WO2023136220A1 - ガスバリア積層体及び包装袋 - Google Patents

ガスバリア積層体及び包装袋 Download PDF

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Publication number
WO2023136220A1
WO2023136220A1 PCT/JP2023/000212 JP2023000212W WO2023136220A1 WO 2023136220 A1 WO2023136220 A1 WO 2023136220A1 JP 2023000212 W JP2023000212 W JP 2023000212W WO 2023136220 A1 WO2023136220 A1 WO 2023136220A1
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Prior art keywords
gas barrier
barrier laminate
layer
thickness
resin
Prior art date
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PCT/JP2023/000212
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English (en)
French (fr)
Japanese (ja)
Inventor
寛之 若林
純一 神永
良樹 越山
裕美子 小島
里佳 石井
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Toppan Inc
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Toppan Inc
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Priority to JP2023574017A priority Critical patent/JPWO2023136220A1/ja
Publication of WO2023136220A1 publication Critical patent/WO2023136220A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present disclosure relates to gas barrier laminates and packaging bags.
  • Packaging materials are required to have permeation-preventing properties (gas barrier properties) against water vapor and the like, which cause deterioration of contents.
  • Patent Document 1 discloses a gas barrier laminate in which a barrier layer is laminated on paper.
  • gas barrier laminate using paper a laminate in which a barrier layer is formed by vapor-depositing metal on paper is known.
  • the barrier layer formed by vapor deposition of metal has a metallic luster, the appearance of the gas barrier laminate as paper is spoiled.
  • the bag is produced with the barrier layer on the inside. . Therefore, gas barrier laminates in which a barrier layer is formed of a metal oxide have been studied so as not to impair the appearance of paper.
  • paper has the characteristic of being easy to process because it has crease-retaining properties (also called dead-holding properties). Therefore, gas barrier laminates using paper are used to produce packaging bags having folds.
  • the barrier layer is formed by the above-mentioned metal oxide. It was found that the formed gas barrier laminate is more likely to cause cracks in the barrier layer and lower gas barrier properties than the gas barrier laminate having the barrier layer formed by vapor deposition of metal.
  • the present disclosure provides a gas barrier laminate using paper and a metal oxide, which has not only initial water vapor barrier properties but also sufficient water vapor barrier properties even after being folded, and It aims at providing the packaging bag containing this.
  • the present disclosure provides the following gas barrier laminate and packaging bag.
  • a paper substrate, an anchor coat layer, a metal oxide layer, and an overcoat layer are provided in this order, and an acrylic resin and an epoxy resin are placed between the anchor coat layer and the metal oxide layer.
  • a gas barrier laminate comprising a resin layer containing at least one resin selected from the group consisting of: , an acrylic urethane resin, a polyester polyurethane resin, and a polyether polyurethane resin.
  • a gas barrier laminate comprising a paper substrate, an anchor coat layer, a resin layer, a metal oxide layer, and an overcoat layer in this order, the cross section of the gas barrier laminate in the thickness direction 3, wherein the softening temperature of the resin layer measured by local thermal analysis is 180° C. or higher.
  • the softening temperature of the resin layer measured by local thermal analysis is 180° C. or higher in a cross section in the thickness direction of the gas barrier laminate.
  • the anchor coat layer contains a polyolefin having a polar group.
  • a gas barrier laminate using paper and a metal oxide the gas barrier laminate having not only initial water vapor barrier properties but also sufficient water vapor barrier properties even after being folded, and A packaging bag containing this can be provided. Since the gas barrier laminate uses paper, it has the characteristic crease retention of paper and contributes to a reduction in the amount of plastic material used. In addition, since the barrier layer is a metal oxide layer, the gas barrier laminate can prevent the appearance of paper from being damaged, and can be used for microwave heating (microwave oven).
  • FIG. 1 is a schematic cross-sectional view showing a gas barrier laminate according to an embodiment of the present disclosure
  • FIG. 1 is a perspective view of a packaging bag according to an embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a gas barrier laminate according to an embodiment of the present disclosure
  • FIG. 1 is a perspective view of a packaging bag according to an embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a gas barrier laminate according to one embodiment.
  • a gas barrier laminate 10 according to one embodiment includes a paper substrate 1, an anchor coat layer 2, a resin layer 3, a metal oxide layer 4, and an overcoat layer 5 in this order.
  • the resin layer 3 is a layer that satisfies at least one of the following conditions (a) and (b), and may be a layer that satisfies both.
  • the gas barrier laminate 10 is provided with the resin layer 3 containing the specific resin or having the specific softening temperature between the anchor coat layer 2 and the metal oxide layer 4, so that not only initial water vapor barrier properties but also , it can have sufficient water vapor barrier properties even after being folded.
  • the inventors of the present invention speculate as follows about the reason why the above effects are achieved.
  • gas barrier laminates using paper by providing an anchor coat layer using polyolefin-based resin or polyvinyl alcohol-based resin between the paper substrate and the barrier layer, there is a tendency to improve the water vapor barrier properties after folding.
