WO2024177084A1 - 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
WO2024177084A1
WO2024177084A1 PCT/JP2024/006126 JP2024006126W WO2024177084A1 WO 2024177084 A1 WO2024177084 A1 WO 2024177084A1 JP 2024006126 W JP2024006126 W JP 2024006126W WO 2024177084 A1 WO2024177084 A1 WO 2024177084A1
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WIPO (PCT)
Prior art keywords
resin layer
laminate
layer
group
less
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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.)
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PCT/JP2024/006126
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English (en)
French (fr)
Japanese (ja)
Inventor
純一 神永
良樹 越山
裕美子 小島
里佳 石井
寛之 若林
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Toppan Holdings Inc
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Toppan Holdings Inc
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Priority to EP24760382.2A priority Critical patent/EP4670966A1/en
Priority to JP2025502756A priority patent/JPWO2024177084A1/ja
Publication of WO2024177084A1 publication Critical patent/WO2024177084A1/ja
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
    • B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
    • B65D31/02—Bags or like containers made of paper and having structural provision for thickness of contents with laminated walls
    • 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
    • B32B27/32—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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • 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
    • B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
    • B65D31/10—Bags or like containers made of paper and having structural provision for thickness of contents with gusseted sides

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 deterioration of the contents.
  • Patent Document 1 discloses a base paper for metallized paper, which has a specific clay coat layer and a resin layer in that order on at least one side of a specific paper substrate, for forming a metallized layer by metallization.
  • the inventors have investigated various laminates that have a paper base material, a first resin layer, an aluminum vapor deposition layer, and a second resin layer as laminates with excellent environmental compatibility. They have found that such laminates have high water vapor permeability and are unstable.
  • the present disclosure provides a laminate with high and stable water vapor barrier properties and a packaging bag using the same.
  • the first resin layer contains at least one selected from the group consisting of polyolefins having an acidic group, polyvinyl alcohol-based resins, and polyurethane-based resins.
  • the first resin layer contains a polyolefin having an acidic group
  • the laminate according to any one of [1] to [5], wherein in an IR spectrum of the first resin layer, a ratio of an area of a peak between 1490 and 1620 cm ⁇ 1 attributable to a salt of a carboxy group to an area of a peak between 1620 and 1770 cm ⁇ 1 attributable to a carboxy group is 0.1 or less.
  • the inventors speculate as follows why conventional laminates have high and unstable water vapor permeability and why the laminate according to the present disclosure has high and stable water vapor barrier properties.
  • the second resin layer is formed, for example, by wet-coating a mixture of resin and solvent on the aluminum vapor deposition layer to form a coating film, and then drying the coating film.
  • the solvent evaporates and the film formation of the second resin layer progresses.
  • the solvent contained in the second resin layer may bump.
  • such bumping of the solvent may cause micro-sized defects, as shown in the examples described below.
  • similar defects may occur in the second resin layer when the coating film for forming the second resin layer is dried, depending on the difference in thermal shrinkage behavior between the paper base material and the second resin layer. These defects that occur in the second resin layer may reach the aluminum vapor deposition layer, as shown in the examples described below.
  • Such defects in the aluminum vapor deposition layer are a factor that causes the water vapor barrier property to become unstable.
  • the laminate has high and stable water vapor barrier properties.
  • the laminate when the laminate is made into a bag to produce a packaging bag, vertical wrinkles may occur at the folded section, and defects in sealing and cutting may occur.
  • the thickness of the aluminum vapor deposition layer less than 100 nm, the occurrence of vertical wrinkles and defects in sealing and cutting is suppressed. This makes it possible to increase the bag production speed.
  • the present disclosure provides a laminate with high and stable water vapor barrier properties and a packaging bag using the same.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to an embodiment of the present disclosure.
  • FIG. 2 is a perspective view showing a packaging bag according to one embodiment of the present disclosure.
  • Fig. 3(a) is a graph showing the distribution of water vapor transmission rate data for the gas barrier laminates of Examples 1 and 2 and Comparative Examples 1, 2 and 7.
  • Fig. 3(b) is a graph showing the distribution of water vapor transmission rate data for the gas barrier laminates of Examples 3 to 5 and Comparative Examples 3 and 4.
