WO2018062331A1 - Laminated body - Google Patents

Laminated body Download PDF

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Publication number
WO2018062331A1
WO2018062331A1 PCT/JP2017/035078 JP2017035078W WO2018062331A1 WO 2018062331 A1 WO2018062331 A1 WO 2018062331A1 JP 2017035078 W JP2017035078 W JP 2017035078W WO 2018062331 A1 WO2018062331 A1 WO 2018062331A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
film
base material
laminate
sealant
Prior art date
Application number
PCT/JP2017/035078
Other languages
French (fr)
Japanese (ja)
Inventor
田中　大介
満 武士田
和佳子 仙頭
和弘 多久島
靖也 飯尾
真一朗 河野
梓 田島
駿行 長谷川
Original Assignee
大日本印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017144857A external-priority patent/JP2018167573A/en
Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Publication of WO2018062331A1 publication Critical patent/WO2018062331A1/en

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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
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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Definitions

  • the present invention relates to a laminate for forming a bag or the like.
  • the non-seal part to which the laminated bodies are not joined constitutes an accommodation part in which the contents are accommodated.
  • the sealing part to which the laminated bodies are joined has sealed the accommodating part.
  • the contents are, for example, cooked foods such as curry, stew and soup, or semi-cooked foods cooked by heating.
  • the laminated body which comprises a bag contains a plastic film as a base material.
  • Patent Document 1 proposes to use polyethylene terephthalate, polypropylene, nylon, or the like as a base material of a laminate.
  • a base material contributes to the improvement of the intensity
  • Nylon is known as a material having high strength. However, nylon has a characteristic that it easily absorbs moisture. For this reason, when nylon is used for the base material, the nylon may be colored by the contents and the appearance of the bag may be impaired, or the laminate strength of the laminate may be reduced.
  • the present invention aims to provide a laminate that can effectively solve such problems.
  • the present invention is a laminate comprising a base material containing 51% by mass or more of polybutylene terephthalate, and at least one of linear low density polyethylene or polypropylene, and a sealant layer constituting the inner surface of the laminate. And a laminated body.
  • the base material containing polybutylene terephthalate may have a multilayer structure including 10 layers or more.
  • the base material containing polybutylene terephthalate may have a single layer structure having an IV value of 1.10 dl / g or more and 1.35 dl / g or less.
  • the sealant layer may include 90% by mass or more of polypropylene.
  • the sealant layer may contain linear low density polyethylene having a melting point of 100 ° C. or higher.
  • the laminate according to the present invention further includes an adhesive layer that is provided on the outer surface side of the sealant layer and includes a cured product of a polyol and an aliphatic isocyanate compound, and the laminate of the aliphatic isocyanate compound with respect to the hydroxy group of the polyol.
  • the molar ratio of isocyanate groups may be 3.5 or more.
  • the laminate according to the present invention comprises: Substrate / adhesive layer / sealant layer, Substrate / printing layer / adhesive layer / sealant layer, Substrate / transparent deposition layer / transparent gas barrier coating film / printing layer / adhesive layer / sealant layer, or base material / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer in this order May be.
  • the piercing strength of the laminate may be 11N or more.
  • the laminate according to the present invention comprises: Substrate / transparent deposition layer / transparent gas barrier coating film / printing layer / adhesive layer / sealant layer, or substrate / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer in this order,
  • the transparent vapor deposition layer may contain aluminum oxide, and a covalent bond between an aluminum atom and a carbon atom may be formed at the interface between the base material and the transparent vapor deposition layer.
  • the impact strength of the laminate may be 800 kJ / m or more.
  • the laminate according to the present invention comprises: Substrate / first adhesive layer / metal foil / second adhesive layer / sealant layer, or substrate / print layer / first adhesive layer / metal foil / second adhesive layer / sealant layer in this order Including
  • the second adhesive layer may contain a cured product of a polyol and an aliphatic isocyanate compound. In this case, the piercing strength of the laminate may be 13N or more.
  • the laminate according to the present invention includes at least a first base material, a second base material, and a sealant layer in this order, and the second base material includes 51% by mass or more of polyethylene terephthalate or 51% by mass or more of polybutylene terephthalate.
  • the first base material may contain 51% by mass or more of polybutylene terephthalate.
  • the piercing strength of the laminate may be 13N or more.
  • the laminate according to the present invention is provided between the first base material and the second base material, the transparent vapor deposition layer provided on the first base material or the second base material, and the transparent vapor deposition layer. And a transparent gas barrier coating film.
  • the transparent vapor deposition layer includes aluminum oxide, and a covalent bond between an aluminum atom and a carbon atom is formed at an interface between the first base material or the second base material and the transparent vapor deposition layer. It may be.
  • the laminate further includes a light-shielding print layer positioned between the first substrate and the second substrate, and the total light transmittance of the laminate is 20% or less. May be.
  • the first base material may include polybutylene terephthalate
  • the second base material may include polyethylene terephthalate
  • the first base material may include polyethylene terephthalate
  • the second base material may include polybutylene terephthalate
  • the laminate can be provided with puncture resistance and heat resistance.
  • FIG. It is a top view which shows the test piece for evaluating impact strength. It is sectional drawing of the test piece shown in FIG. It is a figure which shows an example of the measuring method of impact strength. It is a figure which shows an example of the measuring method of piercing strength. It is a figure which shows the evaluation result of Example A1-A5 and Comparative Example A1-A3. It is a figure which shows the evaluation result of Example B1-B3 and comparative example B1-B3. It is a figure which shows the evaluation result of Examples C1-C6 and Comparative Examples C1 and C2. It is a figure which shows the evaluation result of Examples D1-D4 and Comparative Examples D1 and D2.
  • FIG. 1 is a front view showing a bag 10 according to the present embodiment.
  • the bag 10 includes a storage portion 17 that stores the contents.
  • FIG. 1 the bag 10 of the state in which the contents are not accommodated is shown. Bag 10 by this embodiment is constituted so that retort processing can be performed.
  • the configuration of the bag 10 will be described.
  • the bag 10 is a gusseted bag configured to be able to stand on its own.
  • the bag 10 includes an upper portion 11, a lower portion 12, and a side portion 13, and has a substantially rectangular outline in a front view.
  • names such as “upper”, “lower” and “side”, and terms such as “upper” and “lower” refer to a bag based on the state in which the bag 10 is self-supporting with the gusset portion down. It is only a relative representation of the position and direction of 10 and its components.
  • position at the time of transport of the bag 10 or use is not limited by the name and terminology in this specification.
  • the bag 10 includes a surface film 14 that constitutes the front surface, a back film 15 that constitutes the back surface, and a lower film 16 that constitutes the lower portion 12.
  • the lower film 16 is disposed between the front film 14 and the back film 15 in a state where the lower film 16 is folded at the folded portion 16f.
  • the term “surface film”, “back film” and “lower film” described above is merely a partition of each film according to the positional relationship, and the method of providing a film when manufacturing the bag 10 It is not limited by the above terms.
  • the bag 10 may be manufactured using one film in which the front film 14, the back film 15, and the lower film 16 are continuously provided, or one sheet in which the front film 14 and the lower film 16 are continuously provided. It may be manufactured using a total of two films, a film and one back film 15, and a total of three films, one surface film 14, one back film 15, and one lower film 16. May be used.
  • the inner surfaces of the front film 14, the back film 15, and the lower film 16 are joined together by a seal portion.
  • the seal portion is hatched.
  • the seal portion has an outer edge seal portion extending along the outer edge of the bag 10.
  • the outer edge seal portion includes a lower seal portion 12 a extending in the lower portion 12 and a pair of side seal portions 13 a extending along the pair of side portions 13.
  • the upper portion 11 of the bag 10 is an opening 11b. After the contents are stored in the bag 10, the inner surface of the front film 14 and the inner surface of the back film 15 are joined at the upper portion 11, whereby an upper seal portion is formed and the bag 10 is sealed.
  • the side seal portion 13a and the upper seal portion described later are seal portions configured by joining the inner surface of the surface film 14 and the inner surface of the back film 15.
  • the lower seal portion 12a is formed by bonding the inner surface of the surface film 14 and the inner surface of the lower film 16, and by bonding the inner surface of the back film 15 and the inner surface of the lower film 16. Including a configured seal.
  • the method for forming the seal portion is not particularly limited.
  • the sealing portion may be formed by melting the inner surfaces of the film by heating or the like and welding the inner surfaces, that is, by heat sealing. Or you may form a seal
  • the front film 14 and the back film 15 may be provided with easy opening means 25 for tearing the front film 14 and the back film 15 to open the bag 10.
  • the easy-opening means 25 may include a notch 26 that is formed in the side seal portion 13 a of the bag 10 and serves as a starting point of tearing.
  • a half-cut line formed by laser processing, a cutter, or the like may be provided as the easy-opening means 25 in a portion that becomes a path when the bag 10 is torn.
  • the easy-opening means 25 may include notches and scars formed in the area where the seal portion is formed in the front film 14 and the back film 15.
  • the scar group may include, for example, a plurality of through holes formed so as to penetrate the front film 14 and / or the back film 15.
  • the scar group may include a plurality of holes formed on the outer surface of the front film 14 and / or the back film 15 so as not to penetrate the front film 14 and / or the back film 15.
  • FIG. 2 is a cross-sectional view showing a laminated body 30 constituting the front film 14 and the back film 15.
  • the laminate 30 includes a first film 40 and a sealant film 70 laminated on the first film 40 with an adhesive layer 45 interposed therebetween.
  • the first film 40 is located on the outer surface 30y side
  • the sealant film 70 is located on the inner surface 30x side opposite to the outer surface 30y.
  • the inner surface 30x is a surface facing the accommodating portion 17 side in the bag 10 constituted by the laminate 30, and the outer surface 30y is a surface located on the opposite side of the inner surface 30x.
  • the first film 40 includes at least a base material 41.
  • the first film 40 may further include a print layer 42 provided on the inner surface 30x side of the base material 41.
  • the sealant film 70 includes a sealant layer 71. Therefore, it can be said that the laminated body 30 by this Embodiment is equipped with the base material / printing layer / adhesive layer / sealant layer in order from the outer surface side to the inner surface side. Note that “/” represents a boundary between layers.
  • the first film 40 includes at least a base material 41 constituting the outer surface 30y of the laminate 30. As shown in FIG. 2, the first film 40 may further include a printing layer 42 provided on the inner surface 30 x side of the base material 41.
  • the base material 41 includes polybutylene terephthalate (hereinafter also referred to as PBT) as a main component.
  • PBT polybutylene terephthalate
  • the base material 41 includes 51% by mass or more of PBT.
  • the advantage that the base material 41 includes PBT will be described.
  • the printing layer 42 can be provided on the base material 41 containing PBT similarly to the case of polyethylene terephthalate (hereinafter also referred to as PET).
  • the retort process is a process of heating the bag 10 in a pressurized state using steam or heated hot water after filling the bag 10 with the contents and sealing the bag 10.
  • the temperature of retort processing is 120 degreeC or more, for example.
  • the boil process is a process of filling the bag 10 with the contents and sealing the bag 10 and then bathing the bag 10 under atmospheric pressure.
  • the temperature of boil processing is 90 degreeC or more and 100 degrees C or less, for example.
  • PBT has high strength. For this reason, the stab resistance can be given to the bag 10 similarly to the case where the laminated body which comprises the bag 10 contains nylon.
  • PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 41 containing PBT is arrange
  • any of the following first configuration or second configuration may be adopted.
  • the content of PBT in the base material 41 according to the first configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further 70% by mass or more, particularly preferably 75% by mass or more, and most preferably. 80% by mass or more.
  • the first film 40 can have excellent impact strength and pinhole resistance.
  • PBT used as a main constituent component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, most preferably 100 mol% or more of terephthalic acid as a dicarboxylic acid component.
  • Mol%. 1,4-butanediol as the glycol component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and most preferably 1,4-butanediol during polymerization. It is not included except by-products generated by the ether bond of butanediol.
  • the base material 41 may contain a polyester resin other than PBT.
  • Polyester resins other than PBT include polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polypropylene terephthalate (PPT), as well as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid.
  • PBT resin copolymerized with dicarboxylic acid such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, polycarbonate diol Min can be mentioned copolymerized PBT resin.
  • dicarboxylic acid such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid
  • ethylene glycol 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -Diols
  • the amount of the polyester resin other than PBT is preferably 49% by mass or less, and more preferably 40% by mass or less. If the addition amount of the polyester resin other than PBT exceeds 49% by mass, the mechanical properties as PBT may be impaired, and impact strength, pinhole resistance, and drawability may be insufficient.
  • the base material 41 may contain, as an additive, a polyester-based or polyamide-based elastomer obtained by copolymerizing at least one of a flexible polyether component, a polycarbonate component, and a polyester component. Thereby, the pinhole resistance at the time of bending can be improved.
  • the additive amount of the additive is, for example, 20% by mass. When the addition amount of the additive exceeds 20% by mass, the effect as the additive may be saturated, or the transparency of the base material 41 may be reduced.
  • FIG. 3 is a cross-sectional view showing an example of the layer structure of the first film.
  • the base material 41 of the first film 40 is composed of a multilayer structure including a plurality of layers 41a.
  • Each of the plurality of layers 41a includes PBT as a main component.
  • each of the plurality of layers 41a preferably includes 51% by mass or more of PBT, and more preferably includes 60% by mass or more of PBT.
  • the (n + 1) th layer 41a is directly stacked on the nth layer 41a. That is, no adhesive layer or adhesive layer is interposed between the plurality of layers 41a.
  • the reason why the properties of the PBT film are improved by multilayering is estimated as follows.
  • the resins are laminated, even if the resin composition is the same, a layer interface exists, and crystallization is accelerated by the interface.
  • the growth of large crystals beyond the layer thickness is suppressed. For this reason, it is considered that the size of the crystal (spherulite) becomes small.
  • a general multilayering apparatus multilayer feed block, static mixer, multilayer multimanifold, etc.
  • a method of laminating thermoplastic resins sent from different flow paths using two or more extruders in multiple layers using a feed block, a static mixer, a multi-manifold die, or the like can be used.
  • multilayering resin of the same composition it is also possible to introduce the above multilayering apparatus into the melt line from the extruder to the die using only one extruder.
  • the substrate 41 is composed of a multilayer structure including at least 10 layers, preferably 60 layers or more, more preferably 250 layers or more, and even more preferably 1000 layers or more.
  • the size of spherulites in the unstretched raw PBT can be reduced, and the subsequent biaxial stretching can be carried out stably.
  • the yield stress of PBT in the state of a biaxially stretched film can be made small.
  • the diameter of the spherulite in the unstretched raw PBT is 500 nm or less.
  • the stretching temperature (hereinafter also referred to as MD stretching temperature) in the longitudinal stretching direction (hereinafter referred to as MD) when producing a biaxially stretched film by biaxially stretching the unstretched raw material of PBT is preferably 40 ° C. or higher. Yes, more preferably 45 ° C or higher.
  • MD stretching temperature is preferably 40 ° C. or higher.
  • stretching temperature becomes like this.
  • it is 100 degrees C or less, More preferably, it is 95 degrees C or less.
  • the phenomenon that the orientation of the biaxially stretched film does not occur can be suppressed by setting the MD stretching temperature to 100 ° C. or lower.
  • the draw ratio in MD (hereinafter also referred to as MD draw ratio) is preferably 2.5 times or more. Thereby, a biaxially stretched film can be oriented and a favorable mechanical characteristic and uniform thickness can be implement
  • the stretching temperature (hereinafter also referred to as TD stretching temperature) in the transverse stretching direction (hereinafter also referred to as TD) is preferably 40 ° C. or higher. By setting the TD stretching temperature to 40 ° C. or higher, the film can be prevented from being broken.
  • the TD stretching temperature is preferably 100 ° C. or lower. By setting the TD stretching temperature to 100 ° C. or lower, the phenomenon that the orientation of the biaxially stretched film does not occur can be suppressed.
  • the stretching ratio in TD (hereinafter also referred to as TD stretching ratio) is preferably 2.5 times or more. Thereby, a biaxially stretched film can be oriented and a favorable mechanical characteristic and uniform thickness can be implement
  • MD stretch ratio is 5 times or less, for example.
  • TD relaxation rate is preferably 0.5% or more. Thereby, it can suppress that a fracture
  • the TD relaxation rate is preferably 10% or less. Thereby, sagging etc. arise in a biaxially stretched film of PBT, and it can control that thickness unevenness generate
  • the thickness of the layer 41a of the base material 41 shown in FIG. 3 is preferably 3 nm or more, more preferably 10 nm or more.
  • the thickness of the layer 41a is preferably 200 nm or less, and more preferably 100 nm or less.
  • the thickness of the base material 41 is preferably 9 ⁇ m or more, and more preferably 12 ⁇ m or more.
  • the thickness of the base material 41 is preferably 25 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the base material 41 according to the second configuration is made of a single layer film containing polyester having butylene terephthalate as a main repeating unit.
  • the base material 41 is mainly composed of 1,4-butanediol as the glycol component or an ester-forming derivative thereof and terephthalic acid as the dibasic acid component or the ester-forming derivative thereof, and condenses them. Homo- or copolymer-type polyester obtained.
  • the content of PBT in the base material 41 according to the second configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, and most preferably. Is 90% by mass or more.
  • the base material 41 which concerns on a 2nd structure is comprised only with the polybutylene terephthalate and the additive.
  • PBT having a melting point of 200 ° C. or more and 250 ° C. or less and an IV value (intrinsic viscosity) of 1.10 dl / g or more and 1.35 dl / g or less Is preferred. Furthermore, those having a melting point of 215 ° C. or more and 225 ° C. or less and an IV value of 1.15 dl / g or more and 1.30 dl / g or less are particularly preferable. These IV values may be satisfied by the whole material constituting the base material 41. The IV value can be calculated based on JIS K 7367-5: 2000.
  • the base material 41 which concerns on a 2nd structure may contain polyester resins other than PBT, such as PET, in 30 mass% or less.
  • PET polyester resins other than PBT
  • the base material 41 contains PET in addition to PBT, PBT crystallization can be suppressed, and the stretchability of the PBT film can be improved.
  • blended with PBT of the base material 41 the polyester which uses ethylene terephthalate as a main repeating unit can be used.
  • the base material 41 is a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a colorant, a crystallization inhibitor, a crystallization accelerator, if necessary. Etc. may be contained.
  • the polyester resin pellets used as the raw material of the base material 41 have a moisture content of 0.05% by weight or less, preferably 0.01% by weight or less before heating and melting in order to avoid a decrease in viscosity due to hydrolysis during heating and melting. It is preferable to use after sufficiently pre-drying so that
  • the crystallization temperature region of the polymer is cooled at a certain rate or more, that is, the raw fabric cooling rate is an important factor.
  • the raw fabric cooling rate is, for example, 200 ° C./second or more, preferably 250 ° C./second or more, particularly preferably 350 ° C./second or more. Since the unstretched original film formed at a high cooling rate maintains a low crystalline state, the stability of the bubbles during stretching is improved. Furthermore, since film formation at high speed is possible, film productivity is also improved.
  • the cooling rate is less than 200 ° C./sec, it is considered that the crystallinity of the obtained unstretched original fabric is increased and the stretchability is lowered. In extreme cases, the stretching bubble may burst and stretching may not continue.
  • the unstretched raw material containing PBT as a main component is conveyed to a space where biaxial stretching is performed while maintaining the atmospheric temperature at 25 ° C. or lower, preferably 20 ° C. or lower. Thereby, even if it is a case where residence time becomes long, the crystallinity of the unstretched original fabric immediately after film-forming can be maintained.
  • the biaxial stretching method for obtaining a stretched film by stretching an unstretched raw fabric is not particularly limited.
  • the longitudinal direction and the lateral direction may be simultaneously stretched by the tubular method or the tenter method, or the longitudinal direction and the lateral direction may be sequentially stretched.
  • the tubular method can obtain a stretched film having a good balance of physical properties in the circumferential direction, and is particularly preferably employed.
  • the unstretched raw material introduced into the stretching space is inserted between a pair of low-speed nip rolls, and then heated by a stretching heater while air is being pressed therein. After stretching, air is blown onto the stretched film by a cooling shoulder air ring.
  • the stretching ratio is preferably 2.7 times or more and 4.5 times or less for MD and TD, respectively, in consideration of stretching stability, strength physical properties of the stretched film, transparency, and thickness uniformity.
  • the stretching temperature is preferably 40 ° C. or higher and 80 ° C. or lower, and particularly preferably 45 ° C. or higher and 65 ° C. or lower. Since the unstretched original fabric produced at the above-described high cooling rate has low crystallinity, the unstretched original fabric can be stably stretched even when the stretching temperature is relatively low. Further, by setting the stretching temperature to 80 ° C. or less, it is possible to suppress stretching bubble shaking and obtain a stretched film with good thickness accuracy. In addition, by setting the stretching temperature to 40 ° C. or higher, it is possible to suppress the occurrence of excessive stretch-oriented crystallization due to low-temperature stretching, thereby preventing whitening of the film.
  • the base material 41 produced as described above is constituted by a single layer containing, for example, polyester having butylene terephthalate as a main repeating unit. According to the above-described production method, since the unstretched raw film is formed at a high cooling rate, even when the unstretched raw fabric is constituted by a single layer, a low crystalline state can be maintained, For this reason, an unstretched original fabric can be extended
  • the printed layer 42 is a layer printed on the base material 41 in order to show product information or impart aesthetics to the bag 10.
  • the print layer 42 expresses characters, numbers, symbols, figures, patterns, and the like.
  • an ink for gravure printing or an ink for flexographic printing can be used as a material constituting the printing layer 42.
  • the ink constituting the printing layer 42 includes a binder and a pigment.
  • the binder includes, for example, polyurethane as in the adhesive layer 45 described later.
  • Polyurethane is a cured product produced by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent. Details of the polyol and the isocyanate compound will be described in the paragraph of the adhesive layer 45.
  • the pigment of the printing layer 42 is a colored powder and exists in the binder with a predetermined distribution density.
  • the color exhibited by the pigment is not particularly limited, and various pigments such as red, blue, green, white, and black can be used.
  • the average particle diameter of the pigment may be 0.1 ⁇ m or more and 1 ⁇ m or less, or 0.5 ⁇ m or more and 1 ⁇ m or less.
  • White pigments generally have larger dimensions than other color pigments.
  • the average particle diameter of the white pigment is 0.5 ⁇ m or more and 1 ⁇ m or less.
  • the average particle diameter of the pigment can be measured by a dynamic light scattering method.
  • the print layer 42 may be composed of a single layer or may include a plurality of layers.
  • the printing layer 42 may include a first layer that includes a pigment that exhibits a first color, and a second layer that includes a pigment that exhibits a second color different from the first color.
  • the thickness of one layer of the printing layer 42 is, for example, not less than 0.5 ⁇ m and not more than 3 ⁇ m.
  • FIG. 4 is a cross-sectional view illustrating another example of the layer configuration of the stacked body 30.
  • the 1st film 40 of the laminated body 30 is located in the inner surface 30x side of the base material 41, and may further contain the transparent gas barrier layer 35 which has transparency.
  • the printing layer 42 is located on the inner surface 30 x side of the transparent gas barrier layer 35.
  • the laminated body 30 in the example shown in FIG. 4 includes a base material / transparent gas barrier layer / printing layer / adhesive layer / sealant layer in order from the outer surface side to the inner surface side.
  • the transparent gas barrier layer 35 is formed on the surface on the inner surface 30x side of the substrate 41 and includes at least a transparent vapor deposition layer 36 made of an inorganic material having transparency.
  • the transparent gas barrier layer 35 may further include a transparent gas barrier coating film 37 that is formed on the inner surface 30x side of the transparent vapor deposition layer 36 and has transparency.
  • the laminated body 30 is provided with a base material / transparent deposition layer / transparent gas barrier coating film / printing layer / adhesive layer / sealant layer in order from the outer surface side to the inner surface side.
