WO2023176432A1 - Packaging material for aqueous content and packaging bag for aqueous content - Google Patents

Packaging material for aqueous content and packaging bag for aqueous content Download PDF

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Publication number
WO2023176432A1
WO2023176432A1 PCT/JP2023/007358 JP2023007358W WO2023176432A1 WO 2023176432 A1 WO2023176432 A1 WO 2023176432A1 JP 2023007358 W JP2023007358 W JP 2023007358W WO 2023176432 A1 WO2023176432 A1 WO 2023176432A1
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Prior art keywords
layer
packaging material
mass
thickness
anchor coat
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PCT/JP2023/007358
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French (fr)
Japanese (ja)
Inventor
里佳 石井
純一 神永
良樹 越山
裕美子 小島
寛之 若林
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凸版印刷株式会社
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Publication of WO2023176432A1 publication Critical patent/WO2023176432A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B15/085—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 comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present disclosure relates to a packaging material for aqueous contents and a packaging bag for aqueous contents.
  • Patent Document 1 listed below discloses a gas barrier laminate in which a barrier layer is laminated on paper.
  • Paper has the characteristic of being easy to process because it has crease retention properties (also referred to as dead-hold properties).
  • crease retention properties also referred to as dead-hold properties.
  • packaging bags with creases tend to have poor moisture barrier properties near the creases. Therefore, especially when packaging bags contain aqueous contents, there is a demand for improved moisture barrier properties after folding.
  • One aspect of the present disclosure has been made in view of the above circumstances, and provides a packaging material and packaging bag that reduces the amount of plastic material used and has excellent moisture barrier properties even after being folded.
  • the purpose is to
  • One aspect of the present disclosure is a packaging material including at least a gas barrier laminate in which a paper base material, an anchor coat layer, a vapor deposition layer, and an overcoat layer are laminated in this order, is 50% by mass or more based on the total mass of the gas barrier laminate, the vapor deposited layer contains a metal or a metal oxide, the overcoat layer contains a polyolefin having a carboxylic acid group, and the thickness of the overcoat layer Provided is a packaging material for aqueous contents having a diameter of more than 3 ⁇ m.
  • the anchor coat layer may contain a polyolefin having a carboxylic acid group.
  • the ratio of the thickness of the overcoat layer to the thickness of the anchor coat may be 1 to 20.
  • the above packaging material for water-based contents may further include a sealant layer on the side of the overcoat layer opposite to the vapor deposited layer.
  • Another aspect of the present disclosure provides a packaging bag for aqueous contents formed by bag-making the above-mentioned packaging material for aqueous contents.
  • a packaging material and a packaging bag that have excellent moisture barrier properties even after being folded, while reducing the amount of plastic material used.
  • FIG. 1 is a schematic cross-sectional view showing a packaging material according to an embodiment of the present disclosure.
  • FIG. 1 is a schematic cross-sectional view showing a packaging material 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.
  • FIG. 1 is a schematic cross-sectional view showing a packaging material according to one embodiment.
  • the packaging material 20 includes a gas barrier laminate 10 in which a paper base material 1, an anchor coat layer 2, a vapor deposition layer 3, and an overcoat layer 4 are laminated in this order.
  • the paper base material 1 is not particularly limited, and is appropriately selected depending on the use of the packaging bag to which the gas barrier laminate 10 is applied.
  • the paper base material 1 may be paper whose main component is pulp derived from plants. Specific examples of the paper base material 1 include wood-free paper, special wood-free paper, coated paper, art paper, cast-coated paper, imitation paper and kraft paper, and glassine paper.
  • the thickness of the paper base material 1 may be, for example, 20 to 500 g/m 2 or 30 to 100 g/m 2 .
  • the thickness of the paper base material 1 may be, for example, 20 to 100 ⁇ m or 30 to 70 ⁇ m.
  • the paper base material 1 may be provided with a coat layer (not shown) on the side in contact with the anchor coat layer 2 described below.
  • a coat layer (not shown) on the side in contact with the anchor coat layer 2 described below.
  • the coat layer plays the role of filling in the unevenness of the surface of the paper base material 1, and the anchor coat layer 2 is uniformly formed without defects. It can be formed into a film.
  • the coating layer includes, for example, various copolymers such as styrene/butadiene, styrene/acrylic, and ethylene/vinyl acetate as binder resin; polyvinyl alcohol resin, cellulose resin, paraffin (WAX), etc. Clay, kaolin, calcium carbonate, talc, mica, etc. may be included as fillers.
  • the thickness of the coating layer may be, for example, 1 to 10 ⁇ m or 3 to 8 ⁇ m.
  • the mass of the paper base material 1 is 50% by mass or more with respect to the total mass of the packaging material 20. If the mass of the paper base material 1 is 50 mass% or more with respect to the total mass of the packaging material 20, the amount of plastic material used can be sufficiently reduced. Such packaging material 20 has excellent recyclability.
  • the mass of the paper base material 1 may be 60 mass% or more, 70 mass% or more, or 75 mass% or more with respect to the total mass of the packaging material 20, from the viewpoint of further reducing the amount of plastic material used. .
  • the anchor coat layer 2 is a layer provided on the surface of the paper base material to improve the adhesion between the paper base material 1 and the vapor deposition layer 3 and to improve the moisture barrier properties of the gas barrier laminate 10. be.
  • the anchor coat layer 2 may contain a polyolefin having a carboxylic acid group (a group in which a hydrogen atom of a carboxyl group is substituted with a metal atom such as a sodium atom).
  • Such an anchor coat layer 2 has excellent flexibility and can suppress cracking of the vapor deposited layer after bending (bending), and can improve the adhesion between the anchor coat layer 2 and the vapor deposited layer 3. can.
  • the anchor coat layer 2 contains a polyolefin having a carboxylic acid group, and becomes a dense film due to the crystallinity of the polyolefin. Further, since the anchor coat layer 2 contains a polyolefin having a carboxylic acid group, the moisture barrier properties of the packaging material are further improved.
  • a polyolefin having a carboxylic acid group is a salt of a copolymer of an olefin such as ethylene or propylene and an unsaturated carboxylic acid (an unsaturated compound having a carboxyl group such as acrylic acid, methacrylic acid, or maleic anhydride). good.
  • the salt include sodium salt, potassium salt, and the like.
  • the anchor coat layer 2 includes, for example, a polyolefin other than the polyolefin having a carboxylic acid group, a silane coupling agent, an organic titanate, a polyacrylic, a polyester, a polyurethane, a polycarbonate, a polyurea, a polyamide, a polyimide. , melamine, phenol, etc.
  • the content of the polyolefin having a carboxylic acid group in the anchor coat layer 2 is 50% by mass or more, 60% by mass or more, 70% by mass or more based on the total mass of the anchor coat layer 2, from the viewpoint of improving the moisture barrier properties of the packaging material. It may be at least 80% by mass, at least 90% by mass, at least 95% by mass, or at least 100% by mass.
  • the thickness of the anchor coat layer 2 may be, for example, 1 ⁇ m or more, or 2 ⁇ m or more, or 20 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less.
  • the thickness of the anchor coat layer 2 is 1 ⁇ m or more, unevenness on the surface of the paper base material 1 can be easily filled, and the vapor deposition layer 3 can be uniformly laminated.
  • the thickness of the anchor coat layer 2 is 20 ⁇ m or less, the thickness of the anchor coat layer 2 does not become too thick, and the vapor deposited layer on the anchor coat layer 2 is less likely to crack due to bending.
  • the moisture barrier property is less likely to deteriorate after bending, it is possible to have excellent water resistance after bending and to uniformly stack the vapor deposited layer 3 while keeping costs down. Furthermore, since the thickness of the anchor coat layer is 20 ⁇ m or less, it prevents the coating amount of the coating liquid that forms the anchor coat layer 2 from becoming too large on the paper base material, resulting in excellent coating suitability. Problems such as deterioration of smoothness and generation of wrinkles on the base material can be suppressed. In addition, since the deterioration of the smoothness of the coated surface can be suppressed, the barrier properties may be lowered due to the vapor deposited layer 3 not being stacked uniformly, and the vapor deposited layer may become non-uniform. It is possible to suppress the occurrence of cracks, and the deterioration of the barrier properties after bending due to the generation of cracks.
  • Examples of the solvent contained in the coating liquid for anchor coat layer 2 include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, and 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.
  • the solvent contained in the coating liquid of the anchor coat layer 2 contains at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water. Good too.
  • the solvent contained in the coating liquid of the anchor coat layer 2 may contain at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, and water, from the viewpoint of reducing the load on the environment.
  • the anchor coat layer 2 can be laminated on the paper base material 1 by, for example, applying a coating liquid containing a polyolefin having a carboxylic acid group and a solvent onto the paper base material 1 and drying it.
  • the average particle size of the polyolefin having a carboxylic acid group in the coating solution is 1 ⁇ m or less, 0.7 ⁇ m or less, from the viewpoint of smoothing the coated surface after drying, uniformly laminating the vapor deposited layer 3, and improving barrier properties. Alternatively, it may be 0.5 ⁇ m or less.
  • the vapor deposited layer 3 is a layer in which metal or metal oxide is vapor deposited.
  • the vapor deposited layer 3 may be a layer in which aluminum is vapor deposited, or may contain aluminum oxide (AlO x ), silicon oxide (SiO x ), or the like.
  • the packaging material 20 has the vapor deposited layer 3, the packaging material 20 has excellent resistance not only to liquid water (moisture barrier properties) but also to water vapor (gas barrier properties).
  • the thickness of the vapor deposited layer 3 may be, for example, 10 to 300 nm or 30 to 100 nm. When the thickness of the vapor deposition layer 3 is 10 nm or more, the vapor deposition layer 3 can be easily formed uniformly. When the thickness of the vapor deposited layer 3 is 300 nm or less, curling of the vapor deposited layer 3 and generation of cracks in the vapor deposited layer 3 can be sufficiently suppressed, and the vapor deposited layer 3 has sufficient gas barrier performance and flexibility. easy to have.
  • the vapor deposition layer 3 can be formed by a vacuum evaporation method, a sputtering method, a chemical vapor deposition method (CVD method), or the like.
  • the vapor deposition layer 3 is preferably formed by vacuum film formation from the viewpoint of gas barrier properties and film uniformity.