  • Fig. 3(c) is a graph showing the distribution of water vapor transmission rate data for the gas barrier laminates of Examples 6 to 8 and Comparative Examples 5 and 6.
  • Fig. 4(a) is an observation image of the gas barrier laminate of Comparative Example 2.
  • Fig. 3(a) is a graph showing the distribution of water vapor transmission rate data for the gas barrier laminates of Examples 1 and 2 and Comparative Examples 1, 2 and 7.
  • Fig. 3(b) is a graph showing the distribution
  • FIG. 4(b) is an observation image of the gas barrier laminate of Comparative Example 1.
  • Fig. 4(c) is an observation image of the gas barrier laminate of Example 1.
  • Fig. 4(d) is an observation image of the gas barrier laminate of Example 2.
  • Fig. 4(e) is an observation image of the gas barrier laminate of Comparative Example 7.
  • Fig. 5(a) is an observation image of the gas barrier laminate A.
  • Fig. 5(b) is an observation image of the gas barrier laminate B.
  • Fig. 5(c) is an observation image of the gas barrier laminate C.
  • the laminate of this embodiment is a laminate having a structure in which at least a paper base material, a first resin layer, an aluminum vapor deposition layer, and a second resin layer are laminated in this order, and the thickness of the aluminum vapor deposition layer is 60 nm or more and less than 100 nm.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to one embodiment.
  • the laminate 10 according to one embodiment includes a paper base material 3, a first resin layer 1, an aluminum vapor deposition layer 4, and a second resin layer 2, in this order.
  • the thickness of the laminate 10 may be 20 to 100 ⁇ m, 30 to 80 ⁇ m, or 40 to 60 ⁇ m. When the thickness of the laminate 10 is within the above range, the laminate 10 can more stably obtain higher water vapor barrier properties.
  • the water vapor permeability of the gas barrier laminate 10 at a temperature of 40° C. and a relative humidity of 90% may be 5 g/( m2 ⁇ day) or less, 4 g/( m2 ⁇ day) or less, 3 g/( m2 ⁇ day) or less, 2 g/( m2 ⁇ day) or less, or 1 g/( m2 ⁇ day) or less.
  • the water vapor permeability refers to a value measured by the method in the examples described later.
  • the paper base material 3 may be paper whose main component is plant-derived pulp. Specific examples of the paper base material 3 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 3 may be 20 to 500 g/m 2 or 30 to 100 g/m 2 .
  • the paper base material 3 may have a coating layer at least on the side of the paper base material 3 that contacts the first resin layer 1.
  • the paper base material 3 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 3.
  • 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 rate of change in the cross direction (CD) dimensions of the paper base material 3 in a 40°C, 90% RH environment relative to the dimensions in a 40°C, 20% RH environment may be 0.3% or more, 0.4% or more, or 0.6% or more, and may be 1.5% or less, 1.3% or less, or 1.0% or less.
  • the rate of change in the machine direction (MD) dimensions of the paper base material 3 in a 40°C, 90% RH environment relative to the dimensions in a 40°C, 20% RH environment may be 0.05% or more, and 0.20% or less.
  • 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 3 may be 20 to 100 ⁇ m, 30 to 80 ⁇ m, or 40 to 60 ⁇ m. When the thickness of the paper base material 3 is within the above range, the laminate 10 can more stably obtain higher water vapor barrier properties.
  • the ratio of the thickness of the coating layer to the thickness of the paper base material 3 may be 3-25%, or 5-20%. If this ratio is within the above range, the laminate 10 can more stably obtain higher water vapor barrier properties.
  • 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 first resin layer 1 is provided on the surface of the paper substrate 3 to improve adhesion between the paper substrate 3 and the aluminum vapor deposition layer 4 described later, and to improve the gas barrier properties of the laminate.
  • the first resin layer 1 may contain at least one selected from the group consisting of polyolefins having acidic groups, polyvinyl alcohol-based resins, and polyurethane-based resins. From the viewpoint of being able to more stably obtain higher water vapor barrier properties, the first resin layer 1 is preferably a polyolefin having acidic groups and a polyurethane-based resin, and more preferably a polyolefin having acidic groups.
