WO2024085092A1 - 積層体及び包装袋 - Google Patents

積層体及び包装袋 Download PDF

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Publication number
WO2024085092A1
WO2024085092A1 PCT/JP2023/037251 JP2023037251W WO2024085092A1 WO 2024085092 A1 WO2024085092 A1 WO 2024085092A1 JP 2023037251 W JP2023037251 W JP 2023037251W WO 2024085092 A1 WO2024085092 A1 WO 2024085092A1
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WIPO (PCT)
Prior art keywords
layer
laminate
vapor deposition
aluminum
aluminum vapor
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/JP2023/037251
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English (en)
French (fr)
Japanese (ja)
Inventor
純一 神永
寛之 若林
良樹 越山
裕美子 小島
里佳 石井
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Toppan Holdings Inc
Original Assignee
Toppan Holdings Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toppan Holdings Inc filed Critical Toppan Holdings Inc
Priority to EP23879735.1A priority Critical patent/EP4596238A4/en
Priority to AU2023363440A priority patent/AU2023363440B2/en
Priority to CN202380072124.8A priority patent/CN120035516A/zh
Priority to JP2024506666A priority patent/JP7537644B1/ja
Publication of WO2024085092A1 publication Critical patent/WO2024085092A1/ja
Priority to JP2024130686A priority patent/JP7848835B2/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/02—Metal coatings
    • D21H19/08—Metal coatings applied as vapour, e.g. in vacuum
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/22—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/84—Paper comprising more than one coating on both sides of the substrate

Definitions

  • This disclosure relates to a laminate and a packaging bag.
  • packaging materials are used according to the contents.
  • Packaging materials are required to have gas barrier properties that prevent the permeation of water vapor, which can cause the contents to deteriorate.
  • packaging materials are required to have oil resistance to prevent the oil contained in the contents from seeping out, depending on the contents.
  • Patent Document 1 discloses a laminate in which a barrier layer is laminated onto paper.
  • Paper has the characteristic of being easy to process due to its crease retention (also called dead-hold property).
  • crease retention also called dead-hold property.
  • cracks occur in the barrier layer and oil resistance decreases when making packaging bags with sharper creases (pillow packaging, three-sided seal packaging, and gusset packaging).
  • the present disclosure therefore aims to provide a laminate using paper that has sufficient oil resistance not only at the initial stage but also after being folded, and a packaging bag that includes the laminate.
  • the anchor coat layer contains a polyolefin or polyvinyl alcohol resin having a polar group.
  • the overcoat layer contains a polyolefin having a polar group.
  • the laminate uses paper, it has the crease retention characteristic of paper and contributes to reducing the amount of plastic material used.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to an embodiment of the present disclosure.
  • FIG. 1 is a perspective view showing a packaging bag according to an embodiment of the present disclosure.
  • the laminate according to the present embodiment is a laminate having a structure in which at least a paper base material, an anchor coat layer, an aluminum vapor deposition layer, and an overcoat layer are laminated in this order, and the aluminum vapor deposition layer is a laminate having a half-width of the peak of the (111) crystal plane of aluminum in X-ray diffraction measurement of 1.6° or more.
  • the half-width in X-ray diffraction of the aluminum vapor deposition layer represents the degree of lattice distortion of the aluminum crystal structure. If the distortion is large, the half-width becomes large, and if the distortion is small, the half-width becomes small. In addition, the smaller the distortion, the denser the aluminum crystal structure is.
  • the half-width of the aluminum vapor deposition layer is 1.6° or more, so that the denseness of the aluminum crystal structure can be appropriately reduced to a sparse state.
  • the stress applied to the aluminum vapor deposition layer when the laminate is folded is distributed throughout the layer, and it is possible to suppress the occurrence of cracks in the aluminum vapor deposition layer when folded, and to reduce the cracks occurring in the aluminum vapor deposition layer. Therefore, according to the laminate, not only initial oil resistance but also sufficient oil resistance can be obtained even after folding.
  • the half-width of the aluminum vapor deposition layer within the above range, it is possible to obtain not only the initial water vapor barrier property but also sufficient water vapor barrier property even after folding.
  • the laminate when a material having oxygen barrier property is used for the anchor coat layer, by setting the half-width of the aluminum vapor deposition layer within the above range, it is possible to obtain not only the initial oxygen barrier property but also sufficient oxygen barrier property even after folding.
  • the laminate according to this embodiment is useful as an oil-resistant laminate or a gas barrier laminate.
  • conventional gas barrier laminates have room for improvement in that the water vapor barrier properties deteriorate when stored under high temperature and high humidity conditions.
  • a gas barrier laminate that had deteriorated water vapor barrier properties after being stored under high temperature and high humidity conditions (40°C, 90% humidity environment) was observed under a microscope using transmitted light, numerous tiny bright spots were confirmed, which suggests that the water vapor barrier properties were deteriorated due to the occurrence of transmission defects in the aluminum deposition layer.
  • the laminate according to this embodiment has an aluminum deposition layer in which the half-width of the peak of the aluminum (111) crystal plane in X-ray diffraction measurement is 1.6° or more, and therefore it is possible to suppress the occurrence of transmission defects in the aluminum deposition layer even when stored under high temperature and high humidity conditions, and thus suppress the deterioration of the water vapor barrier properties.
