WO2023095915A1 - バリアフィルム、積層体及び包装袋 - Google Patents

バリアフィルム、積層体及び包装袋 Download PDF

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Publication number
WO2023095915A1
WO2023095915A1 PCT/JP2022/043811 JP2022043811W WO2023095915A1 WO 2023095915 A1 WO2023095915 A1 WO 2023095915A1 JP 2022043811 W JP2022043811 W JP 2022043811W WO 2023095915 A1 WO2023095915 A1 WO 2023095915A1
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Prior art keywords
layer
barrier film
softening temperature
skin layer
skin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/043811
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English (en)
French (fr)
Japanese (ja)
Inventor
美季 福上
郁子 山川
薫 古田
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Toppan Inc
Original Assignee
Toppan Inc
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=86539688&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2023095915(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Toppan Inc filed Critical Toppan Inc
Priority to EP22898697.2A priority Critical patent/EP4424510A4/en
Priority to CN202280075231.1A priority patent/CN118265610A/zh
Priority to JP2023540912A priority patent/JP7377425B2/ja
Publication of WO2023095915A1 publication Critical patent/WO2023095915A1/ja
Priority to JP2023182325A priority patent/JP2023184583A/ja
Priority to JP2023183286A priority patent/JP2024008961A/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Definitions

  • the present disclosure relates to barrier films, laminates and packaging bags.
  • Barrier films are mainly widely used as packaging materials for foods and medical drugs that undergo heat sterilization such as boiling and retorting. In packaging these contents, a particular emphasis has been placed on reducing the oxygen permeability.
  • a polyethylene terephthalate film having high heat resistance is generally used as a base material for the barrier film used in the packaging material for such heat sterilization.
  • Patent Document 3 proposes a polypropylene-based film formed from a blend of polypropylene and an ethylene/ ⁇ -olefin copolymer
  • Patent Document 4 proposes a blend of polypropylene and an ethylene/ ⁇ -olefin copolymer.
  • a polypropylene film having a layer formed from a blend of and a layer formed from a polypropylene resin has been proposed.
  • JP 2020-40257 A Japanese Patent Application Laid-Open No. 2021-20391 JP-A-63-291929 JP-A-63-290743
  • An object of the present invention is to provide a barrier film capable of imparting strength, a laminate using the same, and a packaging bag.
  • the present disclosure includes a substrate layer containing polypropylene, a vapor deposition layer containing an inorganic oxide, and a gas barrier layer in this order, and the substrate layer comprises at least a first skin layer, a core layer and a second skin layer.
  • the softening temperature of each layer of the base material layer is measured by local thermal analysis (LTA)
  • the first skin layer has at least one softening temperature of 120 ° C. or higher.
  • the core layer has at least one softening temperature above 190°C and the second skin layer has at least one softening temperature below 160°C.
  • the substrate layer includes the first skin layer, the core layer, and the second skin layer each having a softening temperature within the specific range described above.
  • the strength is increased, it is possible to keep the oxygen permeability low even after heat sterilization, and it is possible to provide sufficient adhesion strength between films (interlayers) even after heat sterilization.
  • the barrier film is laminated with the sealant layer or the sealant layer and the second base layer to form a laminate, the adhesion strength between the barrier film and the sealant layer and/or the second base layer is increased. be able to. Therefore, by using the barrier film, it is possible to keep the oxygen permeability low even after heat sterilization, and to provide sufficient adhesion strength between films (interlayers) even after heat sterilization. It is possible to obtain a laminate and a packaging bag using the same.
  • the barrier film when the softening temperature of the first skin layer is measured by LTA, at least one softening temperature may exist between 120°C and 170°C. In this case, the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the barrier film when the softening temperature of the second skin layer is measured by LTA, at least one softening temperature may exist between 120°C and 160°C. In this case, the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the first skin layer and the second skin layer may contain a copolymer of propylene and ⁇ -olefin.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the barrier film when the softening temperature of each layer of the base material layer is measured by LTA, the softening temperature higher than any softening temperature present in the first skin layer and the second skin layer is the core May be present in layers. In this case, the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment.
  • the barrier film when the softening temperature of each layer of the base material layer is measured by LTA, the softening temperature higher than any softening temperature present in the second skin layer exists in the first skin layer. may In this case, the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment. Further, when the barrier film is laminated with the sealant layer or the sealant layer and the second base layer to form a laminate, the adhesion strength between the barrier film and the sealant layer and/or the second base layer can be increased. can be enhanced.
  • both the thickness of the first skin layer and the thickness of the second skin layer may be 2.0 ⁇ m or less.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the deposited layer may contain at least one selected from the group consisting of aluminum oxide and silicon oxide.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the gas barrier layer may contain a water-soluble polymer having a hydroxyl group and at least one selected from the group consisting of metal alkoxides, silane coupling agents, and hydrolysates thereof. good.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the vapor deposition layer may be formed on the surface of the first skin layer opposite to the core layer.
  • the barrier film may include an anchor coat layer between the first skin layer and the deposition layer.
  • the present disclosure also provides a laminate comprising the barrier film of the present disclosure and a sealant layer, the sealant layer comprising polyolefin.
  • the laminate may further include a second substrate layer on the surface of the barrier film opposite to the sealant layer, and the second substrate layer may contain polyolefin. Since the laminate uses the barrier film of the present disclosure, it is possible to keep the oxygen permeability low even after heat sterilization, and sufficient adhesion strength between the films even after heat sterilization. It is possible to have Moreover, the laminate is useful as a monomaterial packaging material.
  • the present disclosure also provides a packaging bag formed by bag-making the laminate of the present disclosure. Since the packaging bag uses the laminate of the present disclosure, it is possible to keep the oxygen permeability low even after heat sterilization, and sufficient adhesion strength between the films even after heat sterilization. It is possible to have Moreover, the said packaging bag is useful as a monomaterial packaging material.
  • the present disclosure includes a base material layer containing polypropylene, a vapor deposition layer containing an inorganic oxide, and a gas barrier layer in this order, and the base material layer consists of a skin layer and a core layer in order from the vapor deposition layer side.
  • LTA local thermal analysis
  • the barrier film since the base layer includes the skin layer and the core layer having a softening temperature in the specific range, the adhesion strength between the films is increased, and oxygen permeation is improved even after heat sterilization. It is possible to suppress the degree of adhesion to a low level, and to provide sufficient adhesion strength between the films even after the heat sterilization treatment. Therefore, by using the barrier film, it is possible to keep the oxygen permeability low even after heat sterilization, and it is possible to provide sufficient adhesion strength between the films even after heat sterilization. A laminate and a packaging bag using the same can be obtained.
  • the skin layer may contain a copolymer of propylene and ⁇ -olefin.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the skin layer may contain an ethylene-1-butene-propylene random copolymer.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment.