  • the first resin layer 1 contains a polyolefin having acidic groups
  • the first resin layer 1 has excellent flexibility, and can suppress cracking of the aluminum vapor deposition layer 4 described below after bending (folding), and can improve adhesion between the first resin layer 1 and the aluminum vapor deposition layer 4.
  • a polyolefin having acidic groups it is possible to form a dense film due to the crystallinity of the polyolefin, and water vapor barrier properties are expressed.
  • the crystallinity of the polyolefin results in water vapor barrier properties, and the presence of acidic groups results in adhesion with the aluminum vapor deposition layer 4.
  • the polyolefin having an acidic 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 acidic groups copolymers of ethylene or propylene with unsaturated carboxylic acids (unsaturated compounds having carboxyl groups such as acrylic acid, methacrylic acid, maleic anhydride, etc.), unsaturated carboxylic acid esters, and salts of carboxylic acids neutralized with basic compounds may be used, as well as copolymers with vinyl acetate, epoxy compounds, chlorine compounds, urethane compounds, polyamide compounds, etc. It is preferable that the first resin layer 1 contains an ethylene-unsaturated carboxylic acid copolymer, as this provides a more stable water vapor barrier property.
  • unsaturated carboxylic acids unsaturated compounds having carboxyl groups such as acrylic acid, methacrylic acid, maleic anhydride, etc.
  • unsaturated carboxylic acid esters unsaturated carboxylic acid esters
  • salts of carboxylic acids neutralized with basic compounds may be used, as well as copolymers with vinyl acetate, epoxy compounds, chlorine compounds,
  • polyolefins having acidic groups include copolymers of acrylic acid esters and maleic anhydride, ethylene-vinyl acetate copolymers, and ethylene-glycidyl methacrylate copolymers.
  • a resin in which the acidic group is neutralized with ammonia e.g., ZAIKXEN AC manufactured by Sumitomo Seika Chemicals
  • ionomer resins in which the acidic group is neutralized with sodium hydroxide or potassium hydroxide e.g., Chemipearl series manufactured by Mitsui Chemicals.
  • the amount of remaining metal ions can be confirmed by the IR spectrum of the first resin.
  • the ratio (A COOX /A COOH ) of the area of the peak derived from the carboxyl group to the area of the peak derived from the carboxyl group salt (A COOX ) is 0.1 or less, it is possible to suppress pitting corrosion of the aluminum vapor deposition layer even when the laminate is stored for a long period of time.
  • a peak derived from a carboxy group appears near 1700 cm -1
  • a peak derived from a salt of a carboxy group appears generally between 1490 and 1620 cm -1 , depending on the type of salt.
  • peaks derived from a sodium salt of a carboxy group and a potassium salt of a carboxy group appear near 1540 cm -1
  • a peak derived from an ammonium salt of a carboxy group appears near 1520 cm -1 .
  • the polyvinyl alcohol-based resin When the first resin layer 1 contains a polyvinyl alcohol-based resin, the polyvinyl alcohol-based resin has hydroxyl groups, which easily bond with metals such as aluminum in the aluminum vapor-deposited layer 4, making it easier to improve the adhesion between the aluminum vapor-deposited layer 4 and the first resin layer 1. In addition, such a first resin layer 1 has excellent flexibility and can suppress cracking of the aluminum vapor-deposited layer 4 after bending (folding). Furthermore, the first resin layer 1 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.
  • Polyurethane resins are obtained by bonding the acid groups of acid group-containing polyurethane with the amino groups of polyamines acting as crosslinkers.
  • polyurethane resins can be said to be a reaction product of acid group-containing polyurethane and polyamine, or to be formed by crosslinking acid group-containing polyurethane with polyamine.
  • the bond between the acid groups of the acid group-containing polyurethane and the amino groups of the polyamine 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, etc.).
  • 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 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 first resin layer 1 tend to be good.
  • the sum of the urethane group concentration and the urea group concentration is equal to or less than the upper limit value of the above range, it tends to prevent the first resin layer 1 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).
  • polyurethane-based resins can contain aromatic rings, and therefore the constituent units of the acid group-containing polyurethane may contain aromatic hydrocarbon rings as the hydrocarbon rings.