  • the vapor deposition layer 3 may be formed by vacuum vapor deposition because the film formation rate is fast and productivity is high.
  • vacuum evaporation methods film formation by electron beam heating is preferable because the film formation rate can be easily controlled by the irradiation area, electron beam current, etc., and the temperature of the evaporation material can be raised and lowered in a short time.
  • the overcoat layer 4 is a layer provided on the surface of the vapor deposition layer 3 so as to be in contact with the vapor deposition layer 3, and contains a polyolefin having a carboxylic acid group. Since the overcoat layer 4 contains a polyolefin having a carboxylic acid group, the packaging material 20 has excellent moisture barrier properties even after being folded. Examples of the polyolefin having a carboxylic acid group include the polyolefin having a carboxylic acid group contained in the anchor coat layer 2 described above. The polyolefin having a carboxylic acid group contained in the overcoat layer 4 may be different from the polyolefin having a carboxylic acid group contained in the anchor coat layer 2, or may be the same from the viewpoint of ease of manufacture.
  • the overcoat layer 4 contains polyolefin having a carboxylic acid group, it has excellent flexibility and can suppress cracking of the vapor deposited layer 3 after bending (after bending). It is possible to improve the adhesion with. Since the overcoat layer 4 contains polyolefin having a carboxylic acid group, it becomes a dense film due to the crystallinity of the polyolefin. Further, since the overcoat layer 4 contains polyolefin having a carboxylic acid group, it can also serve as a heat-sealing layer, so that bags can be manufactured without providing a heat-sealing layer.
  • the overcoat layer 4 contains, for example, a coupling agent such as a silane coupling agent; polyacrylic, polyester, polyurethane, polycarbonate, polyurea, polyamide, polyolefin emulsion, polyimide, melamine, It may contain resin such as phenol; organic titanate, etc.
  • a coupling agent such as a silane coupling agent
  • the content of the polyolefin having a carboxylic acid group in the overcoat layer 4 is 50% by mass or more, 60% by mass or more, 70% by mass or more based on the total mass of the overcoat layer 4, from the viewpoint of improving the moisture barrier properties of the packaging material. It may be at least 80% by mass, at least 90% by mass, at least 95% by mass, or at least 100% by mass.
  • the thickness of the overcoat layer 4 is over 3 ⁇ m. Since the thickness of the overcoat layer 4 is more than 3 ⁇ m, the packaging material 20 has excellent moisture barrier properties even after being folded.
  • the thickness of the overcoat layer 4 may be 3.5 ⁇ m or more, 4 ⁇ m or more, 4.5 ⁇ m or more, or 5 ⁇ m or more. As the thickness of the overcoat layer 4 becomes thicker, the proportion of the paper base material decreases, and thus the recyclability decreases. Therefore, the thickness of the overcoat layer 4 is 20 ⁇ m or less, less than 20 ⁇ m, from the viewpoint of maintaining recyclability, suppressing costs, having excellent adhesion with the vapor deposited layer 3, and fully exhibiting moisture barrier properties.
  • the thickness of the overcoat layer 4 may be 10 ⁇ m or less, 8 ⁇ m or less, 6 ⁇ m or less, or 5 ⁇ m or less.
  • Examples of the solvent contained in the coating liquid for overcoat layer 4 include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, and 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.
  • the solvent contained in the coating liquid of the anchor coat layer 2 contains at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water. Good too.
  • the solvent contained in the coating liquid of the anchor coat layer 2 may contain at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, and water, from the viewpoint of reducing the load on the environment.
  • the overcoat layer 4 can be laminated on the vapor deposited layer 3 by, for example, applying a coating liquid containing a polyolefin having a carboxylic acid group and a solvent onto the vapor deposited layer 3 and drying the coating liquid.
  • the average particle size of the polyolefin having a carboxylic acid group in the coating liquid is 1 ⁇ m or less, 0.7 ⁇ m or less, or 0.7 ⁇ m or less, from the viewpoint of increasing the rising temperature during heat sealing and preventing blocking during transportation of the packaging material. It may be 5 ⁇ m or less.
  • the ratio of the thickness of overcoat layer 4 to the thickness of anchor coat layer 2 is 1 or more and 1.5 or more from the viewpoint of bending resistance. , or 1.8 or more. From the viewpoint of coatability and recyclability, the ratio of the thickness of the overcoat layer 4 to the thickness of the anchor coat layer 2 is 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 8 or less, 6 or less, It may be 5 or less, or 4 or less.
  • the total thickness of the anchor coat layer 2 and overcoat layer 4 is 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 25 ⁇ m or less, It is preferably 21 ⁇ m or less, 20 ⁇ m or less, 18 ⁇ m or less, 15 ⁇ m or less, or 12 ⁇ m or less.
  • FIG. 2 is a schematic cross-sectional view showing a packaging material according to another embodiment.
  • the packaging material 30 shown in FIG. 2 includes a gas barrier laminate 10 and a sealant layer 21 laminated on the gas barrier laminate 10, and the overcoat layer 4 of the gas barrier laminate 10 and the sealant layer 21 are bonded together as an adhesive layer It is bonded via 22.
  • the packaging material 30 includes the sealant layer 21 on the side of the overcoat layer 4 opposite to the vapor deposited layer 3.
  • the material of the sealant layer 21 may be polyolefin.
  • the material of the sealant layer 21 may be polypropylene similarly to the base material layer of the packaging material.
  • the sealant layer 21 may be, for example, a stretched or unstretched polypropylene film.
  • the thickness of the sealant layer 21 may be, for example, 15 ⁇ m or more, 200 ⁇ m or less, or 100 ⁇ m or less.
  • the adhesive layer 22 is for bonding the gas barrier laminate 10 and the sealant layer 21 together.
  • the adhesive constituting the adhesive layer 22 include polyurethane resins in which a difunctional or higher-functional isocyanate compound is applied to a base material such as polyester polyol, polyether polyol, acrylic polyol, or carbonate polyol.
  • a base material such as polyester polyol, polyether polyol, acrylic polyol, or carbonate polyol.
  • Various polyols may be used alone or in combination of two or more.
  • a carbodiimide compound, an oxazoline compound, an epoxy compound, a phosphorus compound, a silane coupling agent, etc. may be blended with the above-mentioned polyurethane resin for the purpose of promoting adhesion.
  • the thickness of the adhesive layer may be, for example, 0.5 to 10 g/m 2 from the viewpoint of obtaining desired adhesive strength, trackability, processability, etc.
  • a material whose polymer component is derived from biomass or a material having biodegradability may be used.
  • an adhesive having barrier properties may be used for the adhesive layer 22.
  • the Cobb300 value (initial) of the packaging material may be 0.3 g/m 2 or less, 0.2 g/m 2 or less, or 0.1 g/m 2 or less from the viewpoint of excellent moisture barrier properties.
  • the Cobb300 value (initial) means the Cobb300 value measured at a portion other than the folded portion of the packaging material, and is measured by the method described in the Examples below.
  • FIG. 3 is a perspective view showing a gusset bag 40 made of the gas barrier laminate 10 (packaging material 20).
  • a packaging bag is manufactured by sealing the upper opening of the gusset bag 40.
  • the gusset bag 40 has portions where the gas barrier laminate 10 is bent (bent portions B1 and B2).
  • the folded portion B1 is a portion where the gas barrier laminate 10 is valley-folded when viewed from the innermost layer side
  • the bent portion B2 is a portion where the gas barrier laminate 10 is mountain-folded when viewed from the innermost layer side.
  • the packaging bag may be formed into a bag shape by folding one gas barrier laminate in half so that the overcoat layer 4 faces each other, then bending it appropriately to obtain the desired shape, and heat-sealing it.
  • two gas barrier laminates may be stacked so that the overcoat layer 4 faces each other, and then heat-sealed to form a bag shape.
  • the packaging bag contains aqueous contents.
  • the aqueous content means a content containing at least water.
  • the packaging bag according to the present embodiment has excellent moisture barrier properties even if it has a bent portion, and can sufficiently suppress the aqueous contents from seeping out.
  • a gusset bag is cited as an example of a packaging bag, but the packaging material according to this embodiment may be used to produce, for example, a pillow bag, a three-sided seal bag, or a standing pouch.
  • a packaging material comprising at least a gas barrier laminate in which a paper base material, an anchor coat layer, a vapor deposition layer, and an overcoat layer are laminated in this order,
  • the mass of the paper base material is 50% by mass or more with respect to the total mass of the packaging material
  • the vapor deposited layer contains a metal or a metal oxide
  • the overcoat layer contains a polyolefin having a carboxylic acid group
  • Example 1 A coating liquid containing a polyolefin having a carboxylic acid group (product Chemipearl S100, ionomer system, average particle size: ⁇ 0.1 ⁇ m, solvent: water, IPA, manufactured by Mitsui Chemicals) was coated with a bar coater and dried in an oven to form an anchor coat layer. The thickness of the anchor coat layer was 2 ⁇ m. Next, AL was deposited on the anchor coat layer by a vacuum deposition method to form a deposited layer. The thickness of the deposited layer was 50 nm.
  • a polyolefin having a carboxylic acid group product Chemipearl S100, ionomer system, average particle size: ⁇ 0.1 ⁇ m, solvent: water, IPA, manufactured by Mitsui Chemicals
  • a solution containing a polyolefin having a carboxylic acid group (trade name: Chemipearl S100, ionomer type, average particle size: less than 0.1 ⁇ m, solvent: water, IPA, manufactured by Mitsui Chemicals) was applied on the vapor deposition layer using a bar coater.
  • the mixture was dried in an oven to form an overcoat layer to obtain a gas packaging material.
  • the thickness of the overcoat layer was 5 ⁇ m.
  • the content of paper base material in the packaging material was 82% by mass.
  • Example 2 A packaging material was obtained in the same manner as in Example 1 except that the thickness of the overcoat layer was 10 ⁇ m. The content of paper base material in the packaging material was 76% by mass.
  • Example 3 A packaging material was obtained by the same operation as in Example 1, except that the thickness of the anchor coat layer was 3 ⁇ m and the thickness of the overcoat layer was 12 ⁇ m. The content of paper base material in the packaging material was 73% by mass.