  • the inventors speculate as follows about the reason why such an effect is obtained.
  • the generation of transmission defects in the aluminum vapor deposition layer is caused by pitting of aluminum caused by corrosive ions and expansion and contraction stress caused by dimensional changes accompanying moisture absorption and desorption of the paper base material. From the viewpoint of the crystallinity of the aluminum vapor deposition layer, it can be said that the higher the crystallinity, the better it is in terms of resistance to corrosive ions, but in terms of stress resistance, amorphous materials, which are more likely to follow expansion and contraction, are considered to be superior.
  • the aluminum vapor deposition layer is considered to have a structure in which the amorphous part is filled around the crystallites.
  • the broadening of the X-ray diffraction line width of aluminum is due to the diameter of the crystallites and the distortion of the crystals.
  • a narrow X-ray diffraction line width is considered to be a state in which the crystallites made of an ideal crystal lattice and the amorphous part are clearly separated. Therefore, when the X-ray diffraction line width is narrow, it is presumed that pitting in the amorphous part and destruction of the ideal crystal lattice or between the crystal and amorphous due to expansion and contraction stress are more likely to occur.
  • a wide X-ray diffraction line width is considered to be a state in which a distorted crystal structure is adopted and the separation between the crystal and amorphous parts is unclear. Therefore, it is presumed that when the X-ray diffraction line width is wide, pitting corrosion and destruction due to stretching stress are suppressed, and transmission defects are less likely to occur.
  • the half-width in the X-ray diffraction of the aluminum vapor deposition layer be 1.6° or more, it is possible to suppress the occurrence of transmission defects in the aluminum vapor deposition layer and suppress deterioration of the water vapor barrier property even when the laminate is stored under high temperature and high humidity conditions. This effect is more pronounced when the half-width is 2.0° or more.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to one embodiment.
  • the laminate 10 according to one embodiment comprises, in this order, a paper base material 1, an anchor coat layer 2, an aluminum vapor deposition layer 3, and an overcoat layer 4.
  • the thickness of the laminate 10 may be 20 to 100 ⁇ m, 30 to 80 ⁇ m, or 40 to 60 ⁇ m. If the thickness of the laminate 10 is within the above range, the laminate 10 can obtain better water vapor barrier properties and oil resistance not only initially but also after being folded.
  • the paper base material 1 may be paper whose main component is plant-derived pulp. Specific examples of the paper base material 1 include fine paper, special fine paper, coated paper, art paper, cast coated paper, imitation paper, kraft paper, and glassine paper. The basis weight of the paper base material 1 may be 20 to 500 g/m 2 or 30 to 100 g/m 2 .
  • the paper base material 1 may have a coating layer at least on the side of the paper base material 1 that contacts the anchor coat layer 2.
  • the paper base material 1 may have at least a paper layer and a coating layer.
  • the coating layer may be provided on both surfaces of the paper base material 1.
  • the coating layer may use various copolymers such as styrene-butadiene, styrene-acrylic, and ethylene-vinyl acetate, polyvinyl alcohol resin, cellulose resin, paraffin (wax), etc. as a binder resin, and may contain clay, kaolin, calcium carbonate, talc, mica, etc. as a filler.
  • the coating layer may be a clay coating layer that contains at least clay as a filler.
  • the thickness of the coating layer may be 1.5 ⁇ m or more and 15 ⁇ m or less.
  • the thickness of the coating layer may be 1.8 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, or 6 ⁇ m or more.
  • the thickness of the coating layer may be 12 ⁇ m or less, or 10 ⁇ m or less.
  • the thickness of the paper base material 1 may be 20 to 100 ⁇ m, 30 to 80 ⁇ m, or 40 to 60 ⁇ m. If the thickness of the paper base material 1 is within the above range, the laminate 10 can have better water vapor barrier properties and oil resistance not only initially but also after being folded.
  • the ratio of the thickness of the coating layer to the thickness of the paper base material 1 may be 3-25%, or 5-20%. If this ratio is within the above range, the laminate 10 can obtain better water vapor barrier properties and oil resistance not only initially but also after being folded.
  • the weight of the paper is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the weight of the entire laminate. If the weight of the paper is 50% by mass or more based on the weight of the entire laminate, the amount of plastic material used can be sufficiently reduced, the entire laminate can be said to be made of paper, and it has excellent recyclability.
  • the anchor coat layer 2 is provided on the surface of the paper base material 1 to improve adhesion between the paper base material 1 and the aluminum vapor deposition layer 3 described below, and to improve the gas barrier properties and oil resistance of the laminate.
  • the anchor coat layer 2 may contain a polyolefin or polyvinyl alcohol resin having a polar group.
  • the anchor coat layer 2 contains a polyolefin having a polar group
  • the anchor coat layer 2 has excellent flexibility, and can suppress cracking of the aluminum vapor deposition layer 3 described below after bending (folding), and can improve adhesion between the anchor coat layer 2 and the aluminum vapor deposition layer 3.
  • a polyolefin having a polar group it is possible to form a dense film due to the crystallinity of the polyolefin, and water vapor barrier properties and oil resistance are expressed.
