stretching or biaxial stretching. The stretching ratio in the longitudinal 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 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. Also, the printability on the polypropylene resin layer can be improved. Also, from the viewpoint of the breaking limit of the polypropylene resin layer, the stretching ratio is preferably 15 times or less.

[0120] 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 composed only of propylene. A polypropylene random copolymer is a random copolymer of propylene and other α-olefins other than propylene (such as ethylene, butene-1, 4-methyl-1-pentene, etc.). A polypropylene block copolymer is a copolymer having a polymer block composed of propylene and a polymer block composed of other α-olefins other than the above-mentioned propylene. Among these polypropylenes, from the viewpoint of transparency, it is preferable to use a homopolymer or a random copolymer. When emphasizing the rigidity and heat resistance of the packaging bag, it is preferable to use a homopolymer. When emphasizing impact resistance, etc., it is preferable to use a random copolymer. In addition, polypropylene derived from biomass or polypropylene that has been mechanically recycled or chemically recycled can also be used.

[0121] The content of polypropylene 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.

[0122] Within the range not impairing the characteristics of the present invention, the polypropylene resin layer may contain a resin material other than polypropylene. For example, polyolefins such as polyethylene, (meth)acrylic resins, vinyl resins, cellulose resins, polyamide resins, polyesters, and ionomer resins can be mentioned. Also, within the range not impairing the characteristics of the present invention, the polypropylene resin layer can contain additives. For example, crosslinking agents, antioxidants, antiblocking agents, slip agents, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins can be mentioned.

[0123] 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 setting the thickness of the polypropylene resin layer to 10 μm or more, the strength and heat resistance of the multilayer substrate can be further improved. Moreover, by setting the thickness of the polypropylene resin layer to 50 μm or less, the film-forming property and processing suitability of the multilayer substrate can be further improved.

[0124] The polypropylene resin layer may have a printing layer on its surface. The image formed on the printing layer is not particularly limited, and characters, patterns, symbols, and combinations thereof are represented. From the perspective of environmental load, the formation of the printing layer on the substrate is preferably carried out using ink derived from biomass. The method for forming the printing layer is not particularly limited, and conventional printing methods such as gravure printing, offset printing, and flexographic printing can be mentioned. Among these, from the perspective of environmental load, the flexographic printing method is preferred.

[0125] Also, the polypropylene resin layer may be surface-treated. Thereby, the adhesion with the surface coat layer can be improved. The method of surface treatment is not particularly limited, and examples include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, glow discharge treatment, and chemical treatments such as oxidation treatment using chemical agents.

[0126] (Surface coat layer) The multilayer substrate is provided with a surface coat layer containing a resin material having a polar group on the polypropylene resin layer, and a vapor deposition film having high adhesion can be formed on the surface coat layer, thereby improving the gas barrier property. Moreover, as described later, a packaging container produced using a barrier laminate provided with a surface coat layer has high laminate strength.

[0127] The surface coating layer contains a resin material having a polar group. In the present invention, the polar group refers to a group containing one or more heteroatoms. For example, ester group, epoxy group, hydroxyl group, amino group, amide group, carboxyl group, carbonyl group, carboxylic anhydride group, sulfone group, thiol group, halogen group, etc. can be mentioned. Among these, from the viewpoint of the laminability of the packaging container, a carboxyl group, a carbonyl group, an ester group, a hydroxyl group, and an amino group are preferable, and a carboxyl group and a hydroxyl group are more preferable.

[0128] Examples of the resin material having a polar group include ethylene vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyester, polyethyleneimine, hydroxyl group-containing (meth)acrylic resin, polyamide such as nylon 6, nylon 6,6, MXD nylon, and amorphous nylon, and polyurethane. Polyamide, hydroxyl group-containing (meth)acrylic resin, ethylene vinyl alcohol copolymer, and polyvinyl alcohol are particularly preferable. In one embodiment, the resin material having a polar group is preferably a hydroxyl group-containing (meth)acrylic resin because it can suppress a decrease in gas barrier properties even when heating such as heat sealing is performed when producing a packaging product using a barrier laminate. By using such a resin material, the adhesion of the vapor deposition film formed on the surface coating layer can be significantly improved, and its gas barrier properties can be effectively enhanced.