  • the transparent vapor-deposited layer 36 functions as a layer having a gas barrier function that prevents permeation of oxygen gas and water vapor.
  • Two or more transparent vapor deposition layers 36 may be provided. When it has two or more transparent vapor deposition layers 36, each may have the same composition or different compositions.
  • a method for forming the transparent vapor deposition layer 36 for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a thermal chemical vapor deposition method and a photochemical vapor deposition method.
  • a vapor deposition layer can be formed on a film formation roller using a roller-type vapor deposition film forming apparatus.
  • the transparent vapor deposition layer 36 is formed of an inorganic material having transparency, such as aluminum oxide (aluminum oxide) and silicon oxide.
  • an amorphous thin film of aluminum oxide As the transparent vapor deposition layer 36, it is preferable to use an amorphous thin film of aluminum oxide.
  • the transparent vapor-deposited layer 36 is an amorphous thin film of aluminum oxide represented by the formula AlO X (wherein X represents a number in the range of 0.5 to 1.5). .
  • AlO X amorphous thin film of aluminum oxide represented by the formula AlO X (wherein X represents a number in the range of 0.5 to 1.5).
  • As the transparent vapor-deposited layer 36 an amorphous thin film of aluminum oxide in which the value of X decreases in the depth direction from the film surface toward the inner surface can be used.
  • the amorphous thin film of aluminum oxide is represented by the formula AlOX (wherein X represents a number in the range of 0.5 to 1.5), and extends in the depth direction from the thin film surface toward the inner surface. It is preferable that the value of X increases.
  • the value of X in said formula is 0, it is a perfect inorganic simple substance (pure substance), and is not transparent.
  • the decreasing rate of the value of X is determined by using a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy: XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy: SIMS).
  • a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy: XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy: SIMS).
  • the transparent vapor deposition layer 36 may be a layer made of a mixture of inorganic compounds containing a covalent bond between an aluminum atom and a carbon atom.
  • the transparent vapor deposition layer 36 uses an X-ray photoelectron spectrometer (measuring conditions: X-ray source AlK ⁇ , X-ray output 120 W) and shares aluminum atoms and carbon atoms at the peak measured by ion etching in the depth direction. It may have a gas barrier property that indicates the presence of a bond and has transparency and prevents permeation of oxygen, water vapor, and the like.
  • a covalent bond between a metal atom and a carbon atom may be formed at the interface between the transparent vapor deposition layer 36 and the substrate 41.
  • the transparent vapor deposition layer 36 contains aluminum oxide
  • the covalent bond of an aluminum atom and a carbon atom shall be formed in the interface of the base material 41 and the transparent vapor deposition layer 36.
  • the covalent bond can be detected by measurement by X-ray photoelectron spectroscopy (hereinafter referred to as “XPS measurement” for short).
  • the transparent vapor deposition layer 36 all the bonds containing the carbon atom observed when the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is measured when the interface between the transparent vapor deposition layer 36 and the substrate 41 is measured by XPS measurement. It is preferable that it is within the range of 0.3% or more and 30% or less. Thereby, the adhesiveness of the transparent vapor deposition layer 36 and the base material 41 is strengthened, the transparency is excellent, and a gas barrier vapor deposition film having a well-balanced performance is obtained.
  • the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is less than 0.3%, the adhesion of the transparent vapor-deposited layer 36 is not sufficiently improved, and it is difficult to stably maintain the barrier property.
  • the transparent vapor deposition layer 36 containing aluminum oxide as a main component has an AL (aluminum) / O (oxygen) ratio of transparent vapor deposition on the side opposite to the base material 41 from the interface between the base material 41 and the transparent vapor deposition layer 36.
  • AL aluminum
  • O oxygen
  • the AL / O ratio exceeds 1.0 within a range from the interface between the transparent vapor deposition layer 36 and the base material 41 toward the surface of the transparent vapor deposition layer 36 on the side opposite to the base material 41, Adhesiveness with the transparent vapor deposition layer 36 becomes insufficient, the proportion of aluminum increases, and the transparency of the transparent vapor deposition layer 36 decreases.
  • the thickness of the transparent vapor deposition layer 36 is, for example, 30 mm or more and 150 mm or less. If it is less than 30 mm, the gas barrier property may be insufficient even when the transparent gas barrier coating film 37 is used in combination. On the other hand, if it exceeds 150 mm, the gas barrier performance of the laminate 30 may not be maintained. The reason for this is not clear, but if the thickness of the transparent vapor deposition layer 36 exceeds 150 mm, the flexibility of the laminate 30 is reduced, and when the laminate 30 is used in the bag 10, a part of the transparent vapor deposition layer 36 is not cracked. It is considered that pinholes are generated and gas barrier properties are lowered.
  • the thickness of the transparent vapor deposition layer 36 is preferably 40 mm or more and 130 mm or less, more preferably 50 mm or more and 120 mm or less.
  • the thickness of the transparent vapor-deposited layer 36 can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (trade name: RIX2000 type, manufactured by Rigaku Corporation).
  • RIX2000 type fluorescent X-ray analyzer
  • it can carry out by the method of changing the deposition rate of the transparent vapor deposition layer 36, the method of changing the vapor deposition rate, etc.
  • the surface of the base material 41 on the inner surface 30x side may be subjected to pretreatment such as corona discharge treatment, flame processing, and plasma processing in advance.
  • pretreatment such as corona discharge treatment, flame processing, and plasma processing in advance.
  • the surface of the base material 41 on which the transparent vapor deposition layer 36 is to be formed is pretreated. It is preferable.
  • plasma treatment plasma is supplied to the surface of the base material 41 in a reduced pressure environment of 0.1 Pa or more and 100 Pa or less by the pretreatment apparatus.
  • Plasma uses an inert gas such as argon alone or a mixed gas of oxygen, nitrogen, carbon dioxide and one or more of them as a plasma source gas, and the plasma source gas is excited by a potential difference due to a high-frequency voltage or the like. By doing so, it can be generated.
  • an inert gas such as argon alone or a mixed gas of oxygen, nitrogen, carbon dioxide and one or more of them as a plasma source gas, and the plasma source gas is excited by a potential difference due to a high-frequency voltage or the like. By doing so, it can be generated.
  • the plasma can be confined in the vicinity of the surface of the base material 41 by the pretreatment. Thereby, the shape of the surface of the base material 41, a chemical bonding state, and a functional group can be changed, and the chemical properties of the surface of the base material 41 can be changed. As a result, the adhesion between the base material 41 and the transparent vapor deposition layer 36 can be improved.
  • the transparent gas barrier coating film 37 is a layer that functions as a layer that suppresses permeation of oxygen gas, water vapor, and the like.
  • the transparent gas barrier coating film 37 has a general formula R 1 n M (OR 2 ) m (where R 1 and R 2 represent an organic group having 1 to 8 carbon atoms, and M represents a metal atom) , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and a polyvinyl alcohol as described above
  • R 1 n M (OR 2 ) m (where R 1 and R 2 represent an organic group having 1 to 8 carbon atoms, and M represents a metal atom) , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and a polyvinyl alcohol as described above
  • alkoxide represented by the general formula R 1 n M (OR 2 ) m at least one kind of a partial hydrolyzate of alkoxide and a condensate of hydrolysis of alkoxide can be used. Moreover, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which 1 or more was hydrolyzed, and its mixture may be sufficient.
  • the condensate of hydrolysis of alkoxide a dimer or more of partially hydrolyzed alkoxide, specifically, a dimer to hexamer is used.
  • alkoxide represented by the above general formula R 1 n M (OR 2 ) m as the metal atom represented by M, silicon, zirconium, titanium, aluminum, and the like can be used. Examples of preferable metals include silicon and titanium. In the present invention, alkoxides may be used alone or in combination of two or more different metal atom alkoxides in the same solution.
  • R 1 n M (OR 2 ) m specific examples of the organic group represented by R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others.
  • alkoxide represented by the general formula R 1 n M (OR 2 ) m specific examples of the organic group represented by R 2 include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group, and the like. These alkyl groups in the same molecule may be the same or different.
  • a silane coupling agent or the like may be added.
  • silane coupling agent known organic reactive group containing organoalkoxysilane can be used.
  • an organoalkoxysilane having an epoxy group is preferably used.
  • ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, or ⁇ - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be used.
  • the above silane coupling agents may be used alone or in combination of two or more.
  • the sealant film 70 includes at least a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30.
  • a material constituting the sealant layer 71 one or more resins selected from polyethylene such as low density polyethylene and linear low density polyethylene, and polypropylene can be used.
  • the sealant layer 71 may be a single layer or a multilayer.
  • the sealant layer 71 is preferably made of an unstretched film. “Unstretched” is a concept that includes not only a film that is not stretched at all, but also a film that is slightly stretched due to the tension applied during film formation.
  • the bag 10 composed of the laminate 30 is subjected to sterilization treatment such as boil treatment and retort treatment at a high temperature. Therefore, as the sealant layer 71, a layer having heat resistance that can withstand processing at these high temperatures is used.
  • the melting point of the material constituting the sealant layer 71 is preferably 150 ° C. or higher, and more preferably 160 ° C. or higher. By increasing the melting point of the sealant layer 71, the bag 10 can be retorted at a high temperature, and therefore the time required for the retort process can be shortened.
  • the melting point of the material constituting the sealant layer 71 is lower than the melting point of the resin constituting the base material 41.
  • a material mainly composed of propylene can be used as the material constituting the sealant layer 71.
  • the material having “propylene as a main component” means a material having a propylene content of 90% by mass or more.
  • Specific examples of the material mainly composed of propylene include propylene / ethylene block copolymer, propylene / ethylene random copolymer, polypropylene such as homopolypropylene, or a mixture of polypropylene and polyethylene.
  • the “propylene / ethylene block copolymer” means a material having a structural formula represented by the following formula (I).
  • the “propylene / ethylene random copolymer” means a material having a structural formula represented by the following formula (II).
  • “Homopolypropylene” means a material having the structural formula shown by the following formula (III).
  • the material may have a sea-island structure.
  • the “sea-island structure” means a structure in which polyethylene is discontinuously dispersed in a region where polypropylene is continuous.
  • examples of the material constituting the sealant layer 71 include polyethylene, polypropylene, or a combination thereof.
  • polyethylene include medium density polyethylene, linear low density polyethylene, and combinations thereof.
  • the material constituting the sealant layer has a melting point of, for example, 100 ° C. or higher, more preferably 105 ° C. or higher, and still more preferably 110 ° C. or higher.
  • sealant film for forming a sealant layer having a melting point of 100 ° C. or higher include TUX-HC manufactured by Mitsui Chemicals Tosero, L6101 manufactured by Toyobo, and LS700C manufactured by Idemitsu Unitech.
  • Specific examples of the sealant film for forming a sealant layer having a melting point of 105 ° C. or higher include NB-1 manufactured by Tamapoly.
  • Specific examples of the sealant film for forming a sealant layer having a melting point of 110 ° C. or higher include LS760C manufactured by Idemitsu Unitech, TUX-HZ manufactured by Mitsui Chemicals Tosero, and the like.
  • the sealant layer 71 includes a propylene / ethylene block copolymer.
  • the sealant film 70 including the sealant layer 71 is an unstretched film containing a propylene / ethylene block copolymer as a main component.
  • the propylene / ethylene block copolymer By using the propylene / ethylene block copolymer, the impact resistance of the sealant film 70 can be increased, and thereby the bag 10 can be prevented from being broken due to the impact at the time of dropping.
  • the puncture resistance of the laminated body 30 can be improved.
  • the sealant layer 71 may further contain a thermoplastic elastomer. By using a thermoplastic elastomer, the impact resistance and puncture resistance of the sealant film 70 can be further enhanced.
  • the thermoplastic elastomer is, for example, a hydrogenated styrene thermoplastic elastomer.
  • the hydrogenated styrene-based thermoplastic elastomer has a structure comprising a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one hydrogenated conjugated diene compound.
  • the thermoplastic elastomer may be an ethylene / ⁇ -olefin elastomer.
  • the ethylene / ⁇ -olefin elastomer is a low crystalline or amorphous copolymer elastomer, which is a random copolymer of 50 to 90% by mass of ethylene as a main component and ⁇ -olefin as a comonomer. is there.
  • the content of the propylene / ethylene block copolymer in the sealant layer 71 is, for example, 80% by mass or more, and preferably 90% by mass or more.
  • Examples of the method for producing a propylene / ethylene block copolymer include a method of polymerizing propylene, ethylene, and the like as raw materials using a catalyst.
  • a catalyst Ziegler-Natta type or metallocene catalyst can be used.
  • the thickness of the sealant layer 71 is preferably 30 ⁇ m or more, and more preferably 40 ⁇ m or more.
  • the thickness of the sealant layer 71 is preferably 100 ⁇ m or less, and more preferably 80 ⁇ m or less.
  • the adhesive layer 45 includes an adhesive for bonding the first film 40 and the sealant film 70.
  • the adhesive constituting the adhesive layer 45 is generated from an adhesive composition prepared by mixing a first composition containing a main agent and a solvent and a second composition containing a curing agent and a solvent.
  • an adhesive contains the hardened
  • Examples of adhesives include ether-based two-component reactive adhesives and ester-based two-component reactive adhesives.
  • ether-based two-component reactive adhesive include polyether polyurethane.
  • the polyether polyurethane is a cured product produced by a reaction between a polyether polyol as a main agent and an isocyanate compound as a curing agent.
  • Examples of the ester-based two-component reactive adhesive include polyester polyurethane and polyester.
  • Polyester polyurethane is a cured product produced by a reaction between a polyester polyol as a main agent and an isocyanate compound as a curing agent.
  • an isocyanate compound that reacts with a polyol such as polyether polyol or polyester polyol to produce a cured product there are an aromatic isocyanate compound and an aliphatic isocyanate compound.
  • the aromatic isocyanate compound elutes components that cannot be used in food applications in a high temperature environment such as during heat sterilization (retort treatment).
  • the adhesive layer 45 is in contact with the sealant film 70 constituting the inner surface 30 x of the laminate 30. For this reason, when the adhesive layer 45 contains an aromatic isocyanate compound, a component eluted from the aromatic isocyanate compound may adhere to the contents of the bag 10 constituted by the laminate 30.
  • a cured product generated by a reaction between a polyol as a main agent and an aliphatic isocyanate compound as a curing agent is used as an adhesive constituting the adhesive layer 45.
  • the aliphatic isocyanate include hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI).
  • the laminate strength between the first film 40 and the sealant film 70 is higher than that when an aromatic isocyanate compound is used. Lower.
  • the printing layer 42 is provided on the base material 41 on the sealant film 70 side.
  • the binder contained in the ink constituting the printing layer 42 includes a cured product generated by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent.
  • the isocyanate compound an aliphatic isocyanate compound is used in the same manner as the adhesive layer 45 in order to prevent components that cannot be used in food applications from eluting.
  • the ink constituting the printing layer 42 includes a pigment in addition to polyurethane.
  • the pigment acts to inhibit adhesion between the substrate 41 and the printing layer 42 and / or adhesion between the printing layer 42 and the adhesive layer 45.
  • the first film 40 including the base material 41 and the printing layer 42 is produced and then wound up in a roll shape, the surface and the back surface of the overlapping first film 40 are prevented from coming into close contact with each other. Is required to have a small ratio of the curing agent to the main agent in the binder of the printing layer 42. Accordingly, the fact that the first film 40 includes the printing layer 42 acts to reduce the laminate strength between the first film 40 and the sealant film 70.
  • the pigment is white, the size of the pigment is large. For this reason, the degree to which adhesion by the cured product is inhibited by the pigment is increased, and thus the degree of decrease in the laminate strength is increased.
  • the ratio of the curing agent to the main agent is made larger than before.
  • the weight ratio of the first composition containing the main agent and the solvent to the second composition containing the curing agent and the solvent is conventionally about 0.1.
  • the weight ratio of the second composition containing the curing agent and the solvent to the first composition containing the main agent and the solvent is larger than 0.1, for example, 0.15 or more. Specifically, it is set to 0.15 or 0.2.
  • the reaction between the main agent and the curing agent can be promoted, and the adhesion of the adhesive layer 45 to the first film 40 and the sealant film 70 can be enhanced.
  • the laminate strength between the first film 40 and the sealant film 70 can be increased.
  • the tearability of the stacked body 30 can be improved, and the impact resistance of the stacked body 30 can be increased.
  • the molar ratio of the curing agent (aliphatic isocyanate compound) to the hydroxy group of the main agent (polyol) is conventionally about 3.
  • the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol is preferably 3.5 or more, more preferably 4 or more, and 4.5 or more. Is more preferable. More preferably, the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol is greater than 5.
  • the aliphatic isocyanate compound is expensive, and increasing the amount of the aliphatic isocyanate compound is not preferable in terms of production cost. Further, as the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol increases, the temperature necessary for curing the adhesive composition increases or the time increases. Considering these points, the molar ratio of the aliphatic isocyanate group to the hydroxy group is preferably 7 or less, and more preferably 6 or less.
  • the molar ratio of the isocyanate group of the aliphatic isocyanate to the hydroxyl group of the polyol in the binder of the printing layer 42 is smaller than the molar ratio of the isocyanate group of the aliphatic isocyanate to the hydroxyl group of the polyol in the adhesive layer 45. Become. Even in such a case, as described above, by setting the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol in the adhesive layer 45 to be 3.5 or more, It is believed that the aliphatic isocyanate compound can be moved into the printing layer 42. Thereby, the laminate strength between the first film 40 and the sealant film 70 can be further increased.
  • the adhesive layer 45 is formed by applying the adhesive composition to the first film 40 or the sealant film 70, and then drying the adhesive composition, and reacting with the main agent and the solvent in the adhesive composition. It is formed by curing the agent composition.
  • the adhesive composition after drying the weight per unit area, for example, preferably to 2 g / m 2 or more and a 5 g / m 2 or less, 3 g / m 2 or more and 4g / m 2 It is as follows.
  • the thickness of the adhesive layer 45 is preferably 2 ⁇ m or more and 5 ⁇ m or less, and more preferably 3 ⁇ m or more and 4 ⁇ m or less.
  • the layer structure of the lower film 16 is arbitrary as long as it has an inner surface that can be joined to the inner surface of the front film 14 and the inner surface of the back film 15.
  • the above-described laminate 30 may be used as the lower film 16.
  • a film having an inner surface constituted by a sealant layer and a configuration different from that of the laminate 30 may be used as the lower film 16.
  • a resin material containing PBT as a main component is prepared.
  • the film-like base material 41 is produced by extruding a resin material by a melt extrusion method such as a cast method or a tubular method.
  • an inorganic material such as aluminum oxide may be vapor-deposited on the film-like base material 41 to form the transparent vapor deposition layer 36.
  • a transparent gas barrier coating composition 37 may be formed by applying a transparent gas barrier composition on the transparent vapor deposition layer 36.
  • the printing layer 42 is formed on the substrate 41 or the transparent gas barrier coating film 37.
  • the 1st film 40 provided with these can be obtained.
  • an adhesive composition is prepared by mixing a first composition containing a main agent and a solvent and a second composition containing a curing agent and a solvent. Subsequently, the adhesive composition is applied to the first film 40 or the sealant film 70. For example, it is applied on the printing layer 42 of the first film 40. Subsequently, the applied adhesive composition is dried to volatilize the solvent. Then, the 1st film 40 and the sealant film 70 are laminated
  • an adhesive composition is hardened and the adhesive agent containing the hardened
  • the laminated body 30 provided with the 1st film 40 and the sealant film 70 can be obtained.
  • the front film 14 and the back film 15 which consist of the above-mentioned laminated body 30 are prepared.
  • the lower film 16 in a folded state is inserted between the front film 14 and the back film 15.
  • the inner surfaces of the films are heat-sealed to form seal portions such as the lower seal portion 12a and the side seal portion 13a.
  • the films bonded to each other by heat sealing are cut into an appropriate shape to obtain a bag 10 shown in FIG.
  • the contents 18 are filled into the bag 10 through the opening 11 b of the upper portion 11.
  • the contents 18 are cooked foods containing moisture, such as curry, stew, and soup.
  • the upper part 11 is heat-sealed to form an upper seal part.
  • the bag 10 in which the contents 18 are accommodated and sealed can be obtained.
  • the stab resistance can be given to the bag 10 similarly to the case where the laminated body which comprises the bag 10 contains nylon.
  • the puncture resistance of the laminate constituting the bag 10 is preferably 11N or more, more preferably 13N or more, further preferably 15N or more, and particularly preferably 17N or more.
  • a method for measuring the piercing strength will be described in Example A1 described later.
  • PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 41 containing PBT is arrange
  • the adhesive bond layer 45 for joining the 1st film 40 and the sealant film 70 contains many hardening
  • the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol in the adhesive layer 45 is 3.5 or more.
  • the reaction between the main agent and the curing agent can be promoted, and the adhesion of the adhesive layer 45 to the first film 40 and the sealant film 70 can be enhanced. .
  • the laminate strength between the first film 40 and the sealant film 70 can be increased.
  • an aliphatic isocyanate compound is used as a hardening
  • the tear strength of the bag 10 can be enhanced by increasing the laminate strength between the first film 40 and the sealant film 70.
  • the tearability will be described.
  • the sealant film 70 including the sealant layer 71 has a smaller tensile elastic modulus than the first film 40 including the base material 41, and thus is easily stretched. By the way, when the laminate strength between the first film 40 and the sealant film 70 is low, the sealant film 70 may peel from the first film 40 when the consumer tears the bag 10. In this case, the force applied to the bag 10 by the consumer mainly acts as a force for stretching the sealant film 70 peeled off from the first film 40, so that it becomes difficult to tear the bag 10.
  • the sealant film 70 is peeled off from the first film 40 when the consumer tears the bag 10. Can be suppressed. For this reason, the force which a consumer applies to the bag 10 acts so that the laminated body 30 with which the 1st film 40 and the sealant film 70 were joined may be linearly torn, and the bag 10 can be opened smoothly. Therefore, even if the laminated body 30 constituting the bag 10 is composed of two films, the first film 40 and the sealant film 70, excellent tearability can be realized.
  • the laminate strength of the laminate 30 at a width of 15 mm is preferably 5N or more, and more preferably 6N or more. A method for measuring the laminate strength will be described in Example A1 described later.
  • the base material 41 of the 1st film 40 contains PBT as a main component.
  • PBT has heat resistance and puncture resistance.
  • the base material 41 can be used as a layer constituting the outer surface 30y of the laminate 30. Therefore, according to the present embodiment, using the laminate 30 having a two-layer structure in which the first film 40 and the sealant film 70 are laminated, the bag 10 that requires tearing, heat resistance, and puncture resistance is provided. Can be configured. By making the laminated body 30 into a two-layer structure, costs, man-hours, and the like required for the laminated body 30 and the bag 10 can be reduced as compared with the case of a three-layer structure.
  • the ratio of the thickness occupied by the layer having a certain hardness, such as the base material 41, to the entire laminate 30 is 3 It becomes lower than the case of a layered structure (first base material / second base material / sealant layer). Therefore, regarding tearability, the two-layer structure is disadvantageous compared to the three-layer structure in terms of not only the laminate strength but also the ratio of layers having a certain hardness.
  • the adhesive layer 45 has a two-layer structure by increasing the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol. Even excellent tearability can be realized.
  • the thickness ratio of the sealant layer 71 to the base material 41 is 2.5 or more and 10.0 or less.
  • the sealant layer 71 of the sealant film 70 includes a propylene / ethylene block copolymer. For this reason, the impact resistance of the laminate 30 including the sealant film 70 and the sealant film 70 can be enhanced. Therefore, even when the bag 10 is configured using the laminate 30 having a two-layer structure (a laminate 30 including only one base material), the bag 10 is prevented from being broken by an impact such as dropping. be able to.