  • the crystallinity of the polyolefin results in water vapor barrier properties and oil resistance, and the presence of a polar group results in adhesion with the aluminum vapor deposition layer 3.
  • the polyolefin having a polar group may have at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester.
  • Polyolefins having polar groups may be copolymerized with ethylene or propylene and unsaturated carboxylic acids (unsaturated compounds having carboxyl groups such as acrylic acid, methacrylic acid, and maleic anhydride), unsaturated carboxylic acid esters, and salts of carboxylic acids neutralized with basic compounds.
  • unsaturated carboxylic acids unsaturated compounds having carboxyl groups such as acrylic acid, methacrylic acid, and maleic anhydride
  • unsaturated carboxylic acid esters unsaturated carboxylic acid esters
  • salts of carboxylic acids neutralized with basic compounds may also be used.
  • copolymers with vinyl acetate, epoxy compounds, chlorine compounds, urethane compounds, polyamide compounds, etc. may also be used.
  • polyolefins having polar groups include copolymers of acrylic esters and maleic anhydride, ethylene-vinyl acetate copolymers, and ethylene-glycidyl methacrylate copolymers.
  • the anchor coat layer 2 contains a polyvinyl alcohol-based resin
  • the polyvinyl alcohol-based resin has a polar group (hydroxyl group), which easily bonds with metals such as aluminum in the aluminum vapor deposition layer 3, making it easier to improve the adhesion between the aluminum vapor deposition layer 3 and the anchor coat layer 2.
  • such an anchor coat layer 2 has excellent flexibility and can suppress cracking of the aluminum vapor deposition layer 3 after bending (folding).
  • the anchor coat layer 2 contains a polyvinyl alcohol-based resin, which can improve the oxygen barrier properties of the laminate.
  • Polyvinyl alcohol resins are resins that contain vinyl alcohol as a constituent unit, and examples of polyvinyl alcohol resins include fully saponified polyvinyl alcohol resins, partially saponified polyvinyl alcohol resins, modified polyvinyl alcohol resins, and ethylene-vinyl alcohol copolymer resins. From the viewpoint of oxygen barrier properties, the higher the degree of saponification of the polyvinyl alcohol resin, the more preferable it is, and it may be 95% or more, or 98% or more.
  • the anchor coat layer 2 may contain both a polyolefin having a polar group and a polyvinyl alcohol-based resin.
  • the anchor coat layer 2 may contain other components in addition to the polyolefin having a polar group and the polyvinyl alcohol resin.
  • other components include polyolefins other than the polyolefin having a polar group, silane coupling agents, organic titanates, polyacrylics, polyesters, polyurethanes, polycarbonates, polyureas, polyamides, polyimides, melamines, phenols, etc.
  • the content of the polyolefin or polyvinyl alcohol resin having the polar group in the anchor coat layer 2 may be, for example, 50% by mass or more, 70% by mass or more, 90% by mass or more, or 100% by mass.
  • the thickness of the anchor coat layer 2 may be, for example, 0.5 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more, 20 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less. If the thickness of the anchor coat layer 2 is 0.5 ⁇ m or more, the unevenness of the paper base material described above can be efficiently filled, and the aluminum vapor deposition layer described below can be laminated evenly. Furthermore, if the thickness of the anchor coat layer 2 is 20 ⁇ m or less, the aluminum vapor deposition layer can be laminated evenly while keeping costs down.
  • the anchor coat layer 2 may have a hardness of 0.3 GPa or less as measured by nanoindentation in a cross section in the thickness direction of the laminate 10. Such an anchor coat layer 2 has excellent flexibility, and can suppress cracking of the aluminum vapor deposition layer 3 (described later) after bending (folding), and can improve adhesion between the anchor coat layer 2 and the aluminum vapor deposition layer 3.
  • Solvents contained in the coating liquid for the anchor coat layer 2 include, for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, and butyl acetate. These solvents may be used alone or in combination of two or more.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water are preferred.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, and water are preferred.
  • the anchor coat layer 2 can be formed by applying a coating liquid containing the above-mentioned polyolefin or polyvinyl alcohol resin having polar groups and a solvent, etc., onto the paper substrate, and then drying it.
  • the aluminum vapor-deposited layer 3 is a layer obtained by vapor-depositing aluminum or an aluminum compound.
  • the aluminum vapor-deposited layer 3 may be one obtained by vapor-depositing aluminum, or may contain aluminum oxide (AlO x ), silicon oxide (SiO x ), or the like.
  • the thickness of the aluminum vapor deposition layer 3 may be appropriately set depending on the intended use, but is preferably 10 to 300 nm, more preferably 20 to 100 nm, and even more preferably 30 to 100 nm. By setting the thickness of the aluminum vapor deposition layer 3 to 10 nm or more, the continuity of the aluminum vapor deposition layer 3 is easily ensured, and by setting the thickness to 300 nm or less, the occurrence of curling and cracking can be sufficiently suppressed, and sufficient gas barrier performance, oil resistance, and flexibility can be easily achieved.
  • the thickness of the aluminum vapor deposition layer 3 may be 50 to 300 nm, 60 to 150 nm, or 60 to 100 nm.
