WO2024162391A1 - 積層体、包装材料、包装体及び包装物品 - Google Patents

積層体、包装材料、包装体及び包装物品 Download PDF

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Publication number
WO2024162391A1
WO2024162391A1 PCT/JP2024/003087 JP2024003087W WO2024162391A1 WO 2024162391 A1 WO2024162391 A1 WO 2024162391A1 JP 2024003087 W JP2024003087 W JP 2024003087W WO 2024162391 A1 WO2024162391 A1 WO 2024162391A1
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Prior art keywords
layer
anchor coat
laminate
coat layer
cross
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Ceased
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PCT/JP2024/003087
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English (en)
French (fr)
Japanese (ja)
Inventor
誠司 滝澤
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Toppan Holdings Inc
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Toppan Holdings Inc
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=92146703&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2024162391(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Toppan Holdings Inc filed Critical Toppan Holdings Inc
Priority to JP2024534423A priority Critical patent/JP7544309B1/ja
Priority to EP24750340.2A priority patent/EP4644114A4/en
Priority to CN202480009990.7A priority patent/CN120712176A/zh
Priority to JP2024126139A priority patent/JP2024149642A/ja
Publication of WO2024162391A1 publication Critical patent/WO2024162391A1/ja
Priority to US19/284,524 priority patent/US20250353650A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • B32B27/08—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 synthetic resin
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the present invention relates to a laminate, a packaging material, a package, and a packaged article.
  • Packaging materials for long-term storage of foods, beverages, medicines, etc. are required to have gas barrier properties that prevent oxygen, water vapor, and other gases that can deteriorate the contents from entering the package. Meanwhile, in recent years, there has also been a demand for packaging materials to be highly recyclable, and the movement to switch from conventional packaging materials to highly recyclable all-polyolefin mono-material packages is progressing not only in Japan but also around the world.
  • gas barrier films have been developed for use in packaging materials. For example, there are vapor-deposited films in which an inorganic coating layer of silicon oxide, aluminum oxide, etc. is formed as a gas barrier layer on a polymer film by vacuum deposition or sputtering. Such gas barrier films have the problem that when a polyolefin layer is used as the polymer layer, the gas barrier properties are lower than those of polyester layers such as polyethylene terephthalate. There is also the problem that the adhesion between the polymer film and the inorganic coating layer is insufficient.
  • Packaging materials that are subjected to high temperature and pressure or high temperature and humidity environments such as retort processing or boiling processing require particularly high performance.
  • gas barrier films used in such packaging materials are required to have excellent abuse resistance that allows them to maintain a high level of gas barrier properties even when subjected to physical stress such as bending after harsh processing such as retort processing.
  • gas barrier films are also required to have excellent adhesion that allows them to maintain high interlayer adhesion even after harsh processing such as retort processing.
  • the present invention aims to provide a laminate with excellent resistance to abuse and adhesion, as well as a packaging material, a package, and a packaged article that contain the laminate.
  • a laminate comprising a first substrate layer, an anchor coat layer, and an inorganic barrier layer in this order, the first substrate layer comprising a polyolefin, the anchor coat layer having a cross-sectional composite elastic modulus in the range of 3.5 to 6.5 GPa, and a thickness in the range of 0.4 to 3.0 ⁇ m.
  • the first substrate layer has a layer structure including a skin layer in contact with the anchor coat layer and a core layer
  • the anchor coat layer has a cross-sectional hardness in the range of 200 MPa or more and 350 MPa or less
  • the skin layer has a cross-sectional hardness of 150 MPa or less.
  • a laminate according to the above aspect in which the skin layer has a cross-sectional hardness of 20 MPa or more.
  • a laminate according to any of the above aspects, in which the thickness of the skin layer is within the range of 0.2 to 1.8 ⁇ m.
  • the anchor coat layer is a cured film of an anchor coat agent containing a polyurethane resin and a curing agent
  • the solid mass ratio of the polyurethane resin to the curing agent in the anchor coat agent [curing agent/polyurethane resin] is within the range of 30/100 to 50/100.
  • the inorganic barrier layer contains silicon oxide or aluminum oxide.
  • a packaging material comprising a laminate according to any of the above aspects.
  • a packaging material comprising a sealant layer formed on the surface of the laminate facing the first substrate layer via a first adhesive layer, and a second substrate layer formed on the surface of the laminate facing the inorganic barrier layer via a second adhesive layer.
  • a packaging material according to any of the above aspects for use in a retort pouch.
  • a package including a packaging material according to any of the above aspects.
  • a packaged article including the package according to the above aspect and contents contained therein.
  • the present invention provides a laminate with excellent resistance to abuse and adhesion, as well as a packaging material, a package, and a packaged article that contain the laminate.
  • FIG. 1 is a partial cross-sectional view illustrating an example of a laminate according to a first embodiment of the present invention.
  • FIG. 11 is a partial cross-sectional view illustrating a laminate according to a modified example of the first embodiment.
  • FIG. 5 is a partial cross-sectional view illustrating an example of a packaging material according to a second embodiment of the present invention.
  • FIG. 11 is a partial cross-sectional view illustrating a packaging material according to a modified example of the second embodiment.
  • 1A-1C are cross-sectional views each showing a schematic diagram of a step in the measurement of composite modulus and hardness. Graph showing a load-displacement curve.
  • Fig. 1 is a partial cross-sectional view showing an example of a laminate according to a first embodiment of the present invention.
  • the laminate 10 shown in Fig. 1 includes, in this order, a first base layer 1, an anchor coat layer 2, and an inorganic barrier layer 3. Each layer included in the laminate 10 will be described below.
  • the first base layer 1 is a film that serves as one of the supports, and may be a single layer or a laminate structure including two or more layers.
  • the first substrate layer 1 contains polyolefin.
  • the first substrate layer 1 may be made of a polyolefin film.
  • polyolefin films include polyethylene film (PE), polypropylene film (PP), and polybutene film (PB).
  • the polyolefin film may also be an acid-modified polyolefin film obtained by graft-modifying a polyolefin with an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like.
  • the polyolefin film constituting the first substrate layer 1 may be a stretched film or a non-stretched film. From the standpoint of impact resistance, heat resistance, water resistance, dimensional stability, etc., the polyolefin film may be a stretched film. This makes it possible to make the laminate 10 more suitable for applications in which it is subjected to high temperature and high pressure or high temperature and high humidity environments, such as retort processing or boiling processing. There are no particular limitations on the stretching method.
  • the stretching method may be any method, such as stretching by inflation, uniaxial stretching, or biaxial stretching, as long as it is possible to supply a dimensionally stable film.
  • the thickness of the first substrate layer 1 is not particularly limited, and can be set appropriately depending on the application, for example, within the range of 6 to 200 ⁇ m. In one example, the thickness of the first substrate layer 1 may be within the range of 9 to 50 ⁇ m, or within the range of 12 to 38 ⁇ m, from the viewpoint of obtaining excellent impact resistance and excellent gas barrier properties.
  • the first base layer 1 may be subjected to various pretreatments such as corona treatment, plasma treatment, and frame treatment on the main surface on which the anchor coat layer 2 is formed, as long as the barrier performance is not impaired.
  • a coating layer such as an easy-adhesion layer may also be provided.
  • the laminate 10 includes an anchor coat layer 2 between the first base layer 1 and the inorganic barrier layer 3.
  • the anchor coat layer 2 has a cross-sectional composite elastic modulus in the range of 3.5 to 6.5 GPa at room temperature (25°C) and a thickness in the range of 0.4 to 3.0 ⁇ m.
  • the anchor coat layer 2 imparts excellent abuse resistance and adhesion to the laminate 10.
  • abuse resistance refers to a property that can suppress a decrease in at least one of the oxygen barrier property and the water vapor barrier property even when a Gelbo flex test (a test in which a gas barrier film is repeatedly compressed while being twisted) is performed.
  • the cross-sectional composite elastic modulus of 6.5 GPa or less contributes to improving the abuse resistance of the laminate 10.
  • this composite elastic modulus By setting this composite elastic modulus to 6.5 GPa or less, the anchor coat layer 2 becomes flexible, and the inorganic barrier layer 3 is less likely to crack when physical stress such as bending is applied to the laminate 10.
  • the thickness of the anchor coat layer 2 is in the range of 0.4 to 3.0 ⁇ m. If the thickness of the anchor coat layer 2 is excessively large, the abuse resistance decreases, and even if the cross-sectional composite elastic modulus is 6.5 GPa or less, the desired abuse resistance cannot be obtained.
