WO2017002753A1 - 積層体、包装袋、口栓付包装袋および水素水入り口栓付包装袋 - Google Patents
積層体、包装袋、口栓付包装袋および水素水入り口栓付包装袋 Download PDFInfo
- Publication number
- WO2017002753A1 WO2017002753A1 PCT/JP2016/068986 JP2016068986W WO2017002753A1 WO 2017002753 A1 WO2017002753 A1 WO 2017002753A1 JP 2016068986 W JP2016068986 W JP 2016068986W WO 2017002753 A1 WO2017002753 A1 WO 2017002753A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas barrier
- layer
- laminate
- packaging bag
- adhesive
- Prior art date
Links
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- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D2565/38—Packaging materials of special type or form
- B65D2565/381—Details of packaging materials of special type or form
- B65D2565/387—Materials used as gas barriers
-
- 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
- B65D2575/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
- B65D2575/52—Details
- B65D2575/58—Opening or contents-removing devices added or incorporated during package manufacture
- B65D2575/586—Opening or contents-removing devices added or incorporated during package manufacture with means for reclosing
Definitions
- the present invention relates to a laminate suitably used for making a packaging bag, a packaging bag using the laminate, a packaging bag with a cap attached to the packaging bag, and a packaging bag with the plug.
- the present invention relates to a packaging bag with a hydrogen water inlet stopper filled with hydrogen water.
- a laminate provided with a gas barrier layer for preventing gas permeation is widely used.
- two gas barrier layers may be provided on the laminate.
- an inorganic compound vapor-deposited film layer on which an inorganic compound thin film is vapor-deposited is provided as a first gas barrier layer on one outermost surface of a laminate, and an aluminum foil is provided as a second gas barrier layer.
- a packaging material provided with a layer made of is disclosed. In this packaging material, a layer made of a nylon film is provided between the first gas barrier layer and the second gas barrier layer, and each layer is bonded by a dry laminating method using an adhesive.
- a two-component reactive polyurethane adhesive consists of a main component having a hydroxyl group at the polymer end (polyol component) and a curing agent having an isocyanate group (polyisocyanate component), and forms a urethane bond by the reaction between the hydroxyl group and the isocyanate group. And harden.
- the two-component reactive polyurethane adhesive when moisture is present during the curing process, the moisture reacts with the isocyanate group of the curing agent to generate carbon dioxide. Therefore, when a two-component reaction type polyurethane adhesive is used between the first gas barrier layer and the second gas barrier layer, a problem in appearance occurs. That is, since both the first gas barrier layer and the second gas barrier layer have gas barrier properties, it is difficult for carbon dioxide generated from the adhesive to pass through these layers and escape to the outside air. Therefore, carbon dioxide becomes bubbles and stays between the first gas barrier layer and the second gas barrier layer. Such bubbles can be visually recognized from the outside through the transparent first gas barrier layer, resulting in poor appearance. In addition, when small bubbles are combined to form a large bubble, the large bubble may cause delamination.
- Patent Document 2 when the first gas barrier layer made of a plastic film on which an inorganic thin film is deposited and the second gas barrier layer made of an aluminum foil are bonded with an adhesive, the inorganic thin film of the first gas barrier layer is used.
- a technique is disclosed in which the side on which no is deposited is in contact with the adhesive. According to Patent Document 2, carbon dioxide generated from the adhesive is absorbed by the plastic film, or once absorbed by the plastic film and then escapes from the end surface of the plastic film to the outside air. It does not remain.
- Patent Document 2 when the side on which the inorganic thin film of the first gas barrier layer is not deposited is disposed so as to contact the adhesive, the side on which the inorganic thin film is deposited constitutes the outermost surface of the laminate. Become. In that case, the inorganic thin film may peel off and the gas barrier property may be lowered. In order to suppress the peeling of the inorganic thin film, there is a method of providing a surface protective layer on the inorganic thin film, but in that case, it is not preferable because of the cost for providing the surface protective layer. Patent Document 2 shows that when the material of the plastic film is nylon, the effect cannot be obtained, and there is a problem that the material of the plastic film is limited.
- Patent Document 2 since the technique of Patent Document 2 does not suppress the generation of carbon dioxide from the adhesive itself, the entire amount of generated carbon dioxide is absorbed by the plastic film, or is released to the outside air from the end face of the plastic film. In this case, carbon dioxide remains in the laminate, resulting in poor appearance.
- the present invention has been made in view of the above circumstances, and a laminated body excellent in gas barrier properties, in which the generation of bubbles is reliably suppressed and there is no poor appearance without separately providing a surface protective layer or the like, and the laminated body are used. It is an object of the present invention to provide a packaging bag with a stopper with a stopper attached to the packaging bag, and a packaging bag with a hydrogen water inlet stopper in which hydrogen water is filled in the packaging bag with a stopper.
- the present invention has the following configuration.
- the plurality of gas barrier layers include a first gas barrier layer and a second gas barrier layer, and the first gas barrier layer is made of a gas barrier transparent resin film.
- the second gas barrier layer is made of a metal foil.
- a member made of any one gas barrier layer and a member made of another gas barrier layer Alternatively, a member made of any one gas barrier layer and a member made of a laminate having another gas barrier layer, Alternatively, a member made of a laminate having any one gas barrier layer and a member made of a laminate having another one gas barrier layer, A laminate of [1] to [3], which is a laminate bonded with the adhesive layer (X).
- the laminate has an adhesive layer (Y) composed of an adhesive (y) having a polyol component as a main component and a polyisocyanate component as a curing agent. body.
- a packaging bag comprising the laminate according to any one of [1] to [6].
- a packaging bag with a cap wherein the plug is attached to the packaging bag of [7].
- a packaging bag with a hydrogen water inlet plug wherein the packaging bag with a cap according to any one of [9] to [11] is filled with hydrogen water.
- the packaging bag using the laminate It is possible to provide a packaging bag with a stopper in which a stopper is attached to the bag, and a packaging bag with a hydrogen water inlet stopper in which hydrogen water is filled in the packaging bag with a stopper.
- the laminate of the present invention is a laminate having a plurality of gas barrier layers.
- FIG. 1 is a cross-sectional view showing an example of a laminated body of the present invention.
- a laminated body 10A of this example has two gas barrier layers of a first gas barrier layer 11 and a second gas barrier layer 12. is doing.
- the laminated body 10A of this example further includes a base material layer 13 and a sealant layer 14, and each layer is bonded by an adhesive layer. Specifically, the first gas barrier layer 11, the adhesive layer (X) 21, the base material layer 13, the adhesive layer (Y) 22, the second gas barrier layer 12, the adhesive layer (Y) 22, and the sealant layer. 14 are sequentially laminated.
- the first gas barrier layer 11 is formed of a gas barrier transparent resin film provided with a gas barrier property by providing an inorganic vapor deposition film made of alumina or the like on the surface, and one outermost surface of the laminate 10A is formed on the first gas barrier layer 11. It is composed.
- the inorganic vapor deposition film is provided on the inner surface of the first gas barrier layer 11, that is, the surface in contact with the adhesive layer (X) 21.
- printing (not shown) may be applied to the surface of the gas barrier transparent resin film on the side on which the inorganic vapor deposition film is formed in terms of design and the like.
