WO2025018413A1 - 積層体、包装袋及び包装体 - Google Patents

積層体、包装袋及び包装体 Download PDF

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Publication number
WO2025018413A1
WO2025018413A1 PCT/JP2024/025959 JP2024025959W WO2025018413A1 WO 2025018413 A1 WO2025018413 A1 WO 2025018413A1 JP 2024025959 W JP2024025959 W JP 2024025959W WO 2025018413 A1 WO2025018413 A1 WO 2025018413A1
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WIPO (PCT)
Prior art keywords
layer
laminate
heating
packaging bag
heat shrinkage
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PCT/JP2024/025959
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English (en)
French (fr)
Japanese (ja)
Inventor
悠 荻原
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Toppan Holdings Inc
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Toppan Holdings Inc
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Priority to JP2024573384A priority Critical patent/JP7673883B1/ja
Priority to CN202480045837.XA priority patent/CN121464041A/zh
Publication of WO2025018413A1 publication Critical patent/WO2025018413A1/ja
Priority to JP2025071861A priority patent/JP2025100991A/ja
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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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
    • 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
    • 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
    • B65D29/00—Sacks or like containers made of fabrics; Flexible containers of open-work, e.g. net-like construction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants

Definitions

  • This disclosure relates to laminates, packaging bags, and packaging bodies.
  • Laminates are widely used as packaging materials for foods, medicines, etc., that are subjected to heat sterilization, such as boiling and retort treatments.
  • a known example of a laminate is a laminate that comprises a biaxially oriented PET (polyethylene terephthalate) film, which has excellent heat resistance and toughness, and a polyolefin film, such as polyethylene or polypropylene, as a sealant layer (for example, Patent Document 1).
  • Packaging materials are required to make it easy to remove the contents contained therein.
  • Conventional laminates have room for improvement in terms of removal properties.
  • packaging materials are required to be easy to handle when opened.
  • the present disclosure provides the following laminate, packaging bag, and packaging body.
  • a laminate having a laminate structure comprising, in this order, The maximum opening heights H1 and H2 measured through the following steps satisfy the following conditions: 4mm ⁇ H1 6mm ⁇ H2
  • the maximum opening heights H1 and H2 are (1a) preparing two of the above laminates as test pieces each having a width of 90 mm and a length of 140 mm; (1b) overlapping the two test pieces so that the sealant layers face each other and sealing three sides with a seal width of 5 mm to form a bag; (1c) pouring 70 g of water into the upper end of the bag, and then sealing the upper end with a seal width of 5 mm to obtain a test specimen; (1d) heating the test specimen at a temperature of 128° C.
  • a packaging bag; Contents contained in the packaging bag; and Equipped with The packaging bag is formed using a laminate,
  • the laminate has a laminate structure including a base layer, an intermediate layer, and a sealant layer in this order;
  • the maximum opening heights H1 and H2 measured through the following steps satisfy the following conditions: 4mm ⁇ H1 6mm ⁇ H2
  • the maximum opening heights H1 and H2 are (2a) a step of setting a position 20 mm from the top end of the packaging bag as a first position, setting the center of the packaging bag in the height direction as a second position, cutting the packaging bag from one side to the other side at the first position, discharging the contents, and then measuring a maximum opening height H1 at the first position while the packaging bag is placed on a horizontal table; (2b) after the step (2a), cutting the packaging bag from one side to the other side at the second position and measuring the maximum opening height H2 at the second position while the packaging bag is placed on a horizontal table; It is measured through The package has a loop stiffness value
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to one embodiment.
  • FIG. 2 is a schematic front view of an example of a packaging body.
  • FIG. 3 is an end view taken along imaginary line II of FIG.
  • FIG. 4 is a schematic diagram showing a method for measuring the thermal shrinkage rate upon heating.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to this embodiment.
  • the laminate 1 has a laminate structure including a first base layer 10, a first adhesive layer 20, an intermediate layer 30, a second adhesive layer 40, and a sealant layer 50 in this order.
  • the maximum opening heights H1 and H2 measured through the following steps (1a) to (1f) satisfy the following conditions.
  • the maximum opening heights H1 and H2 satisfy the following conditions, the opening of the packaging bag obtained using the laminate 1 is difficult to close when the opening is placed vertically downward to discharge the contents. Therefore, the packaging bag has excellent dischargeability even without providing the surface of the sealant layer (innermost layer) of the laminate 1 with unevenness that promotes the discharge of the contents by additional processing or the like. 4mm ⁇ H1 6mm ⁇ H2
  • the maximum opening height H1, H2 is the maximum distance between the inner edges of the sealant layers.
  • the maximum opening height H1 is preferably 4.3 mm or more, and more preferably 5.0 mm or more, since this provides better dischargeability.
  • the maximum opening height H1 may be 7.0 mm or less.
  • the maximum opening height H1 may be 4 mm or more and 7.0 mm or less, 4.3 mm or more and 7.0 mm or less, or 5.0 mm or more and 7.0 mm or less.
  • the maximum opening height H2 is preferably 6.3 mm or more, and more preferably 7.0 mm or more, because this allows air to easily enter the entire body of the packaging bag and improves the ease of separation of the contents located at the four corners of the body.
  • the maximum opening height H2 may be 9.0 mm or less.
  • the maximum opening height H2 may be 6.0 mm or more and 9.0 mm or less, 6.3 mm or more and 9.0 mm or less, or 7.0 mm or more and 9.0 mm or less.
  • the maximum opening heights H1 and H2 can be changed, for example, by adjusting the thermal shrinkage rate of the first base material layer and the second base material layer.
  • the MD heat shrinkage rate calculated by the following formula (1) is preferably 1.0% or more, and more preferably 1.8% or more, because the resulting packaging bag opens sufficiently and has better discharging properties.
  • the MD heat shrinkage rate calculated by the following formula (1) is preferably 3.0% or less, from the viewpoint of suppressing poor appearance and poor conveyance.
  • the MD heat shrinkage rate calculated by the following formula (1) may be 1.0% or more and 3.0% or less, or 1.8% or more and 3.0% or less.
  • the TD heat shrinkage rate calculated by the following formula (2) is preferably 1.0% or more, and more preferably 1.8% or more, because the resulting packaging bag opens sufficiently and has better dischargeability.
  • the TD heat shrinkage rate calculated by the following formula (2) is preferably 3.0% or less, from the viewpoint of suppressing poor appearance and poor transport caused by shrinkage during bag making.