  • Example 4 A packaging material was obtained in the same manner as in Example 1 except that the thickness of the overcoat layer was 3.5 ⁇ m. The content of paper base material in the packaging material was 84% by mass.
  • Example 5 A packaging material was obtained by the same operation as in Example 1, except that the thickness of the anchor coat layer was 1 ⁇ m and the thickness of the overcoat layer was 20 ⁇ m. The content of paper base material in the packaging material was 68% by mass.
  • Example 1 A packaging material was obtained in the same manner as in Example 1 except that the thickness of the overcoat layer was 0.5 ⁇ m. The content of paper base material in the packaging material was 88% by mass.
  • Example 2 A packaging material was obtained in the same manner as in Example 1 except that the thickness of the overcoat layer was 2 ⁇ m. The content of paper base material in the packaging material was 86% by mass.
  • the anchor coat layer is made of urethane, which is a cured product of acrylic polyol (acrylic polyol is a polymer of acrylic acid derivative monomers, or a polymer of acrylic acid derivative monomers and other monomers, and has a hydroxyl group at the end) and polyisocyanate.
  • the thickness of the anchor coat layer was 3 ⁇ m
  • the overcoat layer was made of a mixture of PVA and TEOS hydrolyzate
  • the thickness of the overcoat layer was 3.5 ⁇ m.
  • a packaging material was obtained by the same operation as in Example 1 except for the above.
  • the content of paper base material in the packaging material was 85% by mass.
  • Sodium polyacrylate was added as a dispersant to pigment (engineered kaolin, manufactured by Imerys, Varisurf HX, average particle size 9.0 ⁇ m, aspect ratio 80-100) (0.2% to pigment) and dispersed with a Serie mixer.
  • a kaolin slurry having a solid content concentration of 55% was prepared.
  • 100 parts (solid content) of styrene-butadiene latex manufactured by Nippon Zeon Co., Ltd., PNT7868
  • a coating solution for forming an anchor coat layer having a concentration of 50% was obtained.
  • Sodium polyacrylate was added as a dispersant to pigment (engineered kaolin, manufactured by Imerys, Varisurf HX, average particle size 9.0 ⁇ m, aspect ratio 80-100) (0.2% to pigment) and dispersed with a Serie mixer.
  • a kaolin slurry having a solid content concentration of 55% was prepared.
  • a polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117) aqueous solution was prepared to have a solid content concentration of 10% to obtain a PVA aqueous solution.
  • the coating liquid for forming an anchor coat layer was applied in a dry weight amount of 12 g/m 2 (anchor coat layer thickness: 12 ⁇ m). After coating on one side using a blade coater and drying, apply a coating liquid for overcoat layer formation on it in a dry weight of 3.0 g/m 2 (thickness of overcoat layer: 3 ⁇ m). It was coated on one side using a roll coater and dried to obtain a packaging material. The content of paper base material in the packaging material was 79% by mass.
  • a water-absorbing paper was placed on the measurement sample, and a smooth metal roller with a width of 200 mm, a diameter of 90 mm, and a weight of 10 kg was moved over the paper once to wipe off excess water remaining on the measurement sample after water absorption. .
  • the Cobb300 value (g/m 2 ) at a water absorption time of 300 seconds was calculated by multiplying the mass difference by 100.
  • the recyclability of the packaging material was evaluated.
  • the recyclability of the packaging material was evaluated based on the content of paper base material in the packaging material.
  • the evaluation results are shown in Table 1.
  • C The content of paper base material in the packaging material is less than 50% by mass.

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Abstract

This packaging material for aqueous content is a packaging bag comprising at least a gas barrier laminate obtained by laminating, in the sequence listed, a paper substrate, an anchor coating layer, a vapor deposition layer, and an overcoat layer, the paper substrate having a mass of at least 50 mass% relative to the total mass of the packaging material, the vapor deposition layer containing a metal or a metal oxide, the overcoat layer containing a polyolefin that has a carboxylic acid base, and the overcoat layer having a thickness of over 3 μm.

Description

水系内容物用包装材及び水系内容物用包装袋Packaging materials for aqueous contents and packaging bags for aqueous contents
　本開示は、水系内容物用包装材及び水系内容物用包装袋に関する。 The present disclosure relates to a packaging material for aqueous contents and a packaging bag for aqueous contents.
　食品、飲料、医薬品及び化学品等の多くの分野では、それぞれの内容物に応じた包装袋が使用されている。近年、環境意識の高まりから、包装袋に使用するプラスチック材料の量を削減することが求められており、プラスチック材料の代わりに、紙を使用することが検討されている。例えば下記特許文献１では、紙にバリア層を積層するガスバリア積層体が開示されている。 In many fields such as food, beverages, pharmaceuticals, and chemicals, packaging bags are used depending on the contents. In recent years, as environmental awareness has increased, there has been a demand for reducing the amount of plastic materials used in packaging bags, and the use of paper instead of plastic materials is being considered. For example, Patent Document 1 listed below discloses a gas barrier laminate in which a barrier layer is laminated on paper.
特開２０２０－６９７８３号公報JP2020-69783A
　紙は、折り目保持性（デッドホールド性とも称される）を有することから、加工がしやすいという特徴を有する。しかしながら、折り目がある包装袋は、折り目付近の水分バリア性が低下しやすい。そのため、特に包装袋が水系内容物を収容する場合において、折り曲げ後の水分バリア性の向上が求められている。 Paper has the characteristic of being easy to process because it has crease retention properties (also referred to as dead-hold properties). However, packaging bags with creases tend to have poor moisture barrier properties near the creases. Therefore, especially when packaging bags contain aqueous contents, there is a demand for improved moisture barrier properties after folding.
　本開示の一側面は、上記実情に鑑みてなされたものであり、プラスチック材料の使用量を削減しつつ、折り曲げられた後であっても優れた水分バリア性を有する包装材及び包装袋を提供することを目的とする。 One aspect of the present disclosure has been made in view of the above circumstances, and provides a packaging material and packaging bag that reduces the amount of plastic material used and has excellent moisture barrier properties even after being folded. The purpose is to
　本開示の一側面は、紙基材と、アンカーコート層と、蒸着層と、オーバーコート層と、がこの順で積層されたガスバリア積層体を少なくとも備える包装材であって、紙基材の質量が、ガスバリア積層体の全質量に対して５０質量％以上であり、蒸着層が、金属又は金属酸化物を含み、オーバーコート層が、カルボン酸塩基を有するポリオレフィンを含み、オーバーコート層の厚さが３μｍ超である、水系内容物用包装材を提供する。 One aspect of the present disclosure is a packaging material including at least a gas barrier laminate in which a paper base material, an anchor coat layer, a vapor deposition layer, and an overcoat layer are laminated in this order, is 50% by mass or more based on the total mass of the gas barrier laminate, the vapor deposited layer contains a metal or a metal oxide, the overcoat layer contains a polyolefin having a carboxylic acid group, and the thickness of the overcoat layer Provided is a packaging material for aqueous contents having a diameter of more than 3 μm.
　上記水系内容物用包装材において、アンカーコート層は、カルボン酸塩基を有するポリオレフィンを含んでもよい。 In the above packaging material for aqueous contents, the anchor coat layer may contain a polyolefin having a carboxylic acid group.
　上記水系内容物用包装材において、アンカーコートの厚さに対するオーバーコート層の厚さの比率が、１～２０であってもよい。 In the above packaging material for aqueous contents, the ratio of the thickness of the overcoat layer to the thickness of the anchor coat may be 1 to 20.
　上記水系内容物用包装材において、オーバーコート層の蒸着層とは反対側にシーラント層を更に備えていてもよい。 The above packaging material for water-based contents may further include a sealant layer on the side of the overcoat layer opposite to the vapor deposited layer.
　本開示の他の一側面は、上記水系内容物用包装材を製袋してなる水系内容物用包装袋を提供する。 Another aspect of the present disclosure provides a packaging bag for aqueous contents formed by bag-making the above-mentioned packaging material for aqueous contents.
　本開示の一側面によれば、プラスチック材料の使用量を削減しつつ、折り曲げられた後であっても優れた水分バリア性を有する包装材及び包装袋を提供することができる。 According to one aspect of the present disclosure, it is possible to provide a packaging material and a packaging bag that have excellent moisture barrier properties even after being folded, while reducing the amount of plastic material used.
本開示の一実施形態に係る包装材を示す模式断面図である。FIG. 1 is a schematic cross-sectional view showing a packaging material according to an embodiment of the present disclosure. 本開示の一実施形態に係る包装材を示す模式断面図である。FIG. 1 is a schematic cross-sectional view showing a packaging material according to an embodiment of the present disclosure. 本開示の一実施形態に係る包装袋を示す斜視図である。FIG. 1 is a perspective view showing a packaging bag according to an embodiment of the present disclosure.
　以下、場合により図面を参照しながら、本開示の一実施形態について詳細に説明する。ただし、本開示は以下の実施形態に限定されるものではない。 Hereinafter, one embodiment of the present disclosure will be described in detail, with reference to the drawings as the case may be. However, the present disclosure is not limited to the following embodiments.
＜包装材＞
　図１は、一実施形態に係る包装材を示す模式断面図である。一実施形態に係る包装材２０は、紙基材１と、アンカーコート層２と、蒸着層３と、オーバーコート層４と、がこの順に積層されたガスバリア積層体１０からなる。 <Packaging material>
FIG. 1 is a schematic cross-sectional view showing a packaging material according to one embodiment. The packaging material 20 according to one embodiment includes a gas barrier laminate 10 in which a paper base material 1, an anchor coat layer 2, a vapor deposition layer 3, and an overcoat layer 4 are laminated in this order.