[0129] In the present invention, the surface coating layer can be formed using an aqueous emulsion or a solvent-based emulsion. Specific examples of the aqueous emulsion include polyamide-based emulsions, polyethylene-based emulsions, polyurethane-based emulsions, etc. Specific examples of the solvent-based emulsion include polyester-based emulsions, etc.

[0130] The content of the resin material having a polar group in the surface coat layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0131] Within a range not impairing the characteristics of the present invention, the surface coat layer may contain a resin material other than the resin material having a polar group. Also, within a range not impairing the characteristics of the present invention, the surface coat layer can contain additives, for example, crosslinking agents, antioxidants, antiblocking agents, slip agents, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0132] The ratio of the thickness of the surface coat 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 even more preferably 3% or more and 10% or less. By setting the ratio of the thickness of the surface coat layer to the total thickness of the multilayer substrate to 0.08% or more, the adhesion of the vapor deposition film can be further improved, and the gas barrier property can be further improved. Also, the laminate strength of the packaging container can be further improved. Also, 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. Also, as will be described later, the recyclability of a packaging container produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0133] The thickness of the surface coat 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 setting the thickness of the surface coating layer to 0.02 μm or more, the adhesion of the vapor deposition film can be further improved, and the gas barrier property can be further improved. Further, the lamination strength of the packaging container can be further improved. Also, by setting the thickness of the surface coating layer to 10 μm or less, the processability of the multilayer substrate can be further improved. Further, as will be described later, the recyclability of a packaging container produced using a laminate of the barrier laminate of the present invention and a sealant layer made of polypropylene can be improved.

[0134] The multilayer substrate can be manufactured offline. Specifically, a resin composition containing polypropylene is formed into a resin film by using a T-die method or an inflation method, etc., and after stretching, a coating liquid for forming a coating is applied onto the resin film and dried, whereby it can be produced. Also, the multilayer substrate can be manufactured inline. Specifically, a resin composition containing polypropylene is formed into a resin film by using a T-die method or an inflation method, etc., and after stretching in the longitudinal direction (MD direction), a coating liquid for forming a coating is applied onto the resin film and dried, and then it can be produced by stretching in the transverse direction (TD direction). Note that the stretching in the transverse direction may be performed first.

[0135] (Packaging container) The packaging container of the present invention is characterized by including the above-described barrier laminate. Examples of the packaging container include packaging products (packaging bags), lid materials, and laminated tubes.

[0136] Examples of the packaging bag include various forms of packaging bags such as a standing pouch type, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope sticker seal type, a clasp sticker seal type (pillow seal type), a pleated seal type, a flat bottom seal type, a corner bottom seal type, and a gusset type.

[0137] As shown in Fig. 10, the packaging container of the present invention is a packaging bag 30 formed by laminating two barrier laminates (the hatched portions are heat-sealed portions). When the tensile strength in the longitudinal direction (MD direction) of the multilayer substrate is made greater than the tensile strength in the transverse direction (TD direction), it is preferable to fabricate the packaging bag such 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. By adopting such a configuration, it becomes extremely easy to tear the packaging container in the transverse direction. The same applies to the packaging containers exemplified below.

[0138] As shown in Fig. 11, the packaging container of the present invention is a standing pouch 40. Fig. 11 is a diagram schematically showing an example of the configuration of the standing pouch. As shown in Fig. 11, the standing pouch 40 is composed of a body portion (side sheet) 41 and a bottom portion (bottom sheet) 42. At least one of the side sheet 41 and the bottom sheet 42 provided in the standing pouch 40 is composed of the barrier laminate of the present invention.

[0139] In one embodiment, the body portion 41 provided in the standing pouch 40 can be formed by making a bag such that the sealant layer provided in the barrier laminate of the present invention becomes the innermost layer. In another embodiment, two barrier laminates of the present invention are prepared for the side sheet 41, and these are overlapped such that the sealant layers face each other. From both ends of the overlapped barrier laminates, two laminates folded in a V shape are inserted such that the sealant layers are on the outside, and then heat-sealed to form the side sheet 41. According to such a manufacturing method, a stand pouch having a body portion with side gussets can be obtained.