  • the TD heat shrinkage rate calculated by the following formula (2) may be 1.0% or more and 3.0% or less, or 1.8% or more and 3.0% or less.
  • MD heat shrinkage rate (%) (MD length before heating - MD length after heating) / MD length before heating ⁇ 100 ...
  • TD heat shrinkage rate (%) (TD length before heating - TD length after heating) / TD length before heating ⁇ 100 ...
  • MD is the machine direction of the base layer and sealant layer
  • TD is the transverse direction.
  • the orientation angle of the film can be measured using, for example, a phase difference measuring device (product name: KOBRA, manufactured by Oji Scientific Instruments Co., Ltd.), and the MD and TD can be distinguished from the orientation angle.
  • a phase difference measuring device product name: KOBRA, manufactured by Oji Scientific Instruments Co., Ltd.
  • the MD and TD can be distinguished from the orientation angle.
  • the film is a sequentially biaxially oriented polypropylene film, the direction in which the molecular chains are oriented is considered to be TD.
  • the loop stiffness value is preferably 80 mN or more, more preferably 90 mN or more, more preferably 220 mN or less, more preferably 170 mN or less, even more preferably 150 mN or less, even more preferably 130 mN or less, and particularly preferably 105 mN or less.
  • the packaging bag has excellent handling properties when opened.
  • the packaging bag is less likely to twist (twist), making it easier to open and easier to maintain the opened shape.
  • the packaging bag tends to have better dischargeability.
  • the loop stiffness value is 150 mN or less, it is easier to pinch by both hands at both sides and push toward the center of the packaging bag. Therefore, the packaging bag tends to be easier to open stably and has better dischargeability.
  • the packaging bag can be easily opened with light force and easily maintains the opened shape.
  • the loop stiffness value after heating the laminate 1 at 128°C for 15 minutes may be 80 mN to 220 mN, 80 mN to 170 mN, 80 mN to 150 mN, 80 mN to 130 mN, 80 mN to 105 mN, 90 mN to 220 mN, 90 mN to 170 mN, 90 mN to 150 mN, 90 mN to 130 mN, or 90 mN to 105 mN.
  • the loop stiffness value can be measured by the method described in the Examples below.
  • Loop stiffness is a physical property that indicates the rigidity of a film.
  • the loop stiffness increases slightly due to thermal shrinkage after heating, but can be adjusted by the film thickness of the laminate and the crystallinity and Young's modulus of each layer.
  • the larger the film thickness the greater the loop stiffness value tends to be.
  • the higher the crystallinity the greater the loop stiffness value tends to be.
  • the higher the Young's modulus the greater the loop stiffness value tends to be.
  • the smaller the film thickness the smaller the loop stiffness value tends to be.
  • the lower the crystallinity the smaller the loop stiffness value tends to be.
  • the lower the Young's modulus the smaller the loop stiffness value tends to be.
  • the total mass ratio of the polypropylene-based resin in the laminate 1 is preferably 90% by mass or more based on the total amount of the laminate 1, since the laminate 1 is a mono-material packaging material made of a single material and has excellent recyclability.
  • the content of the polypropylene-based resin in the laminate 1 may be 92.5% by mass or more, or 95% by mass or more based on the total amount of the laminate 1.
  • the first base layer 10 is a plastic member that functions as the outermost layer in the laminate 1.
  • the thickness of the first base layer 10 is not particularly limited. Depending on the application, the thickness can be 6 to 200 ⁇ m, but from the viewpoint of reducing materials to reduce the environmental load and from the viewpoint of obtaining excellent heat resistance, impact resistance, and excellent gas barrier properties, the thickness may be 9 to 50 ⁇ m, 12 to 38 ⁇ m, 18 to 30 ⁇ m, or 15 to 30 ⁇ m.
  • the first base layer 10 is, for example, a polyolefin film from the viewpoint of the recyclability of the laminate 1.
  • the first base layer 10 may contain a polypropylene film or may be made of a polypropylene film.
  • the polypropylene film may be an acid-modified polypropylene film obtained by graft-modifying polypropylene with an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like.
  • polypropylene-based resins such as homopolypropylene resin (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, and propylene- ⁇ -olefin copolymer can be used.
  • PP homopolypropylene resin
  • propylene-ethylene random copolymer propylene-ethylene random copolymer
  • propylene-ethylene block copolymer propylene-ethylene block copolymer
  • propylene- ⁇ -olefin copolymer propylene- ⁇ -olefin copolymer
  • the polypropylene film constituting the first base layer 10 may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, tackifiers, and antistatic agents.
  • the polypropylene film constituting the first base layer 10 may be a stretched film or a non-stretched film. Since the polypropylene film has better dischargeability, it is preferable that the polypropylene film is a stretched polypropylene film.
  • the heat shrinkage rate in the MD calculated by the above formula (1) is preferably 2.0% or more, more preferably 3.0% or more, and even more preferably 4.0% or more, since this provides better ejection properties. From the viewpoint of handling properties when the packaging bag is opened, the heat shrinkage rate in the MD may be 5.0% or less.
  • the heat shrinkage rate of the TD calculated by the above formula (2) is preferably more than 0%, more preferably 1.0% or more, and even more preferably 2.0% or more, since this provides better ejection properties. From the viewpoint of handling properties when opening the packaging bag, the heat shrinkage rate of the TD may be 3.0% or less.
  • the difference between S1MD and S1TD is preferably more than 0%, more preferably 1% or more, and even more preferably 1.5% or more, from the viewpoint of tending to make the opening height higher and to provide better dischargeability, and is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less, from the viewpoint of suppressing distortion of the packaging bag that causes packaging defects.
  • the difference between S1 MD and S1 TD may be more than 0% and not more than 5%, more than 0% and not more than 4%, more than 0% and not more than 3%, 1% or more and not more than 5%, 1% or more and not more than 4%, 1% or more and not more than 3%, 1.5% or more and not more than 5%, 1.5% or more and not more than 4%, or 1.5% or more and not more than 3%.
  • the difference between S1 MD and S2 MD is preferably more than 0%, more preferably 0.25% or more, and even more preferably 0.5% or more, from the viewpoint of easily increasing the opening height and tending to provide even better dischargeability, and is preferably 2.5% or less, more preferably 2.0% or less, and even more preferably 1.0% or less, from the viewpoint of suppressing the occurrence of cracks in the gas barrier layer due to differences in base material shrinkage.