［紙基材］
　紙基材１としては、特に限定されるものではなく、ガスバリア積層体１０が適用される包装袋の用途に応じて適宜選択される。紙基材１としては、植物由来のパルプを主成分としている紙であってもよい。紙基材１の具体例としては、上質紙、特殊上質紙、コート紙、アート紙、キャストコート紙、模造紙及びクラフト紙、グラシン紙が挙げられる。紙基材１の厚さは、例えば、２０～５００ｇ／ｍ２、又は３０～１００ｇ／ｍ２であってもよい。紙基材１の厚さは、例えば、２０～１００μｍ、又は３０～７０μｍであってもよい。 [Paper base material]
The paper base material 1 is not particularly limited, and is appropriately selected depending on the use of the packaging bag to which the gas barrier laminate 10 is applied. The paper base material 1 may be paper whose main component is pulp derived from plants. Specific examples of the paper base material 1 include wood-free paper, special wood-free paper, coated paper, art paper, cast-coated paper, imitation paper and kraft paper, and glassine paper. The thickness of the paper base material 1 may be, for example, 20 to 500 g/m 2 or 30 to 100 g/m 2 . The thickness of the paper base material 1 may be, for example, 20 to 100 μm or 30 to 70 μm.
　紙基材１には、後述するアンカーコート層２と接する側にコート層（図示せず）が設けられていてもよい。紙基材１がアンカーコート層２と接する側にコート層を有することで、紙基材１にアンカーコート層２が染み込むことを防ぐことができる。また、紙基材１がアンカーコート層２と接する側にコート層を有することで、コート層が紙基材１の表面の凹凸を埋める目止めの役割を果たし、アンカーコート層２を欠陥なく均一に製膜することができる。コート層には、例えば、バインダー樹脂として、スチレン・ブタジエン系、スチレン・アクリル系、エチレン・酢酸ビニル系等の各種共重合体；ポリビニルアルコール系樹脂、セルロース系樹脂、パラフィン（ＷＡＸ）などが含まれていてもよく、充填材として、クレー、カオリン、炭酸カルシウム、タルク、マイカ等が含まれていてもよい。 The paper base material 1 may be provided with a coat layer (not shown) on the side in contact with the anchor coat layer 2 described below. By having the coat layer on the side where the paper base material 1 is in contact with the anchor coat layer 2, it is possible to prevent the anchor coat layer 2 from seeping into the paper base material 1. In addition, by having a coat layer on the side where the paper base material 1 is in contact with the anchor coat layer 2, the coat layer plays the role of filling in the unevenness of the surface of the paper base material 1, and the anchor coat layer 2 is uniformly formed without defects. It can be formed into a film. The coating layer includes, for example, various copolymers such as styrene/butadiene, styrene/acrylic, and ethylene/vinyl acetate as binder resin; polyvinyl alcohol resin, cellulose resin, paraffin (WAX), etc. Clay, kaolin, calcium carbonate, talc, mica, etc. may be included as fillers.
　コート層の厚さは、例えば、１～１０μｍ、又は３～８μｍであってもよい。 The thickness of the coating layer may be, for example, 1 to 10 μm or 3 to 8 μm.
　紙基材１の質量は、包装材２０の全質量に対して５０質量％以上である。紙基材１の質量が、包装材２０の全質量に対して５０質量％以上であれば、プラスチック材料の使用量を十分に削減することができる。このような包装材２０は、リサイクル性に優れている。紙基材１の質量は、プラスチック材料の使用量をより削減する観点から、包装材２０の全質量に対して、６０質量％以上、７０質量％以上、又は７５質量％以上であってもよい。 The mass of the paper base material 1 is 50% by mass or more with respect to the total mass of the packaging material 20. If the mass of the paper base material 1 is 50 mass% or more with respect to the total mass of the packaging material 20, the amount of plastic material used can be sufficiently reduced. Such packaging material 20 has excellent recyclability. The mass of the paper base material 1 may be 60 mass% or more, 70 mass% or more, or 75 mass% or more with respect to the total mass of the packaging material 20, from the viewpoint of further reducing the amount of plastic material used. .
［アンカーコート層］
　アンカーコート層２は、紙基材の表面上に設けられ、紙基材１と蒸着層３との間の密着性向上や、ガスバリア積層体１０の水分バリア性の向上のために設けられる層である。アンカーコート層２は、カルボン酸塩基（カルボキシル基の水素原子がナトリウム原子等の金属原子に置換された基）を有するポリオレフィンを含むものであってもよい。このようなアンカーコート層２は、柔軟性に優れ、屈曲後（折り曲げ後）に蒸着層の割れを抑制することができると共に、アンカーコート層２と蒸着層３との密着性を向上させることができる。アンカーコート層２は、カルボン酸塩基を有するポリオレフィンを含むことで、ポリオレフィンの結晶性による緻密な膜となる。また、アンカーコート層２がカルボン酸塩基を有するポリオレフィンを含むことにより、包装材の水分バリア性がより優れる。 [Anchor coat layer]
The anchor coat layer 2 is a layer provided on the surface of the paper base material to improve the adhesion between the paper base material 1 and the vapor deposition layer 3 and to improve the moisture barrier properties of the gas barrier laminate 10. be. The anchor coat layer 2 may contain a polyolefin having a carboxylic acid group (a group in which a hydrogen atom of a carboxyl group is substituted with a metal atom such as a sodium atom). Such an anchor coat layer 2 has excellent flexibility and can suppress cracking of the vapor deposited layer after bending (bending), and can improve the adhesion between the anchor coat layer 2 and the vapor deposited layer 3. can. The anchor coat layer 2 contains a polyolefin having a carboxylic acid group, and becomes a dense film due to the crystallinity of the polyolefin. Further, since the anchor coat layer 2 contains a polyolefin having a carboxylic acid group, the moisture barrier properties of the packaging material are further improved.
　カルボン酸塩基を有するポリオレフィンは、エチレン、プロピレン等のオレフィンと、不飽和カルボン酸（アクリル酸、メタクリル酸、無水マレイン酸等のカルボキシル基を有する不飽和化合物）との共重合体の塩であってよい。塩としては、ナトリウム塩、カリウム塩等が挙げられる。 A polyolefin having a carboxylic acid group is a salt of a copolymer of an olefin such as ethylene or propylene and an unsaturated carboxylic acid (an unsaturated compound having a carboxyl group such as acrylic acid, methacrylic acid, or maleic anhydride). good. Examples of the salt include sodium salt, potassium salt, and the like.
　アンカーコート層２は、カルボン酸塩基を有するポリオレフィンに加えて、例えば、カルボン酸塩基を有するポリオレフィン以外のポリオレフィン、シランカップリング剤、有機チタネート、ポリアクリル、ポリエステル、ポリウレタン、ポリカーボネート、ポリウレア、ポリアミド、ポリイミド、メラミン、フェノール等を含んでいてもよい。 In addition to the polyolefin having a carboxylic acid group, the anchor coat layer 2 includes, for example, a polyolefin other than the polyolefin having a carboxylic acid group, a silane coupling agent, an organic titanate, a polyacrylic, a polyester, a polyurethane, a polycarbonate, a polyurea, a polyamide, a polyimide. , melamine, phenol, etc.
　アンカーコート層２におけるカルボン酸塩基を有するポリオレフィンの含有量は、包装材の水分バリア性がより優れる観点から、アンカーコート層２の全質量に対して、５０質量％以上、６０質量％以上、７０質量％以上、８０質量％以上、９０質量％以上、９５質量％以上、又は１００質量％であってもよい。 The content of the polyolefin having a carboxylic acid group in the anchor coat layer 2 is 50% by mass or more, 60% by mass or more, 70% by mass or more based on the total mass of the anchor coat layer 2, from the viewpoint of improving the moisture barrier properties of the packaging material. It may be at least 80% by mass, at least 90% by mass, at least 95% by mass, or at least 100% by mass.
　アンカーコート層２の厚さは、例えば、１μｍ以上、又は２μｍ以上であってもよく、２０μｍ以下、１０μｍ以下、又は５μｍ以下であってもよい。アンカーコート層２の厚さが１μｍ以上であることで、紙基材１の表面の凹凸を埋めやすく、蒸着層３を均一に積層させることができる。また、アンカーコート層２の厚さが２０μｍ以下であることで、アンカーコート層２の厚さが厚くなり過ぎず、アンカーコート層２上の蒸着層に屈曲によるクラックが入りにくくなり、折り曲げられた後の水分バリア性が劣化しにくくなるため、折り曲げ後の耐水性に優れると共に、コストを抑えつつ蒸着層３を均一に積層させることができる。さらに、アンカーコート層の厚さが２０μｍ以下であることで、紙基材へのアンカーコート層２を形成する塗液の塗布量が多くなり過ぎることを防ぐため塗工適性が優れ、塗工面の平滑性の悪化、及び基材への皺の発生等の不具合を抑制できる。また、塗工面の平滑性の悪化を抑制できるため、蒸着層３が均一に積層されないことによるバリア性が低下すること、蒸着層が不均一になることにより、折り曲げ時に不均一な箇所を起点とするクラックが発生すること、及びクラックの発生により、折り曲げ後のバリア性が劣化することを抑制できる。 The thickness of the anchor coat layer 2 may be, for example, 1 μm or more, or 2 μm or more, or 20 μm or less, 10 μm or less, or 5 μm or less. When the thickness of the anchor coat layer 2 is 1 μm or more, unevenness on the surface of the paper base material 1 can be easily filled, and the vapor deposition layer 3 can be uniformly laminated. In addition, because the thickness of the anchor coat layer 2 is 20 μm or less, the thickness of the anchor coat layer 2 does not become too thick, and the vapor deposited layer on the anchor coat layer 2 is less likely to crack due to bending. Since the moisture barrier property is less likely to deteriorate after bending, it is possible to have excellent water resistance after bending and to uniformly stack the vapor deposited layer 3 while keeping costs down. Furthermore, since the thickness of the anchor coat layer is 20 μm or less, it prevents the coating amount of the coating liquid that forms the anchor coat layer 2 from becoming too large on the paper base material, resulting in excellent coating suitability. Problems such as deterioration of smoothness and generation of wrinkles on the base material can be suppressed. In addition, since the deterioration of the smoothness of the coated surface can be suppressed, the barrier properties may be lowered due to the vapor deposited layer 3 not being stacked uniformly, and the vapor deposited layer may become non-uniform. It is possible to suppress the occurrence of cracks, and the deterioration of the barrier properties after bending due to the generation of cracks.