  • the skin layer may have a thickness of 0.2 ⁇ m or more and 2.0 ⁇ m or less.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the ratio of the thickness of the skin layer to the thickness of the core layer may be 1/100 to 1/5.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the deposited layer may contain at least one selected from the group consisting of aluminum oxide and silicon oxide.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the gas barrier layer comprises Si(OR 1 ) 4 and R 2 Si(OR 3 ) 3 (OR 1 and OR 3 are each independently a hydrolyzable group, and R 2 is an organic functional group. or a hydrolyzate thereof and a water-soluble polymer having a hydroxyl group.
  • the barrier film can keep the oxygen permeability lower even after the heat sterilization treatment, and can provide sufficient adhesive strength between the films even after the heat sterilization treatment.
  • the barrier film may include an anchor coat layer between the skin layer and the deposited layer.
  • the barrier film having the above configuration can further improve the adhesion strength between the skin layer and the deposited layer. Therefore, the barrier film can keep the oxygen permeability lower even after heat sterilization, and can provide sufficient adhesion strength between the films even after heat sterilization.
  • the present disclosure also provides a laminate comprising the barrier film of the present disclosure and a sealant layer, the sealant layer comprising polyolefin.
  • the laminate may further include a second substrate layer on the surface of the barrier film opposite to the sealant layer, and the second substrate layer may contain polyolefin. Since the laminate uses the barrier film of the present disclosure, it is possible to keep the oxygen permeability low even after heat sterilization, and sufficient adhesion strength between the films even after heat sterilization. It is possible to have Moreover, the laminate is useful as a monomaterial packaging material.
  • the present disclosure also provides a packaging bag formed by bag-making the laminate of the present disclosure. Since the packaging bag uses the laminate of the present disclosure, it is possible to keep the oxygen permeability low even after heat sterilization, and sufficient adhesion strength between the films even after heat sterilization. It is possible to have Moreover, the said packaging bag is useful as a monomaterial packaging material.
  • the present disclosure it is possible to keep the oxygen permeability low even after heat sterilization, and a barrier that can provide sufficient adhesion strength between films (interlayers) even after heat sterilization A film, a laminate using the same, and a packaging bag can be provided.
  • FIG. 1 is a schematic cross-sectional view showing a barrier film according to one embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a barrier film according to one embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to an embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to an embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to an embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to an embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to an embodiment of the present disclosure
  • a substrate layer containing polypropylene, a vapor deposition layer containing an inorganic oxide, and a gas barrier layer are provided in this order, and the substrate layer comprises at least a first skin layer, a core layer, and a second skin layer.
  • LTA local thermal analysis
  • the core layer has a softening temperature higher than any softening temperature present in the first skin layer and the second skin layer.
  • the softening temperature of each layer of the base material layer is measured by LTA, the softening temperature higher than any softening temperature present in the second skin layer is present in the first skin layer.
  • a substrate layer containing polypropylene, a vapor deposition layer containing an inorganic oxide, and a gas barrier layer are provided in this order, and the substrate layer consists of a skin layer and a core layer in order from the vapor deposition layer side.
  • LTA local thermal analysis
  • the skin layer has at least one softening temperature of 115 ° C. or higher and 170 ° C. or lower
  • the core layer is a barrier film having at least one softening temperature above 190°C.
  • the gas barrier layer is composed of Si(OR 1 ) 4 and R 2 Si(OR 3 ) 3 (OR 1 and OR 3 are each independently hydrolyzable groups, and R 2 is an organic functional group. ), and a water-soluble polymer having a hydroxyl group, which is formed from a coating liquid containing at least one silicon compound or a hydrolyzate thereof selected from [12] to [17] above. Barrier film as described. [19] The barrier film according to any one of [12] to [18] above, comprising an anchor coat layer between the skin layer and the deposited layer. [20] A laminate comprising the barrier film according to any one of [1] to [19] above and a sealant layer, wherein the sealant layer contains polyolefin.
  • the barrier film according to the first aspect comprises a base material layer containing polypropylene, a vapor deposition layer containing an inorganic oxide, and a gas barrier layer in this order, and the base material layer comprises at least a first skin layer, a core layer and It has a multilayer structure comprising three second skin layers in this order, and when the softening temperature of each layer of the base layer is measured by local thermal analysis (LTA), at least one of the first skin layers is 120 ° C. or higher.
  • LTA local thermal analysis
  • the barrier film has two softening temperatures, the core layer has at least one softening temperature above 190°C, and the second skin layer has at least one softening temperature below 160°C.
  • FIG. 1 is a schematic cross-sectional view showing a barrier film according to the first aspect of this embodiment.
  • the barrier film 10a according to this embodiment includes a substrate layer 1a, a deposition layer 2, and a gas barrier layer 3 in this order.
  • the substrate layer 1a is a film (base film) that serves as a support and contains polypropylene.
  • the base material layer 1a is a multi-layered film including at least three layers of a first skin layer 11a, a core layer 12, and a second skin layer 13. As shown in FIG.
  • the base material layer 1a may be a film made of polypropylene, and the polypropylene sheet may be formed into a sheet and the sheet may be stretched by ordinary means to form a uniaxially or biaxially oriented film. Stretching may be performed on a film having a multilayer structure.
  • the substrate layer 1a contains known additives such as antioxidants, stabilizers, lubricants such as calcium stearate, fatty acid amides and erucic acid amides, organic additives such as antistatic agents, silica, zeolite, syloid, hydro Inorganic additives such as particulate lubricants such as talcite and silicon particles may be added depending on the purpose.
  • additives such as antioxidants, stabilizers, lubricants such as calcium stearate, fatty acid amides and erucic acid amides
  • organic additives such as antistatic agents, silica, zeolite, syloid
  • hydro Inorganic additives such as particulate lubricants such as talcite and silicon particles may be added depending on the purpose.
  • the thickness (total thickness) of the base material layer 1a is not particularly limited, but may be, for example, 3 ⁇ m or more and 200 ⁇ m or less, 6 ⁇ m or more and 50 ⁇ m or less, or 10 ⁇ m or more and 30 ⁇ m or less.
  • the core layer 12 is a layer that has at least one softening temperature of 190°C or higher when the softening temperature is measured from the cross section of the film by local thermal analysis (LTA), which will be described later.
  • the at least one softening temperature may be 195° C. or higher, or 198° C. or higher and 220° C. or lower.
  • the softening temperature the temperature measured at the center in the thickness direction of the core layer 12 is used.
  • the at least one softening temperature is 190 ° C. or higher, the heat resistance of the base layer 1a can be improved, it is resistant to heat during heat sterilization, and the base layer 1a shrinks during heat sterilization for packaging. It is possible to prevent the problem that the material cannot be used.
  • the core layer 12 may be a layer having one softening temperature, or may be a layer having a plurality of softening temperatures. When the core layer 12 has multiple softening temperatures, at least one softening temperature should satisfy the above conditions.