  • the difference between S1 TD and S2 TD is preferably more than 0%, more preferably 0.3% or more, and even more preferably 0.4% or more, from the viewpoint of easily increasing the opening height and tending to provide even better dischargeability, and is preferably 2.0% or less, more preferably 1.5% or less, and even more preferably 1.0% or less, from the viewpoint of suppressing the occurrence of cracks in the gas barrier layer due to differences in base material shrinkage.
  • the first base layer 10 may be subjected to various pretreatments such as corona treatment, plasma treatment, and flame treatment on its lamination surface, or a coating layer such as an easy-adhesion layer may be provided.
  • the first adhesive layer 20 is a layered member that bonds the first base material layer 10 and the intermediate layer 30.
  • the second adhesive layer 40 is a layered member that bonds the intermediate layer 30 and the sealant layer 50.
  • polyester-isocyanate resin, urethane resin, polyether resin, etc. can be used as the adhesive material contained in the first adhesive layer 20 and the second adhesive layer 40.
  • a two-liquid curing urethane adhesive that is resistant to retort can be preferably used. From the viewpoint of environmental consideration, the adhesive does not have to contain 3-glycidyloxypropyltrimethoxysilane (GPTMS).
  • the first adhesive layer 20 and the second adhesive layer 40 do not have to contain chlorine.
  • the first adhesive layer 20 and the second adhesive layer 40 can suppress coloring of the recycled resin after recycling and the generation of odor due to heat treatment.
  • the first adhesive layer 20 and the second adhesive layer 40 may be formed of a biomass material and may not contain a solvent.
  • the urethane adhesive contains polyol and polyisocyanate.
  • the first adhesive layer 20 and the second adhesive layer 40 may contain polyurethane obtained by curing the urethane adhesive, or may contain uncured urethane adhesive.
  • Polyols have two or more hydroxyl groups in one molecule.
  • Polyisocyanates have two or more isocyanate groups in one molecule.
  • Polyols and polyisocyanates may react as a base agent and a curing agent, respectively, to produce polyurethane.
  • the polyol may contain at least one selected from the group consisting of polyester polyols and polyether polyols.
  • Polyisocyanates may be used alone or in combination of two or more.
  • examples of polyisocyanates include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, and aromatic polyisocyanate compounds.
  • the thickness of the first adhesive layer 20 is, for example, 0.5 ⁇ m or more and 10 ⁇ m or less. When the thickness of the first adhesive layer 20 is 0.5 ⁇ m or more, peeling between the first substrate layer 10 and the intermediate layer 30 can be effectively suppressed. When the thickness of the first adhesive layer 20 is 10 ⁇ m or less, the laminate 1 can be easily made into a mono-material.
  • the thickness of the first adhesive layer 20 may be 1 ⁇ m or more, 2 ⁇ m or more, 8 ⁇ m or less, 6 ⁇ m or less, or 5 ⁇ m or less.
  • the thickness of the second adhesive layer 40 is, for example, 0.5 ⁇ m or more and 10 ⁇ m or less. When the thickness of the second adhesive layer 40 is 0.5 ⁇ m or more, peeling between the intermediate layer 30 and the sealant layer 50 can be effectively suppressed. When the thickness of the second adhesive layer 40 is 10 ⁇ m or less, the laminate 1 can be easily made into a mono-material.
  • the thickness of the first adhesive layer 20 may be 1 ⁇ m or more, 2 ⁇ m or more, 8 ⁇ m or less, 6 ⁇ m or less, or 5 ⁇ m or less.
  • the intermediate layer 30 has a second base layer 31 and a gas barrier layer 32.
  • the gas barrier layer 32 exhibits gas barrier properties against gases such as water vapor and oxygen.
  • the gas barrier layer 32 has, from the second base layer 31 side, an anchor coat layer 32a, a deposition layer 32b, and a barrier coat layer 32c, in this order.
  • the thickness of the intermediate layer may be the same as that of the first substrate layer 10.
  • the thickness of the second substrate layer 31 may be the same as that of the first substrate layer 10.
  • the second substrate layer 31 is, for example, a polyolefin film from the viewpoint of the recyclability of the laminate 1.
  • the second substrate layer 31 may contain a polypropylene film or may be made of a polypropylene film.
  • the polypropylene film may be the same as that of the first substrate layer 10.
  • the polypropylene film may be added with various additives similar to those of the first substrate layer 10.
  • the second substrate layer 31 contains an antiblocking agent, the addition of the antiblocking agent may be suppressed in order to improve the smoothness of the surface on the side where the deposition layer 32b is provided.
  • the second substrate layer 31 may be subjected to various pretreatments similar to those of the first substrate layer 10, or a coating layer may be provided.
  • the heat shrinkage rate in the MD calculated by the above formula (1) is preferably 1.0% or more, more preferably 2.0% or more, and even more preferably 3.0% or more, since this provides better ejection properties.
  • the heat shrinkage rate in the MD may be 5.0% or less, from the viewpoint of handling properties when the packaging bag is opened.
  • the heat shrinkage rate of the TD calculated by the above formula (2) is preferably more than 0%, more preferably 1.0% or more, and even more preferably 2.0% or more, since this provides better ejection properties.
  • the heat shrinkage rate of the TD may be 3.0% or less, from the viewpoint of handling properties when the packaging bag is opened.
  • the difference between S2MD and S2TD is preferably more than 0%, more preferably 1% or more, and even more preferably 1.5% or more, from the viewpoint of a tendency for the opening height to be increased and for the dischargeability to be further improved, and is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less, from the viewpoint of suppressing distortion of the packaging bag that causes packaging defects of the packaging bag.
  • the difference between S2 MD and S2 TD may be more than 0% and not more than 5%, more than 0% and not more than 4%, more than 0% and not more than 3%, 1% or more and not more than 5%, 1% or more and not more than 4%, 1% or more and not more than 3%, 1.5% or more and not more than 5%, 1.5% or more and not more than 4%, or 1.5% or more and not more than 3%.
  • the anchor coat layer 32a functions as a layer capable of improving the adhesion performance of the deposition layer 32b on the second substrate layer 31, and is provided directly on the second substrate layer 31. Therefore, the anchor coat layer 32a is located between the second substrate layer 31 and the deposition layer 32b.
  • the smoothness of the surface on which the deposition layer 32b is provided in the intermediate layer 30 can be improved.
  • the improved smoothness makes it easier to form the deposition layer 32b uniformly without defects, and makes it easier to exhibit high barrier properties.