　アンカーコート層２の塗液に含まれる溶媒としては、例えば、水、メチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ－プロピルアルコール、ｎ－ブチルアルコール、ｎ－ペンチルアルコール、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、トルエン、ヘキサン、ヘプタン、シクロヘキサン、アセトン、メチルエチルケトン、ジエチルエーテル、ジオキサン、テトラヒドロフラン、酢酸エチル、及び酢酸ブチルが挙げられる。これらの溶媒は一種を単独で用いてもよく、二種以上を併用してもよい。アンカーコート層２の塗液に含まれる溶媒は、特性の観点から、メチルアルコール、エチルアルコール、イソプロピルアルコール、トルエン、酢酸エチル、メチルエチルケトン、及び水からなる群より選ばれる少なくとも一種を含むものであってもよい。アンカーコート層２の塗液に含まれる溶媒は、環境への負荷を減らす観点から、メチルアルコール、エチルアルコール、イソプロピルアルコール、及び水からなる群より選ばれる少なくとも一種を含むものであってもよい。 Examples of the solvent contained in the coating liquid for anchor coat layer 2 include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, and 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. From the viewpoint of properties, the solvent contained in the coating liquid of the anchor coat layer 2 contains at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water. Good too. The solvent contained in the coating liquid of the anchor coat layer 2 may contain at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, and water, from the viewpoint of reducing the load on the environment.
　アンカーコート層２は、例えば、紙基材１上にカルボン酸塩基を有するポリオレフィン及び溶媒を含む塗液を塗布し、乾燥させることで紙基材１上に積層することができる。塗液中におけるカルボン酸塩基を有するポリオレフィンの平均粒径は、乾燥後の塗面を平滑にし、蒸着層３を均一に積層し、バリア性を向上させる観点から、１μｍ以下、０．７μｍ以下、又は０．５μｍ以下であってもよい。 The anchor coat layer 2 can be laminated on the paper base material 1 by, for example, applying a coating liquid containing a polyolefin having a carboxylic acid group and a solvent onto the paper base material 1 and drying it. The average particle size of the polyolefin having a carboxylic acid group in the coating solution is 1 μm or less, 0.7 μm or less, from the viewpoint of smoothing the coated surface after drying, uniformly laminating the vapor deposited layer 3, and improving barrier properties. Alternatively, it may be 0.5 μm or less.
［蒸着層］
　蒸着層３は、金属又は金属酸化物を蒸着した層である。蒸着層３としては、アルミニウムを蒸着した層であってもよく、酸化アルミニウム（ＡｌＯｘ）、酸化ケイ素（ＳｉＯｘ）等を含むものであってもよい。 [Vapour-deposited layer]
The vapor deposited layer 3 is a layer in which metal or metal oxide is vapor deposited. The vapor deposited layer 3 may be a layer in which aluminum is vapor deposited, or may contain aluminum oxide (AlO x ), silicon oxide (SiO x ), or the like.
　アンカーコート層２とオーバーコート層４の間に蒸着層３が存在することによって、より優れた水分バリア性を有する包装材を得ることができる。蒸着層３は樹脂層と比較して緻密な膜であり、ピンホールを除いた状態においては、原子間の間隔は水分子よりも細かい。そのため、包装材２０が蒸着層３を有することにより、包装材２０は液体の水に対する耐性（水分バリア性）だけでなく、水蒸気に対する耐性（ガスバリア性）も優れる。 By the presence of the vapor deposited layer 3 between the anchor coat layer 2 and the overcoat layer 4, a packaging material having better moisture barrier properties can be obtained. The vapor deposited layer 3 is a denser film than the resin layer, and the spacing between atoms is finer than that of water molecules when pinholes are excluded. Therefore, since the packaging material 20 has the vapor deposited layer 3, the packaging material 20 has excellent resistance not only to liquid water (moisture barrier properties) but also to water vapor (gas barrier properties).
　蒸着層３の厚さは、例えば、１０～３００ｎｍ、又は３０～１００ｎｍであってもよい。蒸着層３の厚さが１０ｎｍ以上であることで、蒸着層３を均一に形成しやすくなる。蒸着層３の厚さが３００ｎｍ以下であることで、蒸着層３がカールすること、及び蒸着層３にクラックが発生することを十分に抑制でき、蒸着層３は十分なガスバリア性能及び可撓性を有しやすい。 The thickness of the vapor deposited layer 3 may be, for example, 10 to 300 nm or 30 to 100 nm. When the thickness of the vapor deposition layer 3 is 10 nm or more, the vapor deposition layer 3 can be easily formed uniformly. When the thickness of the vapor deposited layer 3 is 300 nm or less, curling of the vapor deposited layer 3 and generation of cracks in the vapor deposited layer 3 can be sufficiently suppressed, and the vapor deposited layer 3 has sufficient gas barrier performance and flexibility. easy to have.
　蒸着層３は、真空蒸着法、スパッタリング法、化学的気相成長法（ＣＶＤ法）等により形成することができる。蒸着層３は、ガスバリア性及び膜の均一性の観点から、真空成膜手段によって形成することが好ましい。蒸着層３は、成膜速度が速く、生産性が高いことから真空蒸着法であってもよい。真空蒸着法の中でも電子ビーム加熱による成膜手段は、成膜速度を照射面積、電子ビーム電流等で制御しやすいこと、及び蒸着材料への昇温降温が短時間で行えることから好ましい。 The vapor deposition layer 3 can be formed by a vacuum evaporation method, a sputtering method, a chemical vapor deposition method (CVD method), or the like. The vapor deposition layer 3 is preferably formed by vacuum film formation from the viewpoint of gas barrier properties and film uniformity. The vapor deposition layer 3 may be formed by vacuum vapor deposition because the film formation rate is fast and productivity is high. Among vacuum evaporation methods, film formation by electron beam heating is preferable because the film formation rate can be easily controlled by the irradiation area, electron beam current, etc., and the temperature of the evaporation material can be raised and lowered in a short time.
［オーバーコート層］
　オーバーコート層４は、蒸着層３の表面上に、蒸着層３に接するように設けられる層であり、カルボン酸塩基を有するポリオレフィンを含む。オーバーコート層４が、カルボン酸塩基を有するポリオレフィンを含むことにより、包装材２０は、折り曲げられた後であっても優れた水分バリア性を有する。カルボン酸塩基を有するポリオレフィンとしては、上述したアンカーコート層２に含まれるカルボン酸塩基を有するポリオレフィンが挙げられる。オーバーコート層４に含まれるカルボン酸塩基を有するポリオレフィンは、アンカーコート層２に含まれるカルボン酸塩基を有するポリオレフィンと異なっていてもよく、製造の容易性の観点から同一であってもよい。 [Overcoat layer]
The overcoat layer 4 is a layer provided on the surface of the vapor deposition layer 3 so as to be in contact with the vapor deposition layer 3, and contains a polyolefin having a carboxylic acid group. Since the overcoat layer 4 contains a polyolefin having a carboxylic acid group, the packaging material 20 has excellent moisture barrier properties even after being folded. Examples of the polyolefin having a carboxylic acid group include the polyolefin having a carboxylic acid group contained in the anchor coat layer 2 described above. The polyolefin having a carboxylic acid group contained in the overcoat layer 4 may be different from the polyolefin having a carboxylic acid group contained in the anchor coat layer 2, or may be the same from the viewpoint of ease of manufacture.
　オーバーコート層４は、カルボン酸塩基を有するポリオレフィンを含むことにより、柔軟性に優れ、屈曲後（折り曲げ後）に蒸着層３の割れを抑制することができると共に、オーバーコート層４と蒸着層３との密着性を向上させることができる。オーバーコート層４は、カルボン酸塩基を有するポリオレフィンを含むことで、ポリオレフィンの結晶性による緻密な膜となる。また、オーバーコート層４は、カルボン酸塩基を有するポリオレフィンを含むことで、ヒートシール層としての役割も兼ねることができるため、ヒートシール層を設けなくとも製袋することができる。 Since the overcoat layer 4 contains polyolefin having a carboxylic acid group, it has excellent flexibility and can suppress cracking of the vapor deposited layer 3 after bending (after bending). It is possible to improve the adhesion with. Since the overcoat layer 4 contains polyolefin having a carboxylic acid group, it becomes a dense film due to the crystallinity of the polyolefin. Further, since the overcoat layer 4 contains polyolefin having a carboxylic acid group, it can also serve as a heat-sealing layer, so that bags can be manufactured without providing a heat-sealing layer.
　オーバーコート層４には、カルボン酸塩基を有するポリオレフィンに加えて、例えば、シランカップリング剤等のカップリング剤；ポリアクリル、ポリエステル、ポリウレタン、ポリカーボネート、ポリウレア、ポリアミド、ポリオレフィン系エマルジョン、ポリイミド、メラミン、フェノール等の樹脂；有機チタネートなどを含んでいてもよい。 In addition to the polyolefin having a carboxylic acid group, the overcoat layer 4 contains, for example, a coupling agent such as a silane coupling agent; polyacrylic, polyester, polyurethane, polycarbonate, polyurea, polyamide, polyolefin emulsion, polyimide, melamine, It may contain resin such as phenol; organic titanate, etc.
　オーバーコート層４におけるカルボン酸塩基を有するポリオレフィンの含有量は、包装材の水分バリア性がより優れる観点から、オーバーコート層４の全質量に対して、５０質量％以上、６０質量%以上、７０質量％以上、８０質量%以上、９０質量％以上、９５質量％以上、又は１００質量％であってもよい。 The content of the polyolefin having a carboxylic acid group in the overcoat layer 4 is 50% by mass or more, 60% by mass or more, 70% by mass or more based on the total mass of the overcoat layer 4, from the viewpoint of improving the moisture barrier properties of the packaging material. It may be at least 80% by mass, at least 90% by mass, at least 95% by mass, or at least 100% by mass.