  • the present inventors have found that when a barrier layer using a metal oxide is formed on the anchor coat layer, defects tend to occur in the metal oxide layer, resulting in unstable water vapor barrier properties.
  • the metal oxide As a result of intensive studies to solve this problem, it was found that by providing a resin layer containing a specific resin or having a specific softening temperature between the anchor coat layer and the metal oxide layer, the metal oxide The inventors of the present invention have found that it is possible to suppress the occurrence of defects in the layer, and that it is possible to obtain stable and good water vapor barrier properties without variation both at the initial stage and after bending. This is because when a metal oxide layer is formed by vapor deposition or the like, a certain amount of heat is applied to the underlying layer, and the resin layer containing the specific resin or having the specific softening temperature has excellent heat resistance.
  • the above gas barrier laminate By using the above gas barrier laminate, it has a high paper component ratio, stable and excellent water vapor barrier properties, which is compatible with plastic removal and marine garbage problems, and has little barrier property deterioration after bending. It is possible to provide a paper packaging material that has a good appearance and can be used for microwave heating (microwave oven).
  • the paper base material 1 is not particularly limited, and may be appropriately selected according to the use of the packaging bag to which the gas barrier laminate 10 is applied.
  • the paper base material 1 is not particularly limited as long as it is paper containing plant-derived pulp as a main component.
  • Specific examples of the paper substrate 1 include woodfree paper, special woodfree paper, coated paper, art paper, cast coated paper, imitation paper, kraft paper, and glassine paper.
  • the thickness of the paper substrate 1 may be, for example, 30 ⁇ m or more and 100 ⁇ m or less, or 30 ⁇ m or more and 70 ⁇ m or less.
  • the thickness of the paper substrate may be 70% or more of the thickness of the entire gas barrier laminate. If the thickness of the paper substrate is 70% or more of the thickness of the entire gas barrier laminate, it can be said to be excellent in environmental suitability.
  • the paper substrate 1 may be provided with a coat layer at least on the side in contact with the anchor coat layer 2 described later.
  • a coat layer By providing the coat layer, it is possible to prevent the anchor coat layer 2 from soaking into the paper, and it can also play a role of a filler to fill the unevenness of the paper, and the anchor coat layer can be uniformly formed without defects. can be done.
  • a binder resin for example, various copolymers such as styrene-butadiene, styrene-acrylic, ethylene-vinyl acetate, polyvinyl alcohol resin, cellulose resin, paraffin (WAX), etc. are used. Fillers such as clay, kaolin, calcium carbonate, talc, mica, and the like may be included.
  • the coating layer may be a clay coating layer containing at least clay as a filler.
  • the thickness of the coat layer is not particularly limited, but may be, for example, 1 to 10 ⁇ m or 3 to 8 ⁇ m.
  • the mass of the paper is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the mass of the entire gas barrier laminate. If the mass of paper is 50% by mass or more based on the mass of the entire gas barrier laminate, the amount of plastic material used can be sufficiently reduced, and the gas barrier laminate as a whole can be said to be made of paper. , excellent recyclability.
  • the anchor coat layer 2 is provided on the surface of the paper substrate to improve the adhesion between the paper substrate 1 and the resin layer 3 described later and to improve the gas barrier properties of the gas barrier laminate. be.
  • the anchor coat layer 2 may contain at least one of polyolefin and polyvinyl alcohol resin having a polar group. Thereby, the gas barrier laminate 10 is excellent in gas barrier properties (in particular, water vapor barrier properties).
  • the anchor coat layer 2 may contain a polyvinyl alcohol-based resin, since it is more excellent in water vapor barrier properties and oxygen barrier properties.
  • the anchor coat layer 2 contains polyolefin having a polar group, it is possible to form a dense film due to the crystallinity of the polyolefin, thereby exhibiting water vapor barrier properties. Due to the crystallinity of the polyolefin, water vapor barrier properties are exhibited, and by having a polar group, adhesion to the resin layer 3 is exhibited.
  • the polyolefin having a polar group may have at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic acid anhydride group and a carboxylic acid ester.
  • Polyolefins having polar groups include copolymers of ethylene and propylene with unsaturated carboxylic acids (unsaturated compounds with carboxyl groups such as acrylic acid, methacrylic acid and maleic anhydride) and unsaturated carboxylic acid esters, and A salt obtained by neutralizing a carboxylic acid with a basic compound may be used, or a copolymer obtained by copolymerizing vinyl acetate, an epoxy-based compound, a chlorine-based compound, a urethane-based compound, a polyamide-based compound, or the like may be used. .
  • polyolefins having polar groups include copolymers of acrylic acid esters and maleic anhydride, ethylene-vinyl acetate copolymers, and ethylene-glycidyl methacrylate copolymers.