  • the polypropylene used for the core layer 12 may be crystalline polypropylene from the viewpoint of increasing the heat resistance of the base material layer 1a, and is a propylene homopolymer from the viewpoint of further improving the heat resistance for heat sterilization. It may be homopolypropylene. However, a random copolymer of propylene and ⁇ -olefin, or a mixture of the copolymer and homopolypropylene may be used as long as the effect of the present disclosure is not significantly impaired.
  • a first skin layer 11a is provided on one surface of the core layer 12, and a second skin layer 13 is provided on the other surface. Both surfaces of the substrate layer 1a may be formed of the first skin layer 11a and the second skin layer 13 . Other layers may be provided between the core layer 12 and the first skin layer 11a. may Other layers may be provided between the core layer 12 and the second skin layer 13, but the core layer 12 and the second skin layer 13 are in contact with each other without intervening other layers. may
  • the first skin layer 11a is a layer that has at least one softening temperature of 120°C or higher when the softening temperature is measured from the cross section of the film by local thermal analysis (LTA), which will be described later.
  • the at least one softening temperature may be 120° C. or higher and 170° C. or lower, or 125° C. or higher and 168° C. or lower.
  • the softening temperature the temperature measured at the center in the thickness direction of the first skin layer 11a is used.
  • the at least one softening temperature is 120° C. or higher, the heat resistance of the first skin layer 11a does not become too low, and the first skin layer 11a softens during heat sterilization treatment, resulting in a decrease in adhesion and a barrier.
  • the first skin layer 11a may be a layer having one softening temperature, or may be a layer having a plurality of softening temperatures. When the first skin layer 11a has multiple softening temperatures, at least one softening temperature should satisfy the conditions described above.
  • the second skin layer 13 is a layer that has at least one softening temperature of 160°C or lower when the softening temperature is measured from the cross section of the film by local thermal analysis (LTA), which will be described later.
  • the at least one softening temperature may be 120° C. or higher and 160° C. or lower, or 122° C. or higher and 155° C. or lower.
  • the softening temperature the temperature measured at the center in the thickness direction of the second skin layer 13 is used.
  • the second skin layer 13 may be a layer having one softening temperature, or may be a layer having a plurality of softening temperatures. When the second skin layer 13 has multiple softening temperatures, at least one softening temperature should satisfy the conditions described above.
  • the polypropylene used for the first skin layer 11a and the second skin layer 13 may contain a copolymer of propylene and other monomers from the viewpoint of improving adhesion to the core layer 12.
  • Other monomers may be used, for example ⁇ -olefins such as ethylene, 1-butene, 1-hexene.
  • the copolymer may be a random copolymer.
  • Mono-material packaging material using polypropylene film generally has a three-layer structure of outer layer film (second base material layer) / barrier film / sealant layer in order to increase the waist strength and self-standing as a packaging bag. ing.
  • the substrate layer 1a in the barrier film 10a of the present embodiment has a barrier forming surface (a vapor deposition layer and a gas barrier layer forming side) for the purpose of increasing lamination strength with an adjacent layer (second substrate layer or sealant layer).
  • a second skin layer 13 is provided on the surface opposite to the surface of the .
  • the second skin layer 13 has a softening temperature of 160° C. or less. Since the second skin layer 13 has a softening temperature of 160° C. or lower, the flexibility of the second skin layer 13 is increased, and good adhesion strength to the core layer 12 can be obtained.
  • the core layer 12 it is preferable to set the core layer 12 to be the highest in order to reduce the shrinkage of the base material layer 1a during heat sterilization and to maintain the adhesion strength between the layers.
  • the core layer 12 has a softening temperature that is higher than the softening temperatures of both the first skin layer 11 a and the second skin layer 13 .
  • the softening temperature of the first skin layer 11a and the second skin layer 13 facilitates maintaining a balance between the barrier properties after heat sterilization and the adhesion between the layers
  • the softening temperature of the first skin layer 11a is set to It is preferably higher than the softening temperature of the second skin layer 13 .
  • the first skin layer 11a has a softening temperature higher than any softening temperature present in the second skin layer 13 .
  • the softening temperature of the core layer 12 at 190°C or higher may be 10°C or higher, or 20°C or higher, than the softening temperature of the first skin layer 11a at 120°C or higher. In this case, the shrinkage of the base material layer 1a during the heat sterilization treatment can be reduced, and the adhesion strength between the layers after the heat sterilization treatment can be more sufficiently maintained.
  • the softening temperature of the core layer 12 at 190°C or higher may be 35°C or higher, or 45°C or higher, than the softening temperature of the second skin layer 13 at 160°C or lower. In this case, the shrinkage of the base material layer 1a during the heat sterilization treatment can be reduced, and the adhesion strength between the layers after the heat sterilization treatment can be more sufficiently maintained.
  • the softening temperature of the first skin layer 11a at 120°C or higher may be 5°C or higher, or 15°C or higher, than the softening temperature of the second skin layer 13 at 160°C or lower. In this case, it is easier to maintain a sufficient balance between the barrier properties after heat sterilization and the adhesion between the layers.
  • the method of adjusting the softening temperatures of the first skin layer 11a, the core layer 12 and the second skin layer 13 is not particularly limited.
  • the softening temperature of each layer is adjusted by, for example, the type of resin that constitutes each layer, the mixing ratio thereof when using a plurality of resins, the monomer ratio when using a copolymer, and the method of manufacturing each layer. This can be done by adjusting
  • Both the thickness of the first skin layer 11a and the thickness of the second skin layer 13 may be 0.1 ⁇ m or more. If this thickness is 0.1 ⁇ m or more, the first skin layer 11a, the core layer 12 and the second skin layer 13 can be uniformly laminated, and the thickness of the first skin layer 11a and the second skin layer 13 variation can be suppressed. In addition, it is considered that the stress on the deposited layer during the heat sterilization treatment can be sufficiently relaxed, and the deterioration of the barrier property can be suppressed. From this point of view, the thickness of the first skin layer 11a and the second skin layer 13 is preferably 0.3 ⁇ m or more.
  • the upper limit of the thickness of the first skin layer 11a and the second skin layer 13 is not particularly limited, but is preferably 2.0 ⁇ m or less from the viewpoint of sufficiently ensuring the heat resistance of the entire base layer 1a. and more preferably 1.8 ⁇ m or less.
  • the thickness of the core layer 12 may be 2 ⁇ m or more, 10 ⁇ m or more, or 15 ⁇ m or more, and may be 150 ⁇ m or less, 50 ⁇ m or less, or 20 ⁇ m or less.
  • the ratio of the thickness of the first skin layer 11a to the thickness of the core layer 12 may be 1/100 to 1/5. /70 to 1/10.