- the transparent resin film for example, a film made of polyethylene terephthalate (PET), polyester other than PET, polyamide, polypropylene or the like can be used, and a PET film is preferable from the viewpoint of strength and the like.
- PET polyethylene terephthalate
- polyamide polypropylene
- this film is preferably a biaxially stretched film.
- the transparent resin film may be a multilayer film formed by coextruding two or more materials.
- the 1st gas barrier layer 11 may be formed with the film by which the inorganic vapor deposition film was provided in the transparent multilayer film which consists of 2 or more types of transparent resin films.
- the thickness of the first gas barrier layer 11 is not particularly limited, but is preferably 5 to 30 ⁇ m, and more preferably 7 to 16 ⁇ m. If it is more than the lower limit of the said range, sufficient intensity
- a method of providing a chemical vapor deposition film, a barrier coat film, or the like can be employed in addition to the method of providing the inorganic vapor deposition film described above.
- the second gas barrier layer 12 is made of a metal foil such as an aluminum foil, and is disposed at a position other than the outermost surface of the laminate 10A.
- a metal foil such as an aluminum foil
- PET, polyester other than PET, polyamide, polypropylene, and the like are provided with an inorganic vapor deposition film, a chemical vapor deposition film, a barrier coat film, etc. on the second gas barrier layer 12 to provide gas barrier properties.
- a transparent resin film may be used, it is preferable to use a metal foil because it is more excellent in gas barrier properties.
- the thickness of the second gas barrier layer 12 is not particularly limited, but when a metal foil is used, 4 to 30 ⁇ m is preferable, and 6 to 9 ⁇ m is more preferable. If it is more than the lower limit of the said range, sufficient gas-barrier property will be obtained, and if it is below the upper limit of the said range, the thickness of 10 A of laminated bodies will not be enlarged more than necessary.
- the laminated body 10A of this example has a base material layer 13 made of a biaxially stretched polyamide film.
- various properties for example, bending resistance, puncture resistance, impact resistance, wear resistance, cold resistance, heat resistance, Chemical resistance, etc.
- puncture resistance, impact resistance, etc. can be imparted to the laminate 10A.
- the film constituting the base material layer 13 is PET, polyester other than PET, polyamide, polypropylene, polyethylene, polyvinyl chloride, polycarbonate, polyvinyl alcohol, ethylene-acetic acid, depending on the application.
- a uniaxial or biaxially stretched film such as a saponified vinyl copolymer or an unstretched film can be used. These films may be used alone or in a laminate of two or more.
- the thickness of the base material layer 13 is not particularly limited and can be appropriately set according to the characteristics required for the laminate 10A. For example, the thickness is preferably 9 to 30 ⁇ m, more preferably 12 to 16 ⁇ m.
- the laminated body 10A in this example has a heat-sealable sealant layer 14 made of a linear (linear) low density polyethylene film (LLDPE) as a layer constituting the other outermost surface of the laminated body 10A.
- LLDPE linear low density polyethylene film
- the sealant layer 14 should just be formed from the material which has heat-sealability, and is not limited to LLDPE.
- Materials having heat sealability include low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-acrylic acid. Examples thereof include a methyl copolymer, an ethylene-methacrylic acid copolymer, polypropylene, and an ethylene-propylene copolymer.
- LDPE low density polyethylene
- HDPE high density polyethylene
- ethylene-vinyl acetate copolymer ethylene-vinyl acetate copolymer
- ionomer resin ethylene-acrylic acid copolymer
- ethylene-acrylic acid ethylene-acrylic acid. Examples thereof include a methyl copolymer, an ethylene-methacrylic acid copolymer, polypropylene, and an
- the sealant layer 14 may be a multilayer in which a plurality of layers made of one or more of these resins are stacked.
- the thickness of the sealant layer 14 is not particularly limited, but is preferably 30 to 150 ⁇ m, for example, and more preferably 50 to 80 ⁇ m. If it is more than the lower limit of the said range, sufficient heat-sealing property will be obtained, and if it is below the upper limit of the said range, the thickness of 10 A of laminated bodies will not be increased more than necessary.
- each layer is bonded by a dry laminating method using an adhesive, and the adhesive layers (X) having different types of adhesive forming the adhesive layer are used as the adhesive layer. 21 and an adhesive layer (Y) 22.
- the adhesive layer (X) 21 is formed of an adhesive (x) having a polyepoxy resin as a main component and a polyamine resin as a curing agent.
- the adhesive (x) does not generate a gas such as carbon dioxide in the reaction process when it is cured to form the adhesive layer (X).
- the adhesive layer (Y) 22 is an adhesive (two-component reaction type polyurethane-based adhesive) having a polyol component having a hydroxyl group at the polymer terminal as a main agent and a polyisocyanate component having a hydroxyl group at the polymer terminal as a curing agent. Agent) (y).
- the adhesive (y) generates carbon dioxide in the reaction process when it is cured to form the adhesive layer (Y).
- adhesive (x) what has the following (1) as a main ingredient and the following (2) as a hardening
- a two-component epoxy resin (trade name “MAXIVE”) manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used. “Maxive” contains a solvent.
- a polyamine resin comprising a reaction product of metaxylylenediamine or paraxylylenediamine and acrylic acid, methacrylic acid, a derivative of acrylic acid, or a derivative of methacrylic acid.
- each of the adhesive layer (X) and the adhesive layer (Y) is not particularly limited, but the coating amount per 1 m 2 is, for example, 0.5 to 7.0 g / m 2 is preferable, 1.0 to 5.0 g / m 2 is more preferable, and the adhesive layer (Y) is preferably, for example, 2.0 to 5.0 g / m 2 , and 2.5 to 4.0 g / m 2. 2 is more preferable. If it is more than the lower limit of the said range, sufficient adhesive force will be obtained, and if it is below the upper limit of the said range, the thickness of 10 A of laminated bodies will not be increased more than necessary.
- the laminated body 10 ⁇ / b> A includes a first gas barrier layer 11, a second gas barrier layer 12, an adhesive layer (X) 21, an adhesive layer (Y) 22, a base material layer 13, and layers other than the sealant layer 14. You may have more than one layer.
- Various resin films can be used. Specifically, resin films such as PET, polyesters other than PET, polyamide, polyvinyl chloride, polycarbonate, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, and the like can be used. These films may be used alone or in a combination of two or more.
- the total thickness of the laminated body 10A is not particularly limited.
- it when used for the production of a packaging bag, it is preferably 50 to 250 ⁇ m from the viewpoint of ease of bag production and the strength of the produced packaging bag. 80 to 130 ⁇ m is more preferable. If it is more than the lower limit of the said range, it will be excellent in intensity
- the laminated body 10A is a member composed of a laminated body in which the sealant layer 14, the adhesive layer (Y) 22, the second gas barrier layer 12, the adhesive layer (Y) 22, and the base material layer 13 are sequentially laminated.
- (A) 16 and the member (b) made of the first gas barrier layer 11 are manufactured by being bonded together with the adhesive layer (X) 21.
- the adhesive layer (Y) 22 is formed by using an adhesive (y) that generates carbon dioxide in the reaction process at the time of curing when the member (a) 16 that is a laminate is manufactured. Yes.