[0140] In addition, in one embodiment, the bottom sheet 42 included in the standing pouch 40 can be formed by inserting the barrier laminate of the present invention between the side sheets formed into a bag and heat-sealing them. More specifically, the barrier laminate can be formed by folding it in a V shape so that the sealant layer faces outward, inserting it between the side sheets formed into a bag, and heat-sealing it.

[0141] Further, as shown in FIG. 10, the packaging container may be provided with an easy-opening means 51. Examples of the easy-opening means 51 include, as shown in FIG. 10, a notch portion 52 serving as a starting point for tearing, and a half-cut line 53 formed by laser processing, a cutter, or the like as a path for tearing.

[0142] Further, as shown in FIG. 11, the packaging container may be provided with a steam venting mechanism 50. The steam venting mechanism 50 is configured to communicate the inside and outside of the packaging container when the steam pressure inside the packaging container reaches a predetermined value or more, release the steam, and suppress the steam from escaping at locations other than the steam venting mechanism 50. The steam venting mechanism 50 includes a steam venting seal portion 50a protruding from the side seal portion toward the inside of the packaging container, and a non-seal portion 50b isolated from the content storage portion by the steam venting seal portion 50a. The non-seal portion 50b communicates with the outside of the packaging container. By heating the packaging container filled with the contents and having the opening heat-sealed using a microwave oven or the like, the internal pressure increases and the steam seal portion 50a peels off. The steam passes through the steam seal 50a peeling portion and the non-seal portion 50b and escapes to the outside of the packaging container.

[0143] As a heat-sealing method, for example, known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high-frequency sealing, and ultrasonic sealing can be used.

[0144] The content filled in the packaging container is not particularly limited, and the content may be a liquid, powder, or gel. It may also be a food or a non-food.

[0145] (Other embodiments) In another embodiment, the barrier laminate of the present invention includes a multilayer substrate, a vapor deposition film, and a sealant layer. The multilayer substrate is subjected to a stretching treatment. Furthermore, the multilayer substrate includes at least a polypropylene resin layer and a surface resin layer. The surface resin layer contains a resin material having a melting point of 180 °C or higher. The vapor deposition film is composed of an inorganic oxide. In one embodiment, the polypropylene resin layer and the sealant layer are made of the same material, and the same material is polypropylene. In one embodiment, the melting point of the resin material is 265 °C or lower. 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. In one embodiment, the resin material has a polar group. 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. In one embodiment, the resin material is polyamide. In one embodiment, the resin material is ethylene vinyl alcohol. 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. In one embodiment, the multilayer substrate is a coextruded film. In another embodiment, the barrier laminate of the present invention includes a multilayer substrate, a vapor deposition film, and a sealant layer. The multilayer substrate includes at least a polypropylene resin layer and a surface coat layer. The polypropylene resin layer is subjected to a stretching treatment. and the surface coating layer contains a resin material having a polar group, the vapor deposition film is composed of an inorganic oxide. In one embodiment, the polypropylene resin layer and the sealant layer are made of the same material, and the same material is polypropylene. In one embodiment, the ratio of the thickness of the surface coating layer to the total thickness of the multilayer base material is 0.08% or more and 20% or less. In one embodiment, the thickness of the surface coating layer is 0.02 μm or more and 10 μm or less. 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. In one embodiment, the surface coating layer is a layer formed using an aqueous emulsion or a solvent-based emulsion. In one embodiment, the barrier laminate of the present invention further includes a barrier coating layer between the multilayer base material and the vapor deposition film. In one embodiment, the barrier laminate of the present invention is used for packaging container applications. A packaging container according to another aspect of the present invention is characterized by including the above-described barrier laminate.

Examples

[0146] Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples.

[0147] Example 1-1 Polyamide (manufactured by Ube Industries, Ltd., polyamide 6, melting point: 220 °C), an adhesive resin (manufactured by Mitsui Chemicals, Inc., Admer QF500, maleic anhydride-modified polypropylene), and polypropylene (manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 °C) were co-extruded and then successively stretched 5 times in the longitudinal direction (MD direction) and 10 times in the transverse direction (TD direction) using a twin-screw stretching apparatus to produce a 21-μm-thick multilayer substrate comprising a surface resin layer (0.4 μm) made of polyamide, an adhesive resin layer (1 μm) made of an 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%.