  • the thickness ratio is within the above range, the heat resistance of the entire base layer 1a can be more sufficiently ensured, and the adhesion between the layers in the barrier film and the laminate can be further enhanced.
  • the ratio of the thickness of the second skin layer 13 to the thickness of the core layer 12 may be 1/100 to 1/5. /70 to 1/10.
  • the thickness ratio is within the above range, the heat resistance of the entire base layer 1a can be more sufficiently ensured, and the adhesion between the layers in the barrier film and the laminate can be further enhanced.
  • the thickness of the first skin layer 11a and the thickness of the second skin layer 13 may be the same or different.
  • the thickness of the first skin layer 11 a may be less than or equal to the thickness of the second skin layer 13 . Even if the ratio of the thickness of the first skin layer 11a to the thickness of the second skin layer 13 (thickness of the first skin layer 11a/second skin layer 13) is 1/5 to 1/0.5 It may be 1/3 to 1/1.
  • the thickness ratio is within the above range, the heat resistance of the entire base layer 1a can be more sufficiently ensured, and the adhesion between the layers in the barrier film and the laminate can be further enhanced.
  • Polypropylene (including copolymers of propylene and other monomers) used for the base material layer 1a may be a recycled resin, or obtained by polymerizing raw materials derived from biomass such as plants. Other resins may also be used. When these resins are used, they may be used alone or in combination with resins polymerized from ordinary fossil fuels.
  • the softening temperature measurement of each layer is performed from the cross section of the base material layer.
  • the substrate layer may be subjected to corona treatment as a surface treatment on the front and back surfaces of the substrate layer in order to prevent separation between the embedding resin and the substrate layer after embedding.
  • the sample used for the softening temperature measurement may be in the form of a barrier film or laminate instead of the base layer alone.
  • a photocurable resin is used as the embedding resin, and is cured by light irradiation after embedding.
  • the photocurable resin for example, D-800 (trade name) manufactured by Toagosei Co., Ltd. can be used.
  • the cured sample-embedded resin is fixed with an AFM sample holder insert, trimmed with a glass knife at room temperature (25°C), and the cross-section of the substrate layer is cut.
  • Cross-section cutting is performed with a diamond knife until the Cross-sectional cutting with a diamond knife can be performed, for example, at a cutting speed of 1.0 mm/s and a cutting film thickness of 100 nm.
  • the cross-sectioned sample is used for softening temperature measurement while being fixed with an insert for an AFM sample holder.
  • a cross-section cutting device for example, Leica's Ultramicrotome EM UC7 (trade name) and Cryosystem EM FC7 (trade name) can be used. Also, the cutting direction is parallel to the layer interface.
  • 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 0.2V.
  • the set value of the amount of downward displacement of the cantilever for stopping the measurement is 30 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-sectional samples, and cross-sectional 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.
  • the vapor deposition layer is provided on the substrate layer from the viewpoint of improving gas barrier properties against water vapor and oxygen, for example, and preferably has transparency.
  • the deposited layer contains an inorganic oxide, and examples of inorganic oxides that can be used include aluminum oxide, silicon oxide, tin oxide, magnesium oxide, and mixtures thereof. Considering heat sterilization resistance, from the viewpoint of keeping the oxygen permeability lower even after heat sterilization, and from the viewpoint of giving sufficient adhesion strength between films even after heat sterilization, among these, especially aluminum oxide and silicon oxide.
  • the thickness of the deposited layer may be 5-300 nm.
  • the vapor deposition layer has a thickness of 5 nm or more, a film having a uniform and sufficient thickness can be easily obtained, and the function as a gas barrier film can be sufficiently achieved.
  • the thickness of the vapor deposition layer is 300 nm or less, the vapor deposition layer can be provided with flexibility, and even if an external factor such as bending or pulling is applied after the film formation, the vapor deposition layer is less likely to crack.
  • the thickness of the deposited layer is preferably 6 nm or more, more preferably 8 nm or more, and preferably 150 nm or less, more preferably 100 nm or less.
  • the vapor deposition layer can be formed by a normal vacuum vapor deposition method. It is also possible to use other thin film formation methods such as sputtering, ion plating, and plasma vapor deposition (CVD). However, in terms of productivity, the vacuum deposition method is currently the best. As a heating means for the vacuum evaporation method, it is preferable to use any one of electron beam heating, resistance heating, and induction heating. is more preferable. Moreover, in order to improve the adhesion between the vapor deposition layer and the substrate layer and the denseness of the vapor deposition layer, vapor deposition can be performed using a plasma assist method or an ion beam assist method. Further, in order to increase the transparency of the vapor deposition film, reactive vapor deposition may be used in which various gases such as oxygen are injected during the vapor deposition.
  • the surface of the base material layer facing the vapor deposition layer may be subjected to surface treatment such as plasma treatment or corona treatment.
  • An anchor coat layer (not shown) may be provided between them.
  • Coating agents for providing the anchor coat layer include, for example, acrylic resins, epoxy resins, acrylic urethane resins, polyester polyurethane resins, polyether polyurethane resins, and the like. Among these coating agents, acrylic urethane resins and polyester polyurethane resins are preferable from the viewpoint of heat resistance and interlayer adhesive strength.
  • the gas barrier layer is provided for the purpose of protecting the deposition layer and complementing the barrier property.
  • the gas barrier layer may be formed from a coating liquid containing a silicon compound or a hydrolyzate thereof and a water-soluble polymer having hydroxyl groups.
  • the gas barrier layer is formed from a coating liquid containing a water-soluble polymer having a hydroxyl group and at least one selected from the group consisting of metal alkoxides, silane coupling agents, and hydrolysates thereof. can be anything.
  • water-soluble polymers having hydroxyl groups examples include polyvinyl alcohol, polyvinylpyrrolidone, starch, methylcellulose, carboxymethylcellulose, and sodium alginate.
  • PVA polyvinyl alcohol
  • the gas barrier property is further improved, which is preferable.
  • Silicon compounds include, for example, Si(OR 1 ) 4 and R 2 Si(OR 3 ) 3 (OR 1 and OR 3 are each independently hydrolyzable groups, and R 2 is an organic functional group.) It is preferably at least one selected from. Tetraethoxysilane [Si(OC 2 H 5 ) 4 ] is preferably used as Si(OR 1 ) 4 . Tetraethoxysilane is preferably used because it is relatively stable in an aqueous solvent after hydrolysis. Further, R 2 in R 2 Si(OR 3 ) 3 is preferably selected from vinyl group, epoxy group, methacryloxy group, ureido group and isocyanate group.
  • metal alkoxides include compounds represented by the following general formula.
  • R 11 and R 12 are each independently a monovalent organic group having 1 to 8 carbon atoms, preferably an alkyl group such as methyl or ethyl.
  • M represents an n-valent metal atom such as Si, Ti, Al, Zr.