  • the aluminum vapor deposition layer 3 is preferably formed by vacuum deposition from the viewpoints of water vapor and oxygen gas barrier performance, oil resistance, and film uniformity.
  • vacuum deposition is preferred due to its fast deposition speed and high productivity.
  • deposition by electron beam heating is particularly effective because the deposition speed can be easily controlled by the irradiation area and electron beam current, and the deposition material can be heated and cooled in a short time.
  • the aluminum vapor deposition layer 3 is a layer in which the half-width of the peak of the (111) crystal plane of aluminum in X-ray diffraction measurement is 1.6° or more.
  • the half-width may be 1.8° or more, 2.0° or more, or 2.1° or more. If the half-width is 1.6° or more, it is possible to suppress the occurrence of cracks in the aluminum vapor deposition layer 3 when the laminate 10 is folded, and it is possible to suppress the deterioration of the gas barrier property and oil resistance after folding. This effect is more pronounced when the half-width is 2.0° or more.
  • the half-width is 1.6° or more, it is possible to suppress the occurrence of transmission defects in the aluminum vapor deposition layer 3 even when the laminate 10 is stored under high temperature and high humidity conditions (for example, in a 40°C and 90% environment), and it is possible to suppress the deterioration of the water vapor barrier property of the laminate 10. This effect is also more pronounced when the half-width is 2.0° or more.
  • the upper limit of the half-width may be, for example, 15.0° or less, or 10.0° or less, from the viewpoint of the denseness of the aluminum crystal structure.
  • the aluminum vapor-deposited layer is easily corroded. If the crystallinity of the aluminum vapor-deposited layer is low, such a problem is likely to occur. If the half-width is 15.0° or less, even if the resin layer in contact with the aluminum vapor-deposited layer contains an ionomer or a polyvinyl alcohol-based resin with a high saponification degree, the aluminum vapor-deposited layer is unlikely to corrode. This effect is also more pronounced when the half-width is 10.0° or less.
  • the half-width is preferably 1.6° to 15.0°, 1.6° to 10.0°, 1.6° to 7.0°, 1.6° to 5.0°, 2.0° to 15.0°, 2.0° to 10.0°, 2.0° to 7.0°, or 2.0° to 5.0°.
  • the half-width (2 ⁇ ) of the peak of the (111) crystal plane of aluminum in the aluminum deposition layer 3 is measured using an X-ray diffractometer.
  • the X-ray diffractometer for example, ATX-G (product name) manufactured by Rigaku Electric Co., Ltd. can be used.
  • the measurement can be performed from above the overcoat layer 4 by fixing the laminate as a sample on a slide glass.
  • the measurement conditions are as follows.
  • the half-width can be controlled by adjusting the conditions during deposition of the aluminum vapor deposition layer 3.
  • the half-width can be controlled by adjusting the pressure in the deposition chamber during deposition of the aluminum vapor deposition layer 3.
  • the half-width can be increased by increasing the pressure in the deposition chamber, and the half-width can be decreased by decreasing the pressure in the deposition chamber.
  • the pressure in the deposition chamber during deposition of the aluminum vapor deposition layer 3 can be 0.05 Pa or more, 0.10 Pa or more, or 0.20 Pa or more, since it is easy to adjust the half-width to 1.6° or more.
  • the upper limit of the pressure is not particularly limited as long as it is within the range in which deposition of the aluminum vapor deposition layer 3 is possible, but may be, for example, 0.50 Pa or less, or 0.40 Pa or less.
  • the overcoat layer 4 is provided on the surface of the aluminum vapor-deposited layer 3 so as to be in contact with the aluminum vapor-deposited layer 3.
  • the overcoat layer may contain a polyolefin having a polar group.
  • the polyolefin having a polar group may have at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester.
  • Polyolefins having polar groups may be copolymerized with ethylene or propylene and unsaturated carboxylic acids (unsaturated compounds having carboxyl groups such as acrylic acid and methacrylic acid), unsaturated carboxylic acid esters, or salts of carboxylic acids neutralized with basic compounds.
  • unsaturated carboxylic acids unsaturated compounds having carboxyl groups such as acrylic acid and methacrylic acid
  • unsaturated carboxylic acid esters unsaturated carboxylic acid esters
  • salts of carboxylic acids neutralized with basic compounds may also be used.
  • copolymers with vinyl acetate, epoxy compounds, chlorine compounds, urethane compounds, polyamide compounds, etc. may also be used.
  • polyolefins having polar groups include copolymers of acrylic esters and maleic anhydride, ethylene-vinyl acetate copolymers, and ethylene-glycidyl methacrylate copolymers.
  • the overcoat layer 4 has excellent flexibility, can suppress cracking of the aluminum vapor deposition layer after bending (folding), and has excellent adhesion to the aluminum vapor deposition layer. Furthermore, by including polyolefin having the above-mentioned polar groups, it is possible to form a dense film due to the crystallinity of the polyolefin, and water vapor barrier properties and oil resistance are exhibited. Furthermore, by including polar groups, adhesion to the aluminum vapor deposition layer is exhibited. Furthermore, by including polyolefin having the above-mentioned polar groups, the overcoat layer 4 can also serve as a heat seal layer, so there is no need to provide a separate heat seal layer.