  • Polyvinyl alcohol resins are, for example, fully saponified polyvinyl alcohol resins, partially saponified polyvinyl alcohol resins, modified polyvinyl alcohol resins, and ethylene-vinyl alcohol copolymer resins.
  • the degree of polymerization of the polyvinyl alcohol-based resin is preferably 300 or more and 1700 or less. If the degree of polymerization is 300 or more, the gas barrier property and bending resistance of the gas barrier laminate will be good. get better.
  • the anchor coat layer 2 contains a polyvinyl alcohol-based resin
  • the anchor coat layer 2 and the resin layer 3 are excellent in flexibility and can suppress deterioration of the gas barrier property even after bending (after bending). can improve the adhesion of.
  • the anchor coat layer 2 may contain other components in addition to the polyolefin and polyvinyl alcohol resin having the polar group.
  • Other components include, for example, polyolefins other than the above-mentioned polyolefins having polar groups, polyacrylics, polyesters, polyurethanes, polycarbonates, polyureas, melamine, phenols, polyethyleneimine, polylactic acid, polyamides, polyimides, starch and derivatives thereof, and cellulose.
  • Resins such as derivatives, and additives such as silane coupling agents, organic titanates, glycerin, glycols, casein and waxes.
  • the total content of the polyolefin having a polar group and the polyvinyl alcohol resin in the anchor coat layer 2 may be, for example, 50% by mass or more, 70% by mass or more, or 90% by mass or more. , 100% by weight.
  • the thickness of the anchor coat layer 2 may be, for example, 1 ⁇ m or more, 2 ⁇ m or more, 20 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less. If the thickness of the anchor coat layer 2 is 1 ⁇ m or more, the unevenness of the paper substrate can be efficiently filled, and the resin layer 3 and the metal oxide layer 4 described later can be uniformly laminated. Moreover, if the thickness of the anchor coat layer 2 is 20 ⁇ m or less, the above layers can be uniformly laminated while suppressing the cost.
  • Solvents contained in the coating liquid include, for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethylsulfoxide, dimethylformamide, dimethylacetamide, toluene, hexane, Heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate.
  • solvents may be used alone or in combination of two or more.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water are preferred from the viewpoint of properties.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol and water are preferable.
  • the resin layer 3 is provided on the surface of the anchor coat layer, suppresses the occurrence of defects in the metal oxide layer 4, and improves adhesion between the anchor coat layer 2 and the metal oxide layer 4 described later. It is provided for
  • the resin layer 3 satisfies one or both of the following conditions (a) and (b).
  • the resin layer 3 When the resin layer 3 satisfies the condition (a), the resin layer 3 is made of an acrylic urethane resin, an epoxy resin, or a polyester from the viewpoint of stably obtaining better water vapor barrier properties both at the initial stage and after bending. It preferably contains at least one resin selected from the group consisting of polyether-based polyurethane resins and polyether-based polyurethane resins.
  • the resin layer 3 When the resin layer 3 satisfies the condition (a), the resin layer 3 may contain a resin other than the above-described specific resin, but the resin layer 3 exhibits better water vapor barrier properties both at the initial stage and after bending. From the viewpoint of stably obtaining, the content of the specific resin in the resin layer 3 is preferably 50% by mass or more, more preferably 70% by mass or more based on the total amount of the resin layer 3 .
  • the softening temperature of the resin layer 3 measured by local thermal analysis is 180° C. or higher, preferably 185° C. or higher, more preferably 190° C. or higher. It is more preferably 200° C. or higher, and particularly preferably 205° C. or higher.
  • the upper limit of the softening temperature of the resin layer 3 is not particularly limited. If the softening temperature of the resin layer 3 is 180° C. or higher, it is possible to suppress deformation of the resin layer 3 due to heat when the metal oxide layer 4 is formed by vapor deposition or the like. Cracking of the metal oxide layer 4 at the initial stage and after bending is suppressed, and good water vapor barrier properties can be obtained.
  • the softening temperature of the resin layer 3 can be measured in the cross section of the gas barrier laminate 10 in the thickness direction by the following method.
  • a softening temperature is a temperature at which a substance such as a resin exhibits softening behavior.
  • the softening temperature is evaluated by local thermal analysis (LTA) using an atomic force microscope, and the sample is heated by applying a voltage to a cantilever having a heater.
  • LTA local thermal analysis
  • a constant force contact pressure
  • the softening temperature is calculated as the temperature at which the height position (Z displacement) of the cantilever changes due to the change in hardness of the front and rear sample surfaces.
  • a change in the height position of the cantilever means a change due to a rise in the vertical position of the cantilever due to thermal expansion of the sample surface and a change in the vertical position of the cantilever due to softening of the sample surface.
  • MFP-3D-SA trade name
  • AFM atomic force microscope
  • Ztherm a local thermal analysis option
  • AC mode tapping mode
  • contact mode is used for softening temperature measurement.
  • AN2-200 (trade name) manufactured by Anasys Instruments with a spring constant of 0.5 to 3.5 N/m is used.