[0148] Using a roll-to-roll low-temperature plasma chemical vapor deposition apparatus, which is a real machine, a 12-nm-thick carbon-containing silicon oxide vapor deposition film was formed on the surface resin layer of the multilayer substrate produced as described above while applying tension to the multilayer substrate (CVD method). The vapor deposition film formation conditions were as follows. (Formation conditions) · Hexamethyldisiloxane: oxygen gas: helium = 1:10:10 (unit: slm) · Cooling · Electrode drum supply power: 22 kw · Line speed: 100 m / min

[0149] In the carbon-containing silicon oxide vapor deposition film, the ratio C of carbon, the ratio Si of silicon, and the ratio O of oxygen were 32.7%, 29.8%, and 37.5% respectively with respect to the total of 100% of the three elements of silicon, oxygen, and carbon. The ratio of each element was measured by narrow scan analysis under the following measurement conditions using X-ray photoelectron spectroscopy (XPS). (Measurement conditions) Equipment used: "ESCA-3400" (manufactured by Kratos) [1] Spectrum collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV) X-ray output: 150 W (10 kV · 15 mA) X-ray scanning area (measurement region): approximately 6 mm φ Optoelectronic capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV) Emission current: 20 (mA) Etch range: 10 mm φ The ion sputtering was carried out for 30 seconds to collect the spectrum

[0150] 385 g of water, 67 g of isopropyl alcohol, and 9.1 g of 0.5N hydrochloric acid were mixed to obtain a solution with a pH of 2.2. To this solution, 175 g of tetraethoxysilane as a metal alkoxide and 9.2 g of glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed while cooling to 10 °C to obtain Solution A 14.7 g of polyvinyl alcohol with a saponification degree of 99% or more and a polymerization degree of 2400, 324 g of water, and 17 g of isopropyl alcohol were mixed as a water-soluble polymer to obtain Solution B Solution A and Solution B were mixed at a mass ratio of 6.5:3.5 to obtain a barrier coating agent

[0151] The barrier coating agent was spin-coated on the vapor deposition film formed on the multilayer substrate and heat-treated in an oven at 80 °C for 60 seconds to form a barrier coating layer with a thickness of 300 nm

[0152] An unstretched polypropylene film (manufactured by Mitsui Chemicals Tohcello, Inc., CP S) with a thickness of 30 μm was dry-laminated as a sealant layer on the barrier coating layer formed as described above through a polyurethane adhesive (manufactured by Mitsui Chemicals, Inc., Takelac A-969V / Takenate A-5 (mixing ratio 3 / 1)), and allowed to stand at 40 °C for 24 hours to obtain the barrier laminate of the present invention. The thickness of the adhesive layer formed by the polyurethane adhesive was 1 μm The content of polypropylene in the barrier laminate was 94% by mass

[0153] 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 and drying a polypropylene-based heat-sealing material (Arrow Base DA1010N, manufactured by Unitika Ltd.) on the barrier coat layer. The thickness of the sealant layer was 3 μm. The content of polypropylene in the barrier laminate was 95% by mass.

[0154] Example 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 heat-sealable biaxially oriented polypropylene film (P6181, manufactured by Toyo Seikan Kaisha, Ltd.) with a thickness of 30 μm. The content of polypropylene in the barrier laminate was 94% by mass.

[0155] Example 1-4 On the barrier coat layer formed in Example 1-1, as an intermediate layer, a biaxially oriented polypropylene film (P2171, manufactured by Toyo Seikan Kaisha, Ltd.) with a thickness of 30 μm was dry-laminated via a polyurethane adhesive (Takenate A-969V / Takenate A-5 (mixing ratio 3 / 1), manufactured by Mitsui Chemicals, Inc.). Next, a polypropylene-based heat-sealing material (Arrow Base DA1010N, manufactured by Unitika Ltd.) was applied and dried on this biaxially oriented polypropylene film to form a sealant layer with a thickness of 3 μm, and the barrier laminate of the present invention was obtained. The content of polypropylene in the barrier laminate was 95% by mass.

[0156] Example 1-5 A barrier laminate was produced in the same manner as in Example 1-1, except that the polyamide used for producing the multilayer base material was changed to polyvinyl alcohol (Boparal JC-33, manufactured by Nippon Gohsei Co., Ltd., melting point: 200°C) to form the surface resin layer.