  • 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 may be 15 to 65% by mass, or may be 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 first resin layer 1 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 first resin layer 1 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. When the number average molecular weight of the acid group-containing polyurethane is equal to or less than the upper limit of the above range, the coating agent is likely to have an appropriate viscosity. When 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 first resin layer 1 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 first resin layer 1 tends 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 such basic nitrogen atoms 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 first resin layer 1 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 groups/basic nitrogen atoms ratio is within the above range, the first resin layer 1 is likely to exhibit excellent oxygen barrier properties.
  • polyurethane resin a commercially available polyurethane resin may be used, or a polyurethane resin produced by a known production method may be used.
  • 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 first resin layer 1 may contain other components in addition to the polyolefin having an acidic group, the polyvinyl alcohol-based resin, and the polyurethane-based resin.
  • other components include polyolefins other than the polyolefins having an acidic group, silane coupling agents, organic titanates, polyacrylics, polyesters, polyurethanes, polycarbonates, polyureas, polyamides, polyimides, melamine, phenols, etc.
  • the content of at least one resin selected from the group consisting of polyolefins having acidic groups, polyvinyl alcohol-based resins, and polyurethane-based resins in the first resin layer 1 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 first resin layer 1 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 first resin layer 1 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 first resin layer 1 is 20 ⁇ m or less, the aluminum vapor deposition layer can be laminated evenly while keeping costs down.
  • Solvents contained in the coating liquid for the first resin layer 1 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 first resin layer 1 can be provided by applying a coating liquid containing the above-mentioned polyolefin having acidic groups, polyvinyl alcohol-based resin, or polyurethane-based resin, and a solvent, etc., onto the paper substrate 3 to form a coating film, and then drying the coating film.
  • the aluminum vapor-deposited layer 4 is a layer obtained by vapor-depositing aluminum or an aluminum compound.
  • the aluminum vapor-deposited layer 4 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 4 is 60 nm or more, and may be more than 60 nm, 65 nm or more, 67 nm or more, 70 nm or more, more than 70 nm, 75 nm or more, 80 nm or more, 85 nm or more, or 90 nm or more.
  • the thickness of the aluminum vapor deposition layer 4 is less than 100 nm, and may be 95 nm or less, 90 nm or less, or 85 nm or less.
  • the thickness of the aluminum vapor deposition layer 4 may be 60 nm or more and less than 100 nm, 60 nm or more and 95 nm or less, 65 nm or more and 90 nm or less, 67 nm or more and 85 nm or less, 65 nm or more and 95 nm or less, 70 nm or more and 95 nm or less, 75 nm or more and 95 nm or less, 80 nm or more and 95 nm or less, or 85 nm or more and 95 nm or less.
  • the thickness of the aluminum vapor deposition layer 4 is measured by the method of the examples described later.
  • the second resin layer 2 is provided on the surface of the aluminum vapor-deposited layer 4 so as to be in contact with the aluminum vapor-deposited layer 4.
  • the second resin layer 2 may contain a polyolefin having an acidic group.
  • the polyolefin having an acidic 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 acidic 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 acidic groups include copolymers of acrylic acid esters and maleic anhydride, ethylene-unsaturated carboxylic acid copolymers, ethylene-vinyl acetate copolymers, and ethylene-glycidyl methacrylate copolymers.
  • the second resin layer 2 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 acidic groups, a dense film can be formed due to the crystallinity of the polyolefin, and water vapor barrier properties are expressed. Furthermore, by including acidic groups, adhesion to the aluminum vapor deposition layer is expressed. Furthermore, since the second resin layer 2 includes polyolefin having the above-mentioned acidic groups, it can also serve as a heat seal layer, so there is no need to provide a separate heat seal layer.
  • the second resin layer 2 preferably contains an ethylene-unsaturated carboxylic acid copolymer, as this provides a more stable water vapor barrier property.
  • the second resin layer 2 may contain other components in addition to the polyolefin having the acidic group.
  • other components include silane coupling agents, organic titanates, polyacrylics, polyesters, polyurethanes, polycarbonates, polyureas, polyamides, polyolefin-based emulsions, polyimides, melamines, and phenols.