  • the voltage application rate (heating rate) of the cantilever in measuring the softening temperature is 0.5 V/sec.
  • the contact pressure of the cantilever (the amount of change in the amount of deflection of the cantilever (Deflection)) is controlled and measured.
  • the amount of deflection (Deflection) of the cantilever changes depending on the applied voltage without contacting the sample, it is necessary to control the contact pressure after subtracting the amount (Deflection) of the cantilever due to the applied voltage.
  • Ztherm has a Detrend correction function that acquires changes in the amount of deflection (Deflection) of the cantilever with respect to the applied voltage. With the cantilever not in contact with the sample surface, the maximum applied voltage used for measurement is applied to the cantilever to perform Detrend correction.
  • Detrend correction is performed at the maximum applied voltage and the voltage application rate (heating rate) of 0.5 V/sec used for the measurement, and then the measurement is performed.
  • the contact pressure is set to 0.5V.
  • the set value of the amount of downward displacement of the cantilever for stopping the measurement is 50 nm.
  • the softening point is the point where the vertical height (Z displacement) of the cantilever is maximum, and the applied voltage at this point is read.
  • a calibration curve for the applied voltage and the melting point (melting peak temperature).
  • a calibration sample a sample whose melting point (melting peak temperature) value has been measured with a differential scanning calorimeter (DSC) is used, and the softening temperature is measured by changing the measurement position in each calibration sample, and the softening point is applied.
  • a calibration curve is prepared by approximating the average value of the voltage and the melting point (melting peak temperature) with a cubic function by the method of least squares to obtain a calibration curve.
  • the calibration samples are polycaprolactone pellets (melting point: 60°C), low-density polyethylene pellets (melting point: 112°C), polypropylene pellets (melting point: 166°C), and polyethylene terephthalate biaxially oriented film (melting point: 255°C).
  • cross-sectional samples prepared in an environment below the glass transition temperature are used.
  • An ultramicrotome and a cryo system are used to prepare cross-section samples, and cross-section cutting is performed at -80°C for polycaprolactone, -140°C for low-density polyethylene, -40°C for polypropylene, and 25°C for polyethylene terephthalate.
  • the applied voltage at the softening point is converted into temperature and taken as the softening temperature.
  • a method of applying a coating liquid containing a constituent material of the resin layer 3 and a solvent onto the anchor coat layer 2 and drying it can be mentioned.
  • the solvent contained in the coating liquid include esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as methyl ethyl ketone; and aromatic hydrocarbons such as toluene and xylene. is mentioned.
  • the resin layer 3 after drying may be subjected to an aging treatment within a temperature range of about 40° C. or higher and 60° C. or lower, if necessary.
  • Such a resin layer 3 is excellent in heat resistance, can suppress initial cracking of the metal oxide layer 4, and can improve the adhesion between the metal oxide layer 4 and the resin layer 3.
  • the resin layer 3 is preferably in contact with the metal oxide layer 4 from the viewpoint of obtaining the above effect more effectively.
  • the resin layer 3 is preferably in contact with the anchor coat layer 2 from the viewpoint of obtaining the above effect more effectively.
  • the thickness of the resin layer 3 may be, for example, 0.01 ⁇ m or more, 0.05 ⁇ m or more, 0.1 ⁇ m or more, or 0.5 ⁇ m or more. Also, the thickness of the resin layer 3 may be, for example, 3 ⁇ m or less, 2 ⁇ m or less, or 1.5 ⁇ m or less. When the thickness is 0.01 ⁇ m or more, cracking of the metal oxide layer 4 can be suppressed, and better steam barrier properties can be stably obtained at the initial stage and after bending. Moreover, if the thickness is 3 ⁇ m or less, the metal oxide layer can be uniformly laminated while suppressing the cost.
  • the metal oxide layer 4 is a layer containing metal oxide.
  • the metal oxide layer 4 can be formed by vapor-depositing a metal oxide.
  • Metal oxides include aluminum oxide (AlO x ) and silicon oxide (SiO x ).
  • the thickness of the metal oxide layer 4 may be appropriately set depending on the intended use, but is preferably 10 nm or more, 20 nm or more, or 30 nm or more, and may be 100 nm or less, or 80 nm or less.
  • the thickness of the metal oxide layer 4 is 10 nm or more, the continuity of the metal oxide layer 4 can be easily made sufficient, and when it is 100 nm or less, the occurrence of curling and cracks can be sufficiently suppressed, and a sufficient gas barrier can be obtained. Easy to achieve performance and flexibility. Further, by setting the thickness of the metal oxide layer to 10 nm or more and 100 nm or less, the metal oxide layer becomes more difficult to crack, and sufficient water vapor barrier properties can be obtained even after bending.
  • Film formation means include known methods such as a vacuum deposition method, a sputtering method, and a chemical vapor deposition method (CVD method), but the vacuum deposition method is preferred because of its high film formation speed and high productivity.