  • the anchor coat layer 32a can be formed, for example, using an anchor coat agent.
  • urethane resin is preferred.
  • urethane resin include polyester-based polyurethane resin, polyether-based polyurethane resin, and acrylic-based polyurethane resin.
  • polyester-based polyurethane resin and acrylic-based urethane resin are preferred from the viewpoint of heat resistance and interlayer adhesive strength.
  • acrylic polyurethane resin is more preferred as the anchor coating agent.
  • the thickness of the anchor coat layer 32a is not particularly limited, but is preferably in the range of 0.01 to 5 ⁇ m, more preferably in the range of 0.03 to 3 ⁇ m, and particularly preferably in the range of 0.05 to 2 ⁇ m. If the thickness of the anchor coat layer 32a is equal to or greater than the lower limit above, there is a tendency for more sufficient interlayer adhesive strength to be obtained, while if the thickness is equal to or less than the upper limit above, there is a tendency for the desired gas barrier properties to be easily achieved.
  • the method for applying the anchor coat layer 32a onto the second substrate layer 31 can be any known application method without particular limitation, and examples of such methods include immersion (dipping), spraying, coater, printing machine, brushing, etc.
  • examples of the types of coaters and printing machines used in these methods and the application methods thereof include gravure coaters such as direct gravure, reverse gravure, kiss reverse gravure, and offset gravure, reverse roll coaters, microgravure coaters, coaters combined with chamber doctor, air knife coaters, dip coaters, bar coaters, comma coaters, die coaters, etc.
  • the coating amount of the anchor coating layer 32a is preferably 0.01 to 5 g/ m2 , more preferably 0.03 to 3 g/ m2 , in terms of the mass per m2 after the anchor coating agent is applied and dried. If the mass per m2 after the anchor coating agent is applied and dried is equal to or greater than the lower limit, the film tends to be sufficiently formed, whereas if it is equal to or less than the upper limit, the film tends to be sufficiently dried and the solvent is less likely to remain.
  • the method for drying the anchor coat layer 32a is not particularly limited, but examples include natural drying, drying in an oven set at a predetermined temperature, and using a dryer attached to the coater, such as an arch dryer, floating dryer, drum dryer, or infrared dryer. Furthermore, the drying conditions can be appropriately selected depending on the drying method. For example, in the method of drying in an oven, it is preferable to dry at a temperature of 60 to 100°C for about 1 to 2 minutes.
  • a polyvinyl alcohol resin can be used as the anchor coat layer 32a.
  • the polyvinyl alcohol resin may be any resin that has vinyl alcohol units formed by saponifying vinyl ester units, such as polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH).
  • PVA examples include resins obtained by polymerizing vinyl esters such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate, and vinyl versatate alone and then saponifying them.
  • the PVA may be a modified PVA that has been copolymerized or post-modified. Modified PVA can be obtained, for example, by copolymerizing a vinyl ester with an unsaturated monomer that is copolymerizable with the vinyl ester and then saponifying it.
  • unsaturated monomers copolymerizable with vinyl esters include olefins such as ethylene, propylene, isobutylene, ⁇ -octene, ⁇ -dodecene, and ⁇ -octadecene; hydroxyl group-containing ⁇ -olefins such as 3-buten-1-ol, 4-pentyn-1-ol, and 5-hexen-1-ol; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, and undecylenic acid; nitriles such as acrylonitrile and methacrylonitrile; diacetone acrylamide, acrylic Amides such as amide and methacrylamide; olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid; vinyl compounds such as alkyl vinyl ether, di
  • the degree of polymerization of PVA is preferably 300 to 3000. If the degree of polymerization is less than 300, the barrier properties tend to decrease, and if it exceeds 3000, the viscosity is too high and the coating suitability tends to decrease.
  • the saponification degree of PVA is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more.
  • the saponification degree of PVA may be 100 mol% or less, or 99.9 mol% or less.
  • the polymerization degree and saponification degree of PVA can be measured in accordance with the method described in JIS K 6726 (1994).
  • EVOH is generally obtained by saponifying copolymers of ethylene and vinyl acid esters such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate, and vinyl versatate.
  • the degree of polymerization of EVOH is preferably 300 to 3000. If the degree of polymerization is less than 300, the barrier properties tend to decrease, and if it exceeds 3000, the viscosity is too high and the coating suitability tends to decrease.
  • the degree of saponification of the vinyl ester component of EVOH is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more.
  • the degree of saponification of EVOH may be 100 mol% or less, or 99.9 mol% or less.
  • the degree of saponification of EVOH is determined by nuclear magnetic resonance (1H-NMR) measurement, from the peak area of the hydrogen atoms contained in the vinyl ester structure and the peak area of the hydrogen atoms contained in the vinyl alcohol structure.
  • the ethylene unit content of EVOH is 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, and particularly preferably 25 mol% or more.
  • the ethylene unit content of EVOH is preferably 65 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less.
  • the gas barrier properties or dimensional stability can be maintained well under high humidity.
  • the gas barrier properties can be improved.
  • the ethylene unit content of EVOH can be determined by the NMR method.
  • anchor coat layer 32a When a polyvinyl alcohol resin is used as the anchor coat layer 32a, methods for forming the anchor coat layer 32a include coating with a polyvinyl alcohol resin solution, multi-layer extrusion, etc.
  • the deposition layer 32b is a layer (gas barrier layer) that exhibits gas barrier properties against water vapor and oxygen, and contains at least one of a metal and an inorganic oxide.
  • the deposition layer 32b is provided directly on the anchor coat layer 32a.
  • the deposition layer 32b may have a single layer structure or a laminated structure. Therefore, the deposition layer 32b contains at least one of a metal deposition layer and an inorganic oxide layer.
  • examples of the metal contained in the metal deposition layer include aluminum and stainless steel.
  • the inorganic oxide contained in the inorganic oxide layer include aluminum oxide, silicon oxide, magnesium oxide, and tin oxide.
  • the inorganic oxide may be selected from the group consisting of aluminum oxide, silicon oxide, and magnesium oxide.
  • the inorganic oxide layer is preferably a layer using silicon oxide from the viewpoint of excellent tensile stretchability during processing. By using an inorganic oxide layer, high barrier properties can be obtained with a very thin layer within a range that does not affect the recyclability of the laminate 1.
  • the O/Si ratio of the inorganic oxide layer is preferably 1.7 or more.