　オーバーコート層４の厚さは、３μｍ超である。オーバーコート層４の厚さが３μｍ超であることで、包装材２０は、折り曲げられた後であっても優れた水分バリア性を有する。オーバーコート層４の厚さは、３．５μｍ以上、４μｍ以上、４．５μｍ以上、又は５μｍ以上であってもよい。オーバーコート層４の厚さが厚くなるほど紙基材の比率が低下するため、リサイクル性が低下する。そのため、リサイクル性を保ち、コストを抑えつつ蒸着層３との密着性が優れると共に、水分バリア性を十分に発揮することができる観点から、オーバーコート層４の厚さは、２０μｍ以下、２０μｍ未満、１８μｍ以下、１６μｍ以下、１５μｍ以下、１４μｍ以下、１３μｍ以下、又は１２μｍ以下であってもよい。オーバーコート層４の厚さは、１０μｍ以下、８μｍ以下、６μｍ以下、又は５μｍ以下であってもよい。 The thickness of the overcoat layer 4 is over 3 μm. Since the thickness of the overcoat layer 4 is more than 3 μm, the packaging material 20 has excellent moisture barrier properties even after being folded. The thickness of the overcoat layer 4 may be 3.5 μm or more, 4 μm or more, 4.5 μm or more, or 5 μm or more. As the thickness of the overcoat layer 4 becomes thicker, the proportion of the paper base material decreases, and thus the recyclability decreases. Therefore, the thickness of the overcoat layer 4 is 20 μm or less, less than 20 μm, from the viewpoint of maintaining recyclability, suppressing costs, having excellent adhesion with the vapor deposited layer 3, and fully exhibiting moisture barrier properties. , 18 μm or less, 16 μm or less, 15 μm or less, 14 μm or less, 13 μm or less, or 12 μm or less. The thickness of the overcoat layer 4 may be 10 μm or less, 8 μm or less, 6 μm or less, or 5 μm or less.
　オーバーコート層４の塗液に含まれる溶媒としては、例えば、水、メチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ－プロピルアルコール、ｎ－ブチルアルコール、ｎ－ペンチルアルコール、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、トルエン、ヘキサン、ヘプタン、シクロヘキサン、アセトン、メチルエチルケトン、ジエチルエーテル、ジオキサン、テトラヒドロフラン、酢酸エチル、及び酢酸ブチルが挙げられる。これらの溶媒は一種を単独で用いてもよく、二種以上を併用してもよい。アンカーコート層２の塗液に含まれる溶媒は、特性の観点から、メチルアルコール、エチルアルコール、イソプロピルアルコール、トルエン、酢酸エチル、メチルエチルケトン、及び水からなる群より選ばれる少なくとも一種を含むものであってもよい。アンカーコート層２の塗液に含まれる溶媒は、環境への負荷を減らす観点から、メチルアルコール、エチルアルコール、イソプロピルアルコール、及び水からなる群より選ばれる少なくとも一種を含むものであってもよい。 Examples of the solvent contained in the coating liquid for overcoat layer 4 include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, and 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. From the viewpoint of properties, the solvent contained in the coating liquid of the anchor coat layer 2 contains at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water. Good too. The solvent contained in the coating liquid of the anchor coat layer 2 may contain at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, and water, from the viewpoint of reducing the load on the environment.
　オーバーコート層４は、例えば、蒸着層３上にカルボン酸塩基を有するポリオレフィン及び溶媒を含む塗液を塗布し、乾燥させることで蒸着層３上に積層することができる。塗液中におけるカルボン酸塩基を有するポリオレフィンの平均粒径は、ヒートシール時の立ち上がり温度を高めて、包装材の搬送時のブロッキングを防止する観点から、１μｍ以下、０．７μｍ以下、又は０．５μｍ以下であってもよい。 The overcoat layer 4 can be laminated on the vapor deposited layer 3 by, for example, applying a coating liquid containing a polyolefin having a carboxylic acid group and a solvent onto the vapor deposited layer 3 and drying the coating liquid. The average particle size of the polyolefin having a carboxylic acid group in the coating liquid is 1 μm or less, 0.7 μm or less, or 0.7 μm or less, from the viewpoint of increasing the rising temperature during heat sealing and preventing blocking during transportation of the packaging material. It may be 5 μm or less.
　アンカーコート層２の厚さに対するオーバーコート層４の厚さの比率（オーバーコート層４の厚さ／アンカーコート層２の厚さ）は、耐屈曲性の観点から、１以上、１．５以上、又は１．８以上であってもよい。アンカーコート層２の厚さに対するオーバーコート層４の厚さの比率は、塗工性及びリサイクル性の観点から、３０以下、２５以下、２０以下、１５以下、１０以下、８以下、６以下、５以下、又は４以下であってもよい。 The ratio of the thickness of overcoat layer 4 to the thickness of anchor coat layer 2 (thickness of overcoat layer 4/thickness of anchor coat layer 2) is 1 or more and 1.5 or more from the viewpoint of bending resistance. , or 1.8 or more. From the viewpoint of coatability and recyclability, the ratio of the thickness of the overcoat layer 4 to the thickness of the anchor coat layer 2 is 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 8 or less, 6 or less, It may be 5 or less, or 4 or less.
　紙基材に対する樹脂材料の使用量を少なくすることによりリサイクル性がより優れる観点から、アンカーコート層２とオーバーコート層４の厚さの合計は、５０μｍ以下、４０μｍ以下、３０μｍ以下、２５μｍ以下、２１μｍ以下、２０μｍ以下、１８μｍ以下、１５μｍ以下、又は１２μｍ以下であることが好ましい。 From the viewpoint of better recyclability by reducing the amount of resin material used for the paper base material, the total thickness of the anchor coat layer 2 and overcoat layer 4 is 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, It is preferably 21 μm or less, 20 μm or less, 18 μm or less, 15 μm or less, or 12 μm or less.
　図２は、他の一実施形態に係る包装材を示す模式断面図である。図２に示す包装材３０は、ガスバリア積層体１０と、ガスバリア積層体１０に積層されるシーラント層２１と、を備えており、ガスバリア積層体１０のオーバーコート層４とシーラント層２１とが接着層２２を介して接着されている。言い換えると、包装材３０は、オーバーコート層４の蒸着層３とは反対側にシーラント層２１を備えている。 FIG. 2 is a schematic cross-sectional view showing a packaging material according to another embodiment. The packaging material 30 shown in FIG. 2 includes a gas barrier laminate 10 and a sealant layer 21 laminated on the gas barrier laminate 10, and the overcoat layer 4 of the gas barrier laminate 10 and the sealant layer 21 are bonded together as an adhesive layer It is bonded via 22. In other words, the packaging material 30 includes the sealant layer 21 on the side of the overcoat layer 4 opposite to the vapor deposited layer 3.
　包装材３０をモノマテリアル包材とするために、シーラント層２１の材質は、ポリオレフィンであってもよい。シーラント層２１の材質は、包装材の基材層と同様に、ポリプロピレンであってもよい。シーラント層２１は、例えば、延伸又は未延伸のポリプロピレンフィルムであってもよい。 In order to make the packaging material 30 a monomaterial packaging material, the material of the sealant layer 21 may be polyolefin. The material of the sealant layer 21 may be polypropylene similarly to the base material layer of the packaging material. The sealant layer 21 may be, for example, a stretched or unstretched polypropylene film.
　シーラント層２１の厚さは、例えば１５μｍ以上であってもよく、２００μｍ以下又は１００μｍ以下であってもよい。 The thickness of the sealant layer 21 may be, for example, 15 μm or more, 200 μm or less, or 100 μm or less.
　接着層２２は、ガスバリア積層体１０とシーラント層２１とを接着するものである。接着層２２を構成する接着剤としては、例えば、ポリエステルポリオール、ポリエーテルポリオール、アクリルポリオール、カーボネートポリオール等の主剤に対し、二官能以上のイソシアネート化合物を作用させたポリウレタン樹脂などが挙げられる。各種ポリオールは、１種を単独で又は２種以上を組み合わせて使用してもよい。接着層２２は、接着促進を目的として、上述のポリウレタン樹脂に、カルボジイミド化合物、オキサゾリン化合物、エポキシ化合物、リン化合物、シランカップリング剤等が配合されてもよい。接着層の厚さとしては、所望の接着強度、追随性、及び加工性等を得る観点から、例えば、０．５～１０ｇ／ｍ２であってもよい。接着層２２には、環境配慮の観点から高分子成分がバイオマス由来であるものや生分解性を持つものを使用してもよい。また、接着層２２にはバリア性を有する接着剤を用いてもよい。 The adhesive layer 22 is for bonding the gas barrier laminate 10 and the sealant layer 21 together. Examples of the adhesive constituting the adhesive layer 22 include polyurethane resins in which a difunctional or higher-functional isocyanate compound is applied to a base material such as polyester polyol, polyether polyol, acrylic polyol, or carbonate polyol. Various polyols may be used alone or in combination of two or more. In the adhesive layer 22, a carbodiimide compound, an oxazoline compound, an epoxy compound, a phosphorus compound, a silane coupling agent, etc. may be blended with the above-mentioned polyurethane resin for the purpose of promoting adhesion. The thickness of the adhesive layer may be, for example, 0.5 to 10 g/m 2 from the viewpoint of obtaining desired adhesive strength, trackability, processability, etc. For the adhesive layer 22, from the viewpoint of environmental consideration, a material whose polymer component is derived from biomass or a material having biodegradability may be used. Further, an adhesive having barrier properties may be used for the adhesive layer 22.
　包装材のＣｏｂｂ３００値（初期）は、水分バリア性に優れる観点から、０．３ｇ／ｍ２以下、０．２ｇ／ｍ２以下、又は０．１ｇ／ｍ２以下であってもよい。Ｃｏｂｂ３００値（初期）は、包装材の折り曲げ部以外で測定されるＣｏｂｂ３００値を意味し、後述の実施例に記載の方法により測定される。 The Cobb300 value (initial) of the packaging material may be 0.3 g/m 2 or less, 0.2 g/m 2 or less, or 0.1 g/m 2 or less from the viewpoint of excellent moisture barrier properties. The Cobb300 value (initial) means the Cobb300 value measured at a portion other than the folded portion of the packaging material, and is measured by the method described in the Examples below.
＜包装袋＞
　図３は、ガスバリア積層体１０（包装材２０）からなるガゼット袋４０を示す斜視図である。ガゼット袋４０の上部の開口部をシールすることで包装袋が製造される。ガゼット袋４０はガスバリア積層体１０が折り曲げられている箇所（折り曲げ部Ｂ１，Ｂ２）を有する。折り曲げ部Ｂ１は、最内層側からみてガスバリア積層体１０が谷折りされている箇所であり、他方、折り曲げ部Ｂ２は、最内層側からみてガスバリア積層体１０が山折りされている箇所である。 <Packaging bag>
FIG. 3 is a perspective view showing a gusset bag 40 made of the gas barrier laminate 10 (packaging material 20). A packaging bag is manufactured by sealing the upper opening of the gusset bag 40. The gusset bag 40 has portions where the gas barrier laminate 10 is bent (bent portions B1 and B2). The folded portion B1 is a portion where the gas barrier laminate 10 is valley-folded when viewed from the innermost layer side, while the bent portion B2 is a portion where the gas barrier laminate 10 is mountain-folded when viewed from the innermost layer side.