  • the content of the polyolefin having an acidic group in the second resin 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 second resin layer adjacent to the aluminum vapor deposition layer contains metal ions such as sodium or potassium, when the laminate is stored for a long period of time, the metal ions may corrode the aluminum, causing pinhole defects in the aluminum vapor deposition layer, as in the case of the first resin layer.
  • metal ions such as sodium or potassium
  • the metal ions may corrode the aluminum, causing pinhole defects in the aluminum vapor deposition layer, as in the case of the first resin layer.
  • a polyolefin having acidic groups is used for the second resin layer, it is preferable to use a resin in which the acidic groups have been neutralized with ammonia, which evaporates during the drying process and does not remain in the dried film, as in the case of the first resin layer (for example, ZAIXXEN AC manufactured by Sumitomo Seika Chemicals).
  • the amount of remaining metal ions can be confirmed by the IR spectrum of the second resin layer, as in the first resin layer.
  • the ratio (A COOX /A COOH ) of the area of the peak derived from the carboxyl group to the area of the peak derived from the carboxyl group salt (A COOX ) to be 0.1 or less, it is possible to suppress pitting corrosion of the aluminum vapor deposition layer even when the laminate is stored for a long period of time.
  • the thickness of the second resin layer 2 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 second resin layer 2 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 second resin layer 2 is 20 ⁇ m or less, it can fully fulfill the adhesion and barrier properties with the aluminum vapor deposition layer while keeping costs down. Furthermore, by setting the thickness of the second resin layer 2 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.
  • Solvents contained in the coating liquid for the second resin 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 second resin layer 2 can be provided by applying a coating liquid containing the above-mentioned polyolefin having acidic groups and a solvent on the aluminum vapor deposition layer to form a coating film, and then drying the coating film.
  • the melting point of the polyolefin having acidic 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 acidic groups is 160°C or less, the start-up temperature during heat sealing tends to be lower. If the melting point of the polyolefin having acidic groups is 70°C or more, blocking tends to be less likely to occur in a high-temperature environment.
  • the particle size is preferably large so that the contact area is small.
  • 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.
  • ⁇ 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 second resin layers 2 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 so that the second resin layers 2 face each other, and then heat sealing them 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 has a highly stable water vapor barrier property even though it uses a paper base material.
  • 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.
  • Clay-coated papers 1 to 3 were prepared as paper substrates.
  • Example 1 Clay-coated paper 1 was used as the paper substrate. On the surface (on the clay-coated layer) of the paper substrate, ZAIKXEN AC (manufactured by Sumitomo Seika Chemicals, aqueous dispersion of ammonium salt of ethylene-acrylic acid copolymer) was applied by a gravure coater to form a coating film. The coating film was dried to obtain a first laminate in which a first resin layer (thickness: 3 ⁇ m, A COOX /A COOH : 0.03) was formed on the clay-coated layer.
  • ZAIKXEN AC manufactured by Sumitomo Seika Chemicals, aqueous dispersion of ammonium salt of ethylene-acrylic acid copolymer
  • Aluminum was deposited on the surface of the first resin layer while conveying the first laminate by a roll-to-roll type vacuum deposition device to form an aluminum deposition layer (thickness: 66 nm).
  • the method for measuring the thickness of the deposition layer will be described later.
  • Chemipearl S100 manufactured by Mitsui Chemicals, aqueous dispersion of metal salt of ethylene-unsaturated carboxylic acid copolymer
  • a COOX /A COOH was calculated by the following measurement method.
  • IR spectrum of the first resin layer and the second resin layer of the obtained gas barrier laminate was measured using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, product name: Frontier).
  • the peak area between 1620 and 1770 cm -1 was determined as the area of the peak derived from the carboxyl group (A COOH ).
  • the peak area between 1490 and 1620 cm -1 was determined as the area of the peak derived from the carboxyl group salt (A COOX ). From these results, the ratio of the area of the peak derived from the salt of the carboxy group to the area of the peak derived from the carboxy group (A COOX /A COOH ) was calculated.