  • the vacuum evaporation methods electron beam heating is particularly effective because the film formation rate can be easily controlled by adjusting the irradiation area and electron beam current, and the heating and cooling of the evaporation material can be performed in a short time. be.
  • the gas barrier laminate 10 can obtain good water vapor barrier properties. Moreover, since the metal oxide layer 4 does not have metallic luster, the packaging bag using the gas barrier laminate 10 has a good appearance when opened and can be used for microwave heating (microwave oven). It is preferable that the gas barrier laminate does not include a layer formed by vapor deposition of metal from the viewpoint of making the appearance good when the bag is opened and enabling the use for microwave heating.
  • Overcoat layer 5 is provided on the surface of metal oxide layer 4 so as to be in contact with metal oxide layer 4 .
  • the overcoat layer 5 may contain a polyolefin having polar groups.
  • the polyolefin having a polar group may have at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic acid anhydride group and a carboxylic acid ester.
  • Polyolefins with polar groups include copolymers of ethylene and propylene with unsaturated carboxylic acids (unsaturated compounds with carboxyl groups such as acrylic acid and methacrylic acid) and unsaturated carboxylic acid esters, and carboxylic acids with basic properties. Salts neutralized with compounds may also be used, and copolymers with vinyl acetate, epoxy-based compounds, chlorine-based compounds, urethane-based compounds, polyamide-based compounds, and the like may also be used.
  • polystyrene resin having a polar group specifically, a copolymer of acrylic acid ester and maleic anhydride, an ethylene-vinyl acetate copolymer, an ethylene-glycidyl methacrylate copolymer, etc. may be used.
  • the overcoat layer 5 By containing a polyolefin having a polar group, the overcoat layer 5 has excellent flexibility, can suppress cracking of the metal oxide layer after bending (after bending), and has adhesion with the metal oxide layer. Excellent for Furthermore, by including the above-described polyolefin having a polar group, it is possible to obtain a gas barrier laminate having excellent water vapor barrier properties. In addition, since the overcoat layer 5 contains the polyolefin having the polar group, the overcoat layer 5 can also serve as a heat seal layer.
  • the overcoat layer 5 may contain other components in addition to the above polyolefin having a polar group.
  • Other components include, for example, silane coupling agents, organic titanates, polyacrylics, polyesters, polyurethanes, polycarbonates, polyureas, polyamides, polyolefin emulsions, polyimides, melamine, and phenols.
  • the content of the polyolefin having a polar group in the overcoat layer 5 may be, for example, 50% by mass or more, 70% by mass or more, 90% by mass or more, or 100% by mass. good.
  • the thickness of the overcoat layer 5 may be, for example, 2 ⁇ m or more, 3 ⁇ m or more, 10 ⁇ m or less, 8 ⁇ m or less, or 5 ⁇ m or less. If the thickness of the overcoat layer 5 is 2 ⁇ m or more, the role of the heat seal layer described above can be fully exhibited. In addition, if the thickness of the overcoat layer 5 is 10 ⁇ m or less, it is possible to sufficiently exhibit adhesion to the metal oxide layer and barrier properties while suppressing costs.
  • a method of providing the overcoat layer 5 includes a method of applying a coating liquid containing the above-described polyolefin and a solvent onto the metal oxide layer and drying the coating liquid.
  • Solvents contained in the coating liquid include, for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethylsulfoxide, dimethylformamide, dimethylacetamide, toluene, hexane, Heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate.
  • solvents may be used alone or in combination of two or more.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water are preferred from the viewpoint of properties.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol and water are preferable.
  • the polyolefins having polar groups contained in the anchor coat layer 2 and the overcoat layer 5 may be of the same type or different types. It is preferable that the
  • gas barrier laminate according to the present embodiment
  • present disclosure may include gas barrier laminates other than this.
  • FIG. 2 is a perspective view showing a gusset bag 20 made of the gas barrier laminate 10.
  • FIG. A packaging bag is manufactured by sealing the upper opening of the gusset bag 20 .
  • the gusset bag 20 has portions (folded portions B1, B2) where the gas barrier laminate 10 is folded.
  • the bent portion B1 is a portion where the gas barrier laminate 10 is valley-folded when viewed from the innermost layer side
  • the bent portion B2 is a portion where the gas barrier laminate 10 is mountain-folded when viewed from the innermost layer side.
  • the packaging bag is made into a bag shape by folding one sheet of the gas barrier laminate in two so that the overcoat layers 5 face each other, then appropriately folding it into a desired shape and heat-sealing it.
  • two gas barrier laminates may be stacked such that the overcoat layers 5 face each other, and then heat-sealed to form a bag shape.
  • the heat seal strength may be 2N or more, or 4N or more. Although the upper limit of the heat seal strength is not particularly limited, it may be 10 N or less, for example.