  • the overcoat layer 4 may contain other components in addition to the polyolefin having the polar group.
  • examples of other components include silane coupling agents, organic titanates, polyacrylics, polyesters, polyurethanes, polycarbonates, polyureas, polyamides, polyolefin emulsions, polyimides, melamines, and phenols.
  • the content of the polyolefin having a polar group in the overcoat layer 4 may be, for example, 50% by mass or more, 70% by mass or more, 90% by mass or more, or 100% by mass.
  • the thickness of the overcoat layer 4 may be, for example, 0.05 ⁇ m or more, 0.5 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more, 20 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less. If the thickness of the overcoat layer 4 is 0.05 ⁇ m or more, it can fully fulfill the role of the heat seal layer described above. Furthermore, if the thickness of the overcoat layer 4 is 20 ⁇ m or less, it can fully fulfill the adhesion and barrier properties with the aluminum vapor deposition layer while suppressing costs. Furthermore, by setting the thickness of the overcoat layer 4 to 2 ⁇ m or more and 10 ⁇ m or less, the aluminum vapor deposition layer becomes less likely to crack, and sufficient water vapor barrier properties and oil resistance can be obtained even after bending.
  • the thickness of the overcoat layer 4 is set to 2 ⁇ m or more and 10 ⁇ m or less, and the thickness of the aluminum vapor deposition layer 3 is set to 20 nm or more and 100 nm or less, the aluminum vapor deposition layer 3 is less likely to crack, and the effect of being able to obtain sufficient water vapor barrier properties and oil resistance even after bending is particularly remarkable.
  • the overcoat layer 4 may have a hardness of 0.3 GPa or less as measured by nanoindentation at a cross section in the thickness direction of the laminate 10. Such an overcoat layer 4 has excellent flexibility, can suppress cracking of the aluminum vapor deposition layer 3 after bending (folding), and can suppress deterioration of gas barrier properties and oil resistance.
  • Solvents contained in the coating liquid for the overcoat layer 4 include, for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, and butyl acetate. These solvents may be used alone or in combination of two or more.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water are preferred.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, and water are preferred.
  • the overcoat layer 4 can be provided by applying a coating liquid containing the above-mentioned polyolefin having polar groups and a solvent on the aluminum vapor deposition layer and drying it.
  • the melting point of the polyolefin having polar groups in the coating liquid is preferably 70 to 160°C, more preferably 80 to 120°C. If the melting point of the polyolefin having polar groups is low, there is an advantage in that the start-up temperature during heat sealing can be lowered. If the melting point of the polyolefin having polar groups is low, there is an increased risk of blocking in a high-temperature environment. From the viewpoint of preventing blocking, it is preferable that the particle size is large so that the contact area is small. Although not particularly limited, the particle size may be specifically 1 nm or more, 0.1 ⁇ m or more, 1 ⁇ m or less, 0.7 ⁇ m or less, or 0.5 ⁇ m or less.
  • the anchor coat layer 2 and the overcoat layer 4 are measured from the cross section of the laminate 10.
  • the laminate sample including the anchor coat layer 2 and the overcoat layer 4 is cut into a rectangular or wedge shape with a razor and embedded in resin.
  • a photocurable resin e.g., D-800 manufactured by Toa Gosei Co., Ltd.
  • D-800 manufactured by Toa Gosei Co., Ltd.
  • the hardened sample embedding resin is fixed with an insert for an AFM sample holder, trimming is performed with a glass knife at room temperature (25°C) and the cross section of the laminate is cut, and the cross section is cut with a diamond knife at a cutting speed of 1.0 mm/s and a cutting film thickness of 200 nm until a mirror surface is obtained.
  • the sample with the cross section exposed is used for measurement by the nanoindentation method while being fixed with an insert for an AFM sample holder.
  • an ultramicrotome EMUC7 manufactured by Leica can be used as the cross section cutting device.
  • the cutting direction is parallel to the layer interface.
  • the hardness and composite modulus of the anchor coat layer and the overcoat layer represent the hardness and composite modulus calculated by the nanoindentation method.
  • the nanoindentation method is a measurement method in which a quasi-static indentation test is performed on a target measurement object to obtain the mechanical properties of the sample.
  • a Hysitron TI-Premier (trade name) manufactured by Bruker Japan Co., Ltd. can be used as the measurement device.
  • a Berkovich type diamond indenter manufactured by Bruker Japan Co., Ltd. can be used as the indenter.
  • the diamond indenter is used to scan the cross section of the sample to obtain a shape image of the sample, and the measurement position of the desired layer is specified. Then, in a displacement control mode at room temperature (25°C), the indenter is indented to a depth of 80 nm at a indentation speed of 80 nm/sec, and then the maximum depth is held for 1 second, and then the load is removed at a speed of 80 nm/sec.
  • the calculation method of the hardness and composite modulus is to test fused quartz as a standard sample in advance, and calibrate the relationship between the contact depth and the contact projected area of the indenter and the sample. Thereafter, the unloading curve in the region of 60 to 95% of the maximum load at the time of unloading is analyzed by the Oliver-Pharr method, and the hardness and composite elastic modulus are calculated.