  • m is an integer from 1 to n.
  • metal alkoxides include tetraethoxysilane [Si(OC 2 H 5 ) 4 ] and triisopropoxyaluminum [Al(O-2′-C 3 H 7 ) 3 ]. Tetraethoxysilane and triisopropoxyaluminum are preferred because they are relatively stable in aqueous solvents after hydrolysis.
  • Silane coupling agents include compounds represented by the following general formulas. Si(OR 21 ) p (R 22 ) 3-p R 23 (2)
  • R 21 represents an alkyl group such as a methyl group or an ethyl group
  • R 22 represents an alkyl group, an aralkyl group, an aryl group, an alkenyl group, an alkyl group substituted with an acryloxy group, or a methacryloxy group.
  • R 23 represents a monovalent organic functional group
  • p represents an integer of 1-3.
  • R 21 or R 22 may be the same or different.
  • the monovalent organic functional group represented by R 23 includes a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, an alkyl group substituted with a halogen atom, or a monovalent organic functional group containing an isocyanate group. groups. Compounds obtained by converting these silane coupling agents into multimers such as dimers and trimers may be used.
  • silane coupling agents include vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane and other silane coupling agents. .
  • the gas barrier layer is made by dissolving a water-soluble polymer in water or a water/alcohol mixed solvent, and mixing it with silicon compounds, metal alkoxides, silane coupling agents, etc. directly or by pre-hydrolyzing them. Then, after coating this mixed solution on the vapor-deposited layer, it can be formed by heating and drying.
  • Known additives such as isocyanate compounds, dispersants, stabilizers, viscosity modifiers, and colorants may be added to this solution as required within a range that does not impair gas barrier properties.
  • the ratio of PVA in the mixed solution is preferably 20% by mass or more and 50% by mass or less, based on the total solid content of the mixed solution, and 25% by mass. It is more preferable that the content is at least 40% by mass or less.
  • the proportion of PVA is 20% by mass or more, the flexibility of the film is maintained and the gas barrier layer is easily formed.
  • the proportion of PVA is 50% by mass or less, the barrier film can provide sufficient gas barrier properties.
  • the thickness of the gas barrier layer may be 0.05 ⁇ m or more, or 0.1 ⁇ m or more, and may be 10 ⁇ m or less, or 1 ⁇ m or less.
  • the barrier film according to the second aspect includes a base material layer containing polypropylene, a vapor deposition layer containing an inorganic oxide, and a gas barrier layer in this order, the base material layer sequentially from the vapor deposition layer side, a skin layer,
  • LTA local thermal analysis
  • the skin layer has at least one softening temperature of 115 ° C. or higher and 170 ° C. or lower
  • the core layer is a barrier film with at least one softening temperature above 190°C.
  • FIG. 2 is a schematic cross-sectional view showing a barrier film according to the second aspect of this embodiment.
  • the barrier film 10b according to this embodiment includes a substrate layer 1b, a deposition layer 2, and a gas barrier layer 3 in this order.
  • the substrate layer 1b is a film (base film) that serves as a support and contains polypropylene.
  • the substrate layer 1b is a multi-layered film composed of two layers, a skin layer 11b and a core layer 12, in order from the deposition layer side.
  • the base material layer 1b may be a film made of polypropylene, and the polypropylene sheet may be formed into a sheet and the sheet may be stretched by ordinary means to form a uniaxially or biaxially oriented film. Stretching may be performed on a film having a multilayer structure.
  • the substrate layer 1b contains known additives such as antioxidants, stabilizers, lubricants such as calcium stearate, fatty acid amides and erucic acid amides, organic additives such as antistatic agents, silica, zeolite, syloid, hydro Inorganic additives such as particulate lubricants such as talcite and silicon particles may be added depending on the purpose.
  • additives such as antioxidants, stabilizers, lubricants such as calcium stearate, fatty acid amides and erucic acid amides
  • organic additives such as antistatic agents, silica, zeolite, syloid
  • hydro Inorganic additives such as particulate lubricants such as talcite and silicon particles may be added depending on the purpose.
  • the thickness (total thickness) of the base layer 1b is not particularly limited, but may be, for example, 3 ⁇ m or more and 200 ⁇ m or less, 6 ⁇ m or more and 50 ⁇ m or less, or 10 ⁇ m or more and 30 ⁇ m or less.
  • the skin layer 11b is a layer that has at least one softening temperature between 115°C and 170°C when the softening temperature is measured from the cross section of the film by local thermal analysis (LTA), which will be described later.
  • the at least one softening temperature may be 120° C. or higher, 125° C. or higher, or 130° C. or higher from the viewpoint of improving heat resistance, and may be 165° C. or lower or 160° C. or lower from the viewpoint of imparting flexibility.
  • the softening temperature the temperature measured at the center in the thickness direction of the skin layer 11b is used. When at least one of the softening temperatures is 115° C.
  • the skin layer 11b may be a layer having one softening temperature, or may be a layer having a plurality of softening temperatures. When skin layer 11b has a plurality of softening temperatures, at least one softening temperature should satisfy the conditions described above.
  • the polypropylene used for the skin layer 11b may contain a copolymer of propylene and other monomers from the viewpoint of improving adhesion to the core layer 12.
  • Other monomers may be used, for example ⁇ -olefins such as ethylene, 1-butene, 1-hexene.
  • Skin layer 11b may contain a copolymer of propylene and ⁇ -olefin.
  • the copolymer may be a random copolymer.
  • the polypropylene used for the skin layer 11b is propylene and two or more types of ⁇ from the viewpoint of keeping the oxygen permeability lower even after heat sterilization and from the viewpoint of giving sufficient adhesion strength between films even after heat sterilization.
  • - may include random copolymers with olefins, and may include ethylene-1-butene-propylene random copolymers.
  • the content of ethylene in the polypropylene used for the skin layer 11b is the content of polypropylene from the viewpoint of keeping the oxygen permeability lower even after heat sterilization and from the viewpoint of giving sufficient adhesion strength between films even after heat sterilization. Based on the total amount, it may be 1% by mass or more, 1.5% by mass or more, or 2% by mass or more, 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, or 3 0.5 mass % or less may be sufficient.
  • the content of 1-butene in the polypropylene used for the skin layer 11b is 1% by mass or more, 1.5% by mass or more, based on the total amount of polypropylene, from the viewpoint of keeping the oxygen permeability lower even after heat sterilization.
  • it may be 2% by mass or more, and may be 5% by mass or less, 4% by mass or less, or 3.5% by mass or less.