  • the heat seal strength is measured by stacking two gas barrier laminates 10 so that the overcoat layers 5 face each other, heat sealing with a heat sealer under the conditions of 120° C., 0.2 MPa, and 1 second. A strip having a width of 15 mm was cut out, and the maximum load was measured when T-shaped peeling was performed at a peeling speed of 300 mm/min.
  • the packaging bag can contain contents such as food and medicine. Especially in food, it is suitable for containing sweets and the like.
  • the packaging bag according to the present embodiment can maintain high gas barrier properties even if it has a shape with a bent portion.
  • a gusset bag is used as an example of a packaging bag, but the gas barrier laminate according to the present embodiment may be used to produce, for example, a pillow bag, a three-sided seal bag, or a standing pouch. .
  • a mixed solution of acrylic polyol and polyisocyanate was coated on the anchor coat layer so that the thickness after drying was 1 ⁇ m, and dried by heating to form a resin layer composed of an acrylic urethane resin.
  • SiO x vapor deposition was performed on the resin layer by a vacuum vapor deposition method to form a metal oxide layer with a thickness of 30 nm.
  • An aqueous polyolefin dispersion containing a salt of a carboxyl group was applied onto the metal oxide layer using a bar coater and dried in an oven to form an overcoat layer having a thickness of 3 ⁇ m.
  • a gas barrier laminate was thus obtained.
  • the mass of paper in the gas barrier laminate was 81% by mass.
  • Example 2 A gas barrier laminate was obtained in the same manner as in Example 1, except that the anchor coat layer was formed by applying a polyolefin aqueous dispersion containing a salt of a carboxyl group with a bar coater and drying it in an oven.
  • the mass of paper in the gas barrier laminate was 81% by mass.
  • Example 3 A gas barrier laminate was obtained in the same manner as in Example 1, except that the thickness of the metal oxide layer was 10 nm. The mass of paper in the gas barrier laminate was 81% by mass.
  • Example 4 A gas barrier laminate was obtained in the same manner as in Example 1, except that the thickness of the metal oxide layer was 100 nm. The mass of paper in the gas barrier laminate was 81% by mass.
  • Example 5 A gas barrier laminate was obtained in the same manner as in Example 1, except that the thickness of the resin layer was 0.01 ⁇ m. The mass of paper in the gas barrier laminate was 82% by mass.
  • Example 6 A gas barrier laminate was obtained in the same manner as in Example 1, except that the thickness of the resin layer was 3 ⁇ m. The mass of paper in the gas barrier laminate was 78% by mass.
  • Example 7 A gas barrier laminate was obtained in the same manner as in Example 1, except that the thickness of the anchor coat layer was 1 ⁇ m. The mass of paper in the gas barrier laminate was 83% by mass.
  • Example 8 A gas barrier laminate was obtained in the same manner as in Example 1, except that the thickness of the anchor coat layer was 5 ⁇ m. The mass of paper in the gas barrier laminate was 78% by mass.
  • Example 9 A gas barrier laminate was obtained in the same manner as in Example 1, except that the overcoat layer had a thickness of 2 ⁇ m. The mass of paper in the gas barrier laminate was 82% by mass.
  • Example 10 A gas barrier laminate was obtained in the same manner as in Example 1, except that the overcoat layer had a thickness of 10 ⁇ m.
  • the mass of paper in the gas barrier laminate was 72% by mass.
  • Example 11 A gas barrier laminate was obtained in the same manner as in Example 1, except that AlO x was used as the material for the metal oxide layer.
  • the mass of paper in the gas barrier laminate was 81% by mass.
  • Example 12 A gas barrier laminate was obtained by the same operation as in Example 1, except that the resin layer was formed by the following method. Specifically, an epoxy resin solution was applied onto the anchor coat layer using a bar coater and dried in an oven to form a resin layer having a thickness of 3 ⁇ m.
  • the mass of paper in the gas barrier laminate was 81% by mass.
  • Example 13 A gas barrier laminate was obtained in the same manner as in Example 12, except that the anchor coat layer was formed by applying an aqueous dispersion of polyolefin containing a salt of a carboxyl group with a bar coater and drying it in an oven.
  • the mass of paper in the gas barrier laminate was 81% by mass.
  • Example 1 A gas barrier laminate was obtained in the same manner as in Example 1, except that the metal oxide layer was deposited on the anchor coat layer without forming the resin layer.
  • the mass of paper in the gas barrier laminate was 82% by mass.
  • Example 2 A gas barrier laminate was obtained in the same manner as in Example 2, except that the metal oxide layer was deposited on the anchor coat layer without forming the resin layer.
  • the mass of paper in the gas barrier laminate was 82% by mass.
  • Example 3 A gas barrier laminate was obtained in the same manner as in Example 1, except that a resin layer was formed on the surface of the paper base on the clay coat layer side without forming an anchor coat layer.
  • the mass of paper in the gas barrier laminate was 85% by mass.
  • Example 4 The anchor coat layer was formed according to the material, thickness and formation method of the resin layer in Example 1, and the resin layer was formed according to the material, thickness and formation method of the anchor coat layer in Example 1.