  • the hardness of the anchor coat layer 2 and the overcoat layer 4 measured by nanoindentation at a cross section in the thickness direction of the laminate 10 may be 0.3 GPa or less. This reduces the direct transmission of deformation stress of the paper base material caused by bending of the laminate to the aluminum vapor deposition layer, preventing defects from occurring in the aluminum vapor deposition layer, thereby suppressing deterioration of the gas barrier properties and oil resistance after bending. From this perspective, the hardness of the anchor coat layer 2 and the overcoat layer 4 may be 0.25 GPa or less, or may be 0.2 GPa or less.
  • the lower limit of the hardness is not particularly limited, but from the perspective of obtaining sufficient strength to maintain gas barrier properties and oil resistance, it can be 0.05 MPa or more.
  • ⁇ Packaging bag> 2 is a perspective view showing a gusset bag 20 made of the laminate 10.
  • a packaging bag is manufactured by sealing the opening at the top of the gusset bag 20.
  • the gusset bag 20 has portions where the laminate 10 is folded (folded portions B1, B2).
  • the folded portion B1 is a portion where the laminate 10 is folded in a valley direction as viewed from the innermost layer side
  • the folded portion B2 is a portion where the laminate 10 is folded in a mountain direction as viewed from the innermost layer side.
  • the packaging bag may be made by folding one laminate in half so that the overcoat layers 4 face each other, then folding appropriately into the desired shape and heat sealing it to form a bag shape, or it may be made by stacking two laminates together so that the overcoat layers 4 face each other, and then heat sealing it to form a bag shape.
  • the heat seal strength may be 2N or more, or 4N or more.
  • the upper limit of the heat seal strength is not particularly limited, but may be, for example, 10N or less.
  • the packaging bag can contain food, medicine, and other contents. It is particularly suitable for containing food such as sweets.
  • the packaging bag according to this embodiment can maintain high gas barrier properties and oil resistance even when it has a shape with folded sections.
  • a gusset bag is given as an example of a packaging bag, but the laminate according to this embodiment may be used to produce, for example, a pillow bag, a three-sided sealed bag, or a standing pouch.
  • a bar coater onto the surface of the clay coat layer side of a paper substrate (thickness including the clay coat layer: 55 ⁇ m) having a 5 ⁇ m thick clay coat layer, and then dried in an oven to form an anchor coat layer with a thickness of 3 ⁇ m.
  • Al deposition layer (aluminum deposition layer) with a thickness of 50 nm.
  • the pressure in the deposition chamber during aluminum deposition was adjusted to the value shown in Table 1.
  • Example 2 A laminate was obtained in the same manner as in Example 1, except that the pressure in the deposition chamber when forming the Al deposition layer was changed to the value shown in Table 1.
  • Example 3 A laminate was obtained in the same manner as in Example 1, except that the paper substrate was changed to a paper substrate having a clay coating layer with a thickness of 5 ⁇ m (thickness including the clay coating layer: 50 ⁇ m).
  • Example 6 A laminate was obtained in the same manner as in Example 1, except that the pressure in the deposition chamber when forming the Al vapor deposition layer was changed to the value shown in Table 1, and the thickness of the Al vapor deposition layer was changed to the value shown in Table 1.
  • PVA polyvinyl alcohol
  • Example 9 A laminate was obtained in the same manner as in Example 8, except that the pressure in the deposition chamber when forming the Al deposition layer was changed to the value shown in Table 2.
  • Clay-coated paper 1 was prepared as the paper substrate.
  • an Al vapor deposition layer was formed on the anchor coat layer using a roll-to-roll induction heating vacuum deposition device.
  • the pressure in the deposition chamber during Al vapor deposition and the thickness of the Al vapor deposition layer were adjusted to the values shown in Table 3.
  • Example 11 A laminate was obtained in the same manner as in Example 10, except that the paper substrate was changed to clay-coated paper 2, and the pressure in the deposition chamber when forming the Al vapor deposition layer and the thickness of the Al vapor deposition layer were changed to the values shown in Table 3.
  • Example 12 A laminate was obtained in the same manner as in Example 10, except that the Al vapor-deposited layer was formed by the following method. That is, the Al vapor-deposited layer was formed on the anchor coat layer by a roll-to-roll EB heating type vacuum vapor deposition apparatus. The pressure in the vapor deposition chamber during Al vapor deposition and the thickness of the Al vapor-deposited layer were adjusted to the values shown in Table 3.
  • Example 13 A laminate was obtained in the same manner as in Example 12, except that the paper substrate was changed to clay-coated paper 2.
  • Example 14 A laminate was obtained in the same manner as in Example 12, except that the paper substrate was changed to clay-coated paper 3.
  • Clay-coated paper 2 was prepared as the paper substrate.
  • an Al vapor deposition layer was formed on the anchor coat layer using a roll-to-roll EB heating vacuum deposition device.
  • the pressure in the deposition chamber during Al deposition and the thickness of the Al vapor deposition layer were adjusted to the values shown in Table 3.
  • Example 16 A laminate was obtained in the same manner as in Example 15, except that the paper substrate was changed to clay-coated paper 1, and the pressure in the deposition chamber when forming the Al vapor deposition layer and the thickness of the Al vapor deposition layer were changed to the values shown in Table 3.