  • the impact strength of the laminate 30 is preferably 800 kJ / m or more, more preferably 900 kJ / m or more, still more preferably 1000 kJ / m or more, and particularly preferably 1100 kJ / m or more. .
  • a method for measuring the impact strength will be described in Example A1 described later.
  • the laminate The impact strength of 30 can be increased to 800 kJ / m or more.
  • the laminate for constituting the bag is required to have a characteristic that prevents the bag from being broken even when a sharp member with a sharp tip contacts the bag, so-called stab resistance.
  • stab resistance Conventionally, for example, in a laminate described in JP 2012-2231992 A, puncture resistance is ensured by a polyamide resin such as nylon contained in a deposited film.
  • nylon is easy to absorb moisture and has poor heat resistance.
  • the polyester resin which exists in the outer surface side of nylon has contributed to the heat resistance of a laminated body.
  • the dimensions of the resin material may change due to absorption of moisture such as water vapor in the atmosphere, that is, moisture absorption. Further, the degree of moisture absorption varies depending on the resin material. For example, the dimensions of the polyamide resin are more likely to change due to moisture absorption than the dimensions of the polyester resin. For this reason, when using a coextruded stretched film of a polyester resin and a polyamide resin as in JP 2012-2231992 A, the dimensions of the polyamide resin change relatively greatly based on the difference in hygroscopicity. Warpage may occur in the coextruded stretched film.
  • the purpose of this embodiment is to provide a laminate that can effectively solve such problems.
  • FIG. 5 is a cross-sectional view illustrating an example of the layer configuration of the stacked body 30 in the present embodiment.
  • the laminate 30 includes at least a first film 40, a metal foil 47, and a sealant film 70 in this order.
  • the metal foil 47 is bonded to the first film 40 via the first adhesive layer 46, and is bonded to the sealant film 70 via the second adhesive layer 48.
  • the first film 40 includes the base material 41, and the sealant film 70 includes the sealant layer 71.
  • the first film 40 may further include a printing layer 42 provided on the inner surface 30 x side of the base material 41. Therefore, the laminate 30 according to the present embodiment is, in order from the outer surface side to the inner surface side, base material / first adhesive layer / metal foil / second adhesive layer / sealant layer, or Substrate / printing layer / first adhesive layer / metal foil / second adhesive layer / sealant layer, It can be said that it has. Note that “/” represents a boundary between layers.
  • first film 40 the first adhesive layer 46, the metal foil 47, the second adhesive layer 48, and the sealant film 70 will be described in detail.
  • the substrate 41 of the first film 40 includes polybutylene terephthalate as a main component, as in the first embodiment described above.
  • the 1st base material 51 contains 51 mass% or more PBT.
  • the configuration of the first base material 51 including PBT any of the first configuration and the second configuration described with respect to the base material 41 in the first embodiment described above may be adopted.
  • the first adhesive layer 46 includes a first adhesive for bonding the first film 50 and the metal foil 47.
  • the first adhesive include an ether-based two-component reactive adhesive, an ester-based two-component reactive adhesive, and the like, as in the case of the adhesive layer 45 in the first embodiment described above. be able to.
  • the first adhesive constituting the first adhesive layer 46 a cured product generated by a reaction between a polyol as a main agent and an aromatic isocyanate compound as a curing agent is used.
  • an aromatic isocyanate compound as a curing agent, the laminate strength between the first film 40 and the metal foil 47 can be further increased.
  • polyether polyol and polyester polyol can be used as polyol, it is preferable to use polyester polyol.
  • the molar ratio of the isocyanate group of the aromatic isocyanate compound to the hydroxyl group of the polyol in the first adhesive constituting the first adhesive layer 46 is in the range of 1 to 5, for example.
  • the metal foil 47 is provided between the first film 40 and the sealant film 70 in order to improve the barrier property against water vapor and oxygen.
  • the metal material constituting the metal foil 47 is, for example, aluminum.
  • the thickness of the metal foil 47 is, for example, not less than 5 ⁇ m and not more than 15 ⁇ m.
  • the second adhesive layer 48 includes a second adhesive for bonding the metal foil 47 and the sealant film 70.
  • the second adhesive include ether-based two-component reaction type adhesives.
  • the ether-based two-component reaction type adhesive include polyurethane as in the case of the first adhesive. Polyurethane is a cured product produced by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent.
  • polyether polyol and polyester polyol can be used as polyol, it is preferable to use polyester polyol.
  • aromatic isocyanate compounds and aliphatic isocyanate compounds exist as isocyanate compounds.
  • aromatic isocyanate compounds elute components that cannot be used in food applications under high-temperature environments such as heat sterilization.
  • the 2nd adhesive bond layer 48 is located in the inner surface 30x side rather than the metal foil 47, as shown in FIG. For this reason, when the 2nd adhesive bond layer 48 contains an aromatic isocyanate compound, the component eluted from the aromatic isocyanate compound may adhere to the content of the bag 10 comprised by the laminated body 30.
  • a second adhesive constituting the second adhesive layer 48 a cured product produced by a reaction between a polyol as a main agent and an aliphatic isocyanate compound as a curing agent is used. Suggest to use. Thereby, it can prevent that the component which cannot be used for the food use resulting from the 2nd adhesive bond layer 48 adheres to the content.
  • the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxy group of the polyether polyol in the second adhesive constituting the second adhesive layer 48 is in the range of 1 to 5, for example.
  • the sealant film 70 includes at least a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30.
  • a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30.
  • the material constituting the sealant layer 71 as in the case of the first embodiment described above, one or two or more selected from polyethylene such as low density polyethylene and linear low density polyethylene, and polypropylene are used. Resin can be used.
  • the first film 40 and the metal foil 47 described above are prepared. Subsequently, the first film 40 and the metal foil 47 are laminated via the first adhesive layer 46 by a dry laminating method. Thereafter, the laminate including the first film 40 and the metal foil 47 and the sealant film 70 are laminated via the second adhesive layer 48 by a dry laminating method. Thereby, the laminated body 30 provided with the 1st film 40, the metal foil 47, and the sealant film 70 can be obtained.
  • the metal foil 47 and the sealant film 70 are first laminated via the second adhesive layer 48, and then the first film 40 and the laminate including the metal foil 47 and the sealant film 70 are laminated to the first adhesive layer.
  • the stacked body 30 may be manufactured by stacking via 46.
  • the base material 41 of the first film 40 includes PBT as a main component.
  • the base material 41 which concerns on a 1st structure since the composition of each layer 41a is the same, it can suppress that the 1st film 40 containing the base material 41 warp.
  • the composition is the same in the base material 41 which concerns on a 2nd structure, for example, since the base material 41 is a single layer film comprised only by PBT and an additive, the 1st film containing the base material 41 40 can be prevented from warping. Thereby, the laminated body 30 can be manufactured efficiently.
  • the laminated body 30 which comprises the surface film 14 and the back surface film 15 of the bag 10 contains the base material 41 which has PBT as a main component
  • PBT is excellent in printability.
  • the printing layer 42 can be provided on the base material 41 containing PBT similarly to the case of polyethylene terephthalate.
  • PBT is excellent in heat resistance. For this reason, it is possible to prevent the base material 41 from being deformed or the strength of the base material 41 from being lowered when the bag 10 is subjected to boil processing or retort processing. PBT has high strength.
  • the puncture strength of the laminated body 30 and the bag 10 can be increased similarly to the case where the laminated body constituting the bag 10 includes nylon.
  • the puncture strength of the laminate 30 is preferably 13N or more, more preferably 15N or more, and further preferably 17N or more.
  • PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 41 containing PBT is arrange
  • the laminate 30 constituting the front film 14 and the back film 15 of the bag 10 includes the metal foil 47. For this reason, since it can suppress that the water vapor
  • the sealant layer 71 of the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains a propylene-ethylene block copolymer. For this reason, the impact resistance and puncture resistance of the bag 10 can be enhanced.
  • a conventional laminate includes a PET film, a nylon film, and a sealant film.
  • Nylon has the property of being easy to absorb moisture while having high strength, so the nylon film is disposed between the PET film and the sealant film.
  • the nylon is easily colored by the contents of the bag, the appearance of the bag may be impaired.
  • the purpose of this embodiment is to provide a laminate that can effectively solve such problems.
  • FIG. 6 is a cross-sectional view illustrating an example of a layer configuration of the stacked body 30 according to the third embodiment.
  • the laminate 30 includes at least a first film 50, a second film 60, and a sealant film 70 in this order.
  • the first film 50 is located on the outer surface 30y side
  • the sealant film 70 is located on the inner surface 30x side opposite to the outer surface 30y.
  • the first film 50 includes at least a first base material 51.
  • the second film 60 includes at least a second base material 61.
  • the sealant film 70 includes at least a sealant layer 71.
  • the first film 50 and the second film 60 are joined by a first adhesive layer 55, and the second film 60 and the sealant film 70 are joined by a second adhesive layer 65. Therefore, it can be said that the laminate 30 according to the present embodiment includes the first base material / first adhesive layer / second base material / second adhesive layer / sealant layer in order from the outer surface side to the inner surface side. .
  • “/” represents a boundary between layers.
  • a printing layer may be provided on the first base material 51 or the second base material 61 between the first base material 51 and the second base material 61.
  • first film 50 the first adhesive layer 55, the second film 60, the second adhesive layer 65, and the sealant film 70 will be described in detail.
  • the first substrate 51 of the first film 50 includes the first substrate 51 that constitutes the outer surface 30 y of the laminate 30.
  • the 1st base material 51 contains polybutylene terephthalate as a main ingredient like base material 41 in the above-mentioned 1st embodiment.
  • the 1st base material 51 contains 51 mass% or more PBT.
  • any of the first configuration and the second configuration described with respect to the base material 41 in the first embodiment described above may be adopted.
  • the first adhesive layer 55 includes a first adhesive for bonding the first film 50 and the second film 60.
  • the first adhesive include an ether-based two-component reactive adhesive, an ester-based two-component reactive adhesive, and the like, as in the case of the adhesive layer 45 in the first embodiment described above. be able to.
  • the second film 60 includes at least a second base material 61.
  • the 2nd base material 61 contains PET as a main component.
  • the 2nd base material 61 contains 51 mass% or more of PET.
  • the 2nd base material 61 can have heat resistance because the 2nd base material 61 contains PET.
  • fusing point of the 2nd base material 61 becomes high, and the hygroscopic property of the 2nd base material 61 becomes low. Thereby, when heating the bag 10, it can suppress that a hole opens in the 2nd base material 61 resulting from the overheated water.
  • the heat resistance of PET is higher than the heat resistance of PBT.
  • the heat resistance of the laminated body 30 can be improved. Thereby, for example, when the bag 10 is heated with a microwave oven and the temperature of the contents becomes high, it is possible to prevent the laminated body 30 from being damaged and the performance of the laminated body 30 from being deteriorated.
  • the thickness of the second substrate 61 is preferably 9 ⁇ m or more, more preferably 12 ⁇ m or more. Moreover, the thickness of the 2nd base material 61 becomes like this. Preferably it is 25 micrometers or less, More preferably, it is 20 micrometers or less. By setting the thickness of the second substrate 61 to 9 ⁇ m or more, the second substrate 61 has sufficient strength. Moreover, the 2nd base material 61 comes to show the outstanding moldability by the thickness of the 2nd base material 61 being 25 micrometers or less. For this reason, the process which processes the laminated body 30 and manufactures the bag 10 can be implemented efficiently.
  • the second adhesive layer 65 includes a second adhesive for bonding the second film 60 and the sealant film 70.
  • the second adhesive include ether-based two-component reaction type adhesives.
  • the ether-based two-component reaction type adhesive include polyurethane as in the case of the first adhesive. Polyurethane is a cured product produced by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent.
  • polyether polyol and polyester polyol can be used as polyol, it is preferable to use polyester polyol.
  • aromatic isocyanate compounds and aliphatic isocyanate compounds exist as isocyanate compounds.
  • aromatic isocyanate compounds elute components that cannot be used in food applications under high-temperature environments such as heat sterilization.
  • the second adhesive layer 65 is in contact with the sealant film 70 as shown in FIG.
  • the component eluted from the aromatic isocyanate compound may adhere to the content of the bag 10 comprised by the laminated body 30.
  • a second adhesive constituting the second adhesive layer 65 a cured product produced by a reaction between a polyol as a main agent and an aliphatic isocyanate compound as a curing agent is used. Suggest to use. Thereby, it can prevent that the component which cannot be used for the food use resulting from the 2nd adhesive bond layer 65 adheres to the contents.
  • the second film 60 when the second film 60 does not have a barrier property such as a gas barrier property, and the first adhesive layer 55 includes an aromatic isocyanate compound, the second film 60 was eluted from the aromatic isocyanate compound. It is also conceivable that components adhere to the contents.
  • the polyol as the main agent and the aliphatic isocyanate compound as the curing agent react as the first adhesive constituting the first adhesive layer 55. It is preferable to use a cured product produced by the above.
  • the sealant film 70 includes at least a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30.
  • a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30.
  • the material constituting the sealant layer 71 as in the case of the first embodiment described above, one or two or more selected from polyethylene such as low density polyethylene and linear low density polyethylene, and polypropylene are used. Resin can be used.
  • the first film 50 and the second film 60 described above are prepared. Subsequently, the first film 50 and the second film 60 are laminated via the first adhesive layer 55 by a dry laminating method. Thereafter, the laminate including the first film 50 and the second film 60 and the sealant film 70 are laminated via the second adhesive layer 65 by a dry laminating method. Thereby, the laminated body 30 provided with the 1st film 50, the 2nd film 60, and the sealant film 70 can be obtained.
  • the second film 60 and the sealant film 70 are first laminated through the second adhesive layer 65, and then the first film 50 and the laminate including the second film 60 and the sealant film 70 are first bonded.
  • the laminated body 30 may be manufactured by laminating via the agent layer 55.
  • the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains the 1st base material 51 which has PBT as a main component
  • PBT is excellent in heat resistance.
  • PBT has high strength.
  • the puncture strength of the laminated body 30 and the bag 10 can be increased similarly to the case where the laminated body constituting the bag 10 includes nylon.
  • the puncture strength of the laminate 30 is preferably 13N or more, more preferably 15N or more, and further preferably 17N or more.
  • PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the 1st substrate 51 containing PBT is arranged on outer surface 30y of layered product 30, the 1st substrate 51 absorbs moisture, and the lamination strength of layered product 30 will fall. Can be suppressed.
  • the laminated body 30 contains the 2nd base material 61 which has PET as a main component, Compared with the case where the 2nd base material 61 consists of nylon, the 2nd base material 61 is. It can suppress coloring with the contents. Thereby, it can suppress that the external appearance of the bag 10 is impaired. Moreover, it can suppress that foaming arises due to the water
  • the second base material 61 contains nylon, caprolactam, etc., which is a raw material of nylon from nylon and whose elution standard is defined in Ministry of Health and Welfare Notification No. 370 “Apparatus and Containers and Packaging”, There is a risk of mixing with the contents.
  • the possibility that caprolactam etc. elute can be reduced by comprising the 2nd base material 61 with PET.
  • the laminated body 30 which comprises the surface film 14 and the back surface film 15 of the bag 10 contains the 2nd base material 61 which has PET as a main component, compared with the case where the 2nd base material 61 consists of PBT,
  • the heat resistance of the laminate 30 can be increased. Thereby, for example, when the bag 10 is heated and the temperature of the contents is increased, the surface film 14 and the back film 15 are damaged and the performance of the surface film 14 and the back film 15 is prevented from being deteriorated. it can.
  • the first substrate 51 includes 51 mass% or more of PBT
  • the second substrate 61 includes 51 mass% or more of PET, whereby the stab resistance and heat resistance of the laminate 30.
  • the example which raises is shown.
  • the present invention is not limited to this, and the first substrate 51 includes 51% by mass or more of PET, and the second substrate 61 includes 51% by mass or more of PBT. You may increase the nature.
  • the PBT of the second substrate 61 the PBT according to the first configuration described in the first embodiment or the PBT according to the second configuration can be used.
  • the fact that the second base material 61 contains 51% by mass or more of PBT and the first base material 51 contains 51% by mass or more of PET contributes to the improvement of the dimensional stability and printability of the laminate 30.
  • both the 1st base material 51 and the 2nd base material 61 may contain 51 mass% or more of PBT.
  • the PBT in this case the PBT according to the first configuration described above or the PBT according to the second configuration can be used.
  • Table 1 summarizes examples of combinations of materials constituting the first base member 51 and the second base member 61.
  • the notation “PBT” means that 51 mass% or more of PBT is contained in the resin constituting the film of the first base material 51 or the second base material 61.
  • the expression “PET” means that 51% by mass or more of PET is contained in the resin constituting the film of the first base material 51 or the second base material 61.
  • the 1st base material 51 contains PET or PBT
  • PET has a relatively higher melting point than PBT.
  • the heat resistance of the outer surface 30y of the laminated body 30 improves more. Therefore, when the seal part of the bag 10 is formed by heat sealing, the heat sealing can be performed at a higher temperature.
  • the transparent vapor deposition layer 36 which consists of an inorganic material which has transparency in the position between the 1st base material 51 and the 2nd base material 61 in the 1st base material 51 or / and the 2nd base material 61 is provided. It may be.
  • the transparent vapor deposition layer 36 may be provided on the surface on the inner surface 30x side of the first base material 51 as shown in FIG. 7, and the surface on the outer surface 30y side of the second base material 61 as shown in FIG. May be provided.
  • a transparent gas barrier coating film 37 having transparency may be provided on the transparent vapor deposition layer 36. Specific configurations of the transparent vapor deposition layer 36 and the transparent gas barrier coating film 37 are the same as those in the first embodiment.
  • a covalent bond between a metal atom and a carbon atom may be formed at the interface between the transparent vapor deposition layer 36 and the first substrate 51 or the second substrate 61.
  • the transparent deposition layer 36 includes aluminum oxide
  • a covalent bond between an aluminum atom and a carbon atom may be formed at the interface between the first substrate 51 or the second substrate 61 and the transparent deposition layer 36.
  • Covalent bonds can be detected by XPS measurements.
  • the existence ratio of the covalent bond of an aluminum atom and a carbon atom is observed when the interface between the transparent vapor deposition layer 36 and the first substrate 51 or the second substrate 61 is measured by XPS measurement. It is preferable that it is within the range of 0.3% or more and 30% or less of all the bonds containing carbon atoms. Thereby, the adhesiveness of the transparent vapor deposition layer 36 and the 1st base material 51 or the 2nd base material 61 is strengthened, transparency is excellent, and the thing of the performance with sufficient balance as a gas barrier property vapor deposition film is obtained.
  • the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is less than 0.3%, the adhesion of the transparent vapor-deposited layer 36 is not sufficiently improved, and it is difficult to stably maintain the barrier property.
  • the AL (aluminum) / O (oxygen) ratio of the transparent vapor-deposited layer 36 mainly composed of aluminum oxide is such that the first substrate 51 or the second substrate 61 and the interface between the transparent vapor-deposited layer 36 are the first.
  • it is preferably 1.0 or less.
  • the transparent vapor deposition layer 36 When forming the transparent vapor deposition layer 36 on the 1st base material 51 or the 2nd base material 61, it pre-processes, such as a corona discharge process, a flame process, and a plasma process, to the surface of the 1st base material 51 or the 2nd base material 61 previously. You may give it.
  • a covalent bond between a metal atom and a carbon atom is formed at the interface between the transparent vapor deposition layer 36 and the first base material 51 or the second base material 61, the first group on which the transparent vapor deposition layer 36 is to be formed.
  • the surface of the material 51 or the second base 61 is preferably pretreated.
  • plasma is supplied to the surface of the first base material 51 or the second base material 61 in a reduced pressure environment of 0.1 Pa or more and 100 Pa or less by the pretreatment apparatus.
  • Plasma uses an inert gas such as argon alone or a mixed gas of oxygen, nitrogen, carbon dioxide and one or more of them as a plasma source gas, and the plasma source gas is excited by a potential difference due to a high-frequency voltage or the like. By doing so, it can be generated.
  • the plasma can be confined in the vicinity of the surface of the first substrate 51 or the second substrate 61 by the pretreatment. Thereby, the shape of the surface of the 1st substrate 51 or the 2nd substrate 61, a chemical bond state, and a functional group are changed, and the chemical property of the surface of the 1st substrate 51 or the 2nd substrate 61 is changed. Can be changed. This makes it possible to improve the adhesion between the first substrate 51 or the second substrate 61 and the transparent vapor deposition layer 36.
  • the laminate 30 including two plastic films described in the third embodiment further includes a printing layer having a light shielding property (hereinafter referred to as a light shielding printing layer).
  • a light shielding printing layer a printing layer having a light shielding property
  • the same parts as those in the third embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the description thereof may be omitted.
  • the laminated body constituting the bag may be required to have a high light shielding property in order to preserve the contents while preventing the contents from being altered.
  • the above-mentioned Patent Document 1 proposes to provide a light-shielding printing layer having a light-shielding property on a base material containing a resin such as polyethylene terephthalate.
  • the light-shielding print layer is obtained by printing an ink containing a pigment and a binder on a substrate with a sufficient thickness.
  • an ink component such as a pigment, a binder, and a residual solvent generates an unpleasant odor (hereinafter also referred to as a strange odor), and the strange odor may permeate the sealant layer and adhere to the contents. .
  • Such off-flavors are particularly problematic when the contents are food.
  • the purpose of this embodiment is to provide a laminate that can effectively solve such problems.
  • FIG. 9 is a cross-sectional view illustrating an example of a layer configuration of the stacked body 30 according to the fourth embodiment.
  • FIG. 10 is sectional drawing which shows the other example of the layer structure of the laminated body 30 in 4th Embodiment.
  • the laminate 30 includes at least the first film 50, the second film 60, and the sealant film 70 in this order.
  • the first film 50 includes at least a first substrate 51 and a light-shielding print layer 52 provided on the surface of the first substrate 51 on the second film 60 side.
  • the 1st film 50 may further contain the pattern printing layer 53 located between the 1st base material 51 and the light shielding printing layer 52, as shown in FIG.
  • the second film 60 includes at least a second base material 61.
  • the sealant film 70 includes at least a sealant layer 71.
  • the first film 50 and the second film 60 are joined by a first adhesive layer 55, and the second film 60 and the sealant film 70 are joined by a second adhesive layer 65.
  • the laminate 30 according to the present embodiment has a first base material / light-shielding print layer / first adhesive layer / second base material / second adhesive layer / sealant layer in order from the outer surface side to the inner surface side.
  • first substrate / the pattern printing layer / the light-shielding printing layer / the first adhesive layer / the second substrate / the second adhesive layer / the sealant layer “/” represents a boundary between layers.
  • the configurations of the first base material 51, the first adhesive layer 55, the second base material 61, the second adhesive layer 65, and the sealant layer 71 are the same as in the case of the third embodiment. Is omitted.
  • the light shielding print layer 52 is a layer configured so that the laminate 30 has a light shielding property.
  • the light-shielding print layer 52 has an ink containing a pigment and a binder.
  • the thickness of the light-shielding print layer 52 is, for example, 2 ⁇ m or more, preferably 3 ⁇ m or more, and more preferably 4 ⁇ m or more.
  • the thickness of the light-shielding printing layer 52 is preferably 10 ⁇ m or less, more preferably 6 ⁇ m or less.
  • the total light transmittance of the laminate 30 including the light-shielding print layer 52 is at least 20% or less, preferably 15% or less, and more preferably 10% or less.
  • the total light transmittance refers to the ratio of the total transmitted light amount that has passed through the laminate 30 to the total incident light amount of light incident on the test piece made of the laminate 30 including the light-shielding print layer 52. Since the test piece usually has light diffusibility, the total light transmittance is the sum of the parallel light transmittance and the diffuse transmittance. The total light transmittance is measured according to an optical characteristic test method JIS-K7361-1 using an integrating sphere defined by JIS.
  • the light-shielding print layer 52 has an achromatic layer containing, for example, an achromatic color ink.