  • the thickness of the anchor coat layer 2 is excessively small, the influence of contraction of the first base layer 1 is transmitted to the inorganic barrier layer 3 during processing such as retorting, and the gas barrier property decreases. Therefore, if the thickness of the anchor coat layer 2 is less than 0.4 ⁇ m, the gas barrier properties will decrease after treatment in a high-temperature, high-pressure or high-temperature, high-humidity environment, such as retort treatment, and the desired gas barrier properties and abuse resistance will not be obtained even if the composite elastic modulus of the cross section of the anchor coat layer 2 is 6.5 GPa or less.
  • a cross-sectional composite modulus of 3.5 GPa or more contributes to improving the adhesion of the laminate 10.
  • the adhesion of the laminate 10 is improved, and delamination between the anchor coat layer 2 and the inorganic barrier layer 3 is less likely to occur even after processing in a high temperature and high pressure or high temperature and high humidity environment such as retort processing.
  • the thickness of the anchor coat layer is 3.0 ⁇ m or less. If the thickness of the anchor coat layer 2 is made excessively large, the adhesion decreases, and even if the composite modulus is 3.5 GPa or more, the desired adhesion cannot be obtained.
  • the laminate 10 is endowed with excellent abuse resistance and adhesion. Since the laminate 10 having the anchor coat layer 2 has excellent abuse resistance and adhesion, it can maintain good gas barrier properties and high interlayer adhesion even when subjected to physical stress such as bending after treatment in a harsh environment such as retort treatment.
  • This composite elastic modulus is measured using a nanoindentation method, and will be explained later with reference to the drawings.
  • the anchor coat layer 2 preferably has a cross-sectional composite elastic modulus in the range of 4.0 to 6.0 GPa at room temperature (25°C).
  • the anchor coat layer 2 also preferably has a thickness in the range of 0.5 to 3.0 ⁇ m, and more preferably in the range of 0.7 to 2.0 ⁇ m.
  • the anchor coat layer 2 also functions as a planarizing layer, and allows the inorganic barrier layer 3 to be formed uniformly without defects, thereby further improving the gas barrier properties of the laminate 10.
  • the anchor coat layer 2 can be formed using an anchor coat agent.
  • anchor coat agents include polyester-based polyurethane resin, polyether-based polyurethane resin, and water-dispersible polyurethane resin.
  • the anchor coating agent contains, for example, a polyurethane resin and a curing agent, which will be described below.
  • the polyurethane resin may be a reaction product of a polyurethane resin having an acid group (hereinafter also referred to as an "acid group-containing polyurethane resin") and a polyamine compound. That is, the polyurethane resin may be obtained by bonding the acid group of the acid group-containing polyurethane with the amino group of the polyamine compound.
  • the bond between the acid group of the acid group-containing polyurethane resin and the amino group of the polyamine compound may be an ionic bond (e.g., an ionic bond between a carboxyl group and a tertiary amino group) or a covalent bond (e.g., an amide bond).
  • an ionic bond e.g., an ionic bond between a carboxyl group and a tertiary amino group
  • a covalent bond e.g., an amide bond
  • the acid group-containing polyurethane that constitutes the polyurethane resin has anionic properties and self-emulsifying properties due to the presence of acid groups, and is also called anionic self-emulsifying polyurethane.
  • the acid groups of the acid group-containing polyurethane can bond with the amino groups (primary amino groups, secondary amino groups, tertiary amino groups, etc.) of the polyamine that constitutes the polyurethane resin.
  • the acid groups include carboxyl groups and sulfonic acid groups.
  • the acid groups can usually be neutralized with a neutralizing agent (base), and may form a salt with the base.
  • the acid groups may be located at the terminal or side chain of the acid group-containing polyurethane, but it is preferable that they are located at least in the side chain.
  • the acid value of the acid group-containing polyurethane can be selected within a range in which the acid group-containing polyurethane is water-dispersible, and can be 5 to 100 mgKOH/g, or may be 10 to 70 mgKOH/g, or may be 15 to 60 mgKOH/g.
  • the acid value of the acid group-containing polyurethane is equal to or greater than the lower limit of the above range, the acid group-containing polyurethane is easily water-dispersible, and uniform dispersion of the polyurethane resin and other materials and dispersion stability of the anchor coating agent are easily ensured.
  • the acid value of the acid group-containing polyurethane is measured by a method in accordance with JIS K 0070.
  • the sum of the urethane group concentration and urea group concentration of the acid group-containing polyurethane can be 15% by mass or more, and may be 20 to 60% by mass, from the viewpoint of gas barrier properties.
  • the gas barrier properties of the base layer tend to be good.
  • the sum of the urethane group concentration and urea group concentration is equal to or less than the upper limit value of the above range, it tends to prevent the base layer from becoming rigid and brittle.
  • the urethane group concentration refers to the ratio of the molecular weight of the urethane group (59 g/equivalent) to the molecular weight of the constituent units of the polyurethane resin.
  • the urea group concentration refers to the ratio of the molecular weight of the urea group (primary amino group (amino group): 58 g/equivalent, secondary amino group (imino group): 57 g/equivalent) to the molecular weight of the constituent units of the polyurethane resin.
  • the urethane group concentration and urea group concentration can be calculated based on the charge base of the reaction components, i.e., the usage ratio of each component.
  • the acid group-containing polyurethane can have at least rigid units (units composed of hydrocarbon rings) and short-chain units (e.g., units composed of hydrocarbon chains).
  • the constituent units of the acid group-containing polyurethane may contain a hydrocarbon ring (at least one of aromatic and non-aromatic hydrocarbon rings) derived from a polyisocyanate component, a polyhydroxy acid component, a polyol component, or a chain extender component (particularly, at least a polyisocyanate component).
  • the polyurethane resin may contain an aromatic ring, and therefore the constituent units of the acid group-containing polyurethane may contain an aromatic hydrocarbon ring as the hydrocarbon ring.
  • the proportion of units composed of hydrocarbon rings in the structural units of the acid group-containing polyurethane can be 10 to 70% by mass, or alternatively 15 to 65% by mass, or alternatively 20 to 60% by mass, relative to the total of all structural units.
  • the proportion of units composed of hydrocarbon rings is equal to or greater than the lower limit of the above range, the gas barrier properties of the undercoat layer tend to be good.
  • the proportion of units composed of hydrocarbon rings is equal to or less than the upper limit of the above range, the undercoat layer tends to be prevented from becoming rigid and brittle.
  • the number average molecular weight of the acid group-containing polyurethane can be appropriately selected, but can be 800 to 1,000,000, or may be 800 to 200,000, or may be 800 to 100,000.
  • the anchor coating agent is likely to have a suitable viscosity.
  • the number average molecular weight of the acid group-containing polyurethane is equal to or more than the lower limit of the above range, the gas barrier properties of the undercoat layer are likely to be good.
  • the number average molecular weight of the acid group-containing polyurethane is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene.
  • the acid group-containing polyurethane may be crystalline in order to enhance the gas barrier property.
  • the glass transition temperature of the acid group-containing polyurethane may be 100°C or higher, may be 110°C or higher, or may be 120°C or higher. When the glass transition temperature of the acid group-containing polyurethane is 100°C or higher, the gas barrier property of the undercoat layer is likely to be good.
  • the glass transition temperature of the acid group-containing polyurethane may be 200°C or lower, may be 180°C or lower, or may be 150°C or lower. Therefore, the glass transition temperature of the acid group-containing polyurethane may be 100 to 200°C, may be 110 to 180°C, or may be 120 to 150°C.
  • the glass transition temperature of the acid group-containing polyurethane is measured by differential scanning calorimetry (DSC).
  • the polyamine constituting the polyurethane resin is a compound having two or more basic nitrogen atoms.
  • the basic nitrogen atom is a nitrogen atom that can bond with the acid group of the acid group-containing polyurethane, and examples of this include nitrogen atoms in amino groups such as primary amino groups, secondary amino groups, and tertiary amino groups.
  • the polyamine can be a polyamine having two or more types of amino groups, at least one of which is selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups.
  • polyamines examples include alkylenediamines, polyalkylenepolyamines, and silicon compounds having multiple basic nitrogen atoms.
  • alkylenediamines examples include alkylenediamines having 2 to 10 carbon atoms, such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, and 1,6-hexamethylenediamine.
  • polyalkylenepolyamines examples include tetraalkylenepolyamines.
  • silicon compounds having multiple basic nitrogen atoms include silane coupling agents having multiple basic nitrogen atoms, such as 2-[N-(2-aminoethyl)amino]ethyltrimethoxysilane and 3-[N-(2-aminoethyl)amino]propyltriethoxysilane.