　包装袋は、１枚のガスバリア積層体をオーバーコート層４が対向するように二つ折りにした後、所望の形状になるように適宜折り曲げてヒートシールすることによって袋形状としたものであってもよく、２枚のガスバリア積層体をオーバーコート層４が対向するように重ねた後、ヒートシールすることによって袋形状としたものであってもよい。 The packaging bag may be formed into a bag shape by folding one gas barrier laminate in half so that the overcoat layer 4 faces each other, then bending it appropriately to obtain the desired shape, and heat-sealing it. Often, two gas barrier laminates may be stacked so that the overcoat layer 4 faces each other, and then heat-sealed to form a bag shape.
　包装袋は、水系内容物を収容する。本明細書において、水系内容物とは、少なくとも水を含む内容物を意味する。本実施形態に係る包装袋は、折り曲げ部を有する形状であっても優れた水分バリア性を有し、水系内容物が染み出すことを十分に抑制することができる。 The packaging bag contains aqueous contents. In this specification, the aqueous content means a content containing at least water. The packaging bag according to the present embodiment has excellent moisture barrier properties even if it has a bent portion, and can sufficiently suppress the aqueous contents from seeping out.
　なお、本実施形態においては、包装袋の一例としてガゼット袋を挙げたが、本実施形態に係る包装材を使用して、例えば、ピロー袋、三方シール袋又はスタンディングパウチを作製してもよい。 Note that in this embodiment, a gusset bag is cited as an example of a packaging bag, but the packaging material according to this embodiment may be used to produce, for example, a pillow bag, a three-sided seal bag, or a standing pouch.
　本開示は、例えば、以下の［１］～［５］を含む。
［１］紙基材と、アンカーコート層と、蒸着層と、オーバーコート層と、がこの順で積層されたガスバリア積層体を少なくとも備える包装材であって、
　前記紙基材の質量が、前記包装材の全質量に対して５０質量％以上であり、
　前記蒸着層が、金属又は金属酸化物を含み、
　前記オーバーコート層が、カルボン酸塩基を有するポリオレフィンを含み、
　前記オーバーコート層の厚さが３μｍ超である、水系内容物用包装材。
［２］前記アンカーコート層が、カルボン酸塩基を有するポリオレフィンを含む、［１］に記載の水系内容物用包装材。
［３］前記アンカーコートの厚さに対する前記オーバーコート層の厚さの比率が、１～２０である、［１］又は［２］に記載の水系内容物用包装材。
［４］前記オーバーコート層の前記蒸着層とは反対側にシーラント層を更に備える、［１］～［３］のいずれか一つに記載の水系内容物用包装材。
［５］［１］～［４］のいずれか一つに記載の水系内容物用包装材を製袋してなる水系内容物用包装袋。 The present disclosure includes, for example, the following [1] to [5].
[1] A packaging material comprising at least a gas barrier laminate in which a paper base material, an anchor coat layer, a vapor deposition layer, and an overcoat layer are laminated in this order,
The mass of the paper base material is 50% by mass or more with respect to the total mass of the packaging material,
the vapor deposited layer contains a metal or a metal oxide,
The overcoat layer contains a polyolefin having a carboxylic acid group,
A packaging material for aqueous contents, wherein the overcoat layer has a thickness of more than 3 μm.
[2] The packaging material for aqueous contents according to [1], wherein the anchor coat layer contains a polyolefin having a carboxylic acid group.
[3] The packaging material for aqueous contents according to [1] or [2], wherein the ratio of the thickness of the overcoat layer to the thickness of the anchor coat is 1 to 20.
[4] The packaging material for aqueous contents according to any one of [1] to [3], further comprising a sealant layer on the side of the overcoat layer opposite to the vapor deposition layer.
[5] A packaging bag for aqueous contents made from the packaging material for aqueous contents according to any one of [1] to [4].
　以下、実施例により本開示をさらに詳細に説明するが、本開示はこれらの例に限定されるものではない。 Hereinafter, the present disclosure will be explained in more detail with reference to examples, but the present disclosure is not limited to these examples.
＜ガスバリア積層体の作製＞
（実施例１）
　紙基材（コート紙、紙の厚さ：５５μｍ、６０ｇ／ｍ２、クレーコート層の厚さ：５μｍ）のクレーコート層側の表面上に、カルボン酸塩基を有するポリオレフィンを含む塗液（商品名：ケミパールＳ１００、アイオノマー系、平均粒径：＜０．１μｍ、溶媒：水、ＩＰＡ、三井化学製）をバーコーターで塗工し、オーブンで乾燥させ、アンカーコート層を形成した。アンカーコート層の厚さは２μｍであった。次いで、アンカーコート層上に、真空蒸着法にてＡＬ蒸着を施し、蒸着層を形成した。蒸着層の厚さは５０ｎｍであった。次いで、蒸着層上にカルボン酸塩基を有するポリオレフィンを含む溶液（商品名：ケミパールＳ１００、アイオノマー系、平均粒径：０．１μｍ未満、溶媒：水、ＩＰＡ、三井化学製）をバーコーターで塗工し、オーブンで乾燥させ、オーバーコート層を形成し、ガス包装材を得た。オーバーコート層の厚さは５μｍであった。包装材における紙基材の含有量は８２質量％であった。 <Production of gas barrier laminate>
(Example 1)
A coating liquid containing a polyolefin having a carboxylic acid group (product Chemipearl S100, ionomer system, average particle size: <0.1 μm, solvent: water, IPA, manufactured by Mitsui Chemicals) was coated with a bar coater and dried in an oven to form an anchor coat layer. The thickness of the anchor coat layer was 2 μm. Next, AL was deposited on the anchor coat layer by a vacuum deposition method to form a deposited layer. The thickness of the deposited layer was 50 nm. Next, a solution containing a polyolefin having a carboxylic acid group (trade name: Chemipearl S100, ionomer type, average particle size: less than 0.1 μm, solvent: water, IPA, manufactured by Mitsui Chemicals) was applied on the vapor deposition layer using a bar coater. The mixture was dried in an oven to form an overcoat layer to obtain a gas packaging material. The thickness of the overcoat layer was 5 μm. The content of paper base material in the packaging material was 82% by mass.
（実施例２）
　オーバーコート層の厚さを１０μｍにしたこと以外は、実施例１と同様の操作によって包装材を得た。包装材における紙基材の含有量は７６質量％であった。 (Example 2)
A packaging material was obtained in the same manner as in Example 1 except that the thickness of the overcoat layer was 10 μm. The content of paper base material in the packaging material was 76% by mass.
（実施例３）
　アンカーコート層の厚さを３μｍにしたこと、及びオーバーコート層の厚さを１２μｍにしたこと以外は、実施例１と同様の操作によって包装材を得た。包装材における紙基材の含有量は７３質量％であった。 (Example 3)
A packaging material was obtained by the same operation as in Example 1, except that the thickness of the anchor coat layer was 3 μm and the thickness of the overcoat layer was 12 μm. The content of paper base material in the packaging material was 73% by mass.
（実施例４）
　オーバーコート層の厚さを３．５μｍにしたこと以外は、実施例１と同様の操作によって包装材を得た。包装材における紙基材の含有量は８４質量％であった。 (Example 4)
A packaging material was obtained in the same manner as in Example 1 except that the thickness of the overcoat layer was 3.5 μm. The content of paper base material in the packaging material was 84% by mass.
（実施例５）
　アンカーコート層の厚さを１μｍにしたこと、及びオーバーコート層の厚さを２０μｍにしたこと以外は、実施例１と同様の操作によって包装材を得た。包装材における紙基材の含有量は６８質量％であった。 (Example 5)
A packaging material was obtained by the same operation as in Example 1, except that the thickness of the anchor coat layer was 1 μm and the thickness of the overcoat layer was 20 μm. The content of paper base material in the packaging material was 68% by mass.
（比較例１）
　オーバーコート層の厚さを０．５μｍにしたこと以外は、実施例１と同様の操作によって包装材を得た。包装材における紙基材の含有量は８８質量％であった。 (Comparative example 1)
A packaging material was obtained in the same manner as in Example 1 except that the thickness of the overcoat layer was 0.5 μm. The content of paper base material in the packaging material was 88% by mass.
（比較例２）
　オーバーコート層の厚さを２μｍにしたこと以外は、実施例１と同様の操作によって包装材を得た。包装材における紙基材の含有量は８６質量％であった。 (Comparative example 2)
A packaging material was obtained in the same manner as in Example 1 except that the thickness of the overcoat layer was 2 μm. The content of paper base material in the packaging material was 86% by mass.
（比較例３）
　アンカーコート層を、アクリルポリオール（アクリルポリオールとは、アクリル酸誘導体モノマーの重合物、又はアクリル酸誘導体モノマーとその他モノマーの重合体であり、末端に水酸基を有する）とポリイソシアネートの硬化物であるウレタン硬化型アクリル樹脂としたこと、アンカーコート層の厚さを３μｍにしたこと、オーバーコート層をＰＶＡとＴＥＯＳの加水分解物の混合物で形成したこと、及びオーバーコート層の厚さを３．５μｍとしたこと以外は、実施例１と同様の操作によって包装材を得た。包装材における紙基材の含有量は８５質量％であった。 (Comparative example 3)
The anchor coat layer is made of urethane, which is a cured product of acrylic polyol (acrylic polyol is a polymer of acrylic acid derivative monomers, or a polymer of acrylic acid derivative monomers and other monomers, and has a hydroxyl group at the end) and polyisocyanate. The thickness of the anchor coat layer was 3 μm, the overcoat layer was made of a mixture of PVA and TEOS hydrolyzate, and the thickness of the overcoat layer was 3.5 μm. A packaging material was obtained by the same operation as in Example 1 except for the above. The content of paper base material in the packaging material was 85% by mass.