  • An achromatic color is a color described only by lightness among the three-dimensional colors of hue, lightness, and saturation. Examples of achromatic colors include white, gray, and black.
  • the thickness of the achromatic layer is, for example, 1 ⁇ m or more and 3 ⁇ m or less.
  • the achromatic layer is preferably a single color layer extending over the entire surface of the first substrate 51 in the same plane. In the following description, a printed layer having a region where the dot area ratio is 100% is also referred to as a solid layer.
  • a printed layer having a region in which the area ratio of white halftone dots is 100% is referred to as a white solid layer.
  • a printed layer having a region where the area ratio of black halftone dots is 100% is referred to as a black solid layer.
  • the white solid layer is formed by solid printing white ink containing a white pigment on the first substrate 51.
  • the black solid layer is formed by solid printing black ink containing a black pigment on the first substrate 51.
  • the light-shielding print layer 52 may include a plurality of stacked achromatic layers. Hereinafter, a specific layer configuration of the light-shielding print layer 52 will be described.
  • the light-shielding print layer 52 may be composed of, for example, a black solid layer.
  • the pattern printing layer 53 is laminated
  • the bag 10 is visually recognized from the outer surface 30y side of a laminated body
  • the light shielding printing layer 52 is observed as a background of the pattern printing layer 53.
  • the shading print layer 52 consists only of a black solid layer, it becomes difficult to visually recognize the pattern print layer 53. Therefore, when the laminate 30 includes the pattern print layer 53, the light-shielding print layer 52 is located in the outer surface 30y side of the black solid layer, as described below, in addition to the black solid layer. It is preferable to further include a coloring layer.
  • the light-shielding print layer 52 may include a white solid layer and an achromatic layer that are sequentially stacked from the first base material 51 side to the inner surface 30x side.
  • the achromatic layer may be a white solid layer or a black solid layer.
  • the achromatic layer may be an ash solid layer formed by solid printing gray ink on the first base material 51.
  • the gray ink can be obtained, for example, by mixing a white ink containing a white pigment and a black ink containing a black pigment.
  • the gray ink preferably has a white ink blending ratio higher than that of the black ink.
  • the color of the achromatic layer is a pattern compared to the case where the black solid layer is laminated on the inner surface 30x side of the white solid layer.
  • the influence on the color of the print layer 53 can be suppressed.
  • the number of achromatic layers is not limited to two.
  • the light-shielding print layer 52 may include three or four or more achromatic layers stacked.
  • the light-shielding print layer 52 may include a white solid layer, a white solid layer, and an ash solid layer that are sequentially stacked from the first base material 51 side to the inner surface 30x side.
  • the light-shielding print layer 52 may be composed of a white solid layer. Even when the light-shielding print layer 52 does not include the above-described black solid layer or ash solid layer, the light-shielding print layer 52 can have sufficient light-shielding properties by increasing the thickness of the white solid layer.
  • the light-shielding print layer 52 may have a chromatic color layer containing chromatic ink.
  • a chromatic color means a color or color that includes all three dimensions of hue, lightness, and saturation. In other words, a chromatic color is a color other than an achromatic color.
  • the thickness of the chromatic color layer is, for example, not less than 0.3 ⁇ m and not more than 2 ⁇ m.
  • the chromatic color layer is preferably a single color layer extending over the entire surface of the first substrate 51 in the same plane.
  • the light-shielding print layer 52 may include a plurality of stacked chromatic color layers.
  • the light-shielding print layer 52 may include both an achromatic color layer and a chromatic color layer.
  • the light-shielding print layer 52 includes one or more achromatic layers and one or more chromatic layers located on the inner surface 30x side of the achromatic layer.
  • the light-shielding print layer 52 may include one or more chromatic color layers and one or more achromatic layers positioned on the inner surface 30x side of the chromatic color layer.
  • the light-shielding print layer 52 may include a white solid layer and a chromatic color layer that are sequentially stacked from the first base material 51 side to the inner surface 30x side.
  • the pattern print layer 53 is a layer provided by printing in order to show product information or impart aesthetics to the bag 10.
  • the picture print layer 53 expresses characters, numbers, symbols, figures, pictures, and the like.
  • a plurality of color layers spreads in the same plane.
  • gravure printing ink or flexographic printing ink can be used as a material constituting the pattern printing layer 53.
  • FINAT manufactured by DIC Graphics Corporation can be given as FINAT manufactured by DIC Graphics Corporation.
  • the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains the 1st base material 51 which has PBT as a main component
  • PBT is excellent in printability.
  • the light-shielding print layer 52 and the pattern print layer 53 can be provided on the first substrate 51 containing PBT.
  • PBT is excellent in heat resistance. For this reason, when performing the retort process, the boil process, etc. to the bag 10, it can suppress that the 1st base material 51 deform
  • the puncture strength of the laminated body 30 and the bag 10 can be increased similarly to the case where the laminated body constituting the bag 10 includes nylon.
  • the puncture strength of the laminate 30 is preferably 13N or more, more preferably 15N or more, and further preferably 17N or more.
  • PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the 1st substrate 51 containing PBT is arranged on outer surface 30y of layered product 30, the 1st substrate 51 absorbs moisture, and the lamination strength of layered product 30 will fall. Can be suppressed.
  • the laminated body 30 includes a light-shielding print layer 52 positioned between the first base material 51 and the second base material 61. For this reason, it can suppress that external light permeate
  • the laminated body 30 contains the 2nd base material 61 which has PET or PBT as a main component, Compared with the case where the 2nd base material 61 consists of nylon, the light shielding printing layer 52. It is possible to prevent the off-flavor generated in step S from passing through the second film 60 and the sealant film 70 and adhering to the contents. Moreover, compared with the case where the 2nd base material 61 consists of PBT, the heat resistance of the laminated body 30 can be improved. Thereby, for example, when the bag 10 is heated, it is possible to prevent the front film 14 and the back film 15 from being damaged and the performance of the front film 14 and the back film 15 from being deteriorated.
  • the laminate 30 including the light-shielding print layer 52 is a transparent vapor deposition layer 36 or a transparent gas barrier coating film 37 positioned on the transparent vapor deposition layer 36. May be further provided.
  • the transparent vapor deposition layer 36 may be provided on the surface on the inner surface 30 x side of the first base material 51.
  • the laminated body 30 is, in order from the outer surface side to the inner surface side, first substrate / transparent vapor deposition layer / transparent gas barrier coating film / light-shielding printing layer / first adhesive layer / second substrate / second adhesive layer. / It can be said that it has a sealant layer.
  • the transparent vapor deposition layer 36 may be provided on the surface of the second base 61 on the outer surface 30y side.
  • the laminated body 30 is in order from the outer surface side to the inner surface side.
  • the bag 10 showed the example which is a gusset type bag, the specific structure of the bag 10 is not specifically limited.
  • the bag 10 may be a so-called pillow bag produced by forming a back-sealed seal portion so that a single laminate is formed into a cylindrical shape.
  • the bag 10 may be a four-side sealed bag or a three-side sealed bag.
  • Examples A1 to A5 and Comparative Examples A1 to A3 described below are examples relating to the case where there is only one plastic film constituting the base material of the laminate described in the first embodiment.
  • Examples B1 to B3 and Comparative Examples B1 to B3 are examples related to the case where the laminate includes a metal foil positioned between the base material and the sealant layer described in the second embodiment.
  • Examples C1 to C6 and Comparative Examples C1 and C2 are examples relating to the case where there are two plastic films constituting the base material of the laminate described in the third embodiment.
  • Examples D1 to D4 and Comparative Examples D1 and D2 there are two plastic films constituting the base material of the laminate described in the fourth embodiment, and the laminate further includes a light-shielding print layer.
  • Example A1 (Production of laminate) A film-like base material 41 including a plurality of layers 41a described in the first configuration and manufactured by a casting method was prepared.
  • the content of PBT in each layer 41a was 80%, the number of layers 41a was 1024, and the thickness of the base material 41 was 15 ⁇ m.
  • the printing layer 42 was formed on the film-like substrate 41 by gravure printing.
  • white ink ceramic FB manufactured by Dainichi Seika Kogyo was used as an ink for forming the printing layer 42.
  • the thickness of the printing layer 42 was 1 ⁇ m.
  • an adhesive composition was prepared by mixing a first composition containing a main agent and a solvent and a second composition containing a curing agent and a solvent.
  • RU-40 manufactured by Rock Paint Co., Ltd. was used as the first composition containing the main agent and the solvent.
  • RU-40 contains a polyester polyol.
  • H-4 manufactured by Rock Paint Co., Ltd. was used as the second composition containing a curing agent and a solvent.
  • H-4 contains an aliphatic isocyanate compound.
  • the weight ratio of the second composition to the first composition was 0.15.
  • the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxy group of the polyol in the adhesive composition was 4.5.
  • the adhesive composition was applied on the printing layer 42 of the first film 40. Subsequently, the adhesive composition applied on the first film 40 was dried to volatilize the solvent. Then, the 1st film 40 and the sealant film 70 were laminated
  • a sealant film 70 including a sealant layer 71 was prepared.
  • As the sealant layer 71 an unstretched polypropylene film ZK93FM manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the sealant layer 71 was 70 ⁇ m.
  • the laminate strength between the first film 40 and the sealant film 70 of the laminate 30 was measured.
  • Tensilon universal material testing machine RTC-1310 manufactured by A & D was used as a measuring instrument. Specifically, first, the laminate 30 was cut out, and as shown in FIG. 11, a rectangular test piece 80 in which the first film 40 and the sealant film 70 were peeled by 15 mm in the long side direction was prepared. The width (length of short side) of the test piece 80 was 15 mm. Thereafter, as shown in FIG. 12, the already peeled portions of the first film 40 and the sealant film 70 were respectively held by the gripping tool 81 and the gripping tool 82 of the measuring instrument.
  • each of the grips 81 and 82 is pulled at a speed of 50 mm / min in a direction opposite to each other in the direction orthogonal to the surface direction of the portion where the first film 40 and the sealant film 70 are still laminated.
  • the average value of tensile stress in the region was measured.
  • the spacing S between the gripping tools 81 and 82 when starting the pulling was 30 mm, and the spacing S between the gripping tools 81 and 82 when finishing the pulling was 60 mm.
  • FIG. 13 is a diagram illustrating a change in tensile stress with respect to the distance S between the gripping tools 81 and 82. As shown in FIG. 13, the change of the tensile stress with respect to the interval S enters the second region (stable region) having a smaller change rate than the first region through the first region.
  • the average value of the tensile stress in the stable region was measured, and the average value was taken as the laminate strength of the laminate 30.
  • the environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%.
  • the laminate strength at a width of 15 mm was 6.7 N.
  • the long laminate 30 was cut out so that the width W1 was 15 mm and the length W2 was 100 mm, and the test piece 90 was produced.
  • the width W1 of the test piece 90 is parallel to the direction of the height S1 of the bag 10 shown in FIG.
  • the length W2 of the test piece 90 is parallel to the flow direction when the base material 41 is formed, and is parallel to the direction of the width S2 of the bag 10 shown in FIG.
  • a cut 28 was formed at the center of the test piece 90 in the width W1 direction.
  • the test piece 90 was manually torn in the direction of the length W2 starting from the notch 28. As a result, the test piece 90 could be torn in the direction of the length W2 without the sealant film 70 of the laminated body 30 extending along the way.
  • FIG. 16 is a cross-sectional view of the test piece 90 of FIG.
  • the test piece 90 has a width W3 of 15 mm and a length W4 of 50 mm, a seal portion 101 is formed over a length W5 of 10 mm from one end, and a length of 40 mm from the other end. The seal portion is not formed.
  • the unsealed portion of one laminate 30 and the unsealed portion of the other laminate 30 are opposite to each other in a direction perpendicular to the surface direction of the seal portion 101.
  • the end of the unsealed portion of one laminated body 30 and the end of the unsealed portion of the other laminated body 30 are respectively connected to the jig 102. , 103.
  • the distance T between the jigs 102 and 103 in the direction orthogonal to the surface direction of the seal portion 101 was 40 mm.
  • the strength was measured. Evaluation was performed using a digital impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd. As the hammer for applying an impact to the test piece 100, a 2J hammer was used. As a result, the impact strength was 1056 kJ / m.
  • the piercing strength of the laminate 30 was measured according to JIS Z1707 7.4.
  • Tensilon universal material testing machine RTC-1310 manufactured by A & D was used. Specifically, as shown in FIG. 18, a semicircular needle 110 having a diameter of 1.0 mm and a tip shape radius of 0.5 mm from the outer surface 30y side with respect to the test piece of the laminated body 30 in a fixed state. was stabbed at a speed of 50 mm / min (50 mm per minute), and the maximum value of stress until the needle 110 penetrated the laminate 30 was measured. About five or more test pieces, the maximum value of stress was measured, and the average value was defined as the piercing strength of the laminate 30. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. As a result, the piercing strength was 15N.
  • the two laminates 30 are overlapped and heated at 190 ° C. for 1 second to heat seal the inner surfaces 30x of the laminate 30 and fill with 200 g of water as the contents to fill the four-side sealed bag 10.
  • the height S1 of the bag 10 was 180 mm, and the width S2 was 130 mm.
  • the bag 10 holding the front film 14 and the back film 15 so as to be horizontal is dropped from a height of 120 cm, It was inspected whether the bag 10 was broken. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
  • Example A2 A laminate 30 was produced in the same manner as in Example A1, except that the weight ratio of the second composition to the first composition was 0.2 when producing the adhesive composition.
  • the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxy group of the polyol in the adhesive composition was 6.
  • the laminate strength of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the laminate strength at a width of 15 mm was 7.1 N. Further, the tearability of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the test piece 90 could be torn in the direction of the length W2 without the sealant film 70 of the laminated body 30 extending along the way. Further, in the same manner as in Example A1, the impact resistance of the laminate in which the inner surfaces 30x of the two laminates 30 were heat-sealed was evaluated. As a result, the impact strength of the laminate was 1137 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 15N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
  • Example A3 A laminate 30 was produced in the same manner as in Example A1, except that the base material 41 having a PBT content of 70% in each layer 41a was used. Further, the laminate strength of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the laminate strength at a width of 15 mm was 6.5 N. Further, the tearability of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the test piece 90 could be torn in the direction of the length W2 without the sealant film 70 of the laminated body 30 extending along the way. Further, in the same manner as in Example A1, the impact resistance of the laminate in which the inner surfaces 30x of the two laminates 30 were heat-sealed was evaluated.
  • the impact strength of the laminate was 912 kJ / m.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1.
  • the piercing strength was 13N.
  • the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
  • Example A1 A laminate 30 was produced in the same manner as in Example A1, except that the weight ratio of the second composition to the first composition was 0.1 when producing the adhesive composition.
  • the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol in the adhesive composition was 3.
  • the laminate strength of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the laminate strength at a width of 15 mm was 4.2 N. Further, the tearability of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the sealant film 70 of the laminate 30 was stretched on the way, and therefore the test piece 90 could not be torn in the direction of the length W2. Further, in the same manner as in Example A1, the impact resistance of the laminate in which the inner surfaces 30x of the two laminates 30 were heat sealed was evaluated. As a result, the impact strength of the laminate was 758 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 15N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. As a result, the bag 10 was broken by the fourth drop.
  • Example A4 The laminated body 30 provided with the base material 41 / adhesive layer 45 / sealant layer 71 in this order from the outer surface side to the inner surface side was produced.
  • the base material 41 as in Example A1, a film-like base material 41 including a plurality of layers 41a and manufactured by a casting method was used.
  • the adhesive composition for constituting the adhesive layer 45 is composed of the first composition containing RU-40 and the second composition containing H-4. Was used.
  • the weight ratio of the second composition to the first composition was 0.10 as in Comparative Example A1.
  • the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol in the adhesive composition was 3.
  • the sealant layer 71 an unstretched polypropylene film ZK500 manufactured by Toray Film Processing Co., Ltd. was used.
  • ZK500 contains the above-mentioned propylene / ethylene block copolymer and elastomer.
  • the thickness of the sealant layer 71 was 70 ⁇ m. It can be said that the laminated body 30 of Example A4 is obtained by deleting the printed layer 42 from the laminated body 30 of Comparative Example A1 and replacing the sealant layer 71 with ZK500.
  • Example A1 In the same manner as in Example A1, the inner surfaces 30x of the two laminates 30 were heat sealed to produce a test piece 100, and the impact strength was measured. As a result, the impact strength was 946 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 15N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
  • Example A5 A laminate 30 was produced in the same manner as in Example A4, except that a film-like substrate 41 containing PBT and produced by a tubular method was used as the substrate 41.
  • the base material 41 was a single layer film composed only of PBT and an additive, and the thickness of the base material 41 was 15 ⁇ m.
  • Example A1 In the same manner as in Example A1, the inner surfaces 30x of the two laminates 30 were heat sealed to produce a test piece 100, and the impact strength was measured. As a result, the impact strength was 838 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 15N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
  • Example A2 A laminate 30 was produced in the same manner as in Example A4 except that an unstretched polypropylene film ZK93FM manufactured by Toray Film Processing Co., Ltd. was used as the sealant layer 71.
  • the thickness of the sealant layer 71 was 70 ⁇ m.
  • Example A1 In the same manner as in Example A1, the inner surfaces 30x of the two laminates 30 were heat sealed to produce a test piece 100, and the impact strength was measured. As a result, the impact strength was 502 kJ / m. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. As a result, the bag 10 was broken by the fourth drop.
  • Comparative Example A3 A laminate 30 was produced in the same manner as in Comparative Example A2, except that Toyobo PET film E5100 (thickness 12 ⁇ m) was used as the substrate 41. Further, the laminate strength of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the laminate strength at a width of 15 mm was 3.8N. Further, the tearability of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the sealant film 70 of the laminate 30 was stretched on the way, and therefore the test piece 90 could not be torn in the direction of the length W2. Further, in the same manner as in Example A1, the impact resistance of the laminate in which the inner surfaces 30x of the two laminates 30 were heat-sealed was evaluated.
  • the impact strength of the laminate was 537 kJ / m.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1.
  • the piercing strength was 10N.
  • the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. As a result, the bag 10 was broken by the fourth drop.
  • FIG. 19 shows the layer configuration and evaluation results of the laminates 30 of Examples A1 to A5 and Comparative Examples A1 to A3. As can be seen from the comparison between Examples A1 to A5 and Comparative Examples A1 and A2, by forming the bag 10 using the laminate 30 having an impact strength of 800 kJ / m or more, the bag does not break even when dropped five times. It was possible to give the bag 10 the drop strength.
  • the sealant layer 71 contains a propylene / ethylene block copolymer or contains an elastomer. Can be said to be preferable.
  • an aliphatic isocyanate compound for the hydroxyl group of the polyol in the adhesive composition It can be said that it is preferable that the molar ratio of the isocyanate groups is high.
  • the composition ratio of the curing agent in the adhesive layer 45 is increased even when an aliphatic isocyanate compound is used as the curing agent.
  • the laminate strength of the laminate 30 could be increased.
  • the impact strength of the laminate 30 could be increased.
  • the tearability in Examples A1, A2, and A3, the test piece 90 could be smoothly torn across the entire area in the direction of the length W2, and thus the evaluation result was “good”.
  • the puncture strength of the laminate 30 was 10 N or less.
  • the puncture strength of the laminate 30 can be 11 N or more, more specifically 13 N or more. We were able to.
  • Example B1 In the same manner as in Example A1, a film-like first base material 51 including a plurality of layers and manufactured by a casting method described in the first configuration was prepared. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the first base material 51 was 15 ⁇ m. Further, a sealant film 70 including a sealant layer 71 was prepared. As the sealant layer 71, an unstretched polypropylene film ZK99S manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the sealant layer 71 was 70 ⁇ m. Further, an aluminum foil having a thickness of 7 ⁇ m was prepared as the metal foil 47.
  • the curvature in the 1st film 40 which consists of base materials 41 was evaluated. Specifically, first, the first film 40 was cut out to produce a square test piece having a side of 10 cm. Subsequently, the height of warpage was measured at each of the four corners of the square test piece. As a result, the maximum value of the height of warpage at the four corners was 0 mm. It should be noted that when the first film 40 is transported along the longitudinal direction thereof, the warp and the crease at the end in the width direction of the first film 40 are suppressed, so that the height of the warp at the four corners of the test piece is high. The maximum value is preferably 5 mm or less, and more preferably 3 mm or less.
  • a first laminating step of laminating the first film 40 and the metal foil 47 through the first adhesive layer 46 by a dry laminating method was performed. Specifically, first, an adhesive containing a solvent was applied to the first film 40, and then the solvent was volatilized by drying the adhesive to form an uncured first adhesive layer 46.
  • As the adhesive TM-556S manufactured by Toyo Morton Co., Ltd. was used as the main agent, and CAT-56 manufactured by Toyo Morton Co., Ltd. was used as the curing agent.
  • TM-556S contains polyester polyol.
  • CAT-56 contains an aromatic isocyanate compound. The molar ratio of the isocyanate group of the aromatic isocyanate compound to the hydroxyl group of the polyol was 3.
  • the 1st film 40 in which the 1st adhesive bond layer 46 was formed, and metal foil 47 were conveyed toward the lami roll for laminating both. Then, the metal foil 47 was press-bonded to the first film 40 using a lami roll, and a laminate of the first film 40 and the metal foil 47 was produced. Subsequently, the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a first adhesive layer 46 containing a cured product of a polyol and an aromatic isocyanate compound. The thickness of the first adhesive layer 46 was 3 ⁇ m.
  • RU-40 manufactured by Rock Paint Co., Ltd. was used as the main agent, and H-4 manufactured by Rock Paint Co., Ltd. was used as the curing agent.
  • RU-40 contains a polyester polyol.
  • H-4 contains an aliphatic isocyanate compound. The molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol was 3.
  • the 2nd laminating process which laminates
  • the laminated body 30 provided with the 1st film 40, the metal foil 47, and the sealant film 70 in order from the outer surface 30y side to the inner surface 30x side was produced.
  • the laminate 30 was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a second adhesive layer 48 containing a cured product of a polyol and an aliphatic isocyanate compound.
  • the thickness of the second adhesive layer 48 was 3 ⁇ m.
  • the layer configuration of the stacked body 30 is expressed as follows. PBT (multilayer) / first adhesive layer / aluminum foil / second adhesive layer / polypropylene
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 19N.
  • Example B2 A laminate 30 was produced in the same manner as in Example B1, except that a film-like substrate 41 containing PBT and produced by a tubular method was used as the substrate 41.
  • the base material 41 was a single layer film composed only of PBT and an additive, and the thickness of the base material 41 was 15 ⁇ m.
  • the curvature in the 1st film 40 was evaluated similarly to the case of Example B1. As a result, the maximum warp height was 0 mm.
  • the curvature of the edge part of the 1st film 40, a bending, etc. were not observed.
  • the layer configuration of the stacked body 30 is expressed as follows. PBT (single layer) / first adhesive layer / aluminum foil / second adhesive layer / polypropylene Subsequently, the piercing strength of the laminate 30 was measured. As a result, the piercing strength was 18N.
  • Example B3 The warpage of the first film 40 made of the base material 41 was evaluated in the same manner as in Example B1 except that the base material 41 having a PBT content of 55% in each layer 41a was used. As a result, the maximum warp height was 0 mm. Moreover, the laminated body 30 was produced similarly to the case of Example B1 using the base material 41 whose PBT content rate is 55%. When the first film 40 made of the base material 41 was transported in the step of producing the laminate 30, no warp or breakage was observed at the end of the first film 40. Moreover, the puncture strength of the laminated body 30 was 13N.