  • the amine value of the polyamine can be 100 to 1900 mgKOH/g, or may be 150 to 1900 mgKOH/g, 200 to 1900 mgKOH/g, 200 to 1700 mgKOH/g, or 300 to 1500 mgKOH/g. If the amine value of the polyamine is equal to or greater than the lower limit of the above range, the gas barrier properties of the undercoat layer tend to be good. If the amine value of the polyamine is equal to or less than the upper limit of the above range, the aqueous dispersion stability of the polyurethane resin tends to be good.
  • the molar ratio of the acid groups of the acid group-containing polyurethane to the basic nitrogen atoms of the polyamine can be 10/1 to 0.1/1, and may be 5/1 to 0.2/1. If the acid group/basic nitrogen atom ratio is within the above range, the undercoat layer is likely to exhibit excellent oxygen barrier properties.
  • the polyurethane resin can be obtained in a state where it is dispersed in an aqueous medium (in the form of an aqueous dispersion).
  • the polyurethane resin can be called an aqueous polyurethane resin.
  • the aqueous medium can be water, a water-soluble or hydrophilic organic solvent, or a mixture thereof.
  • the water-soluble or hydrophilic organic solvent include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; cellosolves; carbitols; and nitriles such as acetonitrile.
  • the aqueous medium can be water or one containing water as the main component.
  • the content of water in the aqueous medium can be 70% by mass or more, and may be 80% by mass or more.
  • the aqueous medium may or may not contain a neutralizing agent (base) that neutralizes the acid group of the acid group-containing polyurethane.
  • the average particle diameter of the dispersed particles is not particularly limited and may be 20 to 500 nm, may be 25 to 300 nm, or may be 30 to 200 nm.
  • the average particle diameter of the dispersed particles is equal to or less than the upper limit of the above range, it is easy to ensure uniform dispersion of the dispersed particles with other materials and dispersion stability of the anchor coating agent, and the gas barrier properties of the base layer formed from the anchor coating agent are likely to be good.
  • the average particle diameter can be measured by diluting with water to a solids concentration of 0.03 to 0.3 mass% and using a concentrated particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-10).
  • polyurethane resin commercially available polyurethane resins may be used, or polyurethane resins produced by known production methods may be used.
  • An example of an aqueous dispersion of polyurethane resin formed from an acid group-containing polyurethane and a polyamine as described above is Takelac (registered trademark) WPB-341A (manufactured by Mitsui Chemicals, Inc.).
  • the method for producing polyurethane resin is not particularly limited, and examples thereof include ordinary aqueous polyurethane resin techniques such as the acetone method and the prepolymer method.
  • urethane catalysts such as amine catalysts, tin catalysts, and lead catalysts may be used as necessary.
  • an inert organic solvent such as ketones such as acetone, ethers such as tetrahydrofuran, and nitriles such as acetonitrile
  • a polyisocyanate compound, a polyhydroxy acid and, if necessary, at least one of a polyol component and a chain extender component are reacted to prepare an acid group-containing polyurethane.
  • a polyisocyanate compound, a polyhydroxy acid, and a polyol component are reacted to generate a prepolymer having an isocyanate group at the end, which is neutralized with a neutralizing agent and dissolved or dispersed in an aqueous medium, and then a chain extender component is added and reacted, and the organic solvent is removed to prepare an aqueous dispersion of an acid group-containing polyurethane.
  • Polyamine is added to the aqueous dispersion of the acid group-containing polyurethane thus obtained, and the mixture is heated as necessary to prepare a polyurethane resin in the form of an aqueous dispersion.
  • the heating temperature can be set to 30 to 60°C.
  • the curing agent is reactive with the polyurethane resin described above.
  • the curing agent is not particularly limited as long as it is reactive with the polyurethane resin in the anchor coating agent, but is preferably an isocyanate compound, a silane coupling agent, or an epoxy compound. Among these, isocyanate compounds are preferred in terms of adhesion to the first base layer 1.
  • any compound having an isocyanate group (-NCO) can be used without any particular limitations.
  • the isocyanate group reacts with the hydroxyl group of the polyurethane resin to form a strong bond. Therefore, by including an isocyanate compound in the anchor coating agent, it is possible to increase the cohesive strength of the coating and improve the adhesion to the first substrate layer 1 and the inorganic barrier layer 3, thereby increasing the practical strength as a packaging material.
  • a polyisocyanate compound having at least two isocyanate groups in the molecule is preferred, and examples thereof include organic polyisocyanate compounds such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hydrogenated toluene diisocyanate, and tetramethylene xylylene diisocyanate, and derivatives of these organic polyisocyanate compounds.
  • organic polyisocyanate compounds such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, isophorone di
  • the isocyanate compound it is preferable to use an isocyanate compound having dispersibility in water (water-dispersible isocyanate compound).
  • water-dispersible isocyanate compound examples include (1) an isocyanate compound obtained by modifying a part of the isocyanate group of the above-mentioned organic polyisocyanate compound with a hydrophilic group such as polyethylene oxide, a carboxyl group or a sulfonic acid group to make it a self-emulsifying type, (2) an isocyanate compound obtained by forcibly emulsifying the above-mentioned organic polyisocyanate compound with a surfactant or the like to make it water-dispersible, (3) various prepolymers derived from the above-mentioned organic polyisocyanate compound, and (4) a compound obtained by blocking a part of the isocyanate group in the above-mentioned organic polyisocyanate with a blocking agent such as alcohols, phenols, oximes,
  • isocyanate compound a commercially available isocyanate compound may be used, or an isocyanate compound produced by a known production method may be used.
  • An example of a commercially available product is Takenate (registered trademark) WD-725 (manufactured by Mitsui Chemicals, Inc.), a water-dispersible type of hexamethylene diisocyanate modified substance.
  • the composite elastic modulus of the cross section of the anchor coat layer 2 can be adjusted, for example, by the solid mass ratio of the polyurethane resin and the curing agent contained in the anchor coat agent.
  • the solid mass ratio of the curing agent to the urethane resin in the anchor coat agent is preferably within the range of 30/100 to 50/100. More preferably, it is in the range of 35/100 to 40/100.
  • the anchor coating agent may contain known additives such as antioxidants, weathering agents, heat stabilizers, lubricants, crystal nucleating agents, UV absorbers, plasticizers, antistatic agents, colorants, fillers, and surfactants, to the extent that the gas barrier properties, wear resistance, and adhesion are not impaired.
  • a known coating method can be used as a method for coating the anchor coat layer 2 on the first substrate layer 1.
  • Known coating methods include, for example, methods using a spray, coater, printer, or brush, and immersion methods (dipping methods).
  • examples of the types of coaters and printers used in these methods and the coating methods thereof include gravure coaters such as direct gravure method, reverse gravure method, kiss reverse gravure method, and offset gravure method, reverse roll coaters, microgravure coaters, coaters combined with chamber doctor, air knife coaters, dip coaters, bar coaters, comma coaters, die coaters, etc.
  • the inorganic barrier layer 3 has gas barrier properties such as oxygen barrier properties and water vapor barrier properties.
  • the inorganic barrier layer 3 preferably contains an inorganic oxide.
  • an inorganic oxide layer as the inorganic barrier layer 3, high barrier properties can be obtained with a very thin layer that does not affect the recyclability of the laminate 10.
  • examples of inorganic oxides contained in the inorganic barrier layer 3 include aluminum oxide, silicon oxide, magnesium oxide, and tin oxide. From the viewpoint of transparency and barrier properties, the inorganic oxide is preferably any one of aluminum oxide, silicon oxide, and magnesium oxide. Furthermore, from the viewpoint of excellent tensile stretchability during processing, it is preferable to contain silicon oxide as the inorganic oxide.
  • the O/Si ratio (mass ratio) of the inorganic barrier layer 3 is preferably 1.7 or more. By suppressing the content of metal Si by setting the O/Si ratio to 1.7 or more, good transparency is easily obtained.
  • the O/Si ratio of the inorganic barrier layer 3 is preferably 2.0 or less. When the O/Si ratio is 2.0 or less, the crystallinity of SiO becomes high. When the crystallinity of SiO becomes high, the inorganic barrier layer 3 can be prevented from becoming too hard, and good tensile resistance can be obtained. This makes it possible to suppress the occurrence of cracks in the inorganic barrier layer 3 when forming the second base layer 14 described later on the inorganic barrier layer 3.
  • the polyolefin film constituting the package may shrink due to heat, but if the O/Si ratio of the inorganic barrier layer 3 is 2.0 or less and has good tensile resistance, it can follow the above shrinkage and suppress the deterioration of the gas barrier property.
  • the O/Si ratio of the inorganic barrier layer 3 is preferably 1.75 or more and 1.9 or less, and more preferably 1.8 or more and 1.85 or less.