- the member (a) 16 has only one gas barrier layer, even if carbon dioxide is generated from the adhesive (y) when the member (a) 16 is manufactured, the generated carbon dioxide is It can permeate
- occur
- the adhesive (x) includes a compound having an aromatic compound such as metaxylylenediamine
- the adhesive layer (X) 21 formed from the adhesive (x) itself has a gas barrier. Also has sex. That is, the laminated body 10A has two gas barrier layers and also has an adhesive layer (X) 21 having gas barrier properties. Therefore, the obtained laminated body 10A has a very high gas barrier property, and is suitable for a packaging material for packaging contents including a substance having a small molecule such as hydrogen water.
- the adhesive (y) is used to bond the sealant layer 14, the second gas barrier layer 12, and the base material layer 13 when the member (a) that is a laminate is manufactured.
- the adhesive layer (Y) 22 formed from the adhesive (y) is superior in adhesive strength to the adhesive layer (X) 21, and particularly superior in adhesive strength with metal. Therefore, when bonding the member (a) and the member (b), an adhesive (x) that does not generate gas is used, while the sealant layer 14 is formed on both surfaces of the second gas barrier layer 12 made of metal foil.
- an adhesive (y) excellent in adhesive strength it is excellent in interlayer adhesive strength, suitable for manufacturing a liquid packaging bag or a large packaging bag, and has an appearance.
- FIG. 2 is a cross-sectional view showing another example of the laminate of the present invention.
- the stacked body 10B in FIG. 2 has two gas barrier layers, a first gas barrier layer 11 and a second gas barrier layer 12, as in the stacked body 10A in FIG.
- the laminated body 10B in FIG. 2 differs from the laminated body 10A in FIG. 1 in that the positions of the base material layer 13 and the second gas barrier layer 12 are interchanged.
- the laminated body 10B is a member made of a laminated body in which a sealant layer 14, an adhesive layer (Y) 22, a base material layer 13, an adhesive layer (Y) 22, and a second gas barrier layer 12 are sequentially laminated.
- (A) 16 and the member (b) made of the first gas barrier layer 11 are manufactured by being bonded together with the adhesive layer (X) 21.
- the adhesive layer (Y) 22 is formed by using the adhesive (y) that generates carbon dioxide in the reaction process at the time of curing when the member (a) 16 that is a laminate is manufactured.
- the generated carbon dioxide can pass through the base material layer 13 and the sealant layer 14 that do not have gas barrier properties and escape to the outside air. Therefore, no bubbles remain in the obtained member (a) 16.
- produce gas such as a carbon dioxide ( x) is used. Therefore, the laminate 10B finally obtained does not contain a gas due to the used adhesive, and the laminate 10B is excellent in appearance without bubbles.
- the laminated body 10B of FIG. 2 when the contents are accommodated by forming a packaging bag with the sealant layer 14 as an inner surface, a base material is interposed between the second gas barrier layer 12 made of metal foil and the contents. Layer 13 is present. Thereby, when the contents are hard, the puncture resistance from the contents is excellent.
- the laminate of the present invention may be an adhesive layer (X) in which all of the adhesive layers that bond the layers are made of the adhesive (x), but as described above, it is more adhesive than the adhesive layer (X). It is preferable to use an adhesive layer (Y) having excellent strength in view of forming a packaging bag having superior strength as well as appearance.
- the laminates 10A and 10B having two gas barrier layers are illustrated, but the laminate of the present invention has at least one adhesive layer (X) between any gas barrier layer and another gas barrier layer.
- 3C includes a first gas barrier layer 11, a second gas barrier layer 12, and a third gas barrier layer 15, and includes one gas barrier layer and another gas barrier closest to the gas barrier layer. From the adhesive (x) between the layers, that is, between the first gas barrier layer 11 and the second gas barrier layer 12, and between the second gas barrier layer 12 and the third gas barrier layer 15, respectively.
- An adhesive layer (X) 21 is disposed.
- 3C has a base material layer 13 and a sealant layer 14, as shown in the figure, between the base material layer 13 and the second gas barrier layer 12, and between the sealant layer 14 and the first sealant layer 14.
- the adhesive layer (Y) 22 is disposed between each of the three gas barrier layers 15.
- the laminated body 10C includes a member (a) 16 composed of a laminated body in which a sealant layer 14, an adhesive layer (Y) 22, and a third gas barrier layer 15 are sequentially laminated, and a second gas barrier layer 12 bonded.
- a member (c) 17 composed of a laminate in which the agent layer (Y) 22 and the base material layer 13 are sequentially laminated, and a member (b) composed of the first gas barrier layer 11 are formed into the adhesive layer (X) 21. It is manufactured by sticking together.
- the adhesive (y) that generates carbon dioxide is used in the reaction process at the time of curing.
- the gas that has passed through the sealant layer 14 and the base material layer 13 having no gas barrier property can escape to the outside air. Therefore, no bubbles remain in the obtained member (a) 16 and member (c) 17.
- gas such as carbon dioxide is generated between these layers.
- the adhesive (x) which is not used is used. Therefore, the laminate 10C finally obtained does not contain a gas due to the used adhesive, and the laminate 10C is excellent in appearance without bubbles.
- each member is bonded together by adhesive layer (X), and when a member is a laminated body, each layer of this laminated body is an adhesive agent.
- the layer (Y) By laminating with the layer (Y), a laminate having both excellent appearance and strength can be obtained.
- the packaging bag of this invention is a bag formed from the laminated body of this invention, and is formed in a bag shape by methods, such as closing a periphery by making a laminated body oppose.
- the sealant layers 14 are opposed to each other, and the periphery is heat-sealed for heat fusion.
- a packaging bag can be manufactured by wearing.
- the shape of the packaging bag is not particularly limited. For example, a flat bag composed of a pair of flat portions, a gusset bag composed of a pair of flat portions and a pair of side portions (gazette portions), and a bottom portion are provided. And bottom gusset bags.
- the laminate forming the packaging bag of the present invention has a plurality of gas barrier layers, and also has an adhesive layer (X) made of an adhesive (x) having excellent gas barrier properties. Therefore, it is suitable for accommodating contents that require a particularly high gas barrier property. Examples of such contents include hydrogen water containing hydrogen with small molecules.
- FIG. 4 is a perspective view showing an example of the packaging bag 30 with a cap of the present invention.
- the packaging bag 30 with a stopper of this example attaches the stopper 50 to the packaging bag 40 formed from the laminated body of this invention. By attaching the stopper 50 in this way, the packaging bag 30 with a stopper that can directly open the contents of the packaging bag 40 is obtained.
- the plug is composed of a spout and a cap (not shown).
- the material, shape, etc. of the plug 50 are not particularly limited, and known ones made of resin molded products can be used, but a plug having gas barrier properties is preferred.
- the packaging bag of this invention is formed from the laminated body which has high gas-barrier property
- the packaging bag with a stopper excellent in gas-barrier property is obtained by making the stopper attached to this also have barrier property.
- the plug having a gas barrier property include a plug provided with a gas barrier property by disposing a film having a gas barrier property in a cylindrical mouth portion protruding from the packaging bag to the outside of the spout of the plug. It is done.