  • Example B1 A laminate 30 was produced in the same manner as in Example B1, except that 15 ⁇ m thick Heptax HBN (manufactured by Gunze Co., Ltd.) was used as the base material 41. Heptax HBN is a two-layer co-pressed film made by co-extrusion of PET and nylon. Moreover, the curvature in the 1st film 40 was evaluated similarly to the case of Example B1. As a result, the degree of warpage was too large, and the four corners of the test piece were rounded, and the height of warpage could not be measured. Moreover, when the 1st film 40 was conveyed, since the edge part in the width direction of the 1st film 40 had broken, the tension
  • Heptax HBN manufactured by Gunze Co., Ltd.
  • the layer configuration of the stacked body 30 is expressed as follows. Heptax HBN / first adhesive layer / aluminum foil / second adhesive layer / polypropylene Subsequently, the piercing strength of the laminate 30 was measured. As a result, the piercing strength was 12N.
  • Example B2 As a substrate, a PET film having a thickness of 12 ⁇ m and a nylon film having a thickness of 15 ⁇ m were prepared. Further, the warpage in the PET film was evaluated in the same manner as in Example B1. As a result, the maximum warp height was 0 mm.
  • an adhesive containing a solvent was applied to the PET film, and then the solvent was evaporated by drying the adhesive to form an uncured first adhesive layer.
  • the adhesive TM-556S manufactured by Toyo Morton Co., Ltd. was used as the main agent, and CAT-56 manufactured by Toyo Morton Co., Ltd. was used as the curing agent.
  • the molar ratio of the isocyanate group of the aromatic isocyanate compound to the hydroxyl group of the polyol was 3.
  • the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a first adhesive layer containing a cured product of a polyol and an aromatic isocyanate compound.
  • the thickness of the first adhesive layer was 3 ⁇ m.
  • the solvent was evaporated by drying the adhesive to form an uncured second adhesive layer.
  • the adhesive TM-556S manufactured by Toyo Morton Co., Ltd. was used as the main agent, and CAT-56 manufactured by Toyo Morton Co., Ltd. was used as the curing agent.
  • the molar ratio of the isocyanate group of the aromatic isocyanate compound to the hydroxyl group of the polyol was 3.
  • an aluminum foil having a thickness of 7 ⁇ m was pressure-bonded to the nylon film to produce a laminate of a PET film, a nylon film, and an aluminum foil.
  • the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a second adhesive layer containing a cured product of a polyol and an aromatic isocyanate compound.
  • the thickness of the second adhesive layer was 3 ⁇ m.
  • the solvent was evaporated by drying the adhesive to form an uncured third adhesive layer.
  • the adhesive RU-40 manufactured by Rock Paint Co., Ltd. was used as the main agent, and H-4 manufactured by Rock Paint Co., Ltd. was used as the curing agent.
  • the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol was 3.
  • a polypropylene film was pressure-bonded to the aluminum foil to prepare a laminate.
  • unstretched polypropylene film ZK99S manufactured by Toray Film Processing Co., Ltd. was used.
  • the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a third adhesive layer containing a cured product of a polyol and an aliphatic isocyanate compound.
  • the thickness of the third adhesive layer was 3 ⁇ m.
  • the layer structure of the laminate is expressed as follows. PET / first adhesive layer / nylon / second adhesive layer / aluminum foil / third adhesive layer / polypropylene Subsequently, the piercing strength of the laminate was measured. As a result, the piercing strength was 19N.
  • Example B3 The warpage in the first film 40 made of the base material 41 was evaluated in the same manner as in Example B1, except that a PET film having a thickness of 12 ⁇ m (Toyobo E5100) was used as the base material 41. As a result, the maximum warp height was 0 mm.
  • the laminated body 30 was produced similarly to the case of Example B1 using the base material 41 which consists of PET films.
  • the first film 40 made of the base material 41 was transported in the step of producing the laminate 30, no warp or breakage was observed at the end of the first film 40.
  • the layer structure of the laminate is expressed as follows. PET / first adhesive layer / aluminum foil / second adhesive layer / polypropylene Subsequently, the piercing strength of the laminate was measured. As a result, the puncture strength was 11N.
  • FIG. 20 shows the layer structure and evaluation results of the laminates of Examples B1 to B3 and Comparative Examples B1 to B3.
  • the components of the laminate excluding the adhesive layer are described in order from the outer surface side layer.
  • the evaluation result was “good”.
  • Comparative Example B1 folds were observed at the end of the film, and the work of adjusting the tension when laminating the first film 40 and the metal foil 47 was necessary, so the evaluation result was “bad”. did.
  • Example C1 In the same manner as in Example A1, a film-like first base material 51 including a plurality of layers and manufactured by a casting method described in the first configuration was prepared. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the first base material 51 was 15 ⁇ m. Moreover, the film-like 2nd film 60 containing the 2nd base material 61 was prepared. As the 2nd base material 61, what contains 100 mass% PET was used. The thickness of the second substrate 61 was 12 ⁇ m. Further, a sealant film 70 including a sealant layer 71 was prepared. As the sealant layer 71, an unstretched polypropylene film ZK207 manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the sealant layer 71 was 60 ⁇ m.
  • the first film 50 and the second film 60 were laminated by the dry laminating method through the first adhesive layer 55.
  • a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used.
  • RU-40 contains a polyester polyol.
  • H-4 contains an aliphatic isocyanate compound.
  • the thickness of the first adhesive layer 55 was 3 ⁇ m.
  • the laminate of the first film 50 and the second film 60 and the sealant film 70 were laminated by the dry laminating method through the second adhesive layer 65 to obtain the laminate 30.
  • the second adhesive layer 65 similarly to the first adhesive layer 55, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used.
  • the thickness of the second adhesive layer 65 was 3 ⁇ m.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N.
  • the coloration resistance of the laminate 30 was evaluated. Specifically, the inner surfaces 30x of the two laminates 30 were sealed to produce a bag containing a commercially available curry as the contents. Subsequently, after the bag was retorted, the bag was opened, and it was visually evaluated whether or not the laminate 30 constituting the bag was colored.
  • the dimensions of the two laminates 30 were 100 mm in length and 100 mm in width, respectively.
  • the shape of the bag was a four-side sealed bag. The bag was retorted by a hot water method at 121 ° C. for 30 minutes. As a result, coloring was not observed.
  • Example C2 As the 1st base material 51 of the 1st film 50, it contains 100 mass% PBT explained by the above-mentioned 2nd composition, Melting
  • the first base 51 was a single layer film composed only of PBT and additives, and the thickness of the first base 51 was 15 ⁇ m.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
  • Example C3 A laminate 30 was produced in the same manner as in Example C1, except that the first base material 51 having a PBT content of 55% in each layer was used. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 13N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
  • Example C4 Example except that PBT constituting the first substrate 51 of Example C1 was used as the second substrate 61 and PET constituting the second substrate 61 of Example C1 was used as the first substrate 51
  • the laminated body 30 was produced like the case of C1.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 16N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
  • Example C5 Example except that PBT constituting the first substrate 51 of Example C2 was used as the second substrate 61 and PET constituting the second substrate 61 of Example C2 was used as the first substrate 51
  • the laminated body 30 was produced like the case of C1.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 16N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
  • Example C6 A laminate 30 was produced in the same manner as in Example C4 except that the second base material 61 having a PBT content of 55% in each layer was used. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 13N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
  • Example C1 A laminate 30 was produced in the same manner as in Example C1, except that a substrate containing 100% by mass of PET was used as the first substrate 51 of the first film 50.
  • the thickness of the first base material 51 was 12 ⁇ m.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example C1. As a result, the puncture strength was 11N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
  • Comparative Example C2 A laminate 30 was produced in the same manner as in Comparative Example C1, except that a nylon film having a thickness of 15 ⁇ m (bonile W manufactured by Kojin Holdings Co., Ltd.) was used as the second substrate 61 of the second film 60. .
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was observed.
  • the layer configuration and evaluation results of the laminates of Examples C1 to C6 and Comparative Examples C1 and C2 are collectively shown in FIG.
  • the first substrate 51 or the second substrate 61 contains PBT, so that both the first substrate 51 and the second substrate 61 are made of PET.
  • the second base material 61 contains nylon. Compared to the case, it was possible to realize better coloring resistance.
  • Examples D1 to D4 and Comparative Example D1 related to the case where there are two plastic films constituting the base material of the laminate described in the fourth embodiment, and the laminate further includes a light-shielding print layer, D2 will be described.
  • Example D1 In the same manner as in Example A1, a film-like first base material 51 including a plurality of layers and manufactured by a casting method described in the first configuration was prepared. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the first base material 51 was 15 ⁇ m. Then, the pattern printing layer 53 was formed on the film-form 1st base material 51 using the final made by DIC graphics. Subsequently, a light shielding printing layer 52 was formed on the pattern printing layer 53. The light-shielding print layer 52 includes a white solid layer and an ash solid layer that are sequentially stacked on the pattern print layer 53.
  • the white solid layer was formed by printing solid white ink twice on the substrate by gravure printing.
  • the first white solid layer was formed by solid printing white ink (manufactured by Toyo Ink Co., Ltd., product name “Fine Star 681AT”) on the pattern printing layer 53.
  • the second white solid layer was formed by solid printing white ink (manufactured by Toyo Ink Co., Ltd., product name “NKFS R69K”) on the first white solid layer.
  • the thickness of the first white solid layer was 1 ⁇ m, and the thickness of the second white solid layer was 1.5 ⁇ m.
  • a plate cylinder having a plate depth of 28 ⁇ m and a plate cylinder line number of 175 was used for the formation of the white solid layer.
  • the gray solid layer is a gray ink in which white ink (manufactured by Toyo Ink, product name “R631AT”) and black ink (manufactured by Toyo Ink, product name “N800LPGT Sumi”) are blended at a blending ratio of 6: 4. It was formed by solid printing once on the white solid layer.
  • a plate cylinder having a plate depth of 22 ⁇ m and a plate cylinder line number of 175 was used for forming the solid ash layer. The thickness of the ash solid layer was 1.5 ⁇ m.
  • a film-like second film 60 including the second substrate 61 was prepared.
  • As the 2nd base material 61 what contains 100 mass% PET was used.
  • the thickness of the second substrate 61 was 12 ⁇ m.
  • a sealant film 70 including a sealant layer 71 was prepared.
  • As the sealant layer 71 an unstretched polypropylene film ZK207 manufactured by Toray Film Processing Co., Ltd. was used.
  • the thickness of the sealant layer 71 was 60 ⁇ m.
  • the first film 50 and the second film 60 were laminated by the dry laminating method through the first adhesive layer 55.
  • a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used.
  • RU-40 contains a polyester polyol.
  • H-4 contains an aliphatic isocyanate compound.
  • the thickness of the first adhesive layer 55 was 3 ⁇ m.
  • the laminate of the first film 50 and the second film 60 and the sealant film 70 were laminated by the dry laminating method through the second adhesive layer 65 to obtain the laminate 30.
  • the second adhesive layer 65 similarly to the first adhesive layer 55, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used.
  • the thickness of the second adhesive layer 65 was 3 ⁇ m.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N.
  • the light shielding properties of the laminate 30 were evaluated. Specifically, the total light transmittance of the laminate 30 when light was incident from the outer surface 30y of the laminate 30 was measured.
  • a haze meter HM-150 which is a total light transmittance measuring device manufactured by Murakami Color Research Laboratory Co., Ltd., was used. As a result, the total light transmittance was 9%.
  • the odor barrier property of the laminate 30 was evaluated. Specifically, the inner surfaces 30x of the two laminates 30 were sealed to form a bag, the bag was heated, the bag was then opened, and whether or not a strange odor was felt was evaluated.
  • the dimensions of the two laminates 30 were 100 mm in length and 100 mm in width, respectively.
  • the shape of the bag was a four-side sealed bag. The bag was heated for 1 minute using an oven controlled at 40 ° C. As a result, no nasty smell was felt.
  • Example D2 As the 1st base material 51 of the 1st film 50, it contains 100 mass% PBT explained by the above-mentioned 2nd composition, Melting
  • the first base 51 was a single layer film composed only of PBT and additives, and the thickness of the first base 51 was 15 ⁇ m.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 9%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, no nasty smell was felt.
  • Example D3 Example except that PBT constituting the first substrate 51 of Example D1 was used as the second substrate 61 and PET constituting the second substrate 61 of Example D1 was used as the first substrate 51
  • the laminated body 30 was produced like the case of D1.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 9%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, no nasty smell was felt.
  • Example D4 Example except that PBT constituting the first base material 51 of Example D2 was used as the second base material 61 and PET constituting the second base material 61 of Example D2 was used as the first base material 51
  • the laminated body 30 was produced like the case of D1.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 9%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, no nasty smell was felt.
  • Example D1 The laminated body 30 was produced like the case of Example D1 except having used the base material containing 100 mass% PET as the 1st base material 51 of the 1st film 50.
  • FIG. The thickness of the first base material 51 was 12 ⁇ m.
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1.
  • the piercing strength was 12N.
  • the total light transmittance of the laminate 30 was measured in the same manner as in Example D1.
  • the total light transmittance was 10%.
  • the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, no nasty smell was felt.
  • Comparative Example D2 A laminate 30 was produced in the same manner as in Comparative Example D1 except that a 15 ⁇ m-thick nylon film (Bonil W manufactured by Kojin Holdings Co., Ltd.) was used as the second substrate 61 of the second film 60. .
  • the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 10%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, a nasty smell was felt.
  • the layer configuration and evaluation results of the laminates of Examples D1 to D4 and Comparative Examples D1 and D2 are collectively shown in FIG. In FIG. 22, in the column “layer configuration”, the components of the laminate excluding the adhesive layer are listed from the top in order from the outer surface side layer.
  • the first base material 51 or the second base material 61 contains PBT, so that both the first base material 51 and the second base material 61 contain PET. Compared to the case of inclusion, a high piercing strength could be realized.
  • the second base material 61 contains nylon. Compared to the case, it was possible to achieve better light-shielding properties and odor barrier properties.

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  • Laminated Bodies (AREA)

Abstract

The present invention provides a laminated body that exhibits piercing resistance and heat resistance. This laminated body is provided with: a substrate which contains at least 51 mass% of polybutylene terephthalate; and a sealant layer which contains at least either a linear low-density polyethylene or polypropylene, and which constitutes the inner surface of the laminated body.

Description

積層体Laminated body
　本発明は、袋などを構成するための積層体に関する。 The present invention relates to a laminate for forming a bag or the like.
　従来、調理済あるいは半調理済の液体、粘体あるいは液体と固体とが混在する内容物を、プラスチック製の積層体から構成された袋に充填密封したものが多く市場に出回っている。袋においては、積層体同士が接合されていない非シール部が、内容物が収容される収容部を構成している。また、積層体同士が接合されているシール部が、収容部を密封している。内容物は、例えば、カレー、シチュー、スープ等の調理済食品、あるいは加熱されることによって調理される半調理済食品である。 Conventionally, many cooked or semi-cooked liquids, viscous bodies, or a mixture of liquids and solids are filled and sealed in bags made of plastic laminates. In the bag, the non-seal part to which the laminated bodies are not joined constitutes an accommodation part in which the contents are accommodated. Moreover, the sealing part to which the laminated bodies are joined has sealed the accommodating part. The contents are, for example, cooked foods such as curry, stew and soup, or semi-cooked foods cooked by heating.
　袋を構成する積層体は、基材としてプラスチックフィルムを含む。例えば特許文献１は、積層体の基材の材料としてポリエチレンテレフタレート、ポリプロピレン又はナイロンなどを用いることを提案している。基材は、積層体の強度の向上に寄与する。 * The laminated body which comprises a bag contains a plastic film as a base material. For example, Patent Document 1 proposes to use polyethylene terephthalate, polypropylene, nylon, or the like as a base material of a laminate. A base material contributes to the improvement of the intensity | strength of a laminated body.
特開２０１４－９４７６７号公報JP 2014-94767 A
　ナイロンは、高い強度を有する材料として知られている。しかしながら、ナイロンは水分を吸収し易いという特性を有する。このため、ナイロンを基材に用いた場合、ナイロンが内容物によって着色されて袋の外観が損なわれてしまうことや、積層体のラミネート強度が低下してしまうことがある。 Nylon is known as a material having high strength. However, nylon has a characteristic that it easily absorbs moisture. For this reason, when nylon is used for the base material, the nylon may be colored by the contents and the appearance of the bag may be impaired, or the laminate strength of the laminate may be reduced.
　本発明は、このような課題を効果的に解決し得る積層体を提供することを目的とする。 The present invention aims to provide a laminate that can effectively solve such problems.
　本発明は、積層体であって、５１質量％以上のポリブチレンテレフタレートを含む基材と、直鎖状低密度ポリエチレン又はポリプロピレンのいずれかを少なくとも含み、前記積層体の内面を構成するシーラント層と、を備える、積層体である。 The present invention is a laminate comprising a base material containing 51% by mass or more of polybutylene terephthalate, and at least one of linear low density polyethylene or polypropylene, and a sealant layer constituting the inner surface of the laminate. And a laminated body.
　本発明による積層体において、ポリブチレンテレフタレートを含む前記基材は、１０層以上を含む多層構造部を有していてもよい。若しくは、ポリブチレンテレフタレートを含む前記基材は、１．１０ｄｌ／ｇ以上且つ１．３５ｄｌ／ｇ以下のＩＶ値を有する単層構造からなっていてもよい。 In the laminate according to the present invention, the base material containing polybutylene terephthalate may have a multilayer structure including 10 layers or more. Alternatively, the base material containing polybutylene terephthalate may have a single layer structure having an IV value of 1.10 dl / g or more and 1.35 dl / g or less.
　本発明による積層体において、前記シーラント層は、９０質量％以上のポリプロピレンを含んでいてもよい。 In the laminate according to the present invention, the sealant layer may include 90% by mass or more of polypropylene.
　本発明による積層体において、前記シーラント層が、１００℃以上の融点を有する直鎖状低密度ポリエチレンを含んでいてもよい。 In the laminate according to the present invention, the sealant layer may contain linear low density polyethylene having a melting point of 100 ° C. or higher.
　本発明による積層体は、前記シーラント層の外面側に設けられ、ポリオールと脂肪族系イソシアネート化合物との硬化物を含む接着剤層を更に備え、前記ポリオールのヒドロキシ基に対する前記脂肪族系イソシアネート化合物のイソシアネート基のモル比が、３．５以上であってもよい。 The laminate according to the present invention further includes an adhesive layer that is provided on the outer surface side of the sealant layer and includes a cured product of a polyol and an aliphatic isocyanate compound, and the laminate of the aliphatic isocyanate compound with respect to the hydroxy group of the polyol. The molar ratio of isocyanate groups may be 3.5 or more.
　本発明による積層体は、
　基材／接着剤層／シーラント層、
　基材／印刷層／接着剤層／シーラント層、
　基材／透明蒸着層／透明ガスバリア性塗布膜／印刷層／接着剤層／シーラント層、又は
　基材／透明蒸着層／透明ガスバリア性塗布膜／接着剤層／シーラント層、をこの順で含んでいてもよい。この場合、前記積層体の突き刺し強度が１１Ｎ以上であってもよい。 The laminate according to the present invention comprises:
Substrate / adhesive layer / sealant layer,
Substrate / printing layer / adhesive layer / sealant layer,
Substrate / transparent deposition layer / transparent gas barrier coating film / printing layer / adhesive layer / sealant layer, or base material / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer in this order May be. In this case, the piercing strength of the laminate may be 11N or more.
　本発明による積層体は、
　基材／透明蒸着層／透明ガスバリア性塗布膜／印刷層／接着剤層／シーラント層、又は
　基材／透明蒸着層／透明ガスバリア性塗布膜／接着剤層／シーラント層、をこの順で含み、
　前記透明蒸着層は、酸化アルミニウムを含み、前記基材と前記透明蒸着層との界面に、アルミニウム原子と炭素原子の共有結合が形成されていてもよい。 The laminate according to the present invention comprises:
Substrate / transparent deposition layer / transparent gas barrier coating film / printing layer / adhesive layer / sealant layer, or substrate / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer in this order,
The transparent vapor deposition layer may contain aluminum oxide, and a covalent bond between an aluminum atom and a carbon atom may be formed at the interface between the base material and the transparent vapor deposition layer.
　本発明による積層体において、前記積層体の衝撃強度が８００ｋＪ／ｍ以上であってもよい。 In the laminate according to the present invention, the impact strength of the laminate may be 800 kJ / m or more.
　本発明による積層体は、
　基材／第１接着剤層／金属箔／第２接着剤層／シーラント層、又は
　基材／印刷層／第１接着剤層／金属箔／第２接着剤層／シーラント層、をこの順で含み、
　前記第２接着剤層は、ポリオール及び脂肪族系イソシアネート化合物の硬化物を含んでいてもよい。この場合、前記積層体の突き刺し強度が１３Ｎ以上であってもよい。 The laminate according to the present invention comprises:
Substrate / first adhesive layer / metal foil / second adhesive layer / sealant layer, or substrate / print layer / first adhesive layer / metal foil / second adhesive layer / sealant layer in this order Including
The second adhesive layer may contain a cured product of a polyol and an aliphatic isocyanate compound. In this case, the piercing strength of the laminate may be 13N or more.
　本発明による積層体は、第１基材、第２基材及びシーラント層をこの順で少なくとも含み、前記第２基材は、５１質量％以上のポリエチレンテレフタレート又は５１質量％以上のポリブチレンテレフタレートを含み、前記第２基材が５１質量％以上のポリエチレンテレフタレートを含む場合、前記第１基材は、５１質量％以上のポリブチレンテレフタレートを含んでいてもよい。この場合、前記積層体の突き刺し強度が１３Ｎ以上であってもよい。 The laminate according to the present invention includes at least a first base material, a second base material, and a sealant layer in this order, and the second base material includes 51% by mass or more of polyethylene terephthalate or 51% by mass or more of polybutylene terephthalate. When the second base material contains 51% by mass or more of polyethylene terephthalate, the first base material may contain 51% by mass or more of polybutylene terephthalate. In this case, the piercing strength of the laminate may be 13N or more.
　本発明による積層体は、前記第１基材と前記第２基材との間において前記第１基材又は前記第２基材に設けられた透明蒸着層と、前記透明蒸着層上に設けられた透明ガスバリア性塗布膜と、を更に含んでいてもよい。 The laminate according to the present invention is provided between the first base material and the second base material, the transparent vapor deposition layer provided on the first base material or the second base material, and the transparent vapor deposition layer. And a transparent gas barrier coating film.
　本発明による積層体において、前記透明蒸着層は、酸化アルミニウムを含み、前記第１基材又は前記第２基材と前記透明蒸着層との界面に、アルミニウム原子と炭素原子の共有結合が形成されていてもよい。 In the laminate according to the present invention, the transparent vapor deposition layer includes aluminum oxide, and a covalent bond between an aluminum atom and a carbon atom is formed at an interface between the first base material or the second base material and the transparent vapor deposition layer. It may be.
　本発明による積層体において、前記積層体は、前記第１基材と前記第２基材との間に位置する遮光印刷層を更に含み、前記積層体の全光線透過率が２０％以下であってもよい。 In the laminate according to the present invention, the laminate further includes a light-shielding print layer positioned between the first substrate and the second substrate, and the total light transmittance of the laminate is 20% or less. May be.
　本発明による積層体において、前記第１基材が、ポリブチレンテレフタレートを含み、前記第２基材が、ポリエチレンテレフタレートを含んでいてもよい。 In the laminate according to the present invention, the first base material may include polybutylene terephthalate, and the second base material may include polyethylene terephthalate.
　本発明による積層体において、前記第１基材が、ポリエチレンテレフタレートを含み、前記第２基材が、ポリブチレンテレフタレートを含んでいてもよい。 In the laminate according to the present invention, the first base material may include polyethylene terephthalate, and the second base material may include polybutylene terephthalate.
　本発明によれば、積層体に耐突き刺し性及び耐熱性を持たせることができる。 According to the present invention, the laminate can be provided with puncture resistance and heat resistance.