  • the O/Si ratio of the inorganic barrier layer can be determined by X-ray photoelectron spectroscopy (XPS). Measurement conditions, for example, include an X-ray photoelectron spectrometer (manufactured by JEOL Ltd., product name: JPS-90MXV) as the measurement device, non-monochromated MgK ⁇ (1253.6 eV) as the X-ray source, and measurement can be performed with an X-ray output of 100 W (10 kV-10 mA). For quantitative analysis to determine the O/Si ratio, relative sensitivity factors of 2.28 for O1s and 0.9 for Si2p can be used.
  • XPS X-ray photoelectron spectrometer
  • the thickness of the inorganic barrier layer 3 is preferably 10 nm or more and 80 nm or less, and more preferably in the range of 15 nm to 60 nm. If the thickness is equal to or more than the lower limit, sufficient barrier performance can be obtained. Furthermore, if the thickness is equal to or less than the upper limit, the occurrence of cracks due to deformation caused by internal stress in the thin film can be suppressed, and deterioration of barrier performance can be suppressed. Note that if the thickness exceeds the upper limit, cracks are more likely to occur due to deformation caused by internal stress, and resistance to abuse also decreases. Furthermore, if the thickness exceeds the upper limit, costs are likely to increase due to an increase in the amount of material used and a longer film formation time, and this is also undesirable from an economic point of view.
  • the inorganic barrier layer 3 can be formed, for example, by vacuum deposition.
  • vacuum deposition physical vapor deposition or chemical vapor deposition can be used.
  • physical vapor deposition include, but are not limited to, vacuum deposition, sputtering, and ion plating.
  • chemical vapor deposition include, but are not limited to, thermal CVD, plasma CVD, and photo CVD.
  • the resistive heating vacuum deposition method the EB (Electron Beam) heating vacuum deposition method, the induction heating vacuum deposition method, the sputtering method, the reactive sputtering method, the dual magnetron sputtering method, the plasma enhanced chemical vapor deposition method (PECVD method), etc. are particularly preferably used.
  • the vacuum deposition method is currently the most superior.
  • the heating means for the vacuum deposition method it is preferable to use any of the following methods: the electron beam heating method, the resistive heating method, or the induction heating method.
  • the laminate 10 may further include a printing layer (not shown).
  • the printing layer is provided at a position visible from the outside of the laminate 10 for the purpose of displaying information about the contents, identifying the contents, or improving the design of the package.
  • the printing layer may be interposed between the first base layer 1 and the anchor coat layer 2.
  • the printing method and printing ink are not particularly limited, and are appropriately selected from known printing methods and printing inks in consideration of printability on the film, design such as color tone, adhesion, safety as a food container, and the like. Examples of printing methods that can be used include gravure printing, offset printing, gravure offset printing, flexographic printing, and inkjet printing. Among them, gravure printing can be preferably used from the viewpoint of productivity and high definition of the pattern.
  • the surface of the first base layer 1 on the side of the anchor coat layer 2 may be subjected to various pretreatments such as corona treatment, plasma treatment, and frame treatment, or a coating layer such as an easy-adhesion layer may be provided.
  • the composite elastic modulus described above can be obtained by a nanoindentation method.
  • a method for measuring the composite elastic modulus will be described below.
  • the measurement target is the anchor coat layer 2 of the laminate 10.
  • a measurement sample (test piece) is obtained from the laminate 10 by a method similar to the method for preparing a measurement sample described in the examples below.
  • test piece is placed in a nanoindenter.
  • the test piece is placed in the nanoindenter so that the indenter of the nanoindenter contacts the cross section of the anchor coat layer 2 perpendicularly.
  • FIG. 5 is a cross-sectional view showing a schematic state in which the indenter 30 is pressed into the anchor coat layer 2 at the maximum depth.
  • h max indicates the maximum depth of pressing into the anchor coat layer 2, i.e., the maximum displacement.
  • a c indicates the contact projected area.
  • h c indicates the contact depth.
  • the load applied to the anchor coat layer 2 and the pressing depth are measured by a nanoindenter. The holding time at the maximum depth is 1 second.
  • the indenter 30 used is a Berkovich-type diamond indenter manufactured by Bruker Japan Ltd.
  • the Berkovich-type diamond indenter has a three-sided pyramid structure, with an internal angle of 142.35°, an angle between the center line and the face of 65.35°, and an aspect ratio of 1:8.
  • the indenter 30 is withdrawn from the anchor coat layer 2.
  • the withdrawal speed is set to 50 nm/sec.
  • the load and indentation depth applied to the anchor coat layer 2 are measured by the nanoindenter.
  • P max indicates the maximum load on the unloading curve.
  • FIG. 6 is a graph showing a load-displacement curve.
  • the vertical axis represents the load P applied to the anchor coat layer 2
  • the horizontal axis represents the pressing depth of the indenter 30, i.e., the displacement h.
  • the indenter 30 is not in contact with the anchor coat layer 2.
  • the position where the displacement h is 0 is the starting point where the load P applied to the anchor coat layer 2 increases from 0.
  • the curve where the load P increases from 0 to the right in response to the increase in the displacement h shows the relationship between the load P and the displacement h in the process of pressing the indenter 30 into the anchor coat layer 2.
  • the curve where the load P decreases to a negative value in response to the decrease in the displacement h is the unloading curve.
  • the unloading curve shows the relationship between the load and the displacement in the process of pulling the indenter 30 out of the anchor coat layer 2.
  • the contact depth h c is calculated by an analysis using the Oliver-Pharr method.
  • the contact depth h c can be calculated by the following formula (1).
  • ⁇ is a constant related to the indenter shape. For a Berkovich indenter, this constant is 0.75.
  • the maximum load P max and maximum displacement h max of the unloading curve can be obtained based on the graph shown in FIG. 6.
  • S is contact stiffness.
  • Contact stiffness S is the slope of an approximation curve obtained by fitting the range of 20 to 95% of the maximum load of the unloading curve in FIG. 6 with the function of the following formula (2) immediately after pulling out.
  • P is the load
  • h is the indentation depth.
  • A, h f , and m are fitting parameters during fitting.
  • the contact projection area A c is calculated based on the shape of the indenter and the contact depth h c .
  • the contact projection area A c can be expressed as a function of the contact depth h c as shown in the following formula (3).
  • formula (3) includes terms called correction terms, including C1 to C5 .
  • C1 to C5 are values determined by using fused quartz as a test piece and performing measurements with maximum loads of 20 ⁇ N to 10 mN, so that the composite elastic modulus Er at each maximum load is 69.6 GPa, which is the composite elastic modulus of fused quartz.
  • the composite elastic modulus Er is calculated based on the contact projection area Ac and the contact stiffness S.
  • the composite elastic modulus Er can be calculated using the following formula (4).
  • the composite elastic modulus Er is measured at multiple points, for example, 20 points, per test piece. The average value of these composite elastic moduli Er is obtained as the composite elastic modulus.
  • the laminate can be modified in various ways.
  • the laminate may have a laminate structure in which the first base layer 1 has a laminated structure with respect to the laminate 10 shown in FIG. 1.
  • the laminate structure preferably includes a skin layer in contact with the anchor coat layer 2 and a core layer.
  • the modified examples are described below with reference to FIG. 2.
  • the matters described with reference to FIG. 1 can be applied alone or in combination to the laminate according to the modified examples described herein.
  • FIG. 2 is a partial cross-sectional view that illustrates a laminate according to a modified example of the first embodiment.
  • the laminate 20 shown in Fig. 2 is similar to the laminate 10 described with reference to Fig. 1, except that the first base layer 1 has a laminate structure including a skin layer 1a and a core layer 1b in contact with the anchor coat layer 2.
  • the matters described for the laminate 10 are also applied to the anchor coat layer 2 in this way, but due to the unique structure of the laminate 20 in which the skin layer 1a is in contact with the anchor coat layer 2 described below, it is preferable that the anchor coat layer 2 has a cross-sectional hardness in the range of 200 MPa to 350 MPa, as described below.
  • the skin layer 1a preferably contains polyolefin, and may be made of a polyolefin film.
  • the resin constituting the polyolefin film may be, for example, a homopolymer of an ⁇ -olefin, such as polyethylene, polypropylene, or polybutene, or a copolymer of two or more types of ⁇ -olefins.
  • the copolymer may be a random copolymer or a block copolymer.
  • the resin constituting the polyolefin film may be a homopolymer of an ⁇ -olefin or a copolymer of two or more types of ⁇ -olefins, either alone or in combination.
  • the resin constituting the polyolefin film is preferably a copolymer of propylene and another ⁇ -olefin.