[0157] Example 2-1 On the corona-treated surface of a biaxially stretched polypropylene film with a thickness of 20 μm (manufactured by Mitsui Chemicals Toagosei Co., Ltd., ME-1), a solution for forming a surface coat layer having the following composition was applied and dried to form a surface coat layer with a thickness of 0.5 μm, thereby producing a multilayer substrate. (Coating liquid composition for forming surface coat layer) · Polyvinyl alcohol 5% by mass (Manufactured by Nippon Synthetic Chemical Industry Co., Ltd., VC-10, degree of polymerization 1000, saponification degree 99.3 mol% or more) · Water 90% by mass · Isopropanol (IPA) 5% by mass

[0158] 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 changed to the multilayer substrate produced as described above. The content of polypropylene in the barrier laminate was 96% by mass.

[0159] 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 content of polypropylene in the barrier laminate was 96% by mass. (Coating liquid composition for forming surface coat layer) · EVOH 75% by mass (Manufactured by Nippon Shokubai Co., Ltd., Eversorb #10) · Water 12.5% by mass · 1-Propanol 12.5% by mass

[0160] Comparative Example 1-1 After extruding the above polypropylene (manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 °C), it was stretched 5 times in the longitudinal direction (MD direction) and 10 times in the transverse direction (TD direction) by 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 base material in Example 1-1 was changed to a polypropylene film produced as described above.

[0161] [[Gas barrier property evaluation]] The barrier laminates obtained in the above Examples and Comparative Examples were cut out to obtain test pieces. Using this test piece, the oxygen permeability (cc / m 2 ·day·atm) and water vapor permeability (g / m 2 ·day) were measured by the following method, and the results are summarized in Table 1.

[0162] [[Oxygen permeability]] Using an oxygen permeability measuring device (manufactured by MOCON, OX-TRAN2 / 20), the test piece was set so that the multilayer base material side was the oxygen supply side, and the oxygen permeability at 23°C and a relative humidity of 90% RH was measured in accordance with JIS K 7126. [[Water vapor permeability]] Using a water vapor permeability measuring device (manufactured by MOCON, PERMATRAN―w 3 / 33), the test piece was set so that the multilayer base material side was the water vapor supply side, and the water vapor permeability at 40°C and a relative humidity of 90% RH was measured in accordance with JIS K 7129.

[0163] [[Lamination strength test]] Samples obtained by cutting the barrier laminates obtained in the above Examples and Comparative Examples into strips 15 mm wide were used with a tensile testing machine (manufactured by Orientec Co., Ltd., Tensilon universal material testing machine), and in accordance with JIS K6854-2, the lamination strength (N / 15 mm) was measured using 90° peeling (T-peeling method) at a peeling speed of 50 mm / min. Specifically, first, the barrier laminate was cut out, and as shown in FIG. 12, a strip-shaped test piece 70 was prepared by peeling the substrate side 71 and the sealant layer side 72 by 15 mm in the long side direction. Then, as shown in FIG. 13, the already peeled portions of the substrate side 71 and the sealant layer side 72 were respectively gripped by the grippers 73 of the measuring instrument. The grippers 73 were pulled in opposite directions at a speed of 50 mm / min in a direction orthogonal to the surface direction of the portion where the substrate side 71 and the sealant layer side 72 were still laminated, and the average value of the tensile stress in the stable region (see FIG. 14) was measured. The interval S between the grippers 73 at the start of the pulling was set to 30 mm, and the interval S between the grippers 73 at the end of the pulling was set to 60 mm. FIG. 14 is a diagram showing the change in the tensile stress with respect to the interval S between the grippers 73. As shown in FIG. 14, the change in the tensile stress with respect to the interval S passes through the first region and enters the second region (stable region) where the change rate is smaller than that of the first region. For the five test pieces 70, the average value of the tensile stress in the stable region was measured, and this average value was taken as the lamination strength. The environment during the measurement was a temperature of 23°C and a relative humidity of 50%. The measurement results are summarized in Table 1.

[0164]

Table 1

[0165] Example 3-1 In the same manner as in Example 1-1, a multilayer substrate was produced, and a vapor deposition film was formed on the multilayer substrate.

[0166] On the vapor deposition film, a barrier coating layer was formed such 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.