- a spout 50A in FIG. 5 is a cross-sectional view showing an example of a spout of a spout provided with gas barrier properties.
- the spout 50A of this example includes a cylindrical mouth portion 55 that is a portion projecting outside from the packaging bag, and a contact portion 56 that is connected to one end of the mouth portion 55 and attached in close contact with the inside of the packaging bag.
- the plug 50A of this example further includes a rod-like blocking prevention member 58 for preventing the inner space of the packaging bag from being blocked by being inserted into the packaging bag.
- a screw thread 59 for screwing a cap (not shown) for closing the mouth portion 55 is formed at the upper part of the outer periphery of the mouth portion 55.
- a flange 54 is provided at the lower part of the outer periphery of the mouth part 55.
- the flange 54 acts as a grip part that is gripped when the spout 50A is attached to the packaging bag.
- the spout 50A is preferably integrally molded with resin, and the type of resin is not particularly limited, but the close contact portion 56 may be attached to the sealant layer of the laminate constituting the packaging bag by heat fusion. Since it is suitable, it is preferable to form with the same material as the sealant layer of a laminated body.
- a barrier cylinder (shaded portion in FIG. 5) 57 having a barrier property is integrally formed with the mouth portion 55 by insert molding.
- the outer diameter of the barrier cylinder 57 is substantially equal to the inner diameter of the mouth portion 55.
- the barrier cylinder 57 is provided over substantially the entire length of the mouth part 55 protruding outside from the packaging bag.
- Examples of the barrier cylinder 57 include a cylinder body formed by injection molding or the like and a film having a gas barrier property wound around the outer periphery of the cylinder body.
- the barrier cylinder 57 can be integrated with the mouth portion 55 by setting the barrier tube 57 in the mold in advance. The film which has a property is provided, and the stopper with which gas barrier property was provided is obtained.
- the film having a gas barrier property examples include a metal foil such as an aluminum foil, an ethylene-vinyl alcohol copolymer (EVOH) film, an inorganic vapor-deposited film, and the like.
- the metal foil is preferable because of its excellent gas barrier property.
- the barrier cylinder 57 using a film having a gas barrier property has been described.
- the barrier cylinder itself is molded by injection molding using a resin having a barrier property such as EVOH resin to provide a film having a gas barrier property. You may use what is not.
- a cap 61 provided with a barrier property may be used as a cap for closing the mouth part of the spout of the plug.
- the cap to which the barrier property is imparted has a film 62 having a gas barrier property in the cap body at a position where the spout mouth is closed (see FIG. 6).
- the film having a gas barrier property includes a film having a metal foil such as an aluminum foil, an ethylene-vinyl alcohol copolymer (EVOH) film, and an inorganic vapor deposition film.
- the surface that is in direct contact with the mouth part of the spout is preferably formed of a layer made of a resin that can be thermally welded to the resin constituting the mouth part. Further, it is preferably formed from a layer made of a resin that can be easily peeled off from the mouth of the spout. It is preferable to use an easy peel film because it can be thermally welded to the spout mouth and can be easily peeled off.
- the surface in contact with the inside of the cap body is preferably formed of a layer made of a resin that can be thermally welded to the cap body.
- the spout mouth and the gas barrier film incorporated in the cap by ultrasonic wave, high frequency dielectric, electromagnetic induction or the like, and the welding method is determined by the material of the gas barrier film.
- the film having gas barrier properties has a metal foil, welding by electromagnetic induction is preferable.
- the film having gas barrier properties is “linear low density polyethylene (LLDPE) film / adhesive / biaxially stretched polyethylene terephthalate (PET) film / from the cap side to the spout side /
- LLDPE linear low density polyethylene
- PET biaxially stretched polyethylene terephthalate
- Each film such as “adhesive / aluminum foil / adhesive / easy peel film” may be laminated by a dry laminating method.
- both the packaging bag and the plug have an excellent gas barrier property. Therefore, it is also suitable for uses that are filled with beverages that are easily altered by oxygen or the like, jelly-like foods, etc., but particularly those that are filled with hydrogen water in which hydrogen is dissolved in small molecules that are easy to permeate films etc. It is suitable for etc.
- the packaging bag with a hydrogen water inlet stopper of the present invention filled with hydrogen water there is no poor appearance of the laminate forming the packaging bag.
- a plug with a gas barrier property as the plug the hydrogen remaining rate in the filled hydrogen water can be maintained high.
- Example 1 A laminate having the structure shown in FIG. 1 was produced as follows. First, an LLDPE film for forming the sealant layer 14, an aluminum foil for forming the second gas barrier layer 12, and a biaxially stretched polyamide film for forming the base material layer 13 are two-component reactive polyurethane.
- the film composition is “sealant layer / adhesive layer (Y) (application amount: 3.5 g / m 2 ) / second
- a member (a) 16 made of a laminate of “gas barrier layer / adhesive layer (Y) (application amount: 3.5 g / m 2 ) / base material layer” was produced.
- the base layer 13 of the obtained member (a) 16 and the member (b) made of a gas barrier transparent resin film for forming the first gas barrier layer 11 are composed of a polyepoxy resin as a main component, and a polyamine.
- the laminate of Example 1 was manufactured by bonding by a dry laminating method using an adhesive (x) having a resin as a curing agent.
- the coating amount of the adhesive layer (X) was 2.0 g / m 2 . Table 1 shows details of the materials used for forming the laminate.
- a packaging bag (gadget bag) having a gusset portion on its side is manufactured as follows, and a stopper having a barrier property is attached to the packaging bag, with the stopper A packaging bag was produced.
- the obtained laminate was cut to obtain a pair of flat part film and a pair of side part film.
- the pair of flat part film and the pair of side part film are aligned so that the sealant layers 14 face each other, and the side seal is 150 to 200 ° C. and the bottom seal is 200 to 250 ° C.
- the packaging bag which is a gusset bag was manufactured.
- a stopper having a barrier property is inserted into the upper end portion of the packaging bag which is not heat-sealed, heat sealing is performed at 150 to 250 ° C., the upper end portion of the packaging bag is closed and the stopper is attached.
- a packaging bag with a cap was obtained. Hydrogen water was accommodated in the obtained plug packaging bag, and the plug was closed with a cap to obtain a hydrogen water inlet plug packaging bag.
- a spout of a stopper having a barrier property when attached to a packaging bag, a cylindrical mouth portion protruding outward from the packaging bag, and a close contact attached to one end of the mouth portion and closely attached to the packaging bag And made of polyethylene having a part.
- a barrier cylinder in which an aluminum foil is wound as a film having a gas barrier property on the outer periphery of a polyethylene cylinder main body is integrated inside the mouth portion of the spout.
- gas barrier property is provided to the plug by integrating the barrier cylinder.
- the appearance evaluation was performed about the obtained laminated body. Moreover, the hydrogen residual rate of the filled hydrogen water was measured about the packaging bag with a hydrogen water inlet stopper. The evaluation and measurement methods are shown below. The results are shown in Table 2.