  • the thickness of the skin layer 11b may be 0.2 ⁇ m or more. If the thickness of the skin layer 11b is 0.2 ⁇ m or more, the skin layer 11b and the core layer 12 can be uniformly laminated. In addition, the oxygen permeability can be kept lower even after the heat sterilization treatment, and sufficient adhesion strength can be provided between the films even after the heat sterilization treatment. From this point of view, the thickness of the skin layer 11b is preferably 0.3 ⁇ m or more. On the other hand, the upper limit of the thickness of the skin layer 11b is not particularly limited. 8 ⁇ m or less. The thickness of the skin layer 11b may be 0.2 ⁇ m or more and 2.0 ⁇ m or less, or 0.3 ⁇ m or more and 1.8 ⁇ m or less.
  • the core layer 12 is a layer that has at least one softening temperature of 190°C or higher when the softening temperature is measured from the cross section of the film by local thermal analysis (LTA), which will be described later.
  • the at least one softening temperature may be 195° C. or higher, 200° C. or higher, 205° C. or higher, or 210° C. or higher, and may be 220° C. or lower, 215° C. or lower, or 210° C. or lower.
  • the softening temperature the temperature measured at the center in the thickness direction of the core layer 12 is used.
  • the at least one softening temperature is 190 ° C.
  • the core layer 12 may be a layer having one softening temperature, or may be a layer having a plurality of softening temperatures. When the core layer 12 has multiple softening temperatures, at least one softening temperature should satisfy the above conditions.
  • the polypropylene used for the core layer 12 may be crystalline polypropylene from the viewpoint of increasing the heat resistance of the base material layer 1b, and is a propylene homopolymer from the viewpoint of further improving the heat resistance for heat sterilization. It may be homopolypropylene. However, a random copolymer of propylene and ⁇ -olefin, or a mixture of the copolymer and homopolypropylene may be used as long as the effect of the present disclosure is not significantly impaired.
  • the softening temperature of the core layer 12 at 190°C or higher may be 20°C or higher, 40°C or higher, or 50°C higher than the softening temperature of the skin layer 11b at 115°C or higher and 170°C or lower. It can be higher than that. In this case, the shrinkage of the base material layer 1b during heat sterilization can be reduced, and the adhesion strength between the layers after heat sterilization can be more sufficiently maintained.
  • the thickness of the core layer 12 may be 2 ⁇ m or more, 10 ⁇ m or more, or 15 ⁇ m or more, and may be 150 ⁇ m or less, 50 ⁇ m or less, or 20 ⁇ m or less.
  • the ratio of the thickness of the skin layer 11b to the thickness of the core layer 12 is 1/100 to 1/5, 1/80 to 1/8, or 1 /70 to 1/10.
  • the thickness ratio is within the above range, the heat resistance of the entire base material layer 1b can be sufficiently ensured, and the oxygen permeability can be suppressed to a lower level even after heat sterilization treatment. Even after the heat sterilization treatment, it is possible to provide sufficient adhesion strength between the films.
  • the base material layer 1b consists of only two layers, the skin layer 11b and the core layer 12. Between the skin layer 11b and the core layer 12, the skin layer 11b and the core layer 12 are in contact with each other without other layers interposed therebetween. Both surfaces of the base material layer 1b are formed of a skin layer 11b and a core layer 12 .
  • the method of adjusting the softening temperatures of the skin layer 11b and the core layer 12 is not particularly limited.
  • the softening temperature of each layer is adjusted by, for example, the type of resin constituting each layer, the mixing ratio thereof when using a plurality of resins, the monomer ratio when using a copolymer (e.g., ethylene content), and , by adjusting the production method of each layer (for example, stretching conditions).
  • Polypropylene (including copolymers of propylene and other monomers) used for the base material layer 1b may be a recycled resin, or obtained by polymerizing raw materials derived from biomass such as plants. Other resins may also be used. When these resins are used, they may be used alone or in combination with resins polymerized from ordinary fossil fuels.
  • the softening temperature measurement of the base material layer of this embodiment is performed by the same method as the softening temperature measurement described in the first aspect.
  • the vapor deposition layer of this embodiment can have the same structure as the vapor deposition layer described in the first aspect.
  • the gas barrier layer of this embodiment can have the same configuration as the gas barrier layer described in the first aspect.
  • laminates 20a and 30a according to the present embodiment include a second substrate layer (outer layer film) 22 and a sealant layer 23 on both sides of the barrier film 10a described above with an adhesive layer 24 interposed therebetween. has a laminated structure.
  • the second base material layer 22 is laminated on the gas barrier layer 3 of the barrier film 10a, and the sealant layer 23 is laminated on the second skin layer 13 of the barrier film 10a.
  • the second base material layer 22 is laminated on the second skin layer 13 of the barrier film 10a, and the sealant layer 23 is laminated on the gas barrier layer 3 of the barrier film 10a.
  • laminates 20b and 30b according to the present embodiment include a second substrate layer (outer layer film) 22 and a sealant layer 23 on both sides of the barrier film 10b with an adhesive layer 24 interposed therebetween. has a laminated structure.
  • the second base material layer 22 is laminated on the gas barrier layer 3 of the barrier film 10b, and the sealant layer 23 is laminated on the core layer 12 of the barrier film 10b.
  • the second base material layer 22 is laminated on the core layer 12 of the barrier film 10b, and the sealant layer 23 is laminated on the gas barrier layer 3 of the barrier film 10b.
  • Polyolefin is used as the material for the second base material layer 22 and the sealant layer 23 in order to make the laminates 20a, 30a, 20b, and 30b into monomaterial packaging materials. Similar to 1b, it is preferred to use polypropylene.
  • polypropylene As the polypropylene used for the second base material layer 22, for example, a film obtained by stretching homopolypropylene can be used in order to impart heat resistance.
  • sealant layer 23 for example, a stretched or unstretched polypropylene film may be used.
  • the thickness of the second base material layer 22 is not particularly limited, it may be, for example, 15 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the sealant layer 23 is not particularly limited, but may be, for example, 15 ⁇ m or more and 200 ⁇ m or less.
  • the adhesive layer 24 bonds the films together.
  • the adhesive that forms the adhesive layer 24 include polyurethane resins obtained by reacting a main agent such as polyester polyol, polyether polyol, acrylic polyol, and carbonate polyol with a difunctional or higher isocyanate compound. You may use various polyols individually by 1 type or in combination of 2 or more types.
  • the adhesive layer 24 may contain a carbodiimide compound, an oxazoline compound, an epoxy compound, a phosphorus compound, a silane coupling agent, or the like in the polyurethane resin described above.
  • the coating amount of the adhesive constituting the adhesive layer 24 may be, for example, 0.5 to 10 g/m 2 from the viewpoint of obtaining desired adhesive strength, conformability, workability, and the like.
  • a biomass-derived polymer component or a biodegradable polymer component may be used.
  • an adhesive having a barrier property may be used for the adhesive layer 24 .
  • a packaging bag can be made using the laminate described above.
  • the packaging bag may be made into a bag shape by folding one sheet of packaging material in two so that the sealant layers face each other, and then heat-sealing three sides. After stacking them so that they face each other, the four sides may be heat-sealed to form a bag shape.