  • the O/Si ratio is 1.7 or more, the content of metal Si is suppressed, and good transparency is easily obtained.
  • the O/Si ratio is preferably 2.0 or less.
  • the crystallinity of SiO is high, and the inorganic oxide layer can be prevented from becoming too hard, and good tensile resistance can be obtained. This makes it possible to suppress the occurrence of cracks in the inorganic oxide layer when the barrier coat layer 32c is laminated.
  • the first base layer 10 may shrink due to heat during boiling or retort treatment, but when the O/Si ratio is 2.0 or less, the inorganic oxide layer easily follows the above shrinkage, and the deterioration of the barrier property can be suppressed.
  • the O/Si ratio of the inorganic oxide layer is preferably 1.75 to 1.9, and more preferably 1.8 to 1.85.
  • the O/Si ratio of the inorganic oxide layer can be determined by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the measurement device is an X-ray photoelectron spectrometer (manufactured by JEOL Ltd., product name: JPS-90MXV)
  • the X-ray source is non-monochromated MgK ⁇ (1253.6 eV)
  • the measurement can be performed with an X-ray output of 100 W (10 kV-10 mA).
  • relative sensitivity factors of 2.28 for O1s and 0.9 for Si2p can be used.
  • the thickness of the deposition layer 32b is, for example, 5 nm or more and 80 nm or less. If the thickness of the deposition layer 32b is 5 nm or more, sufficient water vapor barrier properties can be obtained. Furthermore, if the thickness of the deposition layer 32b is 80 nm or less, the occurrence of cracks due to deformation caused by internal stress in the thin film can be suppressed, and the deterioration of water vapor barrier properties can be suppressed. Note that if the thickness of the deposition layer 32b exceeds 80 nm, costs tend to increase due to an increase in the amount of material used and a longer film formation time, and this is not preferable from an economic standpoint. From the same standpoint as above, the thickness of the deposition layer 32b may be 20 nm or more and 40 nm or less.
  • the deposition layer 32b can be formed, for example, by vacuum deposition.
  • vacuum deposition physical vapor deposition or chemical vapor deposition can be used.
  • physical vapor deposition include, but are not limited to, vacuum deposition, sputtering, and ion plating.
  • chemical vapor deposition include, but are not limited to, thermal CVD, plasma CVD, and photo CVD.
  • the resistive heating vacuum deposition method the EB (Electron Beam) heating vacuum deposition method, the induction heating vacuum deposition method, the sputtering method, the reactive sputtering method, the dual magnetron sputtering method, the plasma enhanced chemical vapor deposition method (PECVD method), etc. are particularly preferably used.
  • the vacuum deposition method is currently the most superior.
  • the heating means for the vacuum deposition method it is preferable to use any of the following methods: the electron beam heating method, the resistive heating method, or the induction heating method.
  • the barrier coat layer 32c is a coating layer having gas barrier properties (gas barrier coating layer) and is provided on the deposition layer 32b.
  • the barrier coat layer 32c is a layer formed using a composition for forming a gas barrier coating layer (hereinafter also referred to as a coating agent) containing at least one selected from the group consisting of a hydroxyl group-containing polymer compound, a metal alkoxide, a silane coupling agent, and hydrolysates thereof, for example.
  • the coating agent preferably contains at least a silane coupling agent or a hydrolysate thereof, more preferably contains at least one selected from the group consisting of a hydroxyl-containing polymer compound, a metal alkoxide, and their hydrolysates, and a silane coupling agent or a hydrolysate thereof, and even more preferably contains a hydroxyl-containing polymer compound or a hydrolysate thereof, a metal alkoxide or a hydrolysate thereof, and a silane coupling agent or a hydrolysate thereof.
  • the coating agent can be prepared, for example, by mixing a metal alkoxide and a silane coupling agent directly, or after having been previously hydrolyzed, with a solution in which a hydroxyl-containing polymer compound, which is a water-soluble polymer, is dissolved in an aqueous solvent (water or a water/alcohol mixture).
  • hydroxyl-containing polymeric compounds used in the coating agent include polyvinyl alcohol, polyvinylpyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate.
  • polyvinyl alcohol (PVA) is preferably used as the coating agent for the barrier coat layer 32c because it has particularly excellent gas barrier properties.
  • the barrier coat layer 32c is preferably formed from a composition containing at least one selected from the group consisting of metal alkoxides represented by the following general formula (I) and their hydrolysates.
  • M(OR 1 ) m (R 2 ) nm ...(I) R1 and R2 are each independently a monovalent organic group having 1 to 8 carbon atoms, and are preferably an alkyl group such as a methyl group or an ethyl group.
  • M represents an n-valent metal atom such as Si, Ti, Al, or Zr.
  • m is an integer from 1 to n.
  • the R1s or R2s may be the same or different.
  • metal alkoxides include tetraethoxysilane [Si(OC 2 H 5 ) 4 ], triisopropoxyaluminum [Al(OC 3 H 7 ) 3 ], etc. Tetraethoxysilane and triisopropoxyaluminum are preferred because they are relatively stable in aqueous solvents after hydrolysis.
  • the silane coupling agent includes a compound represented by the following general formula (II). Si(OR 11 ) p (R 12 ) 3-p R 13 ...(II)
  • R 11 represents an alkyl group such as a methyl group or an ethyl group
  • R 12 represents a monovalent organic group such as an alkyl group, an aralkyl group, an aryl group, an alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group
  • R 13 represents a monovalent organic functional group
  • p represents an integer of 1 to 3.
  • the R 11s or the R 12s may be the same or different.
  • the monovalent organic functional group represented by R 13 include a monovalent organic functional group containing a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, an alkyl group substituted with a halogen atom, or an isocyanate group.
  • silane coupling agents include vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, and ⁇ -methacryloxypropylmethyldimethoxysilane.
  • the silane coupling agent may also be a polymer formed by polymerization of the compound represented by the above general formula (II).
  • a trimer is preferred, and 1,3,5-tris(3-trialkoxysilylalkyl)isocyanurate is more preferred.
  • This is a condensation polymer of 3-isocyanate alkylalkoxysilane. It is known that this 1,3,5-tris(3-trialkoxysilylalkyl)isocyanurate has no chemical reactivity in the isocyanate portion, but the reactivity is ensured by the polarity of the nurate portion.
  • 3-isocyanate alkyl alkoxysilanes are highly reactive and have low liquid stability, whereas 1,3,5-tris (3-trialkoxysilyl alkyl) isocyanurates are not water-soluble due to the polarity of the nurate moiety, but are easily dispersed in aqueous solutions and can maintain a stable liquid viscosity.