[0167] The ratio of the Si element to the C element present on the surface of the barrier coating layer was measured. The measurement was performed by narrow scan analysis under the following measurement conditions using X-ray photoelectron spectroscopy (XPS). In the following examples as well, the ratio of the Si element to the C element present on the surface of the barrier coating layer was measured in the same manner. (Measurement conditions) Equipment used: "ESCA-3400" (manufactured by Kratos) [1] Spectrum acquisition conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV) X-ray output: 150 W (10 kV·15 mA) X-ray scanning area (measurement region): approximately 6 mmφ Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV) Emission current: 20 (mA) etch range: 10 mmφ Ion sputtering was performed for 30 s + 30 s + 60 s (total 120 s), and spectra were collected

[0168] Next, an unstretched polypropylene film with a thickness of 60 μm (manufactured by Toyobo Co., Ltd., P1128) was dry laminated on the barrier coat layer with a two-component curable polyurethane-based adhesive to form a sealant layer, and a barrier laminate in the first aspect was obtained

[0169] Example 3-2 A barrier laminate in the first aspect was produced in the same manner as in Example 3-1, except that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis to form the barrier coat layer

[0170] Example 3-3 A barrier laminate in the first aspect was produced in the same manner as in Example 3-1, except that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis to form the barrier coat layer

[0171] Example 3-4 A barrier laminate in the first aspect was produced in the same manner as in Example 3-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.

[0172] Example 3-5 A barrier laminate in the first aspect was produced in the same manner as in Example 3-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.

[0173] Example 3-6 A barrier laminate according to the first aspect was produced in the same manner as in Example 3-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis.

[0174] Example 4-1 A barrier laminate in the first aspect was produced in the same manner as in Example 3-1, except that the formation of the vapor deposition film was changed as follows. Using a continuous vapor deposition film forming apparatus provided with a pretreatment section in which an oxygen plasma pretreatment apparatus, which is an actual machine, is arranged and separated from a film forming section on the surface resin layer, in the pretreatment section, while applying tension to the multilayer substrate by Roll to Roll, plasma was introduced from a plasma supply nozzle under the following conditions to perform oxygen plasma pretreatment, and in the continuously conveyed film forming section, a reactive resistance heating method was used as a heating means for the vacuum vapor deposition method on the oxygen plasma treated surface to form an aluminum oxide (alumina) vapor deposition film with a thickness of 12 nm (PVD method). (Forming conditions) (Oxygen plasma pretreatment conditions) · Plasma intensity: 200 W·sec / m 2 · Plasma forming gas ratio: oxygen:argon = 2:1 · Applied voltage between pre-treatment drum and plasma supply nozzle: 340 V (Film formation conditions) · Conveying speed: 400 m / min · Oxygen gas supply amount: 20000 sccm

[0175] Example 4-2 A barrier laminate in the first aspect was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis.

[0176] Example 4-3 A barrier laminate in the first aspect was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.

[0177] Example 4-4 A barrier laminate in the first aspect was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.

[0178] Example 4-5 A barrier laminate in the first aspect was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.

[0179] Example 4-6 A barrier laminate in the first aspect was produced in the same manner as in Example 4-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis.

[0180] Example 5-1 The polyamide was changed to ethylene vinyl alcohol (manufactured by Kuraray Co., Ltd., Eval F171B, melting point: 183°C), and a barrier laminate in the first aspect was produced in the same manner as in Example 3-1, except that the surface resin layer was formed.

[0181] Example 5-2 A barrier laminate in the first aspect was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis.

[0182] Example 5-3 A barrier laminate in the first aspect was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.

[0183] Example 5-4 A barrier laminate in the first aspect was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.

[0184] Example 5-5 A barrier laminate in the first aspect was produced in the same manner as in Example 5-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.

[0185] Example 5-6 A barrier laminate in the first aspect was produced in the same manner as in Example 5-1, except that a barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis.

[0186] Example 6-1 A barrier laminate in the first aspect was produced in the same manner as in Example 4-1, except that the polyamide was changed to ethylene vinyl alcohol (manufactured by Kuraray Co., Ltd., Eval F171B, melting point: 183°C) and a surface resin layer was formed.

[0187] Example 6-2 A barrier laminate in the first aspect was produced in the same manner as in Example 6-1, except that a barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis.