本発明の第１の実施の形態における袋を示す正面図である。It is a front view which shows the bag in the 1st Embodiment of this invention. 袋を構成する積層体の層構成の一例を示す断面図である。It is sectional drawing which shows an example of the laminated constitution of the laminated body which comprises a bag. 積層体の第１フィルムの層構成の一例を示す断面図である。It is sectional drawing which shows an example of the laminated constitution of the 1st film of a laminated body. 袋を構成する積層体の層構成のその他の例を示す断面図である。It is sectional drawing which shows the other example of the layer structure of the laminated body which comprises a bag. 第２の実施の形態における積層体の層構成の一例を示す断面図である。It is sectional drawing which shows an example of the laminated constitution of the laminated body in 2nd Embodiment. 第３の実施の形態における積層体の層構成の一例を示す断面図である。It is sectional drawing which shows an example of the laminated constitution of the laminated body in 3rd Embodiment. 第３の実施の形態における積層体の層構成のその他の例を示す断面図である。It is sectional drawing which shows the other example of the layer structure of the laminated body in 3rd Embodiment. 第３の実施の形態における積層体の層構成のその他の例を示す断面図である。It is sectional drawing which shows the other example of the layer structure of the laminated body in 3rd Embodiment. 第４の実施の形態における積層体の層構成の一例を示す断面図である。It is sectional drawing which shows an example of the laminated constitution of the laminated body in 4th Embodiment. 第４の実施の形態における積層体の層構成のその他の例を示す断面図である。It is sectional drawing which shows the other example of the layer structure of the laminated body in 4th Embodiment. ラミネート強度の測定方法の一例を示す図である。It is a figure which shows an example of the measuring method of laminate strength. ラミネート強度の測定方法の一例を示す図である。It is a figure which shows an example of the measuring method of laminate strength. ラミネート強度を測定するために第１フィルムとシーラントフィルムとを引っ張る一対のつかみ具の間の間隔に対する引張応力の変化を示す図である。It is a figure which shows the change of the tensile stress with respect to the space | interval between a pair of grips which pulls a 1st film and a sealant film in order to measure a lamination strength. 引き裂き性を評価するための試験片を示す平面図である。It is a top view which shows the test piece for evaluating tearability. 衝撃強度を評価するための試験片を示す平面図である。It is a top view which shows the test piece for evaluating impact strength. 図１５に示す試験片の断面図である。It is sectional drawing of the test piece shown in FIG. 衝撃強度の測定方法の一例を示す図である。It is a figure which shows an example of the measuring method of impact strength. 突き刺し強度の測定方法の一例を示す図である。It is a figure which shows an example of the measuring method of piercing strength. 実施例Ａ１～Ａ５及び比較例Ａ１～Ａ３の評価結果を示す図である。It is a figure which shows the evaluation result of Example A1-A5 and Comparative Example A1-A3. 実施例Ｂ１～Ｂ３及び比較例Ｂ１～Ｂ３の評価結果を示す図である。It is a figure which shows the evaluation result of Example B1-B3 and comparative example B1-B3. 実施例Ｃ１～Ｃ６及び比較例Ｃ１、Ｃ２の評価結果を示す図である。It is a figure which shows the evaluation result of Examples C1-C6 and Comparative Examples C1 and C2. 実施例Ｄ１～Ｄ４及び比較例Ｄ１、Ｄ２の評価結果を示す図である。It is a figure which shows the evaluation result of Examples D1-D4 and Comparative Examples D1 and D2.
　第１の実施の形態
　図１乃至図４を参照して、本発明の第１の実施の形態について説明する。なお、本件明細書に添付する図面においては、図示と理解のしやすさの便宜上、縮尺および縦横の寸法比等を、実物のそれらから適宜変更し誇張してある。 First Embodiment A first embodiment of the present invention will be described with reference to FIGS. Note that, in the drawings attached to the present specification, for convenience of illustration and understanding, the scale and vertical / horizontal dimension ratios are appropriately changed and exaggerated from those of the actual ones.
　また、本明細書において用いる、形状や幾何学的条件並びにそれらの程度を特定する、例えば、「平行」、「直交」、「同一」等の用語や長さや角度の値等については、厳密な意味に縛られることなく、同様の機能を期待し得る程度の範囲を含めて解釈することとする。 In addition, as used in this specification, the shape and geometric conditions and the degree thereof are specified, for example, terms such as “parallel”, “orthogonal”, “identical”, length and angle values, etc. are strictly Without being bound by meaning, it should be interpreted including the extent to which similar functions can be expected.
　図１は、本実施の形態による袋１０を示す正面図である。袋１０は、内容物を収容する収容部１７を備える。なお、図１においては、内容物が収容されていない状態の袋１０が示されている。本実施の形態による袋１０は、レトルト処理を施すことができるよう構成されている。以下、袋１０の構成について説明する。 FIG. 1 is a front view showing a bag 10 according to the present embodiment. The bag 10 includes a storage portion 17 that stores the contents. In addition, in FIG. 1, the bag 10 of the state in which the contents are not accommodated is shown. Bag 10 by this embodiment is constituted so that retort processing can be performed. Hereinafter, the configuration of the bag 10 will be described.
　袋
　本実施の形態において、袋１０は、自立可能に構成されたガセット式の袋である。袋１０は、上部１１、下部１２及び側部１３を含み、正面図において略矩形状の輪郭を有する。なお、「上部」、「下部」及び「側部」などの名称、並びに、「上方」、「下方」などの用語は、ガセット部を下にして袋１０が自立している状態を基準として袋１０やその構成要素の位置や方向を相対的に表したものに過ぎない。袋１０の輸送時や使用時の姿勢などは、本明細書における名称や用語によっては限定されない。 In the present embodiment, the bag 10 is a gusseted bag configured to be able to stand on its own. The bag 10 includes an upper portion 11, a lower portion 12, and a side portion 13, and has a substantially rectangular outline in a front view. It should be noted that names such as “upper”, “lower” and “side”, and terms such as “upper” and “lower” refer to a bag based on the state in which the bag 10 is self-supporting with the gusset portion down. It is only a relative representation of the position and direction of 10 and its components. The attitude | position at the time of transport of the bag 10 or use is not limited by the name and terminology in this specification.
　図１に示すように、袋１０は、表面を構成する表面フィルム１４、裏面を構成する裏面フィルム１５、及び、下部１２を構成する下部フィルム１６を備える。下部フィルム１６は、折り返し部１６ｆで折り返された状態で、表面フィルム１４と裏面フィルム１５との間に配置されている。 As shown in FIG. 1, the bag 10 includes a surface film 14 that constitutes the front surface, a back film 15 that constitutes the back surface, and a lower film 16 that constitutes the lower portion 12. The lower film 16 is disposed between the front film 14 and the back film 15 in a state where the lower film 16 is folded at the folded portion 16f.
　なお、上述の「表面フィルム」、「裏面フィルム」及び「下部フィルム」という用語は、位置関係に応じて各フィルムを区画したものに過ぎず、袋１０を製造する際のフィルムの提供方法が、上述の用語によって限定されることはない。例えば、袋１０は、表面フィルム１４と裏面フィルム１５と下部フィルム１６が連設された１枚のフィルムを用いて製造されてもよく、表面フィルム１４と下部フィルム１６が連設された１枚のフィルムと１枚の裏面フィルム１５の計２枚のフィルムを用いて製造されてもよく、１枚の表面フィルム１４と１枚の裏面フィルム１５と１枚の下部フィルム１６の計３枚のフィルムを用いて製造されてもよい。 In addition, the term “surface film”, “back film” and “lower film” described above is merely a partition of each film according to the positional relationship, and the method of providing a film when manufacturing the bag 10 It is not limited by the above terms. For example, the bag 10 may be manufactured using one film in which the front film 14, the back film 15, and the lower film 16 are continuously provided, or one sheet in which the front film 14 and the lower film 16 are continuously provided. It may be manufactured using a total of two films, a film and one back film 15, and a total of three films, one surface film 14, one back film 15, and one lower film 16. May be used.
　表面フィルム１４、裏面フィルム１５及び下部フィルム１６は、内面同士がシール部によって接合されている。図１などの袋１０の正面図においは、シール部にハッチングが施されている。 The inner surfaces of the front film 14, the back film 15, and the lower film 16 are joined together by a seal portion. In the front view of the bag 10 shown in FIG. 1 and the like, the seal portion is hatched.
　図１に示すように、シール部は、袋１０の外縁に沿って延びる外縁シール部を有する。外縁シール部は、下部１２に広がる下部シール部１２ａ、及び、一対の側部１３に沿って延びる一対の側部シール部１３ａを含む。なお、内容物が充填される前の状態（内容物が充填されていない状態）の袋１０においては、図１に示すように、袋１０の上部１１は開口部１１ｂになっている。袋１０に内容物を収容した後、表面フィルム１４の内面と裏面フィルム１５の内面とを上部１１において接合することにより、上部シール部が形成されて袋１０が封止される。 As shown in FIG. 1, the seal portion has an outer edge seal portion extending along the outer edge of the bag 10. The outer edge seal portion includes a lower seal portion 12 a extending in the lower portion 12 and a pair of side seal portions 13 a extending along the pair of side portions 13. In addition, in the bag 10 in a state before the contents are filled (a state in which the contents are not filled), as shown in FIG. 1, the upper portion 11 of the bag 10 is an opening 11b. After the contents are stored in the bag 10, the inner surface of the front film 14 and the inner surface of the back film 15 are joined at the upper portion 11, whereby an upper seal portion is formed and the bag 10 is sealed.
　側部シール部１３ａ及び後述する上部シール部は、表面フィルム１４の内面と裏面フィルム１５の内面とを接合することによって構成されるシール部である。一方、下部シール部１２ａは、表面フィルム１４の内面と下部フィルム１６の内面とを接合することによって構成されるシール部、及び、裏面フィルム１５の内面と下部フィルム１６の内面とを接合することによって構成されるシール部を含む。 The side seal portion 13a and the upper seal portion described later are seal portions configured by joining the inner surface of the surface film 14 and the inner surface of the back film 15. On the other hand, the lower seal portion 12a is formed by bonding the inner surface of the surface film 14 and the inner surface of the lower film 16, and by bonding the inner surface of the back film 15 and the inner surface of the lower film 16. Including a configured seal.
　対向するフィルム同士を接合して袋１０を封止することができる限りにおいて、シール部を形成するための方法が特に限られることはない。例えば、加熱などによってフィルムの内面を溶融させ、内面同士を溶着させることによって、すなわちヒートシールによって、シール部を形成してもよい。若しくは、接着剤などを用いて対向するフィルムの内面同士を接着することによって、シール部を形成してもよい。 As long as the opposing films can be joined and the bag 10 can be sealed, the method for forming the seal portion is not particularly limited. For example, the sealing portion may be formed by melting the inner surfaces of the film by heating or the like and welding the inner surfaces, that is, by heat sealing. Or you may form a seal | sticker part by adhere | attaching the inner surfaces of the opposing film using an adhesive agent etc.
　易開封性手段
　表面フィルム１４及び裏面フィルム１５には、表面フィルム１４及び裏面フィルム１５を引き裂いて袋１０を開封するための易開封性手段２５が設けられていてもよい。例えば図１に示すように、易開封性手段２５は、袋１０の側部シール部１３ａに形成された、引き裂きの起点となるノッチ２６を含んでいてもよい。また、袋１０を引き裂く際の経路となる部分には、易開封性手段２５として、レーザー加工やカッターなどで形成されたハーフカット線が設けられていてもよい。 Easy opening means The front film 14 and the back film 15 may be provided with easy opening means 25 for tearing the front film 14 and the back film 15 to open the bag 10. For example, as shown in FIG. 1, the easy-opening means 25 may include a notch 26 that is formed in the side seal portion 13 a of the bag 10 and serves as a starting point of tearing. Further, a half-cut line formed by laser processing, a cutter, or the like may be provided as the easy-opening means 25 in a portion that becomes a path when the bag 10 is torn.
　また、図示はしないが、易開封性手段２５は、表面フィルム１４及び裏面フィルム１５のうちシール部が形成されている領域に形成された切り込みや傷痕群を含んでいてもよい。傷痕群は例えば、表面フィルム１４及び／又は裏面フィルム１５を貫通するように形成された複数の貫通孔を含んでいてもよい。若しくは、傷痕群は、表面フィルム１４及び／又は裏面フィルム１５を貫通しないように表面フィルム１４及び／又は裏面フィルム１５の外面に形成された複数の孔を含んでいてもよい。 Although not shown, the easy-opening means 25 may include notches and scars formed in the area where the seal portion is formed in the front film 14 and the back film 15. The scar group may include, for example, a plurality of through holes formed so as to penetrate the front film 14 and / or the back film 15. Alternatively, the scar group may include a plurality of holes formed on the outer surface of the front film 14 and / or the back film 15 so as not to penetrate the front film 14 and / or the back film 15.
　表面フィルム及び裏面フィルムの層構成
　次に、表面フィルム１４及び裏面フィルム１５の層構成について説明する。図２は、表面フィルム１４及び裏面フィルム１５を構成する積層体３０を示す断面図である。 Next, the layer structure of the front film 14 and the back film 15 will be described. FIG. 2 is a cross-sectional view showing a laminated body 30 constituting the front film 14 and the back film 15.
　図２に示すように、積層体３０は、第１フィルム４０と、接着剤層４５を介して第１フィルム４０に積層されたシーラントフィルム７０と、を備える。第１フィルム４０は、外面３０ｙ側に位置しており、シーラントフィルム７０は、外面３０ｙの反対側の内面３０ｘ側に位置している。内面３０ｘは、積層体３０によって構成された袋１０において収容部１７側を向く面であり、外面３０ｙは、内面３０ｘの反対側に位置する面である。 As shown in FIG. 2, the laminate 30 includes a first film 40 and a sealant film 70 laminated on the first film 40 with an adhesive layer 45 interposed therebetween. The first film 40 is located on the outer surface 30y side, and the sealant film 70 is located on the inner surface 30x side opposite to the outer surface 30y. The inner surface 30x is a surface facing the accommodating portion 17 side in the bag 10 constituted by the laminate 30, and the outer surface 30y is a surface located on the opposite side of the inner surface 30x.
　第１フィルム４０は、基材４１を少なくとも含む。また、第１フィルム４０は、基材４１の内面３０ｘ側に設けられた印刷層４２を更に含んでいてもよい。また、シーラントフィルム７０はシーラント層７１を含む。従って、本実施の形態による積層体３０は、外面側から内面側へ順に
　　基材／印刷層／接着剤層／シーラント層
を備えている、と言える。なお、「／」は層と層の境界を表している。 The first film 40 includes at least a base material 41. The first film 40 may further include a print layer 42 provided on the inner surface 30x side of the base material 41. The sealant film 70 includes a sealant layer 71. Therefore, it can be said that the laminated body 30 by this Embodiment is equipped with the base material / printing layer / adhesive layer / sealant layer in order from the outer surface side to the inner surface side. Note that “/” represents a boundary between layers.
　以下、第１フィルム４０、シーラントフィルム７０及び接着剤層４５についてそれぞれ詳細に説明する。 Hereinafter, each of the first film 40, the sealant film 70, and the adhesive layer 45 will be described in detail.
　（第１フィルム）
　第１フィルム４０は、積層体３０の外面３０ｙを構成する基材４１を少なくとも備える。図２に示すように、第１フィルム４０は、基材４１の内面３０ｘ側に設けられた印刷層４２を更に備えていてもよい。 (First film)
The first film 40 includes at least a base material 41 constituting the outer surface 30y of the laminate 30. As shown in FIG. 2, the first film 40 may further include a printing layer 42 provided on the inner surface 30 x side of the base material 41.
　〔基材〕
　基材４１は、主成分としてポリブチレンテレフタレート（以下、ＰＢＴとも記す）を含む。例えば、基材４１は、５１質量％以上のＰＢＴを含む。以下、基材４１がＰＢＴを含むことの利点について説明する。 〔Base material〕
The base material 41 includes polybutylene terephthalate (hereinafter also referred to as PBT) as a main component. For example, the base material 41 includes 51% by mass or more of PBT. Hereinafter, the advantage that the base material 41 includes PBT will be described.
　ＰＢＴは、寸法安定性に優れており、従って印刷適性に優れる。このため、ポリエチレンテレフタレート（以下、ＰＥＴとも記す）の場合と同様に、ＰＢＴを含む基材４１上に印刷層４２を設けることができる。 PBT has excellent dimensional stability and therefore excellent printability. For this reason, the printing layer 42 can be provided on the base material 41 containing PBT similarly to the case of polyethylene terephthalate (hereinafter also referred to as PET).
　また、ＰＢＴは、耐熱性に優れる。このため、袋１０にボイル処理やレトルト処理を施す際に基材４１が変形したり基材４１の強度が低下したりすることを抑制することができる。レトルト処理とは、内容物を袋１０に充填して袋１０を密封した後、蒸気又は加熱温水を利用して袋１０を加圧状態で加熱する処理である。レトルト処理の温度は、例えば１２０℃以上である。ボイル処理とは、内容物を袋１０に充填して袋１０を密封した後、袋１０を大気圧下で湯煎する処理である。ボイル処理の温度は、例えば９０℃以上且つ１００℃以下である。 Moreover, PBT is excellent in heat resistance. For this reason, it is possible to prevent the base material 41 from being deformed or the strength of the base material 41 from being lowered when the bag 10 is subjected to boil processing or retort processing. The retort process is a process of heating the bag 10 in a pressurized state using steam or heated hot water after filling the bag 10 with the contents and sealing the bag 10. The temperature of retort processing is 120 degreeC or more, for example. The boil process is a process of filling the bag 10 with the contents and sealing the bag 10 and then bathing the bag 10 under atmospheric pressure. The temperature of boil processing is 90 degreeC or more and 100 degrees C or less, for example.
　また、ＰＢＴは、高い強度を有する。このため、袋１０を構成する積層体がナイロンを含む場合と同様に、袋１０に耐突き刺し性を持たせることができる。 Also, PBT has high strength. For this reason, the stab resistance can be given to the bag 10 similarly to the case where the laminated body which comprises the bag 10 contains nylon.
　また、ＰＢＴは、ナイロンに比べて水分を吸収しにくいという特性を有する。このため、ＰＢＴを含む基材４１を積層体３０の外面３０ｙに配置した場合であっても、基材４１が水分を吸収して積層体３０のラミネート強度が低下してしまうことを抑制することができる。 Also, PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 41 containing PBT is arrange | positioned on the outer surface 30y of the laminated body 30, it suppresses that the base material 41 absorbs a water | moisture content and the laminate strength of the laminated body 30 falls. Can do.
　以下、ＰＢＴを含む基材４１の構成について詳細に説明する。本実施の形態における、ＰＢＴを含む基材４１の構成としては、下記の第１の構成又は第２の構成のいずれを採用してもよい。 Hereinafter, the configuration of the base material 41 including PBT will be described in detail. As the configuration of the base material 41 including PBT in the present embodiment, any of the following first configuration or second configuration may be adopted.
　〔基材の第１の構成〕
　第１の構成に係る基材４１におけるＰＢＴの含有率は、５１質量％以上が好ましく、６０質量％以上がより好ましく、さらには７０質量％以上、特には７５質量％以上が好ましく、最も好ましくは８０質量％以上である。ＰＢＴの含有率を５１質量％以上にすることにより、第１フィルム４０に優れたインパクト強度および耐ピンホール性を持たせることができる。 [First Configuration of Substrate]
The content of PBT in the base material 41 according to the first configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further 70% by mass or more, particularly preferably 75% by mass or more, and most preferably. 80% by mass or more. By setting the content of PBT to 51% by mass or more, the first film 40 can have excellent impact strength and pinhole resistance.
　主たる構成成分として用いるＰＢＴは、ジカルボン酸成分として、テレフタル酸が９０モル％以上であることが好ましく、より好ましくは９５モル％以上であり、さらに好ましくは９８モル％以上であり、最も好ましくは１００モル％である。グリコール成分として１，４－ブタンジオールが９０モル％以上であることが好ましく、より好ましくは９５モル％以上であり、さらに好ましくは９７モル％以上であり、最も好ましくは、重合時に１，４－ブタンジオールのエーテル結合により生成する副生成物以外は含まれないことである。 PBT used as a main constituent component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, most preferably 100 mol% or more of terephthalic acid as a dicarboxylic acid component. Mol%. 1,4-butanediol as the glycol component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and most preferably 1,4-butanediol during polymerization. It is not included except by-products generated by the ether bond of butanediol.
　基材４１は、ＰＢＴ以外のポリエステル樹脂を含んでいてもよい。これにより、例えばフィルム状の基材４１を二軸延伸させる場合の成膜性や基材４１の力学特性を調整することができる。
　ＰＢＴ以外のポリエステル樹脂としては、ＰＥＴ、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンナフタレート（ＰＢＮ）、ポリプロピレンテレフタレート（ＰＰＴ）などのポリエステル樹脂のほか、イソフタル酸、オルソフタル酸、ナフタレンジカルボン酸、ビフェニルジカルボン酸、シクロヘキサンジカルボン酸、アジピン酸、アゼライン酸、セバシン酸などのジカルボン酸が共重合されたＰＢＴ樹脂や、エチレングリコール、１，３－プロピレングリコール、１，２－プロピレングリコール、ネオペンチルグリコール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、シクロヘキサンジオール、ポリエチレングリコール、ポリテトラメチレングリコール、ポリカーボネートジオール等のジオール成分が共重合されたＰＢＴ樹脂を挙げることができる。 The base material 41 may contain a polyester resin other than PBT. Thereby, for example, the film formability when the film-like substrate 41 is biaxially stretched and the mechanical properties of the substrate 41 can be adjusted.
Polyester resins other than PBT include polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polypropylene terephthalate (PPT), as well as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid. , PBT resin copolymerized with dicarboxylic acid such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, polycarbonate diol Min can be mentioned copolymerized PBT resin.
　これらＰＢＴ以外のポリエステル樹脂の添加量は、４９質量％以下が好ましく、４０質量％以下がより好ましい。ＰＢＴ以外のポリエステル樹脂の添加量が４９質量％を超えると、ＰＢＴとしての力学特性が損なわれ、インパクト強度や耐ピンホール性、絞り成形性が不十分となることが考えられる。 The amount of the polyester resin other than PBT is preferably 49% by mass or less, and more preferably 40% by mass or less. If the addition amount of the polyester resin other than PBT exceeds 49% by mass, the mechanical properties as PBT may be impaired, and impact strength, pinhole resistance, and drawability may be insufficient.
　基材４１は、添加剤として、柔軟なポリエーテル成分、ポリカーボネート成分、ポリエステル成分の少なくともいずれかを共重合したポリエステル系およびポリアミド系エラストマーを含んでいてもよい。これにより、屈曲時の耐ピンホール性を改善することができる。添加剤の添加量は、例えば２０質量％である。添加剤の添加量が２０質量％を超えると、添加剤としての効果が飽和することや、基材４１の透明性が低下することなどが起こり得る。 The base material 41 may contain, as an additive, a polyester-based or polyamide-based elastomer obtained by copolymerizing at least one of a flexible polyether component, a polycarbonate component, and a polyester component. Thereby, the pinhole resistance at the time of bending can be improved. The additive amount of the additive is, for example, 20% by mass. When the addition amount of the additive exceeds 20% by mass, the effect as the additive may be saturated, or the transparency of the base material 41 may be reduced.
　第１の構成に係るフィルム状の基材４１を作製する方法の一例について説明する。ここでは、キャスト法によってフィルム状の基材４１を作製する方法について説明する。より具体的には、キャスト時に同一の組成の樹脂を多層化してキャストする方法について説明する。 An example of a method for producing the film-like base material 41 according to the first configuration will be described. Here, a method for producing the film-like base material 41 by a casting method will be described. More specifically, a method of casting a resin having the same composition in multiple layers during casting will be described.