  • the packaging bag can accommodate contents such as foods and medicines as contents.
  • the packaging bag may have a shape having a bent portion (folded portion) such as a standing pouch.
  • the packaging bag according to the present embodiment can maintain high gas barrier properties even if it has a shape with a bent portion.
  • Ethylene-1-butene-propylene random copolymer resin is used for the first skin layer
  • homopolypropylene resin is used for the core layer
  • ethylene-propylene random copolymer resin is used for the second skin layer.
  • a substrate film (substrate layer) having a total thickness of 20 ⁇ m was produced by coextrusion of these resins and then biaxial stretching.
  • the thickness of each of the first skin layer and the second skin layer was 0.7 ⁇ m, and the thickness of the core layer was 18.6 ⁇ m.
  • Table 1 shows the softening temperature of each layer.
  • an acrylic primer solution was applied on the first skin layer of the base material layer by gravure coating and dried to form an anchor coat layer with a thickness of 0.1 ⁇ m.
  • a silicon oxide thin film having a thickness of 30 nm was vapor-deposited on the anchor coat layer by reactive vapor deposition using radio-frequency excitation ion plating in an oxygen atmosphere under reduced pressure to form a vapor-deposited layer of inorganic oxide.
  • TEOS tetraethoxysilane
  • methanol methanol
  • hydrochloric acid 0.1N hydrochloric acid
  • PVA polyvinyl alcohol
  • IPA isopropyl alcohol
  • the coating liquid was prepared so that the mass ratio of the SiO 2 solid content (converted value) of TEOS, the R 2 Si(OH) 3 solid content (converted value) of isocyanurate silane, and the PVA solid content was 40/5/55. was prepared to This coating liquid was applied onto the deposited layer by gravure coating, and then dried at 80° C. for 60 seconds to form a gas barrier layer having a thickness of 0.3 ⁇ m. Thus, a barrier film of Example 1-1 having a laminated structure of gas barrier layer/deposited layer/anchor coat layer/first skin layer/core layer/second skin layer was obtained.
  • Example 1-2 Ethylene-1-butene-propylene random copolymer resin was used as the material for the first skin layer, homopolypropylene resin was used as the material for the core layer, and the second skin layer was used so that each layer had a softening temperature as shown in Table 1.
  • a barrier film was obtained in the same manner as in Example 1-1 except that an ethylene-1-butene-propylene random copolymer resin was used as the material of .
  • Example 1-3 Ethylene-propylene random copolymer resin was used as the material for the first skin layer, homopolypropylene resin was used as the material for the core layer, and ethylene was used as the material for the second skin layer so that each layer had a softening temperature as shown in Table 1.
  • - A barrier film was obtained in the same manner as in Example 1-1 except that a propylene random copolymer resin was used.
  • Example 1-4 Ethylene-1-butene-propylene random copolymer resin was used as the material for the first skin layer, homopolypropylene resin was used as the material for the core layer, and the second skin layer was used so that each layer had a softening temperature as shown in Table 1.
  • a barrier film was obtained in the same manner as in Example 1-1, except that an ethylene-propylene random copolymer resin was used as the material for .
  • Example 1-1 Homopolypropylene resin was used as the material for each of the first skin layer, the core layer and the second skin layer so that each layer had a softening temperature as shown in Table 1. Otherwise, the procedure was the same as in Example 1-1. to obtain a barrier film.
  • Example 1-2 Ethylene-1-butene-propylene random copolymer resin was used as the material for the first skin layer so that each layer had a softening temperature as shown in Table 1, and both the material for the core layer and the second skin layer were A barrier film was obtained in the same manner as in Example 1-1 except that a homopolypropylene resin was used.
  • Example 1-3 Ethylene-propylene random copolymer resin was used as the material for the first skin layer and the second skin layer, and homopolypropylene resin was used as the material for the core layer, so that each layer had a softening temperature as shown in Table 1. Otherwise, a barrier film was obtained in the same manner as in Example 1-1.
  • Example 1-4 Ethylene-1-butene-propylene random copolymer resin was used as the material for the first skin layer, homopolypropylene resin was used as the material for the core layer, and the second skin layer was used so that each layer had a softening temperature as shown in Table 1.
  • a barrier film was obtained in the same manner as in Example 1-1, except that an ethylene-propylene random copolymer resin was used as the material for .
  • Example 1-5 Ethylene-propylene random copolymer resin was used as the material for the first skin layer, homopolypropylene resin was used as the material for the core layer, and ethylene was used as the material for the second skin layer so that each layer had a softening temperature as shown in Table 1. - A barrier film was obtained in the same manner as in Example 1-1 except that a propylene random copolymer resin was used.
  • a stretched polypropylene film having a thickness of 20 ⁇ m and the gas barrier layer side surface of the barrier films prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-5 were bonded with a two-component curable urethane adhesive. It was laminated by a dry lamination method through the After that, the second skin layer side surface of the barrier film and an unstretched polypropylene film with a thickness of 60 ⁇ m are laminated by a dry lamination method via a two-liquid curable urethane adhesive to form a laminate having a three-layer structure. made.
  • the sample was placed in a wedge shape 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 and side surfaces are the sample. It was cut with a razor into a shape that is a cross section.
  • 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 cross-section of the sample was cut with a glass knife at room temperature (25°C), and then at a low temperature (-140°C) with a diamond knife at a cutting speed of 1.
  • Final cross-sectional cutting was performed with settings of 0 mm/s and a cutting film thickness of 100 nm, and the cutting was terminated when a mirror surface was obtained.
  • As cross-section cutting devices an ultramicrotome (manufactured by Leica, trade name: EM UC7) and a cryo system (manufactured by Leica, trade name: EM FC7) were used.
  • the cutting direction of the knife was parallel to the layer interface. Cutting was performed from the portion corresponding to the apex of the wedge shape.
  • the cross-sectioned sample was used for softening temperature measurement while being fixed with an insert for an AFM sample holder.
  • the atomic force microscope is MFP-3D-SA (trade name) manufactured by Oxford Instruments Co., Ltd.
  • the local thermal analysis option is the Ztherm system
  • the 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 softening temperature measurement was performed at the central portion in the thickness direction of each layer (first skin layer, core layer and second skin layer) constituting the base material layer.
  • the contact pressure of the cantilever (the amount of change in deflection of the cantilever (Deflection)) is 0.2 V, the voltage application rate (temperature increase rate) is 0.5 V / sec, and the maximum applied voltage is 6.0 V.
  • the sample surface is heated, the sample surface expands and the cantilever position rises.
  • the sample surface was further heated, the sample surface softened, and the measurement was terminated when the cantilever position was lowered by 30 nm.
  • 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 point where the vertical height (Z displacement) of the cantilever was maximum was taken as the applied voltage at the softening point, and the voltage value was read.