  • a gas barrier laminate was obtained by the same operation as in Example 1.
  • the mass of paper in the gas barrier laminate was 81% by mass.
  • the mass of paper in the gas barrier laminate was 81% by mass.
  • Example 5 The anchor coat layer was formed using the material, film thickness and formation method of the resin layer of Example 2, and the resin layer was formed using the material, film thickness and formation method of the anchor coat layer of Example 2.
  • a gas barrier laminate was obtained by the same operation as in Example 2. The mass of paper in the gas barrier laminate was 81% by mass.
  • Example 6 A gas barrier laminate was obtained in the same manner as in Example 1 except that the resin layer was formed using the material, film thickness and formation method of the anchor coat layer of Example 2. The mass of paper in the gas barrier laminate was 78% by mass.
  • the softening temperature of the resin layer was measured by the method shown below.
  • the gas barrier laminates prepared in Examples and Comparative Examples were used as samples, and the samples were wedge-shaped with a base of 1.0 mm and a height of 5.0 mm (the triangular surfaces having the above base and height are the front and back surfaces of the sample, and the bottom surface is and a shape in which the side surface is the cross section of the sample) was cut with a razor.
  • the cut sample was embedded in a photocurable resin and cured with a halogen lamp (manufactured by Kenko Tokina, trade name: KTX-100R).
  • D-800 (trade name) manufactured by Toagosei Co., Ltd. was used as the photocurable resin.
  • the test piece after photocuring was fixed with an insert for an AFM sample holder, and the cross section of the film was cut with a glass knife at room temperature (25°C). After that, final cross-sectional cutting was performed with a diamond knife at room temperature at a cutting speed of 1.0 mm/s and a cutting film thickness of 200 nm.
  • An ultramicrotome manufactured by Leica, trade name: EM UC7
  • a cryosystem manufactured by Leica, trade name: EM FC7 were used as cross-section cutting devices.
  • the cutting direction of the knife was perpendicular to the film thickness direction of the layer.
  • the cross-sectioned test piece was fixed with an AFM sample holder insert and used for softening temperature measurement.
  • Atomic force microscope is MFP-3D-SA (trade name) of Oxford Instruments Co., Ltd.
  • Local thermal analysis option is Zterm system, cantilever has a spring constant of 0.5 to 3.5 N/m.
  • Softening temperature measurement and shape measurement were performed using AN2-200 (trade name) manufactured by Anasys Instruments Co., Ltd. with specifications.
  • the contact pressure of the cantilever (the amount of change in the amount of deflection of the cantilever (Deflectin)) is 2.0 V, the voltage application speed (temperature increase rate) is 0.5 V / sec, and the maximum applied voltage is 7.1 V. That is, when the cross section of the resin layer is heated, the measurement surface expands and the height position of the cantilever rises. When the surface to be measured was further heated, the surface to be measured was softened, and the measurement was completed when the height position of the cantilever was lowered by 50 nm. When the height position reached the maximum applied voltage without falling by 50 nm from the change point, the maximum applied voltage was increased by 0.5 V during the Detrend correction and during the measurement, and the measurement was performed again.
  • the applied voltage at the maximum vertical height position of the cantilever was taken as the applied voltage at the softening point, and the voltage value was read.
  • a calibration curve was created for the applied voltage and the melting point (melting peak temperature).
  • a calibration sample a sample whose melting point (melting peak temperature) value has been measured with a differential scanning calorimeter (DSC) is used, and the softening temperature is measured by changing the measurement position in each calibration sample, and the softening point is applied.
  • a calibration curve was prepared by approximating the average value of the voltage and the melting point (melting peak temperature) with a cubic function by the method of least squares, and used as a calibration curve.
  • the calibration samples are polycaprolactone pellets (melting point: 60°C), low-density polyethylene pellets (melting point: 112°C), polypropylene pellets (melting point: 166°C), and polyethylene terephthalate biaxially oriented film (melting point: 255°C).
  • a cross-sectional sample prepared in an environment below the glass transition temperature was used.
  • An ultramicrotome and a cryo system were used to create cross-section samples, and cross-section cutting was performed under the environment of -80 ° C for polycaprolactone, -140 ° C for low-density polyethylene, -40 ° C for polypropylene, and 25 ° C for polyethylene terephthalate. .
  • the oxygen permeability of the gas barrier laminate using a polyvinyl alcohol resin for the anchor coat layer was measured according to JIS K7126, B method (isobaric method).
  • OXTRAN 2/20 manufactured by Nodern Control was used, and the measurement was performed at a temperature of 30°C and a relative humidity of 70%. While rolling a roller of 600 g at a speed of 300 mm/min, the gas barrier laminate was creased, and the oxygen permeability of the gas barrier laminate after opening was similarly measured.
  • the meanings of "inward folding" and "outward folding" in Tables 1 to 3 are as described above.