  • the water resistance of 3-isocyanate alkyl alkoxysilanes is equivalent to that of 1,3,5-tris (3-trialkoxysilyl alkyl) isocyanurates.
  • 1,3,5-tris(3-trialkoxysilylalkyl)isocyanurates are produced by thermal condensation of 3-isocyanatepropylalkoxysilane, and may contain the raw material 3-isocyanatepropylalkoxysilane, but this does not pose any particular problems. More preferred is 1,3,5-tris(3-trialkoxysilylpropyl)isocyanurate, and even more preferred is 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate.
  • This methoxy group has a fast hydrolysis rate, and those containing propyl groups are relatively inexpensive, so 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate is advantageous in practical use.
  • additives such as isocyanate compounds, dispersants, stabilizers, viscosity adjusters, and colorants can be added to the coating agent as needed, provided that the gas barrier properties are not impaired.
  • the thickness of the barrier coat layer 32c is preferably 50 to 1000 nm, and more preferably 100 to 500 nm. If the thickness of the barrier coat layer 32c is 50 nm or more, there is a tendency for more sufficient gas barrier properties to be obtained, and if it is 1000 nm or less, there is a tendency for sufficient flexibility to be maintained.
  • the coating liquid for forming the barrier coat layer 32c can be applied by, for example, dipping, roll coating, gravure coating, reverse gravure coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset, etc.
  • the coating film formed by applying this coating liquid can be dried by, for example, hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, or a combination of these.
  • the temperature at which the coating film is dried can be, for example, 50 to 150°C, and preferably 70 to 100°C. By keeping the drying temperature within the above range, the occurrence of cracks in the deposition layer 32b and the barrier coat layer 32c can be further suppressed, and excellent barrier properties can be achieved.
  • the barrier coat layer 32c may be formed using a coating agent containing a polyvinyl alcohol resin and a silane compound. If necessary, an acid catalyst, an alkali catalyst, a photopolymerization initiator, etc. may be added to the coating agent.
  • the polyvinyl alcohol resin is as described above.
  • silane compounds include silane coupling agents, polysilazanes, and siloxanes, and more specifically, tetramethoxysilane, tetraethoxysilane, glycidoxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, and hexamethyldisilazane.
  • the sealant layer 50 is a layer that imparts heat sealing properties to the laminate 1. From the viewpoint of recycling suitability of the laminate 1, the sealant layer 50 is a polyolefin film similar to the first base layer 10. In this embodiment, the sealant layer 50 has a single-layer structure and is a resin layer mainly made of polypropylene, but is not limited thereto. The sealant layer 50 may include a polypropylene film or may be made of a polypropylene film.
  • the polypropylene film may be an acid-modified polypropylene film obtained by graft-modifying polypropylene with an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like.
  • polypropylene-based resins such as homopolypropylene resin (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, and propylene- ⁇ -olefin copolymer can be used.
  • the polypropylene film constituting the sealant layer 50 is preferably a non-oriented polypropylene film in order to improve the sealing performance by heat sealing.
  • the polypropylene film constituting the sealant layer 50 may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, tackifiers, and antistatic agents.
  • the thickness of the sealant layer 50 is determined by the weight of the contents, the shape of the packaging bag, etc., but may be generally 30 to 150 ⁇ m thick, or 50 to 80 ⁇ m thick.
  • the thermal shrinkage rate in the MD calculated by the above formula (1) is preferably -1.0% or more, more preferably -0.5% or more, and preferably less than 0%.
  • the TD heat shrinkage calculated by the above formula (2) is preferably 0% or more and 1.0% or less.
  • the sealant layer 50 can be laminated by any of the known methods, including the dry lamination method in which the film-like sealant layer made of the above-mentioned polypropylene is laminated with an adhesive such as a one-component curing or two-component curing urethane adhesive, the non-solvent lamination method in which the film-like sealant layer is laminated using a solvent-free adhesive, and the extrusion lamination method in which the above-mentioned polypropylene is heated and melted, extruded into a curtain shape, and laminated.
  • an adhesive such as a one-component curing or two-component curing urethane adhesive
  • the non-solvent lamination method in which the film-like sealant layer is laminated using a solvent-free adhesive
  • the extrusion lamination method in which the above-mentioned polypropylene is heated and melted, extruded into a curtain shape, and laminated.
  • the dry lamination method is preferred because it has high resistance to retort treatment, especially high-temperature hot water treatment at 120°C or higher.
  • the packaging bag is to be used for treatment at a temperature of 85°C or lower, there are no particular limitations on the lamination method.
  • the laminate according to one embodiment has been described above, but the laminate of the present disclosure is not limited to the above embodiment.
  • the laminate may further include a printed layer.
  • the printing layer can be provided, for example, on at least one surface of the first base layer 10.
  • the printing layer is provided at a position visible from the outside of the laminate 1 for the purpose of displaying information about the contents, identifying the contents, improving concealment, or improving the design of the packaging bag.
  • the printing method and printing ink are not particularly limited, and are appropriately selected from known printing methods and printing inks in consideration of printability on the film, design such as color tone, adhesion, safety as a food container, etc. Examples of printing methods that can be used include gravure printing, offset printing, gravure offset printing, flexographic printing, and inkjet printing. Among them, gravure printing can be preferably used from the viewpoints of productivity and high definition of the pattern.
  • the surface of the layer on which the printing layer is to be formed may be subjected to various pretreatments such as corona treatment, plasma treatment, and frame treatment, or a coating layer such as an easy-adhesion layer may be formed.
  • the laminate of the present disclosure may not include the anchor coat layer 32a.
  • the laminate of the present disclosure may not include the barrier coat layer 32c.
  • the stacking order of the second substrate layer 31, the anchor coat layer 32a, the deposition layer 32b, and the barrier coat layer 32c may be reversed.
  • the laminate of the present disclosure may not include at least one of the first adhesive layer 20 and the second adhesive layer 40.
  • FIG. 2 is a schematic plan view of an example of the package according to this embodiment.
  • the package 200 includes a packaging bag 100 and a content (not shown) contained in the packaging bag.
  • the packaging bag 100 is formed, for example, by stacking two sheets of the laminate 1 so that the sealant layers face each other and heat sealing the four sides.
  • the packaging bag 100 is a four-sided bag having a main body 101 in which the contents are stored and a sealed portion 102 located at the end of the main body 101.