  • the other ⁇ -olefin include ⁇ -olefins having 2 to 6 carbon atoms other than propylene, such as ethylene, 1-butene, and 1-hexene.
  • the content of the other ⁇ -olefin comonomer component contained in the copolymer is preferably within the range of 0.5 to 15 mol%, and more preferably within the range of 0.6 to 11 mol%.
  • propylene-based copolymers examples include ethylene-propylene random copolymers, 1-butene-propylene random copolymers, ethylene-1-butene-propylene random copolymers, and ethylene-propylene block copolymers.
  • the polyolefin film constituting the skin layer 1a may be a stretched film or a non-stretched film. From the viewpoints of impact resistance, heat resistance, water resistance, dimensional stability, etc., the polyolefin film may be a stretched film. This makes it possible to make the laminate 20 more suitable for applications in which it is subjected to high temperature and high pressure or high temperature and high humidity environments such as retort processing and boiling processing.
  • the stretching method is not particularly limited.
  • the stretching method may be any method that can provide a dimensionally stable film, such as stretching by inflation, uniaxial stretching, or biaxial stretching.
  • the first substrate layer 1 including the skin layer 1a and the core layer 1b can be obtained, for example, by co-extruding the resin for forming the skin layer 1a and the resin for forming the core layer 1b, followed by biaxial stretching.
  • the skin layer 1a has a cross-sectional hardness of 150 MPa or less at room temperature (25°C).
  • the cross-sectional hardness of the skin layer 1a of 150 MPa or less contributes to improving the abuse resistance of the laminate 20.
  • the upper limit of the cross-sectional hardness of the anchor coat layer 2 adjacent to the skin layer 1a is preferably 350 MPa or less, as described below.
  • the cross-sectional hardness of the skin layer 1a is 150 MPa or less, whereas the cross-sectional hardness of the anchor coat layer 2 is preferably in the range of 200 MPa or more and 350 MPa or less. In this case, the cross-sectional hardness of the skin layer 1a is significantly lower than the cross-sectional hardness of the anchor coat layer 2. Making the cross-sectional hardness of the skin layer 1a lower than the cross-sectional hardness of the anchor coat layer in this manner is preferable because it suppresses the deterioration of the gas barrier property after retort treatment.
  • the cross-sectional hardness of the skin layer 1a is H1 and the cross-sectional hardness of the anchor coat layer 2 is H2, the difference in cross-sectional hardness between the anchor coat layer 2 and the skin layer 1a (H2-H1) is preferably 50 MPa or more, and more preferably 100 MPa or more.
  • the upper limit of the difference in cross-sectional hardness between the skin layer 1a and the anchor coat layer 2 (H2-H1) is not particularly limited, but may be, for example, 330 MPa or less, or 200 MPa or less.
  • the cross-sectional hardness at room temperature is preferably 20 MPa or more.
  • the effect of improving the adhesion between the anchor coat layer 2 and the skin layer 1a is further enhanced, making it more difficult for interlayer peeling to occur between the anchor coat layer 2 and the first base layer 1.
  • the cross-sectional hardness is more preferably 40 MPa or more. The hardness of this cross section is measured using a nano-indentation method, which will be described later with reference to the drawings.
  • the thickness of the skin layer 1a is preferably in the range of 0.2 to 1.8 ⁇ m. If the thickness of the skin layer 1a is excessively large, the heat resistance decreases, and the barrier performance after retort decreases. Also, if the thickness of the skin layer 1a is excessively small, the adhesion with the anchor coat layer decreases.
  • the thickness of the skin layer 1a is more preferably in the range of 0.6 to 1.4 ⁇ m.
  • the main surface of the skin layer 1a on which the anchor coat layer 2 is formed may be subjected to various pretreatments such as corona treatment, plasma treatment, and flame treatment within a range that does not impair the barrier performance.
  • the core layer 1b includes a polyolefin.
  • the core layer 1b may be made of a polyolefin film.
  • the polyolefin film include a polyethylene film, a polypropylene film, and a polybutene film.
  • the polyolefin film may be an acid-modified polyolefin film obtained by graft-modifying a polyolefin with an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like.
  • the polyolefin film constituting the core layer 1b may be a stretched film or a non-stretched film. From the viewpoints of impact resistance, heat resistance, water resistance, dimensional stability, etc., the polyolefin film may be a stretched film. This makes it possible to make the laminate 20 more suitable for applications in which it is subjected to high temperature and high pressure or high temperature and high humidity environments such as retort processing and boiling processing.
  • the stretching method is not particularly limited.
  • the stretching method may be any method that can provide a dimensionally stable film, such as stretching by inflation, uniaxial stretching, or biaxial stretching.
  • the first substrate layer 1 including the skin layer 1a and the core layer 1b can be obtained, for example, by co-extruding the resin for forming the skin layer 1a and the resin for forming the core layer 1b, followed by biaxial stretching.
  • the thickness of the core layer 1b is not particularly limited.
  • the thickness of the first base layer 1 including the skin layer 1a can be set appropriately depending on the application so that it is within the range of 6 to 200 ⁇ m.
  • the thickness of the first base layer 1 may be within the range of 9 to 50 ⁇ m, or within the range of 12 to 38 ⁇ m, from the viewpoint of obtaining excellent impact resistance and excellent gas barrier properties.
  • the laminate 20 includes an anchor coat layer 2 between the first base layer 1 and the inorganic barrier layer 3.
  • the anchor coat layer 2 has a cross-sectional composite elastic modulus in the range of 3.5 to 6.5 GPa at room temperature (25°C) and a thickness in the range of 0.4 to 3.0 ⁇ m.
  • the anchor coat layer 2 preferably has a cross-sectional hardness in the range of 200 MPa to 350 MPa at room temperature (25°C).
  • the anchor coat layer 2 provides the laminate 20 with excellent abuse resistance and adhesion, as described below.
  • the cross-sectional hardness of 350 MPa or less contributes to improving the abuse resistance of the laminate 20.
  • the anchor coat layer 2 becomes flexible, and the inorganic barrier layer 3 is less likely to crack when physical stress such as bending is applied to the laminate 20.
  • this effect is easily obtained when the cross-sectional hardness of the anchor coat layer 2 is 350 MPa or less and the cross-sectional hardness of the skin layer 1a is 150 MPa or less, and is difficult to obtain by adjusting the upper limit of the cross-sectional hardness of only one of the anchor coat layer 2 and the skin layer 1a.
  • the cross-sectional hardness of the anchor coat layer 2 is 300 MPa or less.
  • a cross-sectional hardness of 200 MPa or more contributes to improving the adhesion of the laminate 20.
  • the cross-sectional hardness 200 MPa or more By making the cross-sectional hardness 200 MPa or more, the adhesion of the laminate 10 is improved, and delamination between the anchor coat layer 2 and the inorganic barrier layer 3 is less likely to occur even after processing in a high temperature and high pressure environment such as retort processing or a high temperature and high humidity environment. It is more preferable that the cross-sectional hardness of the anchor coat layer 2 is 250 MPa or more.
  • the laminate 20 is given excellent gas barrier properties, abuse resistance, and adhesion.
  • the laminate 20 according to this modification not only has excellent gas barrier properties after treatment in a high-temperature, high-pressure, or high-temperature, high-humidity environment such as retort treatment or boiling treatment, but can also maintain good gas barrier properties even when subjected to physical stress such as bending.
  • the laminate 20 according to this modification can maintain high interlayer adhesion strength after treatment in a high-temperature, high-pressure, or high-temperature, high-humidity environment such as retort treatment or boiling treatment. Note that this cross-sectional hardness is measured using the nanoindentation method as described above, and will be described later with reference to the drawings.
  • the anchor coating agent used to form the anchor coating layer 2 may be the same material as the anchor coating agent described for the laminate 10.
  • the hardness of the cross section described above in the anchor coating layer 2 can be adjusted, for example, by the solid mass ratio of the polyurethane resin and the curing agent contained in the anchor coating agent.
  • the solid mass ratio of the curing agent to the urethane resin in the anchor coating agent [curing agent/polyurethane resin] is preferably within the range of 30/100 to 50/100, and more preferably within the range of 35/100 to 40/100.
  • a known coating method can be used to coat the anchor coat layer 2 on the first substrate layer 1, and for example, a method similar to the coating method of the anchor coat agent described for the laminate 10 can be used.
  • the hardness of the cross section described above is obtained by a nanoindentation method. A method for measuring the hardness will be described below.
  • the measurement target is the anchor coat layer 2 of the laminate 10.
  • a measurement sample (test piece) is obtained from the laminate 10 by a method similar to the method for preparing a measurement sample described in the examples below.