  • polyvinyl alcohol manufactured by Kuraray Co., Ltd., product name: Poval 5-98
  • an Al vapor deposition layer was formed on the anchor coat layer using a roll-to-roll EB heating vacuum deposition device.
  • the pressure in the deposition chamber during Al deposition and the thickness of the Al vapor deposition layer were adjusted to the values shown in Table 4.
  • an aqueous dispersion of ethylene-acrylic acid copolymer resin (manufactured by MICHELMAN, product name: MC9100, solids concentration: 20% by mass) was applied onto the Al vapor deposition layer using a gravure coater and dried in an oven to form an overcoat layer with a thickness of 3 ⁇ m. This resulted in a laminate.
  • the half-width of the peak of the (111) crystal plane of aluminum in the Al vapor deposition layer was measured by the following procedure.
  • an X-ray diffraction apparatus product name: ATX-G manufactured by Rigaku Electric Co., Ltd. was used.
  • CuK ⁇ rays were used as the light source, the tube voltage was 50 kV, the tube current was 300 mA, the optical system was a parallel beam optical system, the scanning method was the 2 ⁇ / ⁇ method, the measurement range was 30° to 50°, and the scanning speed was 2°/min.
  • the sampling step was 0.02°, and the slits were S1: 10.0 mm x 1.0 mm, S2: 10.0 mm x 0.5 mm, and Solar (res): 0.4 mm.
  • the laminates obtained in the examples and comparative examples were used as samples, and the paper substrate side was attached to a slide glass with double-sided tape to perform X-ray diffraction measurement.
  • Samples for measuring the hardness and composite modulus of the anchor coat layer and the overcoat layer from the cross-section of the laminate obtained in the examples and comparative examples were prepared by the following procedure. First, the laminate was cut with a razor so that the sample including the anchor coat layer and the overcoat layer was in a rectangular or wedge shape, and the obtained sample was embedded in resin. D-800 photocurable resin manufactured by Toa Gosei Co., Ltd. was used as the embedding resin, and the sample was hardened by light irradiation after embedding.
  • the hardened sample embedding resin was fixed with an insert for an AFM sample holder, trimming and cross-section cutting of the film were performed with a glass knife at room temperature (25°C), and cross-section cutting was performed with a diamond knife at a cutting speed of 1.0 mm/sec and a cutting film thickness of 200 nm until a mirror surface was obtained.
  • the cross-sectioned sample was used for measurement by the nanoindentation method while being fixed with an insert for an AFM sample holder.
  • An ultramicrotome EMUC7 manufactured by Leica was used as the cross-section cutting device. The cutting direction was parallel to the layer interface.
  • the hardness and composite modulus of the anchor coat layer and the overcoat layer represent the hardness and composite modulus calculated by the nanoindentation method.
  • the nanoindentation method is a measurement method in which a quasi-static indentation test is performed on a target measurement object to obtain the mechanical properties of the sample.
  • the measurement device used was a Hysitron TI-Premier (trade name) manufactured by Bruker Japan Co., Ltd.
  • the indenter used was a Berkovich-type diamond indenter manufactured by Bruker Japan Co., Ltd.
  • the diamond indenter was used to scan the cross section of the sample to obtain a shape image of the sample, and the measurement position of the desired layer was specified. Then, at room temperature (25°C), in the displacement control mode, the indentation was performed to a depth of 80 nm at a indentation speed of 80 nm/sec, and then the maximum depth was held for 1 second, and then the load was removed at a speed of 80 nm/sec.
  • the calculation method of the hardness and composite modulus was performed by testing fused quartz as a standard sample in advance, and calibrating the relationship between the contact depth and the contact projected area of the indenter and the sample. The unloading curve in the range of 60 to 95% of the maximum load at the time of unloading was then analyzed by the Oliver-Pharr method to calculate the hardness and composite elastic modulus. The results are shown in Tables 1 to 4.
  • the elongation at break of the anchor coat layer and the overcoat layer was measured by coating a coating liquid for forming the anchor coat layer and the overcoat layer on a supporting substrate, drying the coated substrate, peeling the coated substrate from the supporting substrate, punching out a 1A-type dumbbell-shaped specimen, and measuring the elongation at break according to the method described in JIS K7161.
  • An autograph tester AGS-X manufactured by Shimadzu Corporation was used as the device, and the measurement was performed at a tensile test speed of 50 mm/min in an environment of a temperature of 20°C and a humidity of 65%. The results are shown in Tables 1 to 4.
  • the oil resistance (KIT value) of the surface of the overcoat layer side of the laminate obtained in the examples and comparative examples was measured by the TAPPI UM-557 method (KIT method).
  • KIT method TAPPI UM-557 method
  • a 1500g roller was rolled at a speed of 300mm/min, and the laminate was folded parallel to the MD direction so that the laminate was valley-folded (so that the overcoat layer was on the outer surface) when viewed from the paper substrate side, and the oil resistance (KIT value) of the folded part of the laminate after opening was also measured in the same manner.
  • the KIT value is expressed as grades 0 to 12, and the higher the number, the higher the oil resistance.