  • Example 2 Comparative Examples 7 and 8
  • a gas barrier laminate was obtained in the same manner as in Example 1, except that an aluminum vapor-deposited layer having the thickness shown in Tables 1 and 2 was formed by slowing down the conveying speed of the first laminate when vapor-depositing aluminum.
  • Example 2 A gas barrier laminate was obtained in the same manner as in Example 1, except that an aluminum vapor-deposited layer having the thickness shown in Table 2 was formed by increasing the conveying speed of the first laminate when vapor-depositing aluminum.
  • Example 3 Clay-coated paper 2 was used as the paper substrate.
  • An aqueous solution of Poval 5-98 made by Kuraray, fully saponified PVA was applied to the surface of the paper substrate (on the clay coat layer) with a gravure coater to form a coating film.
  • the coating film was dried to obtain a first laminate in which a first resin layer (thickness: 4 ⁇ m) was formed on the clay coat layer.
  • Aluminum was deposited on the surface of the first resin layer while the first laminate was being conveyed with a roll-to-roll type vacuum deposition device to form an aluminum deposition layer (thickness: 61 nm).
  • Chemipearl S500 (made by Mitsui Chemicals, emulsion of acid-modified polyolefin) was applied to the aluminum deposition layer with a gravure coater to form a coating film, and the coating film was dried to form a second resin layer (thickness: 3 ⁇ m, A COOX /A COOH : 1.25), thereby obtaining a gas barrier laminate.
  • Example 4 A gas barrier laminate was obtained in the same manner as in Example 3, except that an aluminum vapor-deposited layer having the thickness shown in Table 1 was formed by slowing down the conveying speed of the first laminate when vapor-depositing aluminum.
  • Example 3 A gas barrier laminate was obtained in the same manner as in Example 3, except that an aluminum vapor-deposited layer having the thickness shown in Table 2 was formed by increasing the conveying speed of the first laminate when vapor-depositing aluminum.
  • Clay-coated paper 2 was used as the paper substrate.
  • Takelac WPB-341 Mitsubishi Chemicals, polyurethane resin emulsion
  • the coating was dried to obtain a first laminate in which a first resin layer (thickness: 1 ⁇ m) was formed on the clay coat layer.
  • Aluminum was deposited on the surface of the first resin layer while the first laminate was being conveyed by a roll-to-roll vacuum deposition device to form an aluminum deposition layer (thickness: 68 nm).
  • ZAIKXEN AC Suditomo Seika Chemicals, aqueous dispersion of ammonium salt of ethylene-acrylic acid copolymer
  • ZAIKXEN AC Suditomo Seika Chemicals, aqueous dispersion of ammonium salt of ethylene-acrylic acid copolymer
  • Example 7 A gas barrier laminate was obtained in the same manner as in Example 6, except that an aluminum vapor-deposited layer having the thickness shown in Table 1 was formed by slowing down the conveying speed of the first laminate when vapor-depositing aluminum.
  • Example 6 A gas barrier laminate was obtained in the same manner as in Example 6, except that an aluminum vapor-deposited layer having the thickness shown in Table 2 was formed by increasing the conveying speed of the first laminate when vapor-depositing aluminum.
  • Examples 1 to 8 and Comparative Examples 1 to 8 For the gas barrier laminates of the examples and comparative examples, the gas barrier laminates were cut into a total of nine regions, three rows along the TD (CD) and three rows along the MD, to obtain nine measurement samples. The film thickness and water vapor permeability of the aluminum deposition layer were measured using the measurement samples.
  • Figure 3(a) shows a graph representing the distribution of water vapor permeability data for the gas barrier laminates of Examples 1 and 2 and Comparative Examples 1, 2 and 7, with the film thickness of the aluminum vapor-deposited layer on the horizontal axis and the water vapor permeability (unit: g/( m2 ⁇ day)) on the vertical axis.
  • Graphs representing the distribution of water vapor permeability data for the gas barrier laminates of Examples 3 to 5 and Comparative Examples 3 and 4 are shown in Figure 3(b)
  • graphs representing the distribution of water vapor permeability data for the gas barrier laminates of Examples 6 to 8 and Comparative Examples 5 and 6 are shown in Figure 3(c).