  • test piece is placed in a nanoindenter.
  • the test piece is placed in the nanoindenter so that the indenter of the nanoindenter contacts the cross section of the anchor coat layer 2 perpendicularly.
  • a nanoindenter capable of surface detection at 1 ⁇ N is used.
  • trimming of the embedding resin may be performed if necessary.
  • FIG. 5 is a cross-sectional view showing a schematic state in which the indenter 30 is pressed into the anchor coat layer 2 at the maximum depth.
  • h max indicates the maximum depth of pressing into the anchor coat layer 2, i.e., the maximum displacement.
  • a c indicates the contact projected area.
  • h c indicates the contact depth.
  • the load applied to the anchor coat layer 2 and the pressing depth are measured by a nanoindenter. The holding time at the maximum depth is 1 second.
  • the measurement device used is a Hysitron TI-Premier (product name) manufactured by Bruker Japan Co., Ltd.
  • the indenter 30 is a Berkovich-type diamond indenter manufactured by Bruker Japan Co., Ltd.
  • the Berkovich-type diamond indenter has a three-sided pyramid structure, with the interior angle of the indenter being 142.35°, the angle between the center line and the face being 65.35°, and the aspect ratio of the indenter being 1:8.
  • the indenter 30 is withdrawn from the anchor coat layer 2.
  • the withdrawal speed is set to 30 nm/sec.
  • the load applied to the anchor coat layer 2 and the indentation depth are measured by the nanoindenter.
  • P max indicates the maximum load on the unloading curve.
  • FIG. 6 is a graph showing a load-displacement curve.
  • the vertical axis represents the load P applied to the anchor coat layer 2
  • the horizontal axis represents the pressing depth of the indenter 30, i.e., the displacement h.
  • the indenter 30 is not in contact with the anchor coat layer 2.
  • the position where the displacement h is 0 is the starting point where the load P applied to the anchor coat layer 2 increases from 0.
  • the curve where the load P increases from 0 to the right in response to the increase in the displacement h shows the relationship between the load P and the displacement h in the process of pressing the indenter 30 into the anchor coat layer 2.
  • the curve where the load P decreases to a negative value in response to the decrease in the displacement h is the unloading curve.
  • the unloading curve shows the relationship between the load and the displacement in the process of pulling the indenter 30 out of the anchor coat layer 2.
  • the contact depth h c is calculated by an analysis using the Oliver-Pharr method.
  • the contact depth h c can be calculated by the following formula (1).
  • ⁇ is a constant related to the indenter shape. For a Berkovich indenter, this constant is 0.75.
  • the maximum load P max and maximum displacement h max of the unloading curve can be obtained based on the graph shown in FIG. 6.
  • S is contact stiffness.
  • Contact stiffness S is the slope of an approximation curve obtained by fitting the range of 20 to 95% of the maximum load of the unloading curve in FIG. 6 with the function of the following formula (2) immediately after pulling out.
  • P is the load
  • h is the indentation depth.
  • A, h f , and m are fitting parameters during fitting.
  • the contact projection area A c is calculated based on the shape of the indenter and the contact depth h c .
  • the contact projection area A c can be expressed as a function of the contact depth h c as shown in the following formula (3).
  • formula (3) includes terms including C1 to C5 called correction terms in order to correct the influence of the indenter shape.
  • C1 to C5 are values determined by using fused quartz as a test piece, performing measurements with maximum loads of 20 ⁇ N to 10 mN, and determining that the composite elastic modulus Er at each maximum load is 69.6 GPa, which is the composite elastic modulus of fused quartz.
  • the composite elastic modulus Er can be calculated by the following formula (4).
  • the hardness H is calculated based on the contact projection area A c and the maximum load P max of the unloading curve.
  • the hardness H can be calculated by the following formula (5).
  • Hardness H is measured at multiple points on each test piece, for example, 10 to 20 points. The average of these hardness H values is obtained as the hardness mentioned above.
  • FIG. 3 is a partial cross-sectional view showing an example of a packaging material according to a second embodiment of the present invention.
  • the packaging material 100 shown in Fig. 3 includes the laminate 10 according to the first embodiment described above, and includes a sealant layer 11, a first adhesive layer 12, a first substrate layer 1, an anchor coat layer 2, an inorganic barrier layer 3, a second adhesive layer 13, and a second substrate layer 14 in this order.
  • FIG. 4 is a partial cross-sectional view that shows a schematic diagram of a packaging material according to a modified example of the second embodiment.
  • the packaging material 200 shown in FIG. 4 includes the laminate 20 described above, and includes a sealant layer 11, a first adhesive layer 12, a core layer 1b, a skin layer 1a, an anchor coat layer 2, an inorganic barrier layer 3, a second adhesive layer 13, and a second substrate layer 14, in this order.
  • the packaging materials 100 and 200 according to this embodiment have excellent gas barrier properties, abuse resistance, and adhesion after retort treatment.
  • the packaging materials 100 and 200 according to this embodiment can maintain good gas barrier properties and high interlayer adhesion even when subjected to physical stress such as bending after treatment in a high temperature and high pressure or high temperature and high humidity environment such as retort treatment.
  • the layers contained in the packaging materials 100 and 200 other than the layers contained in the laminates 10 and 20 described above are explained below.
  • the sealant layer 11 is formed on the surface of the laminates 10 and 20 on the side of the first base material layer 1 via a first adhesive layer 12.
  • the sealant layer 11 imparts heat sealing properties to the packaging materials 100 and 200.
  • the sealant layer 11 may contain a thermoplastic resin, and a polyolefin resin is preferably used as the thermoplastic resin.
  • the sealant layer 11 preferably contains a polyolefin film, and may be made of a polyolefin film.
  • the thermoplastic resin used as the material for the sealant layer 11 can be appropriately selected depending on the intended use of the packaging materials 100 and 200 and the temperature conditions of boiling, retort processing, etc.
  • the polyolefin film constituting the sealant layer 11 may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, and tackifiers.
  • the thickness of the sealant layer 11 is determined by the mass of the contents contained in the package including the packaging materials 100 and 200, the shape of the package, etc., but is preferably within the range of approximately 30 to 150 ⁇ m.
  • the sealant layer 11 can be formed by a known lamination method, such as a dry lamination method in which a film-like sealant layer is bonded with an adhesive such as a one-component curing or two-component curing urethane adhesive, a non-solvent dry lamination method in which a film-like sealant layer is bonded with a solvent-free adhesive, or an extrusion lamination method in which the above-mentioned thermoplastic resin is heated and melted, extruded into a curtain shape, and bonded together.
  • a known lamination method such as a dry lamination method in which a film-like sealant layer is bonded with an adhesive such as a one-component curing or two-component curing urethane adhesive, a non-solvent dry lamination method in which a film-like sealant layer is bonded with a solvent-free adhesive, or an extrusion lamination method in which the above-mentioned thermoplastic resin is heated and melted, extruded into a
  • the dry lamination method is preferred because it has high resistance to retort treatment, especially high-temperature hot water treatment of 120°C or higher.
  • the package is to be used for an application in which it will be treated at a temperature of 85°C or lower, there are no particular limitations on the lamination method.
  • the second base layer 14 is formed on the inorganic barrier layer 3 side of the laminates 10 and 20 via a second adhesive layer 13.
  • the second base layer 14 may be made of a polyolefin film.
  • the polyolefin film include a polyethylene film (PE), a polypropylene film (PP), and a polybutene film (PB).
  • the polyolefin film include an acid-modified polyolefin film obtained by graft-modifying a polyolefin with an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like.
  • the polyolefin film constituting the second base layer 14 may be a stretched film or a non-stretched film. From the standpoint of impact resistance, heat resistance, water resistance, dimensional stability, etc., the polyolefin film may be a stretched film. This makes it possible to make the packaging materials 100 and 200 more suitable for applications in which retort processing or boiling processing is performed. There are no particular limitations on the stretching method.
  • the stretching method may be any method, such as stretching by inflation, uniaxial stretching, or biaxial stretching, as long as a dimensionally stable film can be supplied.
  • the thickness of the second substrate layer 14 is not particularly limited. Depending on the application of the packaging materials 100 and 200, the thickness of the second substrate layer 14 can be, for example, within the range of 6 to 200 ⁇ m. From the viewpoint of obtaining excellent impact resistance and excellent gas barrier properties, the thickness of the second substrate layer 14 may be within the range of 9 to 50 ⁇ m, or within the range of 12 to 38 ⁇ m.
  • the packaging materials 100 and 200 include a first adhesive layer 12 between the sealant layer 11 and the first base material layer 1, which adheres them together.