  • the shape of the main body 101 is not particularly limited, and may be rectangular when viewed from a specific direction. At least a portion of the outer surface of the main body 101 may be printed.
  • the main body 101 may store a specific gas such as nitrogen in addition to the contents.
  • the sealed portion 102 is a portion where a portion of the sealant layer 50 of the laminate 1 is bonded to another portion. In the sealed portion 102, a portion of the sealant layer 50 of the laminate 1 is in close contact with the other portion.
  • the sealed portion 102 is formed, for example, by heating and compressing (i.e., heat sealing) a portion of the sealant layer 50 of the laminate 1 to the other portion, but is not limited to this.
  • the sealed portion 102 may be formed by cold sealing or the like.
  • the maximum opening heights H1 and H2 of the package 200 which are measured through the following process, satisfy the following conditions.
  • the maximum opening heights H1 and H2 satisfy the following conditions, the opening of the package 200 is difficult to close when the opening is placed vertically downward to discharge the contents, and the package 200 has excellent dischargeability.
  • the first position is shown in FIG. 2 by the imaginary line I-I, where the distance L1 from the top end is 20 mm.
  • the second position is shown in FIG. 2 by the imaginary line II-II, where the distance from both the top end and bottom end is the same, 70 mm.
  • FIG. 3 is an end view at the imaginary line I-I.
  • the maximum opening height H1 is the maximum distance between the inner edges of the sealant layers, as shown in FIG. 3. The same is true for the maximum opening height H2.
  • the numerical ranges of the maximum opening heights H1 and H2 may be the same as those of the maximum opening heights H1 and H2 of the laminate 1.
  • the seal width S of the packaging bag 100 may be, for example, 2 to 10 mm.
  • the width W1 of the packaging bag 100 may be, for example, 80 to 150 mm.
  • the height W2 of the packaging bag 100 may be, for example, 120 to 200 mm.
  • the package 200 may be subjected to a heat treatment at 80°C or more, 120°C or more, or 135°C or less.
  • heat treatment include retort treatment and boiling treatment.
  • Retort processing is a method of sterilizing microorganisms such as mold, yeast, and bacteria by heating and pressurizing them to preserve foods, medicines, etc.
  • the packaging bag containing the food is heated and pressurized at 105-140°C and 0.15-0.30 MPa for 10-120 minutes.
  • steam type which uses heated steam
  • hot water type which uses pressurized heated water. The appropriate type is used depending on the sterilization conditions of the food, etc. that will be contained.
  • Boiling is a method of sterilizing foods, medicines, etc. by moist heat to preserve them.
  • the packaging bag containing the food is sterilized by moist heat at 60-100°C and atmospheric pressure for 10-120 minutes.
  • Boiling is usually performed using a hot water bath at 100°C or less.
  • a hot water bath at 100°C or less.
  • Contents include, for example, food and medicine. Because the packaging bag 100 has excellent drainage properties, the contents may contain water, which is generally difficult to drain.
  • the water content may be, for example, 60% by mass or more, preferably 70% by mass or more, and more preferably 75% by mass or more, based on the total amount of the contents.
  • Contents that contain water include, for example, cooked foods such as soup and pasta sauce, and pet food.
  • the packaging bag may be a standing pouch-shaped packaging bag, a two-sided bag, a three-sided bag, a folded bag, or a gusset bag.
  • the packaging bag may not have a resealable portion and a notch.
  • the packaging bag may have a knot.
  • the notch may be V-shaped, U-shaped, I-shaped, or the like. Also, a group of scars may be formed in place of the notches.
  • OPP1A Biaxially oriented polypropylene film (thickness 20 ⁇ m)
  • OPP1B Biaxially oriented polypropylene film (thickness 20 ⁇ m)
  • OPP1C Biaxially oriented polypropylene film (thickness 20 ⁇ m)
  • PET polyethylene terephthalate film (thickness 12 ⁇ m)
  • OPP2A Biaxially oriented polypropylene film (thickness 20 ⁇ m)
  • OPP2B Biaxially oriented polypropylene film (thickness 20 ⁇ m) (Sealant Layer)
  • CPP-A Non-oriented polypropylene film (thickness 60 ⁇ m)
  • CPP-B Non-oriented polypropylene film (thickness 80 ⁇ m)
  • ⁇ CPP-C Non-oriented polypropylene film (thickness 60 ⁇ m)
  • Acrylic polyol and tolylene diisocyanate were mixed so that the number of NCO groups in tolylene diisocyanate was equal to the number of OH groups in the acrylic polyol, and the mixture was diluted with ethyl acetate so that the total solids content (total amount of acrylic polyol and tolylene diisocyanate) was 5 mass%.
  • ⁇ -(3,4 epoxycyclohexyl)trimethoxysilane was further added to the diluted mixture so that the amount was 5 mass parts per 100 mass parts of the total amount of acrylic polyol and tolylene diisocyanate, and these were mixed to prepare an anchor coating agent.
  • Liquid A A hydrolysis solution with a solid content of 5 mass % ( SiO2 equivalent) obtained by adding 72.1 g of 0.1N hydrochloric acid to 17.9 g of tetraethoxysilane (Si( OC2H5 ) 4 ) and 10 g of methanol and hydrolyzing the mixture by stirring for 30 minutes.
  • Liquid B a 5% by mass water/methanol solution of polyvinyl alcohol (the mass ratio of water:methanol is 95:5).
  • Liquid C A hydrolysis solution obtained by diluting 1,3,5-tris(3-trialkoxysilylpropyl)isocyanurate with a mixed liquid of water/isopropyl alcohol (water:isopropyl alcohol mass ratio 1:1) to a solid content of 5 mass%.
  • a 30 nm thick transparent inorganic oxide layer (silica deposition layer) made of silicon oxide was formed using a vacuum deposition apparatus with electron beam heating.
  • the deposition material type was adjusted to form a silica deposition layer with an O/Si ratio of 1.8.
  • the O/Si ratio was measured using an X-ray photoelectron spectrometer (manufactured by JEOL Ltd., product name: JPS-90MXV) with an X-ray source of non-monochromated MgK ⁇ (1253.6 eV) and an X-ray output of 100 W (10 kV-10 mA). Quantitative analysis to determine the O/Si ratio was performed using relative sensitivity factors of 2.28 for O1s and 0.9 for Si2p.