- Example 2 A packaging bag with a hydrogen water inlet plug is manufactured in the same manner as in Example 1 except that the spout of the plug is not integrated with a barrier cylinder wrapped with aluminum foil and does not have barrier properties. Then, the same evaluation as in Example 1 was performed. The results are shown in Table 2.
- Example 3 Using the materials shown in Table 1, a laminate having the configuration of FIG. 2 was manufactured as follows. First, an LLDPE film for forming the sealant layer 14, a biaxially stretched polyamide film for forming the base material layer 13, and an aluminum foil for forming the second gas barrier layer 12 are formed into a two-component reaction type.
- Adhesion was performed by a dry laminating method using an adhesive (y) which is a polyurethane-based adhesive, and the film configuration was “sealant layer / adhesive layer (Y) (application amount: 3.5 g / m 2 ) / base material layer /
- the member (a) 16 which is an adhesive layer (Y) (application amount: 3.5 g / m 2 ) / second gas barrier layer ” was produced.
- the second gas barrier layer 12 of the obtained member (a) 16 and the member (b) made of a gas barrier transparent resin film for forming the first gas barrier layer 11 are mainly composed of a polyepoxy resin.
- Example 3 was produced by bonding by a dry laminating method using an adhesive (x) having a polyamine resin as a curing agent.
- the coating amount of the adhesive layer (X) was 2.0 g / m 2 .
- a packaging bag with a hydrogen water inlet stopper was produced in the same manner as in Example 1 except that the obtained laminate was used, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.
- Example 4 A laminate of Example 4 was produced in the same manner as in Example 1 except that the second gas barrier layer 12 was replaced with an aluminum foil and a gas barrier transparent resin film similar to the first gas barrier layer 11 was used. A packaging bag with a hydrogen water inlet stopper was produced in the same manner as in Example 1 except that the obtained laminate was used, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.
- Example 5 A packaging bag with a hydrogen water inlet plug was manufactured in the same manner as in Example 1 except that a spout in which a barrier cylinder formed of EVOH resin was integrated with a spout of a polyethylene plug was used. Similar evaluations were made. The results are shown in Table 2.
- Example 6 A laminate of Example 6 was manufactured in the same manner as Example 1 except that a film having gas barrier properties was provided inside the cap that closed the spout mouth as a plug.
- the film having a gas barrier property is a composition of “linear low density polyethylene (LLDPE) film 30 ⁇ m / adhesive / biaxially stretched polyethylene terephthalate (PET) 12 ⁇ m / adhesive / aluminum foil 7 ⁇ m / adhesive / easy peel film 30 ⁇ m”. It was.
- the LLDPE film is “UB-1” manufactured by Tamapoli and has a thickness of 30 ⁇ m.
- the biaxially stretched PET film is “E5200” manufactured by Toyobo Co., Ltd., and has a thickness of 12 ⁇ m.
- Adhesive for dry lamination (y)
- the size of the film having gas barrier properties is a circle having a diameter of 11 mm (the same size as the inside of the cap). After closing the spout with a cap, the mouth of the spout and the film having gas barrier properties of the cap are output using an electromagnetic induction welder (UHT-1500 manufactured by Seidensha Electronics Co., Ltd.), output 1500 W, oscillation frequency 150 kHz, Welding was performed at a sealing time of 0.5 seconds. Evaluation similar to Example 1 was performed. The results are shown in Table 2.