  • a first adhesive layer 12 between the sealant layer 11 and the first base material layer 1, which adheres them together.
  • polyester-isocyanate resins, urethane resins, polyether resins, etc. can be used as the material for the first adhesive layer 12.
  • a two-component curing urethane adhesive that is resistant to retort can be preferably used.
  • the packaging materials 100 and 200 include a second adhesive layer 13 between the second base material layer 14 and the inorganic barrier layer 3 to bond them together.
  • the material of the second adhesive layer 13 is the same as that of the above-mentioned first adhesive layer 12.
  • the thickness of the second adhesive layer 13 is also the same as that of the above-mentioned second adhesive layer 13.
  • a package including the above-mentioned packaging material 100 is provided.
  • a package including the above-mentioned packaging material 200 is provided.
  • These packages may be known bags such as a two-sided bag, a three-sided bag, a two-sided bag, a standing pouch, or a gusset bag, or may be a container including a container body having an opening and a lid that closes the opening. In the latter case, the packaging materials 100 and 200 can be used as at least a part of the lid.
  • the packaging body according to this embodiment has excellent resistance to abuse and adhesion, as explained in relation to the laminates 10 and 20 and the packaging materials 100 and 200.
  • the packaging body according to this embodiment can maintain good gas barrier properties and high interlayer adhesion even when subjected to physical stress such as bending after treatment in a high temperature and high pressure or high temperature and high humidity environment such as retort treatment. Therefore, the packaging body according to this embodiment is suitable for use as, for example, a retort pouch.
  • a packaged article includes the above-mentioned package and a content contained therein.
  • the package has, for example, a sealant layer 11 in contact with a space for containing the content.
  • Any content can be used.
  • the content is a fluid one such as a liquid or an aggregate of rice.
  • Takelac WPB-341A Aqueous dispersion of polyurethane resin formed from acid group-containing polyurethane and polyamine, manufactured by Mitsui Chemicals, Inc., solids concentration 30 mass%.
  • Takenate WD-725 Aqueous dispersion of polyisocyanate having a nonionic group introduced therein, manufactured by Mitsui Chemicals, Inc., solids concentration 99% by mass.
  • the packaging material 100 shown in FIG. 3 was produced by the following method. First, a stretched polypropylene film (thickness 20 ⁇ m) with one side corona-treated was prepared as the first base layer 1. The anchor coating agent AC1 prepared above was applied to the corona-treated surface of this first base layer 1 by gravure roll coating, and dried and cured at 60° C. to form an anchor coating layer 2 (thickness 1.2 ⁇ m).
  • a 40 nm-thick transparent inorganic oxide layer (silica deposition layer) made of silicon oxide was formed as the inorganic barrier layer 3 on the anchor coat layer 2 using a vacuum deposition device using an electron beam heating method, thereby obtaining the laminate 10.
  • a two-component curing polyurethane adhesive (Takelac A525/Takenate A52, manufactured by Mitsui Chemicals, Inc.) was applied to the surface of the first base layer 1 of the laminate 10 obtained above so that the film thickness after drying would be 3 ⁇ m to form a first adhesive layer 12, and the sealant layer 11 was dry laminated.
  • a 100 ⁇ m-thick non-oriented polypropylene film (cast polyethylene; CPP) was used as the sealant layer 11.
  • the same two-component curing polyurethane adhesive as the first adhesive layer 12 was applied to the inorganic barrier layer 3 side of the laminate 10 so that the film thickness after drying was 3 ⁇ m to form the second adhesive layer 13, and the second base material layer 14 was dry laminated.
  • the second base material layer 14 oriented polypropylene (OPP) with a thickness of 30 ⁇ m was used. In this way, the packaging material 100 shown in Figure 3 was obtained.
  • OPP oriented polypropylene
  • Example 4 A packaging material 100 was produced in the same manner as in Example 3, except for the following points: In this example, the thickness of the anchor coat layer 2 was changed from 1.2 ⁇ m to 0.5 ⁇ m.
  • Example 5 A packaging material 100 was produced in the same manner as in Example 3, except for the following points: In this example, the thickness of the anchor coat layer 2 was changed from 1.2 ⁇ m to 2.8 ⁇ m.
  • Example 3 A packaging material 100 was produced in the same manner as in Example 3, except for the following points: In this comparative example, the thickness of the anchor coat layer 2 was changed from 1.2 ⁇ m to 0.3 ⁇ m.
  • Example 4 A packaging material 100 was produced in the same manner as in Example 3, except for the following points: In this comparative example, the thickness of the anchor coat layer 2 was changed from 1.2 ⁇ m to 3.2 ⁇ m.
  • the cut films were embedded in a photocurable resin and cured with a halogen lamp KTX-100R (manufactured by Kenko Tokina Co., Ltd.).
  • the photocurable resin used was D-800 manufactured by Toagosei Co., Ltd.
  • the measurement device used was a Hysitron TI-Premier (trade name) manufactured by Bruker Japan, Ltd., and the indenter used was a Berkovich type diamond indenter manufactured by Bruker Japan, Ltd.
  • the nanoindentation measurement was performed in a displacement control mode by indenting to a depth of 50 nm at a indentation speed of 50 nm/sec, holding at the maximum depth for 1 second, and then unloading at a speed of 50 nm/sec.
  • the measurement was performed by obtaining a shape image of the cross section of the sample using the shape measurement function of a measuring device that scans the sample surface with an indenter, and specifying 20 points on the target layer (anchor coat layer 2) at intervals of 1 ⁇ m or more from the shape image.
  • anchor coat layer 2 the target layer
  • a fused quartz standard sample was tested in advance to calibrate the relationship between the contact depth and the contact projected area of the indenter and sample. After that, the unloading curve in the 60-95% range of the maximum load at the time of unloading was analyzed by the Oliver-Pharr method to calculate the composite elastic modulus.
  • the oxygen transmission rate (OTR) of each sample after the retort treatment was measured using an oxygen transmission tester OX-TRAN (registered trademark) 2/20 manufactured by Modern Control under conditions of a temperature of 30° C. and a relative humidity of 70%. The measurement was performed in accordance with JIS K-7126 Method B (constant pressure method) and ASTM D3985. From the measurement results, the gas barrier properties after the retort treatment were evaluated based on the following criteria. A: The oxygen permeability is 10 cc/m 2 /day/atm or less, and the gas barrier property after retort treatment is excellent. B: The oxygen permeability exceeds 10 cc/m 2 /day/atm, and the gas barrier properties after retort treatment cannot be said to be excellent.
  • the 180° peel strength between the anchor coat layer 2 and the inorganic barrier layer 3 was measured using a tensile tester Tensilon RTC-1250 manufactured by Orientec Co., Ltd. From the measurement results, the adhesion after the retort treatment was evaluated according to the following criteria.
  • C The peel strength is less than 1.5 N/15 mm, and the adhesion after retort treatment is not excellent.
  • Table 1 show that by setting the film thickness of the anchor coat layer 2 in the range of 0.3 to 4.0 ⁇ m and the cross-sectional composite elastic modulus in the range of 3.5 to 6.5 GPa, excellent adhesion and abuse resistance are imparted to the packaging material (laminate). Therefore, a package containing the packaging material according to this embodiment can maintain good gas barrier properties and high interlayer adhesion even when subjected to physical stress such as bending after processing in a high temperature and high pressure or high temperature and high humidity environment such as retort processing or boiling processing.
  • first base layer 1B was prepared under the same conditions as the first base layer 1A, except that an ethylene-propylene random copolymer resin (ethylene content: 7.5 mol%) was used instead of the ethylene-1-butene-propylene random copolymer resin (ethylene content: 5 mol%, 1-butene content: 6 mol%) as the material for the skin layer 1a.
  • an ethylene-propylene random copolymer resin ethylene content: 7.5 mol%
  • ethylene-1-butene-propylene random copolymer resin ethylene content: 5 mol%, 1-butene content: 6 mol%
  • first substrate layer 1C was prepared in the same manner as the first substrate layer 1A, except that an 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 1a instead of the ethylene-1-butene-propylene random copolymer resin (ethylene content: 5 mol%, 1-butene content: 6 mol%).
  • first substrate layer 1D was prepared under the same conditions as the first substrate layer 1A, except that an ethylene-propylene random copolymer resin (ethylene content: 5.0 mol%) was used instead of an ethylene-1-butene-propylene random copolymer resin (ethylene content: 5 mol%, 1-butene content: 6 mol%) as the material for the skin layer 1a.