　ＰＢＴは結晶化速度が速いため、キャスト時にも結晶化が進行する。このとき、多層化せずに単層でキャストした場合には、結晶の成長を抑制しうるような障壁が存在しないために、結晶が大きなサイズに成長してしまい、得られた未延伸原反の降伏応力が高くなる。このため、未延伸原反を二軸延伸する際に破断しやすくなる。また、得られた二軸延伸フィルムの降伏応力が高くなり、二軸延伸フィルムの成形性が不十分になってしまうことが考えられる。
　これに対して、キャスト時に同一の樹脂を多層化すれば、未延伸シートの延伸応力を低減することができる。このため、安定した二軸延伸が可能となり、また、得られた二軸延伸フィルムの降伏応力が低くなる。このことにより、柔軟かつ破断強度の高いフィルムを得ることができる。 Since PBT has a high crystallization speed, crystallization proceeds even during casting. At this time, when cast as a single layer without being multi-layered, there is no barrier that can suppress the growth of the crystal, so the crystal grows to a large size, and the resulting unstretched original fabric is obtained. The yield stress of becomes higher. For this reason, it becomes easy to fracture when the unstretched original fabric is biaxially stretched. Moreover, it is possible that the yield stress of the obtained biaxially stretched film becomes high and the moldability of the biaxially stretched film becomes insufficient.
On the other hand, if the same resin is multilayered at the time of casting, the stretching stress of the unstretched sheet can be reduced. For this reason, stable biaxial stretching is possible, and the yield stress of the obtained biaxially stretched film is reduced. Thereby, a flexible and high breaking strength film can be obtained.
　図３は、第１フィルムの層構成の一例を示す断面図である。樹脂を多層化してキャストすることによって基材４１が作製される場合、図３に示すように、第１フィルム４０の基材４１は、複数の層４１ａを含む多層構造部からなる。複数の層４１ａはそれぞれ、主成分としてＰＢＴを含む。例えば、複数の層４１ａはそれぞれ、好ましくは５１質量％以上のＰＢＴを含み、より好ましくは６０質量％以上のＰＢＴを含む。なお、複数の層４１ａにおいては、ｎ番目の層４１ａの上にｎ＋１番目の層４１ａが直接積層されている。すなわち、複数の層４１ａの間には、接着剤層や接着層が介在されていない。 FIG. 3 is a cross-sectional view showing an example of the layer structure of the first film. When the base material 41 is produced by casting the resin in multiple layers, as shown in FIG. 3, the base material 41 of the first film 40 is composed of a multilayer structure including a plurality of layers 41a. Each of the plurality of layers 41a includes PBT as a main component. For example, each of the plurality of layers 41a preferably includes 51% by mass or more of PBT, and more preferably includes 60% by mass or more of PBT. In the plurality of layers 41a, the (n + 1) th layer 41a is directly stacked on the nth layer 41a. That is, no adhesive layer or adhesive layer is interposed between the plurality of layers 41a.
　多層化によりＰＢＴフィルムの特性が改善される原因については、下記のように推測する。樹脂を積層する場合、樹脂の組成が同一の場合であっても層の界面が存在し、その界面により結晶化が加速される。一方、層の厚みを越えた大きな結晶の成長は抑制される。このため、結晶（球晶）のサイズが小さくなるものと考えられる。 The reason why the properties of the PBT film are improved by multilayering is estimated as follows. When the resins are laminated, even if the resin composition is the same, a layer interface exists, and crystallization is accelerated by the interface. On the other hand, the growth of large crystals beyond the layer thickness is suppressed. For this reason, it is considered that the size of the crystal (spherulite) becomes small.
　多層化により球晶のサイズを小さくするための具体的な方法としては、一般的な多層化装置（多層フィードブロック、スタティックミキサー、多層マルチマニホールドなど）を用いることができる。例えば、二台以上の押出機を用いて異なる流路から送り出された熱可塑性樹脂を、フィードブロックやスタティックミキサー、マルチマニホールドダイ等を用いて多層に積層する方法等を使用することができる。なお、同一の組成の樹脂を多層化する場合、一台の押出機のみを用いて、押出機からダイまでのメルトラインに上述の多層化装置を導入することも可能である。 As a specific method for reducing the size of spherulites by multilayering, a general multilayering apparatus (multilayer feed block, static mixer, multilayer multimanifold, etc.) can be used. For example, a method of laminating thermoplastic resins sent from different flow paths using two or more extruders in multiple layers using a feed block, a static mixer, a multi-manifold die, or the like can be used. In addition, when multilayering resin of the same composition, it is also possible to introduce the above multilayering apparatus into the melt line from the extruder to the die using only one extruder.
　基材４１は、少なくとも１０層以上、好ましくは６０層以上、より好ましくは２５０層以上、更に好ましくは１０００層以上の層４１ａを含む多層構造部からなる。層数を多くすることにより、未延伸原反の状態のＰＢＴにおける球晶のサイズを小さくすることができ、その後の二軸延伸を安定に実施することができる。また、二軸延伸フィルムの状態のＰＢＴの降伏応力を小さくすることができる。好ましくは、未延伸原反のＰＢＴにおける球晶の直径は、５００ｎｍ以下である。 The substrate 41 is composed of a multilayer structure including at least 10 layers, preferably 60 layers or more, more preferably 250 layers or more, and even more preferably 1000 layers or more. By increasing the number of layers, the size of spherulites in the unstretched raw PBT can be reduced, and the subsequent biaxial stretching can be carried out stably. Moreover, the yield stress of PBT in the state of a biaxially stretched film can be made small. Preferably, the diameter of the spherulite in the unstretched raw PBT is 500 nm or less.
　ＰＢＴの未延伸原反を二軸延伸して二軸延伸フィルムを作製する際の、縦延伸方向（以下、ＭＤ）における延伸温度（以下、ＭＤ延伸温度とも記す）は、好ましくは４０℃以上であり、より好ましくは４５℃以上である。ＭＤ延伸温度を４０℃以上にすることにより、フィルムの破断が生じることを抑制することができる。また、ＭＤ延伸温度は、好ましくは１００℃以下であり、より好ましくは９５℃以下である。ＭＤ延伸温度を１００℃以下にすることにより、二軸延伸フィルムの配向が生じないという現象を抑制することができる。 The stretching temperature (hereinafter also referred to as MD stretching temperature) in the longitudinal stretching direction (hereinafter referred to as MD) when producing a biaxially stretched film by biaxially stretching the unstretched raw material of PBT is preferably 40 ° C. or higher. Yes, more preferably 45 ° C or higher. By setting the MD stretching temperature to 40 ° C. or higher, the film can be prevented from being broken. Moreover, MD extending | stretching temperature becomes like this. Preferably it is 100 degrees C or less, More preferably, it is 95 degrees C or less. The phenomenon that the orientation of the biaxially stretched film does not occur can be suppressed by setting the MD stretching temperature to 100 ° C. or lower.
　ＭＤにおける延伸倍率（以下、ＭＤ延伸倍率とも記す）は、好ましくは２．５倍以上である。これにより、二軸延伸フィルムを配向させ、良好な力学特性や均一な厚みを実現することができる。ＭＤ延伸倍率は、例えば５倍以下である。 The draw ratio in MD (hereinafter also referred to as MD draw ratio) is preferably 2.5 times or more. Thereby, a biaxially stretched film can be oriented and a favorable mechanical characteristic and uniform thickness can be implement | achieved. MD stretch ratio is 5 times or less, for example.
　横延伸方向（以下、ＴＤとも記す）における延伸温度（以下、ＴＤ延伸温度とも記す）は、好ましくは４０℃以上である。ＴＤ延伸温度を４０℃以上にすることにより、フィルムの破断が生じることを抑制することができる。また、ＴＤ延伸温度は、好ましくは１００℃以下である。ＴＤ延伸温度を１００℃以下にすることにより、二軸延伸フィルムの配向が生じないという現象を抑制することができる。 The stretching temperature (hereinafter also referred to as TD stretching temperature) in the transverse stretching direction (hereinafter also referred to as TD) is preferably 40 ° C. or higher. By setting the TD stretching temperature to 40 ° C. or higher, the film can be prevented from being broken. The TD stretching temperature is preferably 100 ° C. or lower. By setting the TD stretching temperature to 100 ° C. or lower, the phenomenon that the orientation of the biaxially stretched film does not occur can be suppressed.
　ＴＤにおける延伸倍率（以下、ＴＤ延伸倍率とも記す）は、好ましくは２．５倍以上である。これにより、二軸延伸フィルムを配向させ、良好な力学特性や均一な厚みを実現することができる。ＭＤ延伸倍率は、例えば５倍以下である。 The stretching ratio in TD (hereinafter also referred to as TD stretching ratio) is preferably 2.5 times or more. Thereby, a biaxially stretched film can be oriented and a favorable mechanical characteristic and uniform thickness can be implement | achieved. MD stretch ratio is 5 times or less, for example.
　ＴＤリラックス率は、好ましくは０．５％以上である。これにより、ＰＢＴの二軸延伸フィルムの熱固定時に破断が生じることを抑制することができる。また、ＴＤリラックス率は、好ましくは１０％以下である。これにより、ＰＢＴの二軸延伸フィルムにたるみなどが生じて厚みムラが発生することを抑制することができる。 TD relaxation rate is preferably 0.5% or more. Thereby, it can suppress that a fracture | rupture arises at the time of heat setting of the biaxially stretched film of PBT. The TD relaxation rate is preferably 10% or less. Thereby, sagging etc. arise in a biaxially stretched film of PBT, and it can control that thickness unevenness generate | occur | produces.
　図３に示す基材４１の層４１ａの厚みは、好ましくは３ｎｍ以上であり、より好ましくは１０ｎｍ以上である。また、層４１ａの厚みは、好ましくは２００ｎｍ以下であり、より好ましくは１００ｎｍ以下である。
　また、基材４１の厚みは、好ましくは９μｍ以上であり、より好ましくは１２μｍ以上である。また、基材４１の厚みは、好ましくは２５μｍ以下であり、より好ましくは２０μｍ以下である。基材４１の厚みを９μｍ以上にすることにより、基材４１が十分な強度を有するようになる。また、基材４１の厚みを２５μｍ以下にすることにより、基材４１が優れた成形性を示すようになる。このため、基材４１を含む積層体３０を加工して袋１０を製造する工程を効率的に実施することができる。 The thickness of the layer 41a of the base material 41 shown in FIG. 3 is preferably 3 nm or more, more preferably 10 nm or more. The thickness of the layer 41a is preferably 200 nm or less, and more preferably 100 nm or less.
The thickness of the base material 41 is preferably 9 μm or more, and more preferably 12 μm or more. Moreover, the thickness of the base material 41 is preferably 25 μm or less, more preferably 20 μm or less. By setting the thickness of the base material 41 to 9 μm or more, the base material 41 has sufficient strength. Moreover, the base material 41 comes to show the moldability which was excellent by making the thickness of the base material 41 into 25 micrometers or less. For this reason, the process which processes the laminated body 30 containing the base material 41 and manufactures the bag 10 can be implemented efficiently.
　〔基材の第２の構成〕
　第２の構成に係る基材４１は、ブチレンテレフタレートを主たる繰返し単位とするポリエステルを含む単層フィルムからなる。例えば、基材４１は、グリコール成分としての１，４－ブタンジオール、又はそのエステル形成性誘導体と、二塩基酸成分としてのテレフタル酸、又はそのエステル形成性誘導体を主成分とし、それらを縮合して得られるホモ、またはコポリマータイプのポリエステルを含む。第２の構成に係る基材４１におけるＰＢＴの含有率は、５１質量％以上が好ましく、６０質量％以上がより好ましく、７０質量％以上がさらに好ましく、さらには８０質量％以上が好ましく、最も好ましくは９０質量％以上である。また、第２の構成に係る基材４１は、ポリブチレンテレフタレートと添加剤のみで構成されていることが好ましい。 [Second Configuration of Base Material]
The base material 41 according to the second configuration is made of a single layer film containing polyester having butylene terephthalate as a main repeating unit. For example, the base material 41 is mainly composed of 1,4-butanediol as the glycol component or an ester-forming derivative thereof and terephthalic acid as the dibasic acid component or the ester-forming derivative thereof, and condenses them. Homo- or copolymer-type polyester obtained. The content of PBT in the base material 41 according to the second configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, and most preferably. Is 90% by mass or more. Moreover, it is preferable that the base material 41 which concerns on a 2nd structure is comprised only with the polybutylene terephthalate and the additive.
　基材４１に機械的強度を付与するためには、ＰＢＴのうち、融点が２００℃以上且つ２５０℃以下、ＩＶ値（固有粘度）が１．１０ｄｌ／ｇ以上且つ１．３５ｄｌ／ｇ以下のものが好ましい。さらには、融点が２１５℃以上且つ２２５℃以下、ＩＶ値が１．１５ｄｌ／ｇ以上且つ１．３０ｄｌ／ｇ以下のものが特に好ましい。これらのＩＶ値は、基材４１を構成する材料全体によって満たされていてもよい。ＩＶ値は、ＪＩＳ　Ｋ　７３６７－５：２０００に基づいて算出され得る。 In order to impart mechanical strength to the substrate 41, PBT having a melting point of 200 ° C. or more and 250 ° C. or less and an IV value (intrinsic viscosity) of 1.10 dl / g or more and 1.35 dl / g or less Is preferred. Furthermore, those having a melting point of 215 ° C. or more and 225 ° C. or less and an IV value of 1.15 dl / g or more and 1.30 dl / g or less are particularly preferable. These IV values may be satisfied by the whole material constituting the base material 41. The IV value can be calculated based on JIS K 7367-5: 2000.
　第２の構成に係る基材４１は、ＰＥＴなどＰＢＴ以外のポリエステル樹脂を３０質量％以下の範囲で含んでいてもよい。基材４１がＰＢＴに加えてＰＥＴを含むことにより、ＰＢＴ結晶化を抑制することができ、ＰＢＴフィルムの延伸加工性を向上させることができる。基材４１のＰＢＴに配合するＰＥＴとしては、エチレンテレフタレートを主たる繰返し単位とするポリエステルを用いることができる。例えば、グリコール成分としてのエチレングリコール、二塩基酸成分としてのテレフタル酸を主成分としたホモタイプを好ましく用いることができる。良好な機械的強度特性を付与するためには、ＰＥＴのうち、融点が２４０℃以上且つ２６５℃以下、ＩＶ値が０．５５ｄｌ／ｇ以上且つ０．９０ｄｌ／ｇ以下のものが好ましい。さらには、融点が２４５℃以上且つ２６０℃以下、ＩＶ値が０．６０ｄｌ／ｇ以上且つ０．８０ｄｌ／ｇ以下のものが特に好ましい。
　ＰＥＴの配合量を３０質量％以下にすることにより、未延伸原反及び延伸フィルムの剛性が高くなり過ぎることを抑制することができる。これにより、延伸フィルムがもろくなり、延伸フィルムの耐圧強度、衝撃強度、突刺し強度などが低下してしまうことを抑制することができる。また、未延伸原反を延伸する際の延伸不調が発生することを抑制することができる。 The base material 41 which concerns on a 2nd structure may contain polyester resins other than PBT, such as PET, in 30 mass% or less. When the base material 41 contains PET in addition to PBT, PBT crystallization can be suppressed, and the stretchability of the PBT film can be improved. As PET mix | blended with PBT of the base material 41, the polyester which uses ethylene terephthalate as a main repeating unit can be used. For example, a homotype mainly composed of ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component can be preferably used. In order to impart good mechanical strength characteristics, among PET, those having a melting point of 240 ° C. or more and 265 ° C. or less and an IV value of 0.55 dl / g or more and 0.90 dl / g or less are preferable. Furthermore, those having a melting point of 245 ° C. or more and 260 ° C. or less and an IV value of 0.60 dl / g or more and 0.80 dl / g or less are particularly preferable.
By setting the blending amount of PET to 30% by mass or less, it is possible to suppress the unstretched raw fabric and the stretched film from becoming too rigid. Thereby, a stretched film becomes brittle and it can suppress that the pressure resistance strength, impact strength, puncture strength, etc. of a stretched film fall. Moreover, it is possible to suppress the occurrence of stretching failure when the unstretched raw fabric is stretched.
　基材４１は、必要に応じて、滑剤、アンチブロッキング剤、無機増量剤、酸化防止剤、紫外線吸収剤、帯電防止剤、難燃剤、可塑剤、着色剤、結晶化抑制剤、結晶化促進剤等の添加剤を含んでいてもよい。また、基材４１の原料として用いるポリエステル系樹脂ペレットは、加熱溶融時の加水分解による粘度低下を避けるため、加熱溶融前に水分率が０．０５重量％以下、好ましくは０．０１重量％以下になるように十分予備乾燥を行った上で使用するのが好ましい。 The base material 41 is a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a colorant, a crystallization inhibitor, a crystallization accelerator, if necessary. Etc. may be contained. The polyester resin pellets used as the raw material of the base material 41 have a moisture content of 0.05% by weight or less, preferably 0.01% by weight or less before heating and melting in order to avoid a decrease in viscosity due to hydrolysis during heating and melting. It is preferable to use after sufficiently pre-drying so that
　第２の構成に係るフィルム状の基材４１を作製する方法の一例について説明する。 An example of a method for producing the film-like base material 41 according to the second configuration will be described.
　上述の構成の基材４１のフィルムを安定的に作製するためには、未延伸原反の状態における結晶の成長を抑制することが重要になる。具体的には、押出されたＰＢＴ系溶融体を冷却して成膜する際、該ポリマーの結晶化温度領域をある速度以上で冷却する、すなわち原反冷却速度が重要な因子となる。原反冷却速度は、例えば２００℃／秒以上、好ましくは２５０℃／秒以上、特に好ましくは３５０℃／秒以上である。高い冷却速度で成膜された未延伸原反は、低い結晶状態を保っているため、延伸時のバブルの安定性が向上する。さらには高速での成膜も可能になるので、フィルムの生産性も向上する。冷却速度が２００℃／秒未満である場合、得られた未延伸原反の結晶性が高くなり延伸性が低下することが考えられる。また、極端な場合には、延伸バブルが破裂し、延伸が継続しないことも考えられる。 In order to stably produce the film of the base material 41 having the above-described configuration, it is important to suppress the crystal growth in the unstretched raw fabric. Specifically, when forming the film by cooling the extruded PBT melt, the crystallization temperature region of the polymer is cooled at a certain rate or more, that is, the raw fabric cooling rate is an important factor. The raw fabric cooling rate is, for example, 200 ° C./second or more, preferably 250 ° C./second or more, particularly preferably 350 ° C./second or more. Since the unstretched original film formed at a high cooling rate maintains a low crystalline state, the stability of the bubbles during stretching is improved. Furthermore, since film formation at high speed is possible, film productivity is also improved. When the cooling rate is less than 200 ° C./sec, it is considered that the crystallinity of the obtained unstretched original fabric is increased and the stretchability is lowered. In extreme cases, the stretching bubble may burst and stretching may not continue.
　ＰＢＴを主成分として含む未延伸原反は、雰囲気温度を２５℃以下、好ましくは２０℃以下に保ちながら、二軸延伸を行う空間まで搬送されることが好ましい。これにより、滞留時間が長くなった場合であっても、成膜直後の未延伸原反の結晶性を維持することができる。 It is preferable that the unstretched raw material containing PBT as a main component is conveyed to a space where biaxial stretching is performed while maintaining the atmospheric temperature at 25 ° C. or lower, preferably 20 ° C. or lower. Thereby, even if it is a case where residence time becomes long, the crystallinity of the unstretched original fabric immediately after film-forming can be maintained.
　未延伸原反を延伸させて延伸フィルムを得るための二軸延伸法は、特には限定されない。例えば、チューブラー法又はテンター法により、縦方向及び横方向を同時に延伸してもよく、若しくは、縦方向及び横方向を逐次延伸してもよい。このうち、チューブラー法は、周方向の物性バランスが良好な延伸フィルムを得ることができ、特に好ましく採用される。 The biaxial stretching method for obtaining a stretched film by stretching an unstretched raw fabric is not particularly limited. For example, the longitudinal direction and the lateral direction may be simultaneously stretched by the tubular method or the tenter method, or the longitudinal direction and the lateral direction may be sequentially stretched. Among these, the tubular method can obtain a stretched film having a good balance of physical properties in the circumferential direction, and is particularly preferably employed.
　チューブラー法において、延伸空間に導かれた未延伸原反は、一対の低速ニップロール間に挿通された後、中に空気を圧入しながら延伸用ヒーターで加熱される。延伸終了後、延伸フィルムには、冷却ショルダーエアーリングによりエアーが吹き付けられる。延伸倍率は、延伸安定性や延伸フィルムの強度物性、透明性、および厚み均一性を考慮すると、ＭＤ、およびＴＤそれぞれ２．７倍以上且つ４．５倍以下であることが好ましい。延伸倍率を２．７倍以上にすることにより、延伸フィルムの引張弾性率や衝撃強度を十分に確保することができる。また、延伸倍率を４．５倍以下にすることにより、延伸により過度な分子鎖のひずみが発生することを抑制し、延伸加工時に破断やパンクが発生することを抑制できるので、延伸フィルムを安定に作製することができる。 In the tubular method, the unstretched raw material introduced into the stretching space is inserted between a pair of low-speed nip rolls, and then heated by a stretching heater while air is being pressed therein. After stretching, air is blown onto the stretched film by a cooling shoulder air ring. The stretching ratio is preferably 2.7 times or more and 4.5 times or less for MD and TD, respectively, in consideration of stretching stability, strength physical properties of the stretched film, transparency, and thickness uniformity. By setting the draw ratio to 2.7 times or more, it is possible to sufficiently ensure the tensile elastic modulus and impact strength of the stretched film. In addition, by setting the draw ratio to 4.5 times or less, it is possible to suppress the occurrence of excessive molecular chain distortion due to stretching, and to suppress the occurrence of breakage and puncture during the stretching process, so that the stretched film can be stabilized. Can be produced.
　延伸温度は、４０℃以上且つ８０℃以下が好ましく、特に好ましくは４５℃以上且つ６５℃以下である。上述の高い冷却速度で製造した未延伸原反は、結晶性が低いため、延伸温度が比較的に低温の場合であっても、安定して未延伸原反を延伸することができる。また、延伸温度を８０℃以下にすることにより、延伸バブルの揺れを抑制し、厚み精度の良好な延伸フィルムを得ることができる。また、延伸温度を４０℃以上にすることにより、低温延伸による過度な延伸配向結晶化が発生することを抑制して、フィルムの白化等を防ぐことができる。 The stretching temperature is preferably 40 ° C. or higher and 80 ° C. or lower, and particularly preferably 45 ° C. or higher and 65 ° C. or lower. Since the unstretched original fabric produced at the above-described high cooling rate has low crystallinity, the unstretched original fabric can be stably stretched even when the stretching temperature is relatively low. Further, by setting the stretching temperature to 80 ° C. or less, it is possible to suppress stretching bubble shaking and obtain a stretched film with good thickness accuracy. In addition, by setting the stretching temperature to 40 ° C. or higher, it is possible to suppress the occurrence of excessive stretch-oriented crystallization due to low-temperature stretching, thereby preventing whitening of the film.
　上述のようにして作製される基材４１は、例えば、ブチレンテレフタレートを主たる繰返し単位とするポリエステルを含む単一の層によって構成されている。上述の作製方法によれば、高い冷却速度で未延伸原反を成膜するので、未延伸原反が単一の層によって構成される場合であっても、低い結晶状態を保つことができ、このため、安定して未延伸原反を延伸することができる。 The base material 41 produced as described above is constituted by a single layer containing, for example, polyester having butylene terephthalate as a main repeating unit. According to the above-described production method, since the unstretched raw film is formed at a high cooling rate, even when the unstretched raw fabric is constituted by a single layer, a low crystalline state can be maintained, For this reason, an unstretched original fabric can be extended | stretched stably.