  • FIG. 4(a) is an observation image of the gas barrier laminate of Comparative Example 2.
  • FIG. 4(b) is an observation image of the gas barrier laminate of Comparative Example 1.
  • FIG. 4(c) is an observation image of the gas barrier laminate of Example 1.
  • FIG. 4(d) is an observation image of the gas barrier laminate of Example 2.
  • 4(e) is an observation image of the gas barrier laminate of Comparative Example 7. It can be seen that in Examples 1 and 2 and Comparative Example 7, in which the thickness of the aluminum vapor deposition layer is 60 nm or more, the number of defects occurring along the MD is significantly reduced compared to Comparative Examples 1 and 2, in which the thickness of the aluminum vapor deposition layer is less than 60 nm.
  • a gas barrier laminate A was obtained in the same manner as in Example 3, except that clay-coated paper 3 was used as the paper substrate and the thickness of the aluminum vapor deposition layer was 36 nm.
  • a gas barrier laminate B was obtained in the same manner as in Example 3, except that clay-coated paper 3 was used as the paper substrate and the thickness of the aluminum vapor deposition layer was 52 nm.
  • a gas barrier laminate C was obtained in the same manner as in Example 3, except that clay-coated paper 3 was used as the paper substrate and the thickness of the aluminum vapor deposition layer was 62 nm. The gas barrier laminates A to C were observed for the presence or absence of defects.
  • FIG. 5(a) is an observation image of the gas barrier laminate A.
  • FIG. 5(b) is an observation image of the gas barrier laminate B.
  • FIG. 5(c) is an observation image of the gas barrier laminate C. It can be seen that gas barrier laminate C, in which the thickness of the aluminum vapor deposition layer is 60 nm or more, has fewer light transmitting defects and significantly fewer defects reaching the aluminum vapor deposition layer, compared to gas barrier laminates A and B, in which the thickness of the aluminum vapor deposition layer is less than 60 nm.
  • Comparative Examples 1 to 6 in which the thickness of the aluminum vapor deposition layer was less than 60 nm, the average water vapor permeability and standard deviation were large, and the water vapor barrier properties were not stable, whereas the gas barrier laminates of Examples 1 to 8 had an aluminum vapor deposition layer with a thickness of 60 nm or more, and thus consistently achieved excellent water vapor barrier properties.
  • Comparative Examples 7 and 8 where the thickness of the aluminum vapor deposition layer was 100 nm or more, vertical wrinkles occurred at the folded section, and sealing and cutting defects occurred, resulting in a low upper limit of the bag-making speed. Therefore, Comparative Examples 7 and 8 are not preferable in terms of productivity. On the other hand, in Examples 1 to 8, where the thickness of the aluminum vapor deposition layer was less than 100 nm, the occurrence of vertical wrinkles and sealing and cutting defects was suppressed, and the upper limit of the bag-making speed was high. Therefore, Examples 1 to 8 are excellent in productivity.

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PCT/JP2024/006126 2023-02-22 2024-02-20 積層体及び包装袋 Ceased WO2024177084A1 (ja)

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WO2020262619A1 (ja) * 2019-06-28 2020-12-30 株式会社カネカ 成形体およびその利用
JP6958755B1 (ja) 2020-12-28 2021-11-02 王子ホールディングス株式会社 蒸着紙用原紙および蒸着紙
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
WO2022009608A1 (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
JP2022084283A (ja) * 2020-11-26 2022-06-07 王子ホールディングス株式会社 紙積層体およびその製造方法
JP2022143095A (ja) * 2021-03-17 2022-10-03 三菱製紙株式会社 紙製包装材料

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WO2020262619A1 (ja) * 2019-06-28 2020-12-30 株式会社カネカ 成形体およびその利用
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
WO2022009608A1 (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
JP2022084283A (ja) * 2020-11-26 2022-06-07 王子ホールディングス株式会社 紙積層体およびその製造方法
JP6958755B1 (ja) 2020-12-28 2021-11-02 王子ホールディングス株式会社 蒸着紙用原紙および蒸着紙
JP2022143095A (ja) * 2021-03-17 2022-10-03 三菱製紙株式会社 紙製包装材料

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