- Comparative Example 1 In the same manner as in Example 1, it was obtained after manufacturing a member having a film configuration of “sealant layer / adhesive layer (Y) / second gas barrier layer / adhesive layer (Y) / base material layer”. The base material layer of this member and the gas barrier transparent resin film for forming the first gas barrier layer were adhered by a dry laminating method using an adhesive (y) to produce a laminate of Comparative Example 1. . A packaging bag with a hydrogen water inlet stopper was produced in the same manner as in Example 1 except that the obtained laminate was used, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.
- the present invention it is possible to reliably suppress the generation of bubbles without providing a surface protective layer or the like, and to have a good appearance without gas defects, a packaging bag using the laminate, and the packaging bag. It is possible to provide a packaging bag with a stopper with a stopper attached thereto, and a packaging bag with a hydrogen water inlet stopper in which hydrogen water is filled in the packaging bag with a stopper.
- 10A, 10B, 10C Laminate 11: First gas barrier layer 12: Second gas barrier layer 13: Base material layer 14: Sealant layer 21: Adhesive layer (X) 22: Adhesive layer (Y) 30: Packaging bag with cap 40: Packaging bag 50: Cap 50A: Spout spout
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Abstract
Description
本願は、2015年7月1日に、日本に出願された特願2015-132693号に基づき優先権を主張し、その内容をここに援用する。
たとえば特許文献1には、積層体の一方の最外面に、第1のガスバリア層として、無機化合物の薄膜が蒸着された無機化合物蒸着フィルムの層を設けるとともに、第2のガスバリア層として、アルミニウム箔からなる層を設けた包装材が開示されている。この包装材においては、第1のガスバリア層と第2のガスバリア層との間に、ナイロンフィルムからなる層が設けられ、各層は、接着剤を用いたドライラミネート法により接着されている。
すなわち、第1のガスバリア層と第2のガスバリア層は、いずれもガスバリア性を有するため、接着剤から発生した二酸化炭素はこれらの層を透過して外気に抜けることが困難である。そのため、二酸化炭素は、気泡となって、第1のガスバリア層と第2のガスバリア層との間に留まる。
そして、このような気泡は、透明な第1のガスバリア層を通して外側から視認でき、外観不良となる。また、小さな気泡同士が合一して大きな気泡を形成した場合、この大きな気泡が層間剥離を引き起こす可能性もある。
さらに特許文献2の技術では、接着剤からの二酸化炭素の発生自体を抑制するものではないため、発生した二酸化炭素の全量をプラスチックフィルムで吸収したり、あるいは、プラスチックフィルムの端面から外気に逃したりできない可能性があり、その場合には、二酸化炭素が積層体に残存し、外観不良が生じる。
[1]複数のガスバリア層を有する積層体であって、任意のガスバリア層と他のガスバリア層との間には、ポリエポキシ樹脂を主剤とし、ポリアミン樹脂を硬化剤とする接着剤(x)からなる接着剤層(X)が少なくとも1層設けられている積層体。
[2]前記複数のガスバリア層として、第1のガスバリア層と第2のガスバリア層とを有し、前記第1のガスバリア層が、ガスバリア性透明樹脂フィルムからなる[1]の積層体。
[3]前記第2のガスバリア層が、金属箔からなる[2]の積層体。
[4]任意の1層のガスバリア層からなる部材と他の1層のガスバリア層からなる部材とが、
または、任意の1層のガスバリア層からなる部材と他の1層のガスバリア層を有する積層体からなる部材とが、
または、任意の1層のガスバリア層を有する積層体からなる部材と他の1層のガスバリア層を有する積層体からなる部材とが、
前記接着剤層(X)で貼り合わされた積層体である[1]~[3]の積層体。
[5]前記部材が積層体の場合、前記積層体は、ポリオール成分を主剤とし、ポリイソシアネート成分を硬化剤とする接着剤(y)からなる接着剤層(Y)を有する[4]の積層体。
[6]シーラント層をさらに有し、前記シーラント層は、前記積層体のいずれか一方の最外面を構成している[1]~[5]のいずれかの積層体。
[7][1]~[6]のいずれかの積層体からなる包装袋。
[8][7]の包装袋に水素水が充填された水素水入り包装袋。
[9][7]の包装袋に口栓が取り付けられた口栓付包装袋。
[10]前記口栓がバリア性を有する[9]の口栓付包装袋。
[11]前記口栓はキャップを有し、前記キャップがバリア性を有する[10]に記載の口栓付包装袋。
[12][9]~[11]のいずれかの口栓付包装袋に水素水が充填された水素水入り口栓付包装袋。
〔積層体〕
本発明の積層体は、複数のガスバリア層を有する積層体である。
図1は、本発明の積層体の一例を示す断面図であって、この例の積層体10Aは、第1のガスバリア層11と、第2のガスバリア層12との2層のガスバリア層を有している。また、この例の積層体10Aは、さらに、基材層13と、シーラント層14とを有しており、各層は接着剤層により接着されている。具体的には、第1のガスバリア層11、接着剤層(X)21、基材層13、接着剤層(Y)22、第2のガスバリア層12、接着剤層(Y)22、シーラント層14が順次積層して構成されている。
透明樹脂フィルムは、2種以上の材料を共押出する等して形成された多層フィルムであってもよい。たとえば、第1のガスバリア層11は、2種以上の透明樹脂フィルムからなる透明な多層フィルムに無機蒸着膜が設けられたフィルムにより形成されていてもよい。
第1のガスバリア層11の厚みには特に制限はないが、たとえば5~30μmが好ましく、7~16μmがより好ましい。上記範囲の下限値以上であれば、十分な強度が得られ、上記範囲の上限値以下であれば、積層体10Aの厚みを必要以上に大きくすることがない。
第2のガスバリア層12には、たとえばPET、PET以外のポリエステル、ポリアミド、ポリプロピレン等からなるフィルムに、無機蒸着膜、化学蒸着膜、バリアコート膜等が設けられてガスバリア性が付与されたガスバリア性透明樹脂フィルムを使用してもよいが、ガスバリア性により優れることから、金属箔を用いることが好ましい。
第2のガスバリア層12の厚みには特に制限はないが、金属箔を用いた場合には、4~30μmが好ましく、6~9μmがより好ましい。上記範囲の下限値以上であれば、十分なガスバリア性が得られ、上記範囲の上限値以下であれば、積層体10Aの厚みを必要以上に大きくすることがない。
基材層13の厚みには特に制限はなく、積層体10Aに要求される特性等に応じて適宜設定できるが、たとえば9~30μmが好ましく、12~16μmがより好ましい。
シーラント層14の厚みには特に制限はないが、たとえば30~150μmが好ましく、50~80μmがより好ましい。上記範囲の下限値以上であれば、十分なヒートシール性が得られ、上記範囲の上限値以下であれば、積層体10Aの厚みを必要以上に大きくすることがない。
接着剤層(X)21は、ポリエポキシ樹脂を主剤とし、ポリアミン樹脂を硬化剤とする接着剤(x)から形成されている。接着剤(x)は、硬化して接着剤層(X)を形成する際の反応過程で二酸化炭素等のガスを発生しない。
一方、接着剤層(Y)22は、高分子末端に水酸基を有するポリオール成分を主剤とし、高分子末端に水酸基を有するポリイソシアネート成分を硬化剤とする、接着剤(二液反応型ポリウレタン系接着剤)(y)から形成されている。接着剤(y)は、硬化して接着剤層(Y)を形成する際の反応過程で二酸化炭素を発生する。