　〔印刷層〕
　印刷層４２は、袋１０に製品情報を示したり美感を付与したりするために基材４１に印刷された層である。印刷層４２は、文字、数字、記号、図形、絵柄などを表現する。印刷層４２を構成する材料としては、グラビア印刷用のインキやフレキソ印刷用のインキを用いることができる。 (Print layer)
The printed layer 42 is a layer printed on the base material 41 in order to show product information or impart aesthetics to the bag 10. The print layer 42 expresses characters, numbers, symbols, figures, patterns, and the like. As a material constituting the printing layer 42, an ink for gravure printing or an ink for flexographic printing can be used.
　印刷層４２を構成するインキは、バインダー及び顔料を含む。バインダーは、例えば、後述する接着剤層４５と同様に、ポリウレタンなどを含む。ポリウレタンは、主剤としてのポリオールと、硬化剤としてのイソシアネート化合物とが反応することにより生成される硬化物である。ポリオール及びイソシアネート化合物の詳細については、接着剤層４５の段落で説明する。 The ink constituting the printing layer 42 includes a binder and a pigment. The binder includes, for example, polyurethane as in the adhesive layer 45 described later. Polyurethane is a cured product produced by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent. Details of the polyol and the isocyanate compound will be described in the paragraph of the adhesive layer 45.
　印刷層４２の顔料は、有色の粉末であり、所定の分布密度でバインダー内に存在する。顔料が呈する色が特に限られることはなく、赤色、青色、緑色、白色、黒色などの様々な顔料を用いることができる。例えば顔料の平均粒径は、０．１μｍ以上且つ１μｍ以下であってもよく、０．５μｍ以上且つ１μｍ以下であってもよい。なお、白色の顔料は一般に、その他の色の顔料に比べて大きな寸法を有する。例えば、白色の顔料の平均粒径は、０．５μｍ以上且つ１μｍ以下である。顔料の平均粒径は、動的光散乱法によって測定することができる。 The pigment of the printing layer 42 is a colored powder and exists in the binder with a predetermined distribution density. The color exhibited by the pigment is not particularly limited, and various pigments such as red, blue, green, white, and black can be used. For example, the average particle diameter of the pigment may be 0.1 μm or more and 1 μm or less, or 0.5 μm or more and 1 μm or less. White pigments generally have larger dimensions than other color pigments. For example, the average particle diameter of the white pigment is 0.5 μm or more and 1 μm or less. The average particle diameter of the pigment can be measured by a dynamic light scattering method.
　印刷層４２は、単一の層からなっていてもよく、複数の層を含んでいてもよい。例えば、印刷層４２は、第１の色を呈する顔料を含む第１の層と、第１の色とは異なる第２の色を呈する顔料を含む第２の層と、を含んでいてもよい。印刷層４２の１つの層の厚みは、例えば０．５μｍ以上且つ３μｍ以下である。 The print layer 42 may be composed of a single layer or may include a plurality of layers. For example, the printing layer 42 may include a first layer that includes a pigment that exhibits a first color, and a second layer that includes a pigment that exhibits a second color different from the first color. . The thickness of one layer of the printing layer 42 is, for example, not less than 0.5 μm and not more than 3 μm.
　〔ガスバリア層〕
　図４は、積層体３０の層構成のその他の例を示す断面図である。図４に示すように、積層体３０の第１フィルム４０は、基材４１の内面３０ｘ側に位置し、透明性を有する透明ガスバリア層３５を更に含んでいてもよい。この場合、印刷層４２は、透明ガスバリア層３５の内面３０ｘ側に位置する。図４に示す例における積層体３０は、外面側から内面側へ順に
　　基材／透明ガスバリア層／印刷層／接着剤層／シーラント層
を備えている、と言える。 [Gas barrier layer]
FIG. 4 is a cross-sectional view illustrating another example of the layer configuration of the stacked body 30. As shown in FIG. 4, the 1st film 40 of the laminated body 30 is located in the inner surface 30x side of the base material 41, and may further contain the transparent gas barrier layer 35 which has transparency. In this case, the printing layer 42 is located on the inner surface 30 x side of the transparent gas barrier layer 35. It can be said that the laminated body 30 in the example shown in FIG. 4 includes a base material / transparent gas barrier layer / printing layer / adhesive layer / sealant layer in order from the outer surface side to the inner surface side.
　以下、透明ガスバリア層３５について説明する。透明ガスバリア層３５は、基材４１の内面３０ｘ側の面上に形成され、透明性を有する無機材料からなる透明蒸着層３６を少なくとも含む。また、透明ガスバリア層３５は、透明蒸着層３６の内面３０ｘ側の面上に形成され、透明性を有する透明ガスバリア性塗布膜３７を更に含んでいてもよい。この場合、積層体３０は、外面側から内面側へ順に
　　基材／透明蒸着層／透明ガスバリア性塗布膜／印刷層／接着剤層／シーラント層
を備えている、と言える。 Hereinafter, the transparent gas barrier layer 35 will be described. The transparent gas barrier layer 35 is formed on the surface on the inner surface 30x side of the substrate 41 and includes at least a transparent vapor deposition layer 36 made of an inorganic material having transparency. The transparent gas barrier layer 35 may further include a transparent gas barrier coating film 37 that is formed on the inner surface 30x side of the transparent vapor deposition layer 36 and has transparency. In this case, it can be said that the laminated body 30 is provided with a base material / transparent deposition layer / transparent gas barrier coating film / printing layer / adhesive layer / sealant layer in order from the outer surface side to the inner surface side.
　透明蒸着層３６は、酸素ガスおよび水蒸気などの透過を阻止するガスバリア性の機能を有する層として機能する。なお、透明蒸着層３６は二層以上設けられてもよい。透明蒸着層３６を二層以上有する場合、それぞれが、同一の組成であってもよいし、異なる組成であってもよい。透明蒸着層３６の形成方法としては、例えば、真空蒸着法、スパッタリング法、およびイオンプレ－ティング法等の物理気相成長法（Ｐｈｙｓｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ法、ＰＶＤ法）、あるいは、プラズマ化学気相成長法、熱化学気相成長法、および光化学気相成長法等の化学気相成長法（Ｃｈｅｍｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ法、ＣＶＤ法）等を挙げることができる。具体的には、ローラー式蒸着膜成膜装置を用いて、成膜ローラー上において蒸着層を形成することができる。 The transparent vapor-deposited layer 36 functions as a layer having a gas barrier function that prevents permeation of oxygen gas and water vapor. Two or more transparent vapor deposition layers 36 may be provided. When it has two or more transparent vapor deposition layers 36, each may have the same composition or different compositions. As a method for forming the transparent vapor deposition layer 36, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a thermal chemical vapor deposition method and a photochemical vapor deposition method. Specifically, a vapor deposition layer can be formed on a film formation roller using a roller-type vapor deposition film forming apparatus.
　透明蒸着層３６は、アルミニウム酸化物（酸化アルミニウム）、珪素酸化物などの、透明性を有する無機物で形成されている。透明蒸着層３６としては、酸化アルミニウムの非結晶性の薄膜を使用することが好ましい。具体的には、透明蒸着層３６は、式ＡｌＯＸ（式中、Ｘは、０．５～１．５の範囲の数を表す。）で表される酸化アルミニウムの非結晶性の薄膜である。透明蒸着層３６は、膜表面から内面に向かう深さ方向に向かってＸの値が減少している酸化アルミニウムの非結晶性の薄膜を使用することができる。酸化アルミニウムの非結晶性の薄膜は、式ＡｌＯＸ（式中、Ｘは、０．５～１．５の範囲の数を表す。）で表され、その薄膜表面から内面に向かう深さ方向に向かってＸの値が増加していることが好ましい。なお、上記の式中のＸの値としては、基本的には、Ｘ＝０．５以上のものを使用することができるが、Ｘ＝１．０未満になると、着色が激しく、かつ、透明性に劣ることから、Ｘ＝１．０以上のものを使用することが好ましい。また、Ｘ＝１．５のものは、Ａｌが完全に酸化した状態のものであることから、上限としては、Ｘ＝１．５までのものを使用することができる。なお、上記の式中のＸの値が０の場合、完全な無機単体（純物質）であり、透明ではない。 The transparent vapor deposition layer 36 is formed of an inorganic material having transparency, such as aluminum oxide (aluminum oxide) and silicon oxide. As the transparent vapor deposition layer 36, it is preferable to use an amorphous thin film of aluminum oxide. Specifically, the transparent vapor-deposited layer 36 is an amorphous thin film of aluminum oxide represented by the formula AlO X (wherein X represents a number in the range of 0.5 to 1.5). . As the transparent vapor-deposited layer 36, an amorphous thin film of aluminum oxide in which the value of X decreases in the depth direction from the film surface toward the inner surface can be used. The amorphous thin film of aluminum oxide is represented by the formula AlOX (wherein X represents a number in the range of 0.5 to 1.5), and extends in the depth direction from the thin film surface toward the inner surface. It is preferable that the value of X increases. In addition, as a value of X in the above formula, a value of X = 0.5 or more can be basically used. However, when X is less than 1.0, coloring is intense and transparent. Since it is inferior in property, it is preferable to use the thing of X = 1.0 or more. Moreover, since the thing of X = 1.5 is a thing in the state which Al was completely oxidized, the thing to X = 1.5 can be used as an upper limit. In addition, when the value of X in said formula is 0, it is a perfect inorganic simple substance (pure substance), and is not transparent.
　なお、Ｘの値の減少割合は、例えば、Ｘ線光電子分光装置（Xray Photoelectron Spectroscopy：ＸＰＳ）、二次イオン質量分析装置（Secondary Ion Mass Spectroscopy：ＳＩＭＳ）などの表面分析装置を用い、深さ方向にイオンエッチングするなどして分析する方法を利用して、透明蒸着層３６の元素分析を行うことより確認することができる。 In addition, the decreasing rate of the value of X is determined by using a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy: XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy: SIMS). This can be confirmed by performing an elemental analysis of the transparent vapor deposition layer 36 using a method of analyzing by ion etching or the like.
　透明蒸着層３６は、アルミニウム原子と炭素原子の共有結合を含む無機化合物の混合物からなる層であってもよい。この場合において、透明蒸着層３６は、Ｘ線光電子分光装置（測定条件：Ｘ線源ＡｌＫα、Ｘ線出力１２０Ｗ）を用い、深さ方向にイオンエッチングにより測定したピークにアルミニウム原子と炭素原子の共有結合の存在を示し、また、透明性を有しかつ酸素、水蒸気等の透過を妨げるガスバリア性を有してもよい。 The transparent vapor deposition layer 36 may be a layer made of a mixture of inorganic compounds containing a covalent bond between an aluminum atom and a carbon atom. In this case, the transparent vapor deposition layer 36 uses an X-ray photoelectron spectrometer (measuring conditions: X-ray source AlKα, X-ray output 120 W) and shares aluminum atoms and carbon atoms at the peak measured by ion etching in the depth direction. It may have a gas barrier property that indicates the presence of a bond and has transparency and prevents permeation of oxygen, water vapor, and the like.
　透明蒸着層３６と基材４１との界面には、金属原子と炭素原子の共有結合が形成されていてもよい。例えば、透明蒸着層３６が酸化アルミニウムを含む場合、基材４１と透明蒸着層３６との界面には、アルミニウム原子と炭素原子の共有結合が形成されているものとすることができる。共有結合は、Ｘ線光電子分光法による測定（以下、略して「ＸＰＳ測定」という）によって検出され得る。 A covalent bond between a metal atom and a carbon atom may be formed at the interface between the transparent vapor deposition layer 36 and the substrate 41. For example, when the transparent vapor deposition layer 36 contains aluminum oxide, the covalent bond of an aluminum atom and a carbon atom shall be formed in the interface of the base material 41 and the transparent vapor deposition layer 36. The covalent bond can be detected by measurement by X-ray photoelectron spectroscopy (hereinafter referred to as “XPS measurement” for short).
　また、透明蒸着層３６においては、アルミニウム原子と炭素原子の共有結合の存在比率が、ＸＰＳ測定により透明蒸着層３６と基材４１との界面を測定した場合に観察される炭素原子を含む全結合のうちの０.３％以上且つ３０％以下の範囲内であることが好ましい。これにより、透明蒸着層３６と基材４１との密着性が強化され、透明性も優れ、ガスバリア性の蒸着フィルムとしてバランスのよい性能のものが得られる。 Moreover, in the transparent vapor deposition layer 36, all the bonds containing the carbon atom observed when the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is measured when the interface between the transparent vapor deposition layer 36 and the substrate 41 is measured by XPS measurement. It is preferable that it is within the range of 0.3% or more and 30% or less. Thereby, the adhesiveness of the transparent vapor deposition layer 36 and the base material 41 is strengthened, the transparency is excellent, and a gas barrier vapor deposition film having a well-balanced performance is obtained.
　アルミニウム原子と炭素原子の共有結合の存在比率が０.３％未満であると、透明蒸着層３６の密着性の改善が不十分であり、バリア性を安定して維持することが困難になる。 If the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is less than 0.3%, the adhesion of the transparent vapor-deposited layer 36 is not sufficiently improved, and it is difficult to stably maintain the barrier property.
　さらに、酸化アルミニウムを主成分とする透明蒸着層３６の、ＡＬ（アルミニウム）／Ｏ（酸素）比が、基材４１と透明蒸着層３６との界面から、基材４１とは反対側の透明蒸着層３６の表面に向かって３ｎｍまでの範囲内において、１.０以下であることが好ましい。
　透明蒸着層３６と基材４１との界面から、基材４１とは反対側の透明蒸着層３６の表面に向かう範囲内において、ＡＬ／Ｏの比が１.０を超えると、基材４１と透明蒸着層３６との間の密着性が不十分となり、かつアルミニウムの割合が高まり、透明蒸着層３６の透明性が低下する。 Further, the transparent vapor deposition layer 36 containing aluminum oxide as a main component has an AL (aluminum) / O (oxygen) ratio of transparent vapor deposition on the side opposite to the base material 41 from the interface between the base material 41 and the transparent vapor deposition layer 36. In the range of up to 3 nm toward the surface of the layer 36, it is preferably 1.0 or less.
When the AL / O ratio exceeds 1.0 within a range from the interface between the transparent vapor deposition layer 36 and the base material 41 toward the surface of the transparent vapor deposition layer 36 on the side opposite to the base material 41, Adhesiveness with the transparent vapor deposition layer 36 becomes insufficient, the proportion of aluminum increases, and the transparency of the transparent vapor deposition layer 36 decreases.
　透明蒸着層３６の厚みは、例えば３０Å以上且つ１５０Å以下である。３０Å未満であると、透明ガスバリア性塗布膜３７を併用した場合であってもガスバリア性が不十分となる場合がある。一方、１５０Åを超えると、積層体３０のガスバリア性能を維持できない場合がある。この理由は定かではないが、透明蒸着層３６の厚みが１５０Åを超えると積層体３０の屈曲性が低下し、積層体３０を袋１０に使用した場合に透明蒸着層３６の一部に亀裂ないしピンホールが発生してガスバリア性が低下するものと考えられる。透明蒸着層３６の厚みは、好ましくは、４０Å以上且つ１３０Å以下、より好ましくは、５０Å以上且つ１２０Å以下である。なお、透明蒸着層３６の厚みは、例えば、蛍光Ｘ線分析装置（商品名：ＲＩＸ２０００型、株式会社理学製）を用いて、ファンダメンタルパラメーター法で測定することができる。また、透明蒸着層３６の厚みを変更する手段としては、透明蒸着層３６の堆積速度を変更する方法、蒸着する速度を変更する方法などによって行うことができる。 The thickness of the transparent vapor deposition layer 36 is, for example, 30 mm or more and 150 mm or less. If it is less than 30 mm, the gas barrier property may be insufficient even when the transparent gas barrier coating film 37 is used in combination. On the other hand, if it exceeds 150 mm, the gas barrier performance of the laminate 30 may not be maintained. The reason for this is not clear, but if the thickness of the transparent vapor deposition layer 36 exceeds 150 mm, the flexibility of the laminate 30 is reduced, and when the laminate 30 is used in the bag 10, a part of the transparent vapor deposition layer 36 is not cracked. It is considered that pinholes are generated and gas barrier properties are lowered. The thickness of the transparent vapor deposition layer 36 is preferably 40 mm or more and 130 mm or less, more preferably 50 mm or more and 120 mm or less. The thickness of the transparent vapor-deposited layer 36 can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (trade name: RIX2000 type, manufactured by Rigaku Corporation). Moreover, as a means to change the thickness of the transparent vapor deposition layer 36, it can carry out by the method of changing the deposition rate of the transparent vapor deposition layer 36, the method of changing the vapor deposition rate, etc.
　基材４１の内面３０ｘ側の面上に透明蒸着層３６を形成する場合、基材４１の内面３０ｘ側の面に予めコロナ放電処理、フレーム処理、プラズマ処理などの前処理を施しておいてもよい。特に、透明蒸着層３６と基材４１との界面に、金属原子と炭素原子の共有結合を形成する場合には、透明蒸着層３６を形成しようとする基材４１の面に対し前処理を施すことが好ましい。前処理がプラズマ処理である場合、前処理装置により、０．１Ｐａ以上１００Ｐａ以下の減圧環境下において、基材４１の面に対してプラズマを供給する。プラズマは、アルゴン等の不活性ガス単独又は酸素、窒素、炭酸ガス及びそれらの１種以上のガスとの混合ガスをプラズマ原料ガスとして用い、高周波電圧等による電位差によって、プラズマ原料ガスを励起状態にすることにより、発生させることができる。 In the case where the transparent vapor deposition layer 36 is formed on the inner surface 30x side surface of the base material 41, the surface of the base material 41 on the inner surface 30x side may be subjected to pretreatment such as corona discharge treatment, flame processing, and plasma processing in advance. Good. In particular, when a covalent bond between a metal atom and a carbon atom is formed at the interface between the transparent vapor deposition layer 36 and the base material 41, the surface of the base material 41 on which the transparent vapor deposition layer 36 is to be formed is pretreated. It is preferable. When the pretreatment is plasma treatment, plasma is supplied to the surface of the base material 41 in a reduced pressure environment of 0.1 Pa or more and 100 Pa or less by the pretreatment apparatus. Plasma uses an inert gas such as argon alone or a mixed gas of oxygen, nitrogen, carbon dioxide and one or more of them as a plasma source gas, and the plasma source gas is excited by a potential difference due to a high-frequency voltage or the like. By doing so, it can be generated.
　前処理により、基材４１の表面近傍にプラズマを閉じ込めることができる。これにより、基材４１の表面の形状や、化学的な結合状態や官能基を変化させ、基材４１の表面の化学的性状を変化させることができる。このことにより、基材４１と透明蒸着層３６との密着性を向上させることが可能となる。 The plasma can be confined in the vicinity of the surface of the base material 41 by the pretreatment. Thereby, the shape of the surface of the base material 41, a chemical bonding state, and a functional group can be changed, and the chemical properties of the surface of the base material 41 can be changed. As a result, the adhesion between the base material 41 and the transparent vapor deposition layer 36 can be improved.
　透明ガスバリア性塗布膜３７は、酸素ガスおよび水蒸気などの透過を抑制する層として機能する層である。透明ガスバリア性塗布膜３７は、一般式Ｒ１ ｎＭ（ＯＲ２）ｍ（ただし、式中、Ｒ１、Ｒ２は、炭素数１～８の有機基を表し、Ｍは、金属原子を表し、ｎは、０以上の整数を表し、ｍは、１以上の整数を表し、ｎ＋ｍは、Ｍの原子価を表す。）で表される少なくとも一種以上のアルコキシドと、上記のようなポリビニルアルコ－ル系樹脂および／またはエチレン・ビニルアルコ－ル共重合体とを含有し、さらに、ゾルゲル法触媒、酸、水、および、有機溶剤の存在下に、ゾルゲル法によって重縮合する透明ガスバリア性組成物により得られる。 The transparent gas barrier coating film 37 is a layer that functions as a layer that suppresses permeation of oxygen gas, water vapor, and the like. The transparent gas barrier coating film 37 has a general formula R 1 n M (OR 2 ) m (where R 1 and R 2 represent an organic group having 1 to 8 carbon atoms, and M represents a metal atom) , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and a polyvinyl alcohol as described above A transparent gas barrier composition containing a benzene-based resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. can get.
　上記の一般式Ｒ１ ｎＭ（ＯＲ２）ｍで表されるアルコキシドとしては、アルコキシドの部分加水分解物、アルコキシドの加水分解の縮合物の少なくとも一種以上を使用することができる。また、上記のアルコキシドの部分加水分解物としては、アルコキシ基のすべてが加水分解されている必要はなく、１個以上が加水分解されているもの、および、その混合物であってもよい。アルコキシドの加水分解の縮合物としては、部分加水分解アルコキシドの２量体以上のもの、具体的には、２～６量体のものを使用される。 As the alkoxide represented by the general formula R 1 n M (OR 2 ) m , at least one kind of a partial hydrolyzate of alkoxide and a condensate of hydrolysis of alkoxide can be used. Moreover, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which 1 or more was hydrolyzed, and its mixture may be sufficient. As the condensate of hydrolysis of alkoxide, a dimer or more of partially hydrolyzed alkoxide, specifically, a dimer to hexamer is used.
　上記の一般式Ｒ１ ｎＭ（ＯＲ２）ｍで表されるアルコキシドにおいて、Ｍで表される金属原子としては、ケイ素、ジルコニウム、チタン、アルミニウム、その他などを使用することができる。好ましい金属としては、例えば、ケイ素、チタンなどを挙げることができる。また、本発明において、アルコキシドの用い方としては、単独または二種以上の異なる金属原子のアルコキシドを同一溶液中に混合して使うこともできる。 In the alkoxide represented by the above general formula R 1 n M (OR 2 ) m , as the metal atom represented by M, silicon, zirconium, titanium, aluminum, and the like can be used. Examples of preferable metals include silicon and titanium. In the present invention, alkoxides may be used alone or in combination of two or more different metal atom alkoxides in the same solution.
　また、上記の一般式Ｒ１ ｎＭ（ＯＲ２）ｍで表されるアルコキシドにおいて、Ｒ１で表される有機基の具体例としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ヘキシル基、ｎ－オクチル基、その他などのアルキル基を挙げることができる。また、上記の一般式Ｒ１ ｎＭ（ＯＲ２）ｍで表されるアルコキシドにおいて、Ｒ２で表される有機基の具体例としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、その他などを挙げることができる。なお、同一分子中にこれらのアルキル基は同一であっても、異なってもよい。 In the alkoxide represented by the general formula R 1 n M (OR 2 ) m , specific examples of the organic group represented by R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others. In the alkoxide represented by the general formula R 1 n M (OR 2 ) m , specific examples of the organic group represented by R 2 include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group, and the like. These alkyl groups in the same molecule may be the same or different.
　上記の透明ガスバリア性組成物を調製する際、例えば、シランカップリング剤などを添加してもよい。上記のシランカップリング剤としては、既知の有機反応性基含有オルガノアルコキシシランを用いることができる。特に、エポキシ基を有するオルガノアルコキシシランが好適に用いられ、具体的には、例えば、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、または、β－（３、４－エポキシシクロヘキシル）エチルトリメトキシシランなどを使用することができる。上記のようなシランカップリング剤は、一種または二種以上を混合して用いてもよい。 When preparing the above transparent gas barrier composition, for example, a silane coupling agent or the like may be added. As said silane coupling agent, known organic reactive group containing organoalkoxysilane can be used. In particular, an organoalkoxysilane having an epoxy group is preferably used. Specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be used. The above silane coupling agents may be used alone or in combination of two or more.
　（第２フィルム）
　シーラントフィルム７０は、積層体３０の内面３０ｘを構成するシーラント層７１を少なくとも含む。シーラント層７１を構成する材料としては、低密度ポリエチレン、直鎖状低密度ポリエチレンなどのポリエチレン、ポリプロピレンから選択される１種または２種以上の樹脂を用いることができる。シーラント層７１は、単層であってもよく、多層であってもよい