  • the highest oil resistance given by the KIT test liquid that does not show penetration was used as the evaluation result.
  • the KIT value is preferably 6 or more, and if it is less than 6, the oil resistance for food packaging may not be sufficient. The results are shown in Tables 1 to 4.
  • the water vapor permeability (g/ m2 /day) of the laminates obtained in the examples and comparative examples in an atmosphere of 40°C and 90% RH was measured by the Mocon method in accordance with JIS K7129-2.
  • a water vapor permeability measuring device manufactured by MOCON, product name: PERMATRAN-W3/34G was used for the measurement.
  • the laminates were stored in a thermo-hygrostat at 40°C and 90% RH for one week, and then similar measurements were performed.
  • the water vapor permeability at the initial stage and after storage at 40°C and 90% RH are shown in Tables 1 to 4.
  • the laminates of the examples had good oil resistance (KIT value) not only initially but also after bending. Furthermore, as shown in Tables 1 to 4, the laminates of the examples had water vapor permeability of 6 g/m 2 /d or less even after storage at 40°C and 90% RH for one week, confirming that they could maintain good water vapor barrier properties.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
PCT/JP2023/037251 2022-10-19 2023-10-13 積層体及び包装袋 Ceased WO2024085092A1 (ja)

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EP23879735.1A EP4596238A4 (en) 2022-10-19 2023-10-13 MULTI-LAYER BODY AND PACKAGING BAG
AU2023363440A AU2023363440B2 (en) 2022-10-19 2023-10-13 Multilayer body and packaging bag
CN202380072124.8A CN120035516A (zh) 2022-10-19 2023-10-13 层叠体及包装袋
JP2024506666A JP7537644B1 (ja) 2022-10-19 2023-10-13 積層体及び包装袋
JP2024130686A JP7848835B2 (ja) 2022-10-19 2024-08-07 積層体

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024144753A (ja) * 2022-10-19 2024-10-11 Ｔｏｐｐａｎホールディングス株式会社 積層体
WO2025244037A1 (ja) * 2024-05-22 2025-11-27 Ｔｏｐｐａｎホールディングス株式会社 防湿化粧紙

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2025103175A (ja) * 2023-12-27 2025-07-09 株式会社Ｎｂｃメッシュテック 繊維集合体

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003291296A (ja) * 2002-04-04 2003-10-14 Ishida Co Ltd 積層材料
JP2004204366A (ja) * 2002-12-24 2004-07-22 Toppan Printing Co Ltd 防湿紙およびそれを用いた包装紙、包装袋または紙製容器。
JP2005187969A (ja) * 2003-12-25 2005-07-14 Toppan Printing Co Ltd 電磁波シールド紙およびそれを用いた紙製包装材、紙容器用積層材
JP2020069783A (ja) 2018-10-26 2020-05-07 王子ホールディングス株式会社 ガスバリア性積層体
WO2022009610A1 (ja) * 2020-07-09 2022-01-13 凸版印刷株式会社 ガスバリア積層体及び包装袋
WO2022202168A1 (ja) * 2021-03-22 2022-09-29 凸版印刷株式会社 ガスバリア積層体及びそれを備える包装材

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62101428A (ja) * 1985-10-29 1987-05-11 東洋メタライジング株式会社 包装用フイルム
JP4060935B2 (ja) * 1998-03-31 2008-03-12 大日本印刷株式会社 ガスバリア性フィルムおよびその製造法
JP7124344B2 (ja) * 2018-03-05 2022-08-24 大日本印刷株式会社 ガスバリアフィルム
JP6944022B1 (ja) * 2020-07-09 2021-10-06 凸版印刷株式会社 ガスバリア積層体及び包装袋
CN120035516A (zh) * 2022-10-19 2025-05-23 凸版控股株式会社 层叠体及包装袋

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003291296A (ja) * 2002-04-04 2003-10-14 Ishida Co Ltd 積層材料
JP2004204366A (ja) * 2002-12-24 2004-07-22 Toppan Printing Co Ltd 防湿紙およびそれを用いた包装紙、包装袋または紙製容器。
JP2005187969A (ja) * 2003-12-25 2005-07-14 Toppan Printing Co Ltd 電磁波シールド紙およびそれを用いた紙製包装材、紙容器用積層材
JP2020069783A (ja) 2018-10-26 2020-05-07 王子ホールディングス株式会社 ガスバリア性積層体
WO2022009610A1 (ja) * 2020-07-09 2022-01-13 凸版印刷株式会社 ガスバリア積層体及び包装袋
WO2022202168A1 (ja) * 2021-03-22 2022-09-29 凸版印刷株式会社 ガスバリア積層体及びそれを備える包装材

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4596238A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024144753A (ja) * 2022-10-19 2024-10-11 Ｔｏｐｐａｎホールディングス株式会社 積層体
JP7848835B2 (ja) 2022-10-19 2026-04-21 Ｔｏｐｐａｎホールディングス株式会社 積層体
WO2025244037A1 (ja) * 2024-05-22 2025-11-27 Ｔｏｐｐａｎホールディングス株式会社 防湿化粧紙

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JP7848835B2 (ja) 2026-04-21
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