（比較例４）
　顔料（エンジニアードカオリン、イメリス社製、バリサーフＨＸ、平均粒子径９．０μｍ、アスペクト比８０～１００）に分散剤としてポリアクリル酸ソーダを添加し（対顔料０．２％）、セリエミキサーで分散して固形分濃度５５％のカオリンスラリーを調製した。得られたカオリンスラリー中に、顔料１００部（固形分）に対し水蒸気バリア性樹脂としてスチレン・ブタジエン系ラテックス（日本ゼオン社製、ＰＮＴ７８６８）を１００部（固形分）となるように配合し、固形分濃度５０％のアンカーコート層形成用塗工液を得た。 (Comparative example 4)
Sodium polyacrylate was added as a dispersant to pigment (engineered kaolin, manufactured by Imerys, Varisurf HX, average particle size 9.0 μm, aspect ratio 80-100) (0.2% to pigment) and dispersed with a Serie mixer. A kaolin slurry having a solid content concentration of 55% was prepared. In the obtained kaolin slurry, 100 parts (solid content) of styrene-butadiene latex (manufactured by Nippon Zeon Co., Ltd., PNT7868) as a water vapor barrier resin was blended to 100 parts (solid content) of the pigment. A coating solution for forming an anchor coat layer having a concentration of 50% was obtained.
　顔料（エンジニアードカオリン、イメリス社製、バリサーフＨＸ、平均粒子径９．０μｍ、アスペクト比８０－１００）に分散剤としてポリアクリル酸ソーダを添加し（対顔料０．２％）、セリエミキサーで分散して固形分濃度５５％のカオリンスラリーを調製した。ポリビニルアルコール（クラレ社製、ＰＶＡ１１７）水溶液を固形分濃度１０％となるよう調製し、ＰＶＡ水溶液を得た。得られたカオリンスラリーと、ＰＶＡ水溶液を固形分で顔料：ＰＶＡ水溶液＝１００：１００として固形分濃度が１０％となるよう混合し、オーバーコート層形成用塗工液を得た。 Sodium polyacrylate was added as a dispersant to pigment (engineered kaolin, manufactured by Imerys, Varisurf HX, average particle size 9.0 μm, aspect ratio 80-100) (0.2% to pigment) and dispersed with a Serie mixer. A kaolin slurry having a solid content concentration of 55% was prepared. A polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117) aqueous solution was prepared to have a solid content concentration of 10% to obtain a PVA aqueous solution. The obtained kaolin slurry and a PVA aqueous solution were mixed in a solid content of pigment:PVA aqueous solution = 100:100 so that the solid content concentration was 10% to obtain a coating liquid for forming an overcoat layer.
　紙基紙（クラフト紙、紙の厚さ：５５ｇ／ｍ２）に、アンカーコート層形成用塗工液を乾燥質量で塗工量１２ｇ／ｍ２（アンカーコート層の厚さ：１２μｍ）となるようブレードコーターを用いて片面塗工し、乾燥させた後、その上にオーバーコート層形成用塗工液を乾燥質量で塗工量３．０ｇ／ｍ２（オーバーコート層の厚さ：３μｍ）となるようロールコーターを用いて片面塗工し、乾燥させて、包装材を得た。包装材における紙基材の含有量は７９質量％であった。 On paper base paper (kraft paper, paper thickness: 55 g/m 2 ), the coating liquid for forming an anchor coat layer was applied in a dry weight amount of 12 g/m 2 (anchor coat layer thickness: 12 μm). After coating on one side using a blade coater and drying, apply a coating liquid for overcoat layer formation on it in a dry weight of 3.0 g/m 2 (thickness of overcoat layer: 3 μm). It was coated on one side using a roll coater and dried to obtain a packaging material. The content of paper base material in the packaging material was 79% by mass.
＜Ｃｏｂｂ吸水度評価（初期）＞
　ＪＩＳ－Ｐ８１４０：１９９８に準拠し、測定サンプルの紙基材に対してオーバーコート層側の面を上にして、その上に断面が円形で、断面積が１００ｃｍ２の金属製のシリンダーを測定サンプルとシリンダーとが密着するように設置した。次いで、蒸留水１００ｍｌ±５ｍｌをシリンダーに注ぎ入れ、測定サンプル上に水深が１０ｍｍとなるようにした。蒸留水を注ぎ終わった瞬間を０秒として、３００秒後シリンダーと共に蒸留水を除去した。測定サンプル上に吸水紙を置き、吸水紙の上を幅２００ｍｍ、直径径９０ｍｍ、重さ１０ｋｇの平滑な金属製ローラーで１往復し、吸水後の測定サンプル上に残った余分な水をふき取った。吸水前後の質量差（ｇ）から吸水時間３００秒におけるＣｏｂｂ３００値（ｇ／ｍ２）を質量差×１００により算出した。 <Cobb water absorption evaluation (initial)>
In accordance with JIS-P8140:1998, place a metal cylinder with a circular cross section and a cross-sectional area of 100 cm 2 on top of the paper base material of the measurement sample with the overcoat layer side facing up. and the cylinder were installed so that they were in close contact with each other. Next, 100 ml±5 ml of distilled water was poured into the cylinder so that the water depth was 10 mm above the measurement sample. The moment the distilled water was poured was defined as 0 seconds, and after 300 seconds, the distilled water was removed together with the cylinder. A water-absorbing paper was placed on the measurement sample, and a smooth metal roller with a width of 200 mm, a diameter of 90 mm, and a weight of 10 kg was moved over the paper once to wipe off excess water remaining on the measurement sample after water absorption. . From the mass difference (g) before and after water absorption, the Cobb300 value (g/m 2 ) at a water absorption time of 300 seconds was calculated by multiplying the mass difference by 100.
＜Ｃｏｂｂ吸水度評価（折り曲げ後）＞
　測定サンプルの紙基材に対してオーバーコート層側の面を外側に向けて折り目を付けずに１８０度折り曲げ、３ｋｇのローラーを片道１回だけ転がして折り目を付けた。次いで、余分な力が折り目に加わらないようにしながら測定サンプルを広げ、折り目がシリンダーの断面の中心を通るように配置し、上記のＣｏｂｂ吸水度評価（初期）と同様の方法により折り曲げ後のＣｏｂｂ３００値を算出した。 <Cobb water absorption evaluation (after bending)>
The paper base material of the measurement sample was bent 180 degrees with the overcoat layer side facing outward without creating any creases, and a 3 kg roller was rolled once in each direction to create creases. Next, the sample to be measured is unfolded while making sure that no extra force is applied to the fold, and the fold is placed so that it passes through the center of the cross section of the cylinder. The value was calculated.
＜リサイクル性＞
　包装材のリサイクル性を評価した。包装材のリサイクル性は、包装材における紙基材の含有量により評価した。評価結果を表１に示す。
Ｓ：包装材における紙基材の含有量が８０質量％以上。
Ａ：包装材における紙基材の含有量が７０質量％以上８０質量％未満。
Ｂ：包装材における紙基材の含有量が５０質量％以上７０質量％未満。
Ｃ：包装材における紙基材の含有量が５０質量％未満。 <Recyclability>
The recyclability of the packaging material was evaluated. The recyclability of the packaging material was evaluated based on the content of paper base material in the packaging material. The evaluation results are shown in Table 1.
S: The content of the paper base material in the packaging material is 80% by mass or more.
A: The content of the paper base material in the packaging material is 70% by mass or more and less than 80% by mass.
B: The content of the paper base material in the packaging material is 50% by mass or more and less than 70% by mass.
C: The content of paper base material in the packaging material is less than 50% by mass.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　１…紙基材、２…アンカーコート層、３…蒸着層、４…オーバーコート層、１０…ガスバリア積層体、２０，３０…包装材、４０…ガゼット袋、Ｂ１，Ｂ２…折り曲げ部。 1... Paper base material, 2... Anchor coat layer, 3... Vapor deposition layer, 4... Overcoat layer, 10... Gas barrier laminate, 20, 30... Packaging material, 40... Gusset bag, B1, B2... Folded portion.

Claims (5)

  1. 　紙基材と、アンカーコート層と、蒸着層と、オーバーコート層と、がこの順で積層されたガスバリア積層体を少なくとも備える包装材であって、
    　前記紙基材の質量が、前記包装材の全質量に対して５０質量％以上であり、
    　前記蒸着層が、金属又は金属酸化物を含み、
    　前記オーバーコート層が、カルボン酸塩基を有するポリオレフィンを含み、
    　前記オーバーコート層の厚さが３μｍ超である、水系内容物用包装材。     A packaging material comprising at least a gas barrier laminate in which a paper base material, an anchor coat layer, a vapor deposition layer, and an overcoat layer are laminated in this order,
    The mass of the paper base material is 50% by mass or more with respect to the total mass of the packaging material,
    the vapor deposited layer contains a metal or a metal oxide,
    The overcoat layer contains a polyolefin having a carboxylic acid group,
    A packaging material for aqueous contents, wherein the overcoat layer has a thickness of more than 3 μm.
  2. 　前記アンカーコート層が、カルボン酸塩基を有するポリオレフィンを含む、請求項１に記載の水系内容物用包装材。 The packaging material for aqueous contents according to claim 1, wherein the anchor coat layer contains a polyolefin having a carboxylic acid group.
  3. 　前記アンカーコートの厚さに対する前記オーバーコート層の厚さの比率が、１～２０である、請求項１に記載の水系内容物用包装材。 The packaging material for aqueous contents according to claim 1, wherein the ratio of the thickness of the overcoat layer to the thickness of the anchor coat is 1 to 20.
  4. 　前記オーバーコート層の前記蒸着層とは反対側にシーラント層を更に備える、請求項１に記載の水系内容物用包装材。 The packaging material for aqueous contents according to claim 1, further comprising a sealant layer on a side of the overcoat layer opposite to the vapor deposition layer.
  5. 　請求項１～４のいずれか一項に記載の水系内容物用包装材を製袋してなる水系内容物用包装袋。 A packaging bag for aqueous contents made from the packaging material for aqueous contents according to any one of claims 1 to 4.
PCT/JP2023/007358 2022-03-17 2023-02-28 Packaging material for aqueous content and packaging bag for aqueous content WO2023176432A1 (en)

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