(1)メタキシリレンジアミンから誘導されたグリシジルアミン部位を有するポリエポキシ樹脂。
(2)メタキシリレンジアミンまたはパラキシリレンジアミンと、アクリル酸、メタクリル酸、アクリル酸の誘導体、またはメタクリル酸の誘導体と、の反応生成物からなるポリアミン樹脂。
具体的には、PET、PET以外のポリエステル、ポリアミド、ポリ塩化ビニル、ポリカーボネート、ポリビニルアルコール、エチレン-酢酸ビニル共重合体ケン化物等の樹脂フィルムを用いることができる。これらフィルムは1種単独で用いてもよいし、2種以上を積層して組み合わせて用いてもよい。
しかしながら、部材(a)16は、ガスバリア層を1層しか有していないため、部材(a)16の製造時に接着剤(y)から二酸化炭素が発生しても、発生した二酸化炭素は、ガスバリア性を有しない基材層13やシーラント層14を透過して、外気に抜けることができる。そのため、得られた部材(a)16には気泡は残存しない。
そして、このような部材(a)16の基材層13側に、第1のガスバリア層11である部材(b)を積層する際には、二酸化炭素等のガスを発生しない接着剤(x)を用いている。
そのため、最終的に得られた積層体10Aには、使用した接着剤に起因するガスが含まれることがなく、積層体10Aは気泡のない外観に優れる。
すなわち、任意の1層のガスバリア層からなる部材と他の1層のガスバリア層からなる部材とを貼り合わせる場合、または、任意の1層のガスバリア層からなる部材と他の1層のガスバリア層を有する積層体からなる部材とを貼り合わせる場合、または、任意の1層のガスバリア層を有する積層体からなる部材と他の1層のガスバリア層を有する積層体からなる部材とを貼り合わせる場合には、接着剤層(X)で貼り合わせ、かつ、部材が積層体の場合には、該積層体の各層は接着剤層(Y)で貼り合せることにより、外観と強度との両方が優れる積層体を得ることができる。
図2の積層体10Bは、図1の積層体10Aと同様に、第1のガスバリア層11と、第2のガスバリア層12との2層のガスバリア層を有している。ただし、図2の積層体10Bは、図1の積層体10Aとは、基材層13と第2のガスバリア層12の位置が入れ替わっている点で異なっている。
そして、このような部材(a)16の第2のガスバリア層12側に、第1のガスバリア層11である部材(b)を積層する際には、二酸化炭素等のガスを発生しない接着剤(x)を用いる。
そのため、最終的に得られた積層体10Bには、使用した接着剤に起因するガスが含まれることがなく、積層体10Bは気泡のない外観に優れる。
図3の積層体10Cは、第1のガスバリア層11と、第2のガスバリア層12と、第3のガスバリア層15とを有し、1つのガスバリア層と、このガスバリア層に最も近い他のガスバリア層との間、すなわち、第1のガスバリア層11と第2のガスバリア層12との間、第2のガスバリア層12と第3のガスバリア層15とを間のそれぞれに、接着剤(x)からなる接着剤層(X)21が配置されている。また、図3の積層体10Cは、図示のとおり、基材層13とシーラント層14とを有しており、基材層13と第2のガスバリア層12との間と、シーラント層14と第3のガスバリア層15との間のそれぞれに、接着剤層(Y)22が配置されている。
そして、得られた部材(a)16と部材(c)17と第1のガスバリア層11である部材(b)とを積層する際には、これらの各層間に、二酸化炭素等のガスを発生しない接着剤(x)を用いている。
そのため、最終的に得られた積層体10Cには、使用した接着剤に起因するガスが含まれることがなく、積層体10Cは気泡のない外観に優れる。
本発明の包装袋は、本発明の積層体から形成された袋であり、積層体を対向させて周縁を閉塞する等の方法により、袋状に形成される。たとえば、図1~3に示したように、ヒートシール性のシーラント層14を有する積層体10A、10B、10Cの場合には、シーラント層14同士を対向させて、周縁をヒートシールして熱融着することにより、包装袋を製造できる。
なお、包装袋の形状は、特に限定されるものではなく、例えば、一対の平面部からなる平袋、一対の平面部と一対の側面部(ガゼット部)からなるガゼット袋、さらに底面部を設けた底ガゼット袋等が挙げられる。
このような内容物としては、分子が小さい水素を含む水素水等が挙げられる。
このように口栓50を取り付けることにより、包装袋40の内容物を直接口にできる口栓付包装袋30となる。口栓はスパウトと図示略のキャップからなる。
口栓50の材質、形状等には特に制限はなく、樹脂成形品等からなる公知のものを使用できるが、ガスバリア性を有する口栓が好ましい。本発明の包装袋は、高いガスバリア性を有する積層体から形成されるため、これに取り付ける口栓もバリア性を有するものとすることにより、ガスバリア性に優れた口栓付包装袋が得られる。
ガスバリア性を有する口栓としては、口栓のスパウトのうち包装袋から外部に突出する筒状の口部に、ガスバリア性を有するフィルムを配置することにより、ガスバリア性が付与された口栓が挙げられる。
口部55の外周の上部には、口部55を閉塞するためのキャップ(図示略)を螺着するためのネジ山59が形成されている。また、この例では、口部55の外周の下部には、スパウト50Aを包装袋に取り付ける際に把持される把持部として作用するフランジ54が設けられている。
スパウト50Aは樹脂で一体成形されていることが好ましく、樹脂の種類に特に制限はないが、密着部56は、包装袋を構成している積層体のシーラント層に熱融着により取り付けられることが好適であるため、積層体のシーラント層と同じ材質で形成されることが好ましい。
スパウト50Aをインサート成形で製造する際に、このようなバリア筒57をあらかじめ金型内にセットしておくことにより、バリア筒57を口部55に一体化することができ、口部55にガスバリア性を有するフィルムが設けられ、ガスバリア性が付与された口栓が得られる。
以上ここまでガスバリア性を有するフィルムを用いたバリア筒57を説明してきたが、バリア筒自体をEVOH樹脂等のバリア性を有する樹脂を用いて射出成形等により成形し、ガスバリア性を有するフィルムを設けないものを用いてもよい。
バリア性が付与されたキャップは、キャップ本体内部の、スパウトの口部を閉塞する位置にガスバリア性を有するフィルム62が内蔵されている(図6参照)。
例えば、ガスバリア性を有するフィルムとは、アルミニウム箔等の金属箔、エチレン-ビニルアルコール共重合体(EVOH)フィルム、無機蒸着フィルム等を有するフィルムが挙げられる。
ガスバリア性を有するフィルムのうち、スパウトの口部と直接接する面は、口部を構成する樹脂と熱溶着可能な樹脂からなる層により形成されていることが好ましい。さらに、スパウトの口部と容易に剥離することが可能な樹脂からなる層から形成されていることが好ましい。スパウトの口部と熱溶着可能であり、かつ容易に剥離可能であることから、イージーピールフィルムを用いるのが好ましい。
ガスバリア性を有するフィルムのうち、キャップ本体の内部と接する面は、キャップ本体と熱溶着可能な樹脂からなる層から形成されていることが好ましい。
スパウトの口部と、キャップに内蔵されたガスバリア性を有するフィルムとを超音波、高周波誘電、電磁誘導などにより溶着するのが好ましく、ガスバリア性を有するフィルムの材質により溶着方法は決定される。例えば、ガスバリア性を有するフィルムに金属箔を有する場合、電磁誘導による溶着が好ましい。
ガスバリア性を有するフィルムは、例えばスパウト及びキャップがポリエチレン系樹脂からなる場合、キャップ側からスパウト側に「直鎖状低密度ポリエチレン(LLDPE)フィルム/接着剤/二軸延伸ポリエチレンテレフタレート(PET)フィルム/接着剤/アルミニウム箔/接着剤/イージーピールフィルム」のような各フィルムをドライラミネート法により積層した構造にしてもよい。
このように水素水が充填された本発明の水素水入り口栓付包装袋においては、包装袋を形成している積層体の外観不良がない。また、口栓として、ガスバリア性が付与された口栓を用いることにより、充填された水素水中の水素残存率も高く維持できる。
(実施例1)
図1の構成の積層体を以下のようにして製造した。
まず、シーラント層14を形成するためのLLDPEフィルムと、第2のガスバリア層12を形成するためのアルミニウム箔と、基材層13を形成するための二軸延伸ポリアミドフィルムとを二液反応型ポリウレタン系接着剤である接着剤(y)を用いたドライラミネート法により積層、接着し、フィルム構成が「シーラント層/接着剤層(Y)(塗布量:3.5g/m2)/第2のガスバリア層/接着剤層(Y)(塗布量:3.5g/m2)/基材層」である積層体からなる部材(a)16を製造した。