[0188] Example 6-3 A barrier laminate in the first aspect was produced in the same manner as in Example 6-1, except that a barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.

[0189] Example 6-4 A barrier laminate in the first aspect was produced in the same manner as in Example 6-1, except that a barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.

[0190] Example 6-5 A barrier laminate in the first aspect was produced in the same manner as in Example 6-1, except that a barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.

[0191] Example 6-6 A barrier laminate in the first aspect was produced in the same manner as in Example 6-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis.

[0192] Example 7-1 A coating liquid for forming a surface coat 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 coat layer with a thickness of 0.5 μm, thereby producing a multilayer substrate.

[0193] A hydroxyl group-containing (meth)acrylic resin (number average molecular weight 25,000, glass transition temperature 99 °C, hydroxyl value 80 mgKOH / g) was diluted with a mixed solvent of methyl ketone and ethyl acetate (mixing ratio 1:1) until the solid content concentration reached 10% by mass to prepare a main agent. An ethyl acetate solution containing tolylene diisocyanate (solid content 75% by mass) was added to the main agent as a curing agent to obtain a coating liquid for forming a surface coat layer. The amount of the curing agent used was 10 parts by mass with respect to 100 parts by mass of the main agent.

[0194] Next, a vapor deposition film was formed in the same manner as in Example 2-1.

[0195] Next, a barrier coat layer was formed on the vapor deposition film such 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.

[0196] Next, an unstretched polypropylene film with a thickness of 60 μm (manufactured by Toyobo Co., Ltd., P1128) was dry laminated on the barrier coat layer with a two-component curable polyurethane-based adhesive to form a sealant layer, thereby obtaining a barrier laminate in the second aspect.

[0197] Example 7-2 A barrier laminate in the second aspect was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis.

[0198] Example 7-3 A barrier laminate in the second aspect was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.

[0199] Example 7-4 A barrier laminate in the second aspect was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.

[0200] Example 7-5 A barrier laminate in the second aspect was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.

[0201] Example 7-6 A barrier laminate in the second aspect was produced in the same manner as in Example 7-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis.

[0202] Example 8-1 A barrier laminate was produced in the same manner as in Example 7-1, except that the formation of the vapor deposition film was changed as follows. On the surface coating layer, a silicon oxide (silica) vapor deposition film with a thickness of 20 nm was formed by Roll to Roll while applying tension to a multilayer substrate using an induction heating type vacuum film forming apparatus equipped with a plasma gun, which is an actual machine (PVD method). The vapor deposition film forming conditions were as follows. (Forming conditions) (Plasma irradiation conditions) ·Line speed: 30 m / min ·Vacuum degree: 1.7×10 -2 Pa ·Output: 5.7 kw ·Acceleration voltage: 151 V ·Ar gas flow rate: 7.5 sccm (Film forming conditions) ·Vapor deposition material: SiO ·Reaction gas: O2 ·Reaction gas flow rate: 100 sccm

[0203] Example 8-2 A barrier laminate in the second aspect was produced in the same manner as in Example 8-1, except that a barrier coating layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis.

[0204] Example 8-3 A barrier laminate in the second aspect was produced in the same manner as in Example 8-1, except that a barrier coating layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.

[0205] Example 8-4 A barrier laminate in the second aspect was produced in the same manner as in Example 8-1, except that a barrier coating layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.

[0206] Example 8-5 A barrier laminate in the second aspect was produced in the same manner as in Example 8-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.

[0207] Example 8-6 A barrier laminate in the second aspect was produced in the same manner as in Example 8-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis.

[0208] Example 9-1 A barrier laminate in the second aspect was produced in the same manner as in Example 7-1, except that the formation of the vapor deposition film was changed as follows.