  • an ethylene-propylene random copolymer resin ethylene content: 5.0 mol%
  • ethylene-1-butene-propylene random copolymer resin ethylene content: 5 mol%, 1-butene content: 6 mol%
  • first substrate layer 1E was prepared under the same conditions as those for the first substrate layer 1A, except that an ethylene-propylene random copolymer resin (ethylene content: 3.2 mol%) was used instead of an ethylene-1-butene-propylene random copolymer resin (ethylene content: 5 mol%, 1-butene content: 6 mol%) as the material for the skin layer 1a.
  • an ethylene-propylene random copolymer resin ethylene content: 3.2 mol%
  • ethylene-1-butene-propylene random copolymer resin ethylene content: 5 mol%, 1-butene content: 6 mol%
  • first base layer 1F was prepared under the same conditions as those for the first base layer 1A, except that an ethylene-propylene random copolymer resin (ethylene content: 0.7 mol%) was used as the material for the skin layer 1a instead of an ethylene-1-butene-propylene random copolymer resin (ethylene content: 5 mol%, 1-butene content: 6 mol%).
  • first base layer 1G was prepared under the same conditions as the first base layer 1A, except that an ethylene-propylene random copolymer resin (ethylene content: 0.6 mol%) was used instead of an ethylene-1-butene-propylene random copolymer resin (ethylene content: 5 mol%, 1-butene content: 6 mol%) as the material for the skin layer 1a.
  • an ethylene-propylene random copolymer resin ethylene content: 0.6 mol%
  • ethylene-1-butene-propylene random copolymer resin ethylene content: 5 mol%, 1-butene content: 6 mol%
  • first substrate layer 1H A first substrate layer 1I was prepared under the same conditions as the first substrate layer 1A, except that the thickness of the skin layer 1a was changed from 0.7 ⁇ m to 1.8 ⁇ m and the thickness of the core layer 1b was changed from 19.3 ⁇ m to 18.2 ⁇ m.
  • first substrate layer 1I A first substrate layer 1J was prepared under the same conditions as the first substrate layer 1A, except that the thickness of the skin layer 1a was changed from 0.7 ⁇ m to 0.2 ⁇ m and the thickness of the core layer 1b was changed from 19.3 ⁇ m to 19.8 ⁇ m.
  • Anchor coating agent AC3R was prepared under the same conditions as anchor coating agent AC1, except that the solids mass ratio of the base agent to the curing agent was changed from 47.2/100 to 54.5/100 (curing agent/base agent).
  • the anchor coating agents AC1 to AC3, ACR1, and ACR2 prepared in Test Example 1 were used.
  • the packaging material 200 shown in FIG. 4 was produced by the following method. First, the anchor coating agent AC3 prepared above was applied by gravure roll coating to the surface of the skin layer 1a side of the first base layer 1A prepared above, and then dried and cured at 60°C to form an anchor coating layer 2 (thickness 1.0 ⁇ m).
  • a 40 nm-thick transparent inorganic oxide layer (silica vapor deposition layer) made of silicon oxide was formed as the inorganic barrier layer 3 on the anchor coat layer 2 using a vacuum deposition device using an electron beam heating method, thereby obtaining the laminate 20.
  • a two-component curing polyurethane adhesive base: Takelac A525, curing agent: Takenate A52, manufactured by Mitsui Chemicals, Inc.
  • base Takelac A525, curing agent: Takenate A52, manufactured by Mitsui Chemicals, Inc.
  • a 100 ⁇ m-thick non-oriented polypropylene film was used as the sealant layer 11.
  • the same two-component curing polyurethane adhesive as the first adhesive layer 12 was applied to the inorganic barrier layer 3 side of the laminate 20 so that the film thickness after drying was 3 ⁇ m to form the second adhesive layer 13, and the second base material layer 14 was dry laminated.
  • the second base material layer 14 oriented polypropylene (OPP) with a thickness of 30 ⁇ m was used. In this way, the packaging material 200 shown in FIG. 4 was obtained.
  • OPP polypropylene
  • Example 7 to 17, Comparative Examples 5 to 7 The packaging materials according to Examples 7 to 17 and Comparative Examples 5 to 7 were prepared under the same conditions as in Example 6, except that the first base layer 1A or the anchor coating agent AC3 used in Example 6 was changed to those shown in Table 2. The material was manufactured.
  • Both sides of each packaging material were corona treated at 0.20 kW (apparatus: Corona Treater CT-0212 manufactured by Kasuga Electric Co., Ltd.), and then the film was cut into a wedge shape with a base of 1.0 mm and a height of 5.0 mm using a razor.
  • the cut film was embedded in a photocurable resin and cured with a halogen lamp KTX-100R (manufactured by Kenko Tokina Co., Ltd.).
  • the photocurable resin used was D-800 manufactured by Toagosei Co., Ltd.
  • the measurement device used was a Hysitron TI-Premier (trade name) manufactured by Bruker Japan, Ltd., and the indenter used was a Berkovich type diamond indenter manufactured by Bruker Japan, Ltd.
  • the nanoindentation measurement was performed in a displacement control mode by indenting to a depth of 30 nm at a indentation speed of 30 nm/sec, holding at the maximum depth for 1 second, and then unloading at a speed of 30 nm/sec.
  • the hardness of the anchor coat layer 2 was in the range of 200 to 350 MPa for all of Examples 6 to 17, less than 200 MPa for Comparative Example 5, and more than 350 MPa for Comparative Examples 6 and 7.
  • the results of the hardness of the skin layer 1a are shown in Table 2.
  • the 180° peel strength between the first base layer 1 and the anchor coat layer 2 was measured using a tensile tester Tensilon RTC-1250 manufactured by Orientec Co., Ltd. From the measurement results, the adhesion after the retort treatment was evaluated according to the following criteria.
  • C The peel strength is less than 1.5 N/15 mm, and the adhesion after retort treatment is not excellent.
  • the 180° peel strength between the anchor coat layer 2 and the inorganic barrier layer 3 was measured using a tensile tester Tensilon RTC-1250 manufactured by Orientec Co., Ltd. From the measurement results, the adhesion after the retort treatment was evaluated according to the following criteria.
  • C The peel strength is less than 1.5 N/15 mm, and the adhesion after retort treatment is not excellent.
  • the present invention is not limited to the above-described embodiments, and can be modified in various ways in the implementation stage without departing from the gist of the invention.
  • the embodiments may also be implemented in appropriate combination, in which case the combined effects can be obtained.
  • the above-described embodiments include various inventions, and various inventions can be extracted by combinations selected from the multiple constituent elements disclosed. For example, if the problem can be solved and an effect can be obtained even if some constituent elements are deleted from all the constituent elements shown in the embodiments, the configuration from which these constituent elements are deleted can be extracted as an invention.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
PCT/JP2024/003087 2023-02-02 2024-01-31 積層体、包装材料、包装体及び包装物品 Ceased WO2024162391A1 (ja)

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JP2024534423A JP7544309B1 (ja) 2023-02-02 2024-01-31 積層体、包装材料、包装体及び包装物品
EP24750340.2A EP4644114A4 (en) 2023-02-02 2024-01-31 LAMINATED BODY, PACKAGING MATERIAL, PACKAGING AND PACKAGED ITEM
CN202480009990.7A CN120712176A (zh) 2023-02-02 2024-01-31 层叠体、包装材料、包装体及包装物品
JP2024126139A JP2024149642A (ja) 2023-02-02 2024-08-01 積層体、包装材料、包装体及び包装物品
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WO2009112256A1 (en) * 2008-03-14 2009-09-17 Tetra Laval Holdings & Finance S.A. Mono-axially oriented polymer substrate film
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JP2015208924A (ja) * 2014-04-25 2015-11-24 凸版印刷株式会社 ガスバリア性フィルムおよびガスバリア性積層体
JP2018173165A (ja) * 2017-03-30 2018-11-08 日東電工株式会社 遮熱断熱基板
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WO2022056095A1 (en) 2020-09-11 2022-03-17 Amcor Flexibles North America, Inc. Heat stable multilayer barrier film structure
WO2022220200A1 (ja) 2021-04-13 2022-10-20 凸版印刷株式会社 ガスバリアフィルム、包装材及び包装袋

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WO2009112256A1 (en) * 2008-03-14 2009-09-17 Tetra Laval Holdings & Finance S.A. Mono-axially oriented polymer substrate film
WO2013147090A1 (ja) * 2012-03-29 2013-10-03 リンテック株式会社 ガスバリア性積層体、その製造方法、電子デバイス用部材及び電子デバイス
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JP2018173165A (ja) * 2017-03-30 2018-11-08 日東電工株式会社 遮熱断熱基板
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CN120712176A (zh) 2025-09-26
EP4644114A1 (en) 2025-11-05
US20250353650A1 (en) 2025-11-20

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