  • the coating liquid for the barrier coat layer was applied onto the inorganic oxide layer by gravure roll coating, and then heated and dried in an oven under conditions of a tension of 20 N/m and a drying temperature of 120°C to form an overcoat layer with a thickness of 0.3 ⁇ m. This resulted in a gas barrier film having a laminated structure of the second substrate layer/anchor coat layer/vapor deposition layer/overcoat layer.
  • Laminates of the Examples and Comparative Examples were produced based on the combinations of layers shown in Table 1.
  • the method for producing the laminates was as follows.
  • Examples 1 to 5, Comparative Examples 1, 2, 5, and 6 The first base layer was laminated on the surface of the gas barrier film on the overcoat layer side by a dry lamination method via an adhesive.
  • the sealant layer was similarly laminated on the other surface of the second base layer of the gas barrier film. This produced a laminate having a laminate structure of the first base layer/adhesive layer/overcoat layer/vapor deposition layer/anchor coat layer/second base layer/adhesive layer/sealant layer.
  • An AL foil (thickness: 10 ⁇ m, MD heat shrinkage: 0%, TD heat shrinkage: 0%) was prepared.
  • a first base material layer was laminated on one surface of the AL foil by a dry lamination method via an adhesive.
  • a sealant layer was similarly laminated on the surface of the AL foil opposite to the surface on which the first base material layer was laminated. This produced a laminate having a laminate structure of the first base material layer/adhesive layer/AL foil layer/adhesive layer/sealant layer.
  • ⁇ Loop stiffness value> The laminates of each of the examples and comparative examples were heated at a temperature of 128°C, a time of 15 minutes, and a pressure of 0.3 MPa to perform retort treatment.
  • the loop stiffness value of the laminate after heating was measured.
  • a loop stiffness tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used for the measurement.
  • a test film having a TD of 15 mm and an MD of 200 mm was prepared from the laminate after heating. Both ends of the test film were fixed with a chuck to form a loop having a loop size of 85 mm x 15 mm.
  • This loop was compressed with an indenter under conditions of a compression speed of 3.3 mm/min, a compression time of 3 seconds, and a compression distance of 20 mm, and the load of the indenter at that time was measured.
  • the maximum value of the load measured in this test was adopted as the loop stiffness value.
  • the compression distance refers to the distance when the indenter and the chuck are closest to each other. The results are shown in Table 2.
  • step (1b) an impulse sealer was used.
  • step (1c) water was poured into the bag, and the top of the bag was folded to remove the air from inside the bag, and the top end was sealed in this state.
  • step (1d) the test specimen was heated while placed so that the main surface was horizontal. Heating was performed using a shower method in which water was sprayed onto the test specimen.
  • step (1e) after the water was drained, the inside of the bag was lightly wiped with a Kimwipe to remove moisture.
  • the bag before measuring the maximum opening height H1, the bag was placed on a horizontal table and the main surface of the bag was pressed with the palm of the hand from the bottom to the top with a force of 2 to 3 kg.
  • step (1f) before measuring the maximum opening height H2, the bag was placed on a horizontal table and the main surface of the bag was pressed with the palm of the hand from the bottom to the top with a force of 2 to 3 kg.
  • a layer or laminate to be measured was cut into a size of 200 mm ⁇ 200 mm to prepare a measurement sample 500.
  • two straight lines L1 and L2 each having a length of 120 mm or more and parallel to the TD of the measurement sample 500, were drawn with an interval of 100 mm therebetween.
  • two straight lines L3 and L4 each having a length of 120 mm or more and parallel to the MD of the measurement sample 500, were drawn with an interval of 100 mm therebetween.
  • scale marks N1 to N7 were written at seven points at 20 mm intervals on the line L1. Scale marks were written similarly on the lines L2 to L4.
  • the positions of the scale marks on the lines L1 and L2 were aligned so that when each of the scale marks N1 to N7 on the line L1 and each of the scale marks N1 to N7 on the line L2 were connected by a straight line, the line would be parallel to the MD.
  • the positions of the scale marks on the lines L3 and L4 were aligned so that when each of the scale marks N1 to N7 on the line L3 and each of the scale marks N1 to N7 on the line L4 were connected by a straight line, the line would be parallel to the TD.
  • the measurement sample was heated at 128° C. for 15 minutes under 0.3 MPa. After heating, the measurement sample was left at room temperature (25° C.) for 30 minutes.
  • the maximum opening height and discharge rate of the opening were evaluated according to the following criteria. The results are shown in Table 2. (standard) A: Maximum opening height is more than 25 mm and discharge rate is more than 90%. B: Maximum opening height is 20 mm or more but less than 25 mm and discharge rate is more than 90%. C: Other than A and B ratings.
  • the package was cut from one side to the other at a first position 20 mm from the top end of the package to form an opening.
  • the handleability of the package when it was opened was evaluated by grasping the sealed portions at both ends of the package and pushing the sealed portions in a direction to bring them closer together, and evaluating the amount of force applied and the ease of maintaining the opening shape according to the following criteria A to D.
  • the evaluation was performed according to the following criteria. The results are shown in Table 2. (standard) A: The opening opens with light force and is easy to keep open. B: The opening is easy to open and easy to keep open. C: The packaging bag is stiff and the opening is difficult to open, but it is easy to keep open. D: The opening is twisted (twisted) and difficult to open, and it is difficult to keep open.

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JP2017178357A (ja) 2016-03-30 2017-10-05 東洋製罐株式会社 包装袋
JP2021020391A (ja) * 2019-07-29 2021-02-18 凸版印刷株式会社 積層体及び包装袋
JP2023040683A (ja) * 2021-09-10 2023-03-23 東洋紡株式会社 ラミネート積層体

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TW202019687A (zh) * 2018-10-16 2020-06-01 日商東洋紡股份有限公司 積層膜
JP7035974B2 (ja) * 2018-11-14 2022-03-15 東洋紡株式会社 積層フィルム及びそれからなる包装袋

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Publication number Priority date Publication date Assignee Title
JP2014141302A (ja) * 2012-12-28 2014-08-07 Dainippon Printing Co Ltd レトルト食品用の包装材料
JP2017178357A (ja) 2016-03-30 2017-10-05 東洋製罐株式会社 包装袋
JP2021020391A (ja) * 2019-07-29 2021-02-18 凸版印刷株式会社 積層体及び包装袋
JP2023040683A (ja) * 2021-09-10 2023-03-23 東洋紡株式会社 ラミネート積層体

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