ついで、得られた部材(a)16の基材層13と、第1のガスバリア層11を形成するためのガスバリア性透明樹脂フィルムからなる部材(b)とを、ポリエポキシ樹脂を主剤とし、ポリアミン樹脂を硬化剤とする接着剤(x)を用いたドライラミネート法により接着し、実施例1の積層体を製造した。接着剤層(X)の塗布量は、2.0g/m2とした。
積層体の形成に用いた材料の詳細を表1に示す。
まず、得られた積層体を切り分け、一対の平面部用フィルムと一対の側面部用フィルムを得た。ついで、一対の平面部用フィルムと一対の側面部用フィルムをシーラント層14同士が対向するように合わせて、側部シールを150~200℃、底シールを200~250℃の条件でヒートシールを行い、ガゼット袋である包装袋を製造した。ついで、ヒートシールされていない包装袋の上端部に、バリア性を有する口栓を挿入し、150~250℃の条件でヒートシールを行い、包装袋の上端部を閉塞するとともに口栓を取り付け、口栓付包装袋を得た。
得られた口栓包装袋に水素水を収容し、口栓をキャップで閉塞し、水素水入り口栓包装袋を得た。
なお、バリア性を有する口栓のスパウトとしては、包装袋に取り付けると包装袋から外部に突出する筒状の口部と、口部の一端に連設され、包装袋に密着して取り付けられる密着部とを有するポリエチレン製のものを使用した。この口栓においては、スパウトの口部の内側に、ポリエチレン製の筒本体の外周にガスバリア性を有するフィルムとしてアルミニウム箔が巻かれたバリア筒が一体化されている。このようにバリア筒が一体化されることにより、口栓にガスバリア性が付与されている。
また、水素水入り口栓付包装袋について、充填された水素水の水素残存率を測定した。
評価および測定の方法を以下に示す。
また、結果を表2に示す。
得られた積層体の表面を目視により確認した。
<水素残存率の評価>
口栓付包装袋に水素水を充填し、充填してから16週間経過後の水素水の溶存水素濃度(H2)を測定した。充填直後の水素水の溶存水素濃度(H1)を100%としたときの溶存水素濃度(H2)の数値(%)を求め、その数値(%)を以下のA、B、Cの3段階で評価した。
溶存水素濃度(H1)および(H2)は、有限会社共栄電子研究所製の溶存水素計「KM2100DH」を用いて測定した。水素水入り口栓付包装袋の保存温度および測定温度は23℃とした。また、測定のサンプル数は3とし(n=3)、3つの平均値を採用した。
A;85%以上
B;60%以上~85%未満
C:60%未満
口栓のスパウトとして、アルミニウム箔が巻かれたバリア筒が一体化されておらずバリア性を有しないものを使用した以外は、実施例1と同様にして、水素水入り口栓付包装袋を製造し、実施例1と同様の評価を行った。結果を表2に示す。
表1に示す材料を用いて、図2の構成の積層体を以下のようにして製造した。
まず、シーラント層14を形成するためのLLDPEフィルムと、基材層13を形成するための二軸延伸ポリアミドフィルムと、第2のガスバリア層12を形成するためのアルミニウム箔とを、二液反応型ポリウレタン系接着剤である接着剤(y)を用いたドライラミネート法により接着し、フィルム構成が「シーラント層/接着剤層(Y)(塗布量:3.5g/m2)/基材層/接着剤層(Y)(塗布量:3.5g/m2)/第2のガスバリア層」である部材(a)16を製造した。
ついで、得られた部材(a)16の第2のガスバリア層12と、第1のガスバリア層11を形成するためのガスバリア性透明樹脂フィルムからなる部材(b)とを、ポリエポキシ樹脂を主剤とし、ポリアミン樹脂を硬化剤とする接着剤(x)を用いたドライラミネート法により接着し、実施例3の積層体を製造した。接着剤層(X)の塗布量は、2.0g/m2とした。
得られた積層体を用いた以外は、実施例1と同様にして水素水入り口栓付包装袋を製造し、実施例1と同様の評価を行った。結果を表2に示す。
第2のガスバリア層12をアルミニウム箔に代えて第1のガスバリア層11と同様のガスバリア性透明樹脂フィルムとした以外は、実施例1と同様にして、実施例4の積層体を製造した。
得られた積層体を用いた以外は、実施例1と同様にして水素水入り口栓付包装袋を製造し、実施例1と同様の評価を行った。結果を表2に示す。
ポリエチレン製の口栓のスパウトにEVOH樹脂で成形したバリア筒が一体化されたスパウトを用いた以外は、実施例1と同様にして、水素水入り口栓付包装袋を製造し、実施例1と同様の評価を行った。結果を表2に示す。
口栓としてスパウトの口部を閉塞したキャップの内部にガスバリア性を有するフィルムを設けた以外は、実施例1と同様にして実施例6の積層体を製造した。
ガスバリア性を有するフィルムは、「直鎖状低密度ポリエチレン(LLDPE)フィルム30μm/接着剤/二軸延伸ポリエチレンテレフタレート(PET)12μm/接着剤/アルミニウム箔7μm/接着剤/イージーピールフィルム30μm」の構成とした。
LLDPEフィルムは、タマポリ社製「UB-1」で、厚みは30μmである。
二軸延伸PETフィルムは、東洋紡社製「E5200」で、厚みは12μmである。
アルミニウム箔は、三菱アルミニウム社製で、 厚みは7μmである。
イージーピールフィルムは、東レフィルム加工社製「9501C」で、厚みは30μmである。
接着剤:ドライラミネート用接着剤(y)
ガスバリア性を有するフィルムの大きさは、直径11mmの円形(キャップ内部と同じ大きさ)である。
スパウトをキャップで閉塞後、スパウトの口部と、キャップのガスバリア性を有するフィルムとを、電磁誘導ウエルダー(精電舎電子工業株式会社製 UHT-1500)を用いて、出力1500W、発振周波数150kHz、シール時間0.5秒にて溶着した。
実施例1と同様の評価を行った。結果を表2に示す。
実施例1と同様にして、フィルム構成が「シーラント層/接着剤層(Y)/第2のガスバリア層/接着剤層(Y)/基材層」である部材を製造した後、得られたこの部材の基材層と、第1のガスバリア層を形成するためのガスバリア性透明樹脂フィルムとを、接着剤(y)を用いたドライラミネート法により接着し、比較例1の積層体を製造した。
得られた積層体を用いた以外は、実施例1と同様にして水素水入り口栓付包装袋を製造し、実施例1と同様の評価を行った。結果を表2に示す。
11:第1のガスバリア層
12:第2のガスバリア層
13:基材層
14:シーラント層
21:接着剤層(X)
22:接着剤層(Y)
30:口栓付包装袋
40:包装袋
50:口栓
50A:口栓のスパウト
Claims (12)
- 複数のガスバリア層を有する積層体であって、
任意のガスバリア層と他のガスバリア層との間には、ポリエポキシ樹脂を主剤とし、ポリアミン樹脂を硬化剤とする接着剤(x)からなる接着剤層(X)が少なくとも1層設けられている積層体。 - 前記複数のガスバリア層として、第1のガスバリア層と第2のガスバリア層とを有し、
前記第1のガスバリア層が、ガスバリア性透明樹脂フィルムからなる請求項1に記載の積層体。 - 前記第2のガスバリア層が、金属箔からなる請求項2に記載の積層体。
- 任意の1層のガスバリア層からなる部材と他の1層のガスバリア層からなる部材とが、または、任意の1層のガスバリア層からなる部材と他の1層のガスバリア層を有する積層体からなる部材とが、
または、任意の1層のガスバリア層を有する積層体からなる部材と他の1層のガスバリア層を有する積層体からなる部材とが、
前記接着剤層(X)で貼り合わされた積層体である請求項1~3のいずれか一項に記載の積層体。 - 前記部材が積層体の場合、前記積層体は、ポリオール成分を主剤とし、ポリイソシアネート成分を硬化剤とする接着剤(y)からなる接着剤層(Y)を有する請求項4に記載の積層体。
- シーラント層をさらに有し、前記シーラント層は、前記積層体のいずれか一方の最外面を構成している請求項1~5のいずれか一項に記載の積層体。
- 請求項1~6のいずれか一項に記載の積層体からなる包装袋。
- 請求項7の包装袋に水素水が充填された水素水入り包装袋。
- 請求項7の包装袋に口栓が取り付けられた口栓付包装袋。
- 前記口栓がバリア性を有する請求項9に記載の口栓付包装袋。
- 前記口栓はキャップを有し、前記キャップがバリア性を有する請求項10に記載の口栓付包装袋。
- 請求項9~11のいずれかに記載の口栓付包装袋に水素水が充填された水素水入り口栓付包装袋。
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US20180147814A1 (en) | 2018-05-31 |
JPWO2017002753A1 (ja) | 2018-04-12 |
JP6718870B2 (ja) | 2020-07-08 |
CN107708994A (zh) | 2018-02-16 |
KR20180025868A (ko) | 2018-03-09 |
US10773491B2 (en) | 2020-09-15 |
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