  • a calibration curve was created to calculate the softening temperature of the sample.
  • polycaprolactone melting point: 60°C
  • low-density polyethylene LDPE, melting point: 112°C
  • polypropylene PP, melting point: 166°C
  • PET polyethylene terephthalate
  • the maximum applied voltage during Detrend correction was 3.5 V for polycaprolactone, 5.5 V for low-density polyethylene, 6.7 V for polypropylene, and 7.9 V for polyethylene terephthalate.
  • the contact pressure of the cantilever (amount of change in deflection of the cantilever) was set to 0.2 V, and the voltage application rate (heating rate) was set to 0.5 V/sec. Measurement was performed 20 times while changing the measurement position of the calibration sample, and a calibration curve was created by approximating the average value of the applied voltage at the softening point and the melting point with a cubic function using the least squares method to create a calibration curve.
  • Oxygen permeability measurement was performed on the laminate after the retort treatment. The measurement was performed using an oxygen permeability measuring device (OXTRAN 2/20, manufactured by Modern Control) under conditions of a temperature of 30°C and a relative humidity of 70%. The measurement method conforms to JIS K-7126, B method (isobaric method), and ASTM D3985-81, and the measured value is expressed in units [cm 3 (STP)/m 2 ⁇ day ⁇ atm]. Table 1 shows the results.
  • Example 2-1 Ethylene-1-butene-propylene random copolymer resin (ethylene content: 2.5 mol%, 1-butene content: 3.5 mol%) was used as the material for the skin layer, and homopolypropylene resin was used as the material for the core layer. are used, and these resins are coextruded and then biaxially stretched to form a base film with a total thickness of 20 ⁇ m and a skin layer with a thickness of 0.7 ⁇ m and a core layer with a thickness of 19.3 ⁇ m. (Base material layer) was produced. The thicknesses of the skin layer and the core layer were measured by the thickness method described below. Table 2 shows the softening temperature of each layer.
  • an acrylic primer solution was applied on the skin layer of the base material layer by gravure coating and dried to form an anchor coat layer with a thickness of 0.1 ⁇ m.
  • a silicon oxide thin film having a thickness of 30 nm was vapor-deposited on the anchor coat layer by reactive vapor deposition using radio-frequency excitation ion plating in an oxygen atmosphere under reduced pressure to form a vapor-deposited layer of inorganic oxide.
  • TEOS tetraethoxysilane
  • methanol methanol
  • hydrochloric acid 0.1N hydrochloric acid
  • PVA polyvinyl alcohol
  • IPA isopropyl alcohol
  • the coating liquid was prepared so that the mass ratio of the SiO 2 solid content (converted value) of TEOS, the R 2 Si(OH) 3 solid content (converted value) of isocyanurate silane, and the PVA solid content was 43/10/47. was prepared to This coating liquid was applied onto the deposited layer by gravure coating, and then dried at 80° C. for 60 seconds to form a gas barrier layer having a thickness of 0.3 ⁇ m. Thus, a barrier film of Example 2-1 having a laminated structure of gas barrier layer/deposited layer/anchor coat layer/skin layer/core layer was obtained.
  • Example 2-2 Ethylene-1-butene-propylene random copolymer resin (ethylene content: 2.0 mol%, 1-butene content: 2 .0 mol%) was used, and a base film having a skin layer with a thickness of 0.8 ⁇ m and a core layer with a thickness of 19.2 ⁇ m was produced in the same manner as in Example 2-1. A barrier film was obtained.
  • Example 2-3 Ethylene-propylene random copolymer resin (ethylene content: 5.0 mol%) was used as the material for the skin layer so that each layer had a softening temperature as shown in Table 2.
  • a barrier film was obtained in the same manner as in Example 2-1, except that a base film having a skin layer and a core layer with a thickness of 19.2 ⁇ m was produced.
  • Example 2-4 An ethylene-propylene random copolymer resin (ethylene content: 3.2 mol%) was used as the material for the skin layer so that each layer had a softening temperature as shown in Table 2.
  • a barrier film was obtained in the same manner as in Example 2-1, except that a base film having a skin layer and a core layer with a thickness of 18.5 ⁇ m was produced.
  • Example 2-5 Ethylene-propylene random copolymer resin (ethylene content: 3.2 mol%) was used as the material for the skin layer so that each layer had a softening temperature as shown in Table 2.
  • a barrier film was obtained in the same manner as in Example 2-1, except that a base film having a total thickness of 18 ⁇ m and having a skin layer and a core layer having a thickness of 17.7 ⁇ m was produced.
  • Example 2-1 A barrier film was obtained in the same manner as in Example 2-1, except that a base film (base layer) having a total thickness of 20 ⁇ m was produced only from the material of the core layer.
  • Example 2-2 Ethylene-1-butene-propylene random copolymer resin (ethylene content: 3.2 mol%, 1-butene content: 5 0 mol %) was used in the same manner as in Example 2-1 to obtain a barrier film.
  • Example 2-3 Ethylene-propylene random copolymer resin (ethylene content: 0.7 mol%) was used as the material for the skin layer so that each layer had a softening temperature as shown in Table 2.
  • a barrier film was obtained in the same manner as in Example 2-1, except that a base film having a skin layer and a core layer with a thickness of 19.2 ⁇ m was produced.
  • Oxygen permeability measurement was performed on the laminate after the retort treatment.
  • the measurement was performed using an oxygen permeability measuring device (OXTRAN 2/20, manufactured by Modern Control) under conditions of a temperature of 30°C and a relative humidity of 70%.
  • the measurement method conforms to JIS K-7126, B method (isobaric method), and ASTM D3985-81, and the measured value is expressed in units [cm 3 (STP)/m 2 ⁇ day ⁇ atm]. If the oxygen transmission rate was 2.0 cm 3 (STP)/m 2 ⁇ day ⁇ atm or less, it was determined that the laminate had a low oxygen transmission rate even after the retort treatment. Table 2 shows the results.
  • the lamination strength between the barrier film and the unstretched polypropylene film was measured for the laminate after the retort treatment.
  • the measurement was carried out according to JIS K6854 with a test width of 15 mm, a peeling speed of 300 mm/min, and a peeling angle of T type. Measured values are expressed in units [N/15 mm]. Table 2 shows the results.
  • a packaging bag using a barrier film according to the present disclosure can be used as a packaging material with less deterioration of barrier properties and reduced adhesion even after heat sterilization treatment such as boiling treatment and retort treatment. Moreover, as a monomaterial packaging material, a gas barrier packaging material suitable for recyclability can be provided.

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EP4541580A4 (en) * 2022-06-15 2025-09-17 Toppan Holdings Inc GAS BARRIER LAMINATE, PACKAGING FILM, PACKAGING CONTAINER AND PACKAGED PRODUCT
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