  • the gas barrier laminates of Examples had low water vapor permeability not only at the initial stage but also after folding, and had good water vapor barrier properties. In addition, the gas barrier laminates of Examples showed little variation in water vapor permeability both at the initial stage and after bending, and stably obtained good water vapor barrier properties. In addition, the gas barrier laminate of the example having an anchor coat layer using a polyvinyl alcohol-based resin had low oxygen permeability not only at the initial stage but also after folding, and had good oxygen barrier properties. Furthermore, the gas barrier laminates of the examples, which had an anchor coat layer using a polyvinyl alcohol-based resin, had little variation in oxygen permeability both at the initial stage and after folding, and stably obtained good oxygen barrier properties. According to the gas barrier laminate of the present disclosure, deterioration of contents can be suppressed over a long period of time even when a packaging bag having a shape having a bent portion is formed.

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  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/000212 2022-01-11 2023-01-06 ガスバリア積層体及び包装袋 Ceased WO2023136220A1 (ja)

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Publication number Priority date Publication date Assignee Title
JPS56118992A (en) * 1980-02-25 1981-09-18 Mitsui Petrochemical Ind Production of metal japor deposited paper
JP2003291296A (ja) * 2002-04-04 2003-10-14 Ishida Co Ltd 積層材料
JP2004017449A (ja) * 2002-06-14 2004-01-22 Dainippon Printing Co Ltd 紙容器用積層体およびそれを用いた紙容器
JP2004204366A (ja) * 2002-12-24 2004-07-22 Toppan Printing Co Ltd 防湿紙およびそれを用いた包装紙、包装袋または紙製容器。
JP2010264984A (ja) * 2009-05-12 2010-11-25 Toppan Printing Co Ltd 紙製液体容器
US20140312103A1 (en) * 2011-07-26 2014-10-23 Sig Technology Ag Planar composite with layers of plastic of different vicat softening temperatures
JP2018533506A (ja) * 2015-10-29 2018-11-15 テトラ ラバル ホールディングス アンド ファイナンス エス エイ バリアフィルムを備えるラミネート包装材料及び該ラミネート包装材料から製造された包装容器
US20190270288A1 (en) * 2016-12-09 2019-09-05 Jindal Films Americas Llc High-barrier, metal oxide films
WO2021010040A1 (ja) * 2019-07-12 2021-01-21 王子ホールディングス株式会社 紙積層体
JP2021070311A (ja) * 2019-10-30 2021-05-06 大日本印刷株式会社 積層体及びこれを用いた包装体
WO2021111973A1 (ja) * 2019-12-06 2021-06-10 大日本印刷株式会社 バリア紙、並びに、前記バリア紙を含む容器及び蓋材、並びに、バリア紙の製造方法
WO2021220830A1 (ja) * 2020-04-30 2021-11-04 大日本印刷株式会社 積層体及びこれを用いた包装体
JP2022014245A (ja) * 2020-07-06 2022-01-19 大日本印刷株式会社 酸素吸収性コート積層体

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56118992A (en) * 1980-02-25 1981-09-18 Mitsui Petrochemical Ind Production of metal japor deposited paper
JP2003291296A (ja) * 2002-04-04 2003-10-14 Ishida Co Ltd 積層材料
JP2004017449A (ja) * 2002-06-14 2004-01-22 Dainippon Printing Co Ltd 紙容器用積層体およびそれを用いた紙容器
JP2004204366A (ja) * 2002-12-24 2004-07-22 Toppan Printing Co Ltd 防湿紙およびそれを用いた包装紙、包装袋または紙製容器。
JP2010264984A (ja) * 2009-05-12 2010-11-25 Toppan Printing Co Ltd 紙製液体容器
US20140312103A1 (en) * 2011-07-26 2014-10-23 Sig Technology Ag Planar composite with layers of plastic of different vicat softening temperatures
JP2018533506A (ja) * 2015-10-29 2018-11-15 テトラ ラバル ホールディングス アンド ファイナンス エス エイ バリアフィルムを備えるラミネート包装材料及び該ラミネート包装材料から製造された包装容器
US20190270288A1 (en) * 2016-12-09 2019-09-05 Jindal Films Americas Llc High-barrier, metal oxide films
WO2021010040A1 (ja) * 2019-07-12 2021-01-21 王子ホールディングス株式会社 紙積層体
JP2021070311A (ja) * 2019-10-30 2021-05-06 大日本印刷株式会社 積層体及びこれを用いた包装体
WO2021111973A1 (ja) * 2019-12-06 2021-06-10 大日本印刷株式会社 バリア紙、並びに、前記バリア紙を含む容器及び蓋材、並びに、バリア紙の製造方法
WO2021220830A1 (ja) * 2020-04-30 2021-11-04 大日本印刷株式会社 積層体及びこれを用いた包装体
JP2022014245A (ja) * 2020-07-06 2022-01-19 大日本印刷株式会社 酸素吸収性コート積層体

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