[0209] Using a continuous vapor deposition film forming apparatus provided with a pretreatment section and a film forming section separated from each other by disposing an oxygen plasma pretreatment apparatus, which is an actual machine, on the surface coat layer, in the pretreatment section, while applying tension to the multilayer base material by Roll to Roll, plasma was introduced from a plasma supply nozzle under the following conditions to perform oxygen plasma pretreatment, and in the continuously conveyed film forming section, on the oxygen plasma-treated surface, a reactive resistance heating method was used as a heating means for the vacuum vapor deposition method to form an aluminum oxide (alumina) vapor deposition film with a thickness of 12 nm (PVD method). (Forming conditions) (Oxygen plasma pretreatment conditions) · Plasma intensity: 200 W·sec / m 2 · Plasma forming gas ratio: oxygen:argon = 2:1 · Applied voltage between pretreatment drum - plasma supply nozzle: 340 V (Film forming conditions) · Conveying speed: 400 m / min · Oxygen gas supply amount: 20000 sccm

[0210] Example 9-2 A barrier laminate in the second aspect was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis.

[0211] Example 9-3 A barrier laminate in the second aspect was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.

[0212] Example 9-4 A barrier laminate in the second aspect was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.

[0213] Example 9-5 A barrier laminate in the second aspect was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.

[0214] Example 9-6 A barrier laminate in the second aspect was produced in the same manner as in Example 9-1, except that the barrier coat layer was formed such that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis.

[0215] <<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, in the same manner as above, the oxygen permeability (cc / m 2 ·day·atm) and the 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 of oxygen permeability and water vapor permeability are omitted.

[0216] <<Gas barrier property evaluation (after the gelbo flex test)>> Using the barrier laminates obtained in Examples 3 to 9, cylindrical bags were produced. Using these bags, the gelbo flex test in accordance with ASTM F392 was repeated 10 times. Thereafter, the barrier laminate was cut out from the bag to obtain a test piece. Using this test piece, in the same manner as above, the oxygen permeability (cc / m 2 ·day·atm) and water vapor permeability (g / m 2 ·day) were measured. The results are summarized in Tables 2 to 8. In Tables 2 to 8, the units of oxygen permeability and water vapor permeability are omitted.

[0217]

Table 2

[0218]

Table 3

[0219]

Table 4

[0220]

Table 5

[0221]

Table 6

[0222]

Table 7

[0223]

Table 8

Explanation of Symbols

[0224] 10: Barrier laminate, 11: Multilayer base material, 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 base material, 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 venting mechanism, 60a: Steam seal portion, 60b: Non-seal portion, 70: Test piece, 71: Substrate side, 72: Sealant layer side, 73: Gripping tool, A: Vacuum container, B: Unwinding portion, C: Film-forming drum, D: Winding portion, E: Conveyor roll, F: Evaporation source, G: Reaction gas supply portion, H: Anti-deposition box, I: Vapor deposition material, J: Plasma gun, A1: Vacuum container, B1: Unwinding portion, C1: Cooling / electrode drum, D1: Winding portion, E1: Conveyor roll, F1: Glow discharge plasma, G1: Reaction gas supply portion, H1: Raw material supply nozzle, I1: Raw material gas supply portion, J1: Magnet, K1: Power supply, L1: Vacuum pump

Claims

1. A multilayer substrate having a vapor deposition film and a sealant layer, wherein the multilayer substrate includes at least a polypropylene resin layer and a surface coat layer, the polypropylene resin layer is subjected to a stretching treatment, and the surface coat layer contains a resin material having a polar group, the vapor deposition film is composed of an inorganic oxide, the vapor deposition film is provided on the surface coat layer, a barrier coat layer is provided on a surface of the vapor deposition film opposite to the surface on which the surface coat layer is provided, the barrier coat layer is a gas barrier coating film containing a metal alkoxide and a water-soluble polymer (excluding a gas barrier coating film further containing an inorganic layered compound), A barrier laminate characterized in that the laminate strength between the multilayer substrate and the vapor deposition film is 3 N or more in a width of 15 mm.

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

3. The barrier laminate according to claim 1 or 2, wherein a ratio of a thickness of the surface coat layer to a total thickness of the multilayer substrate is 0.08% or more and 20% or less.

4. The barrier laminate according to any one of claims 1 to 3, wherein the thickness of the surface coat layer is 0.02 μm or more and 10 μm or less.

5. 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. The barrier laminate according to any one of claims 1 to 4.

6. The barrier laminate according to any one of claims 1 to 5, wherein the surface coat layer is a layer formed using an aqueous emulsion or a solvent-based emulsion.

7. The barrier laminate according to any one of claims 1 to 6, which is used for packaging container applications.

8. A packaging container comprising the barrier laminate according to any one of claims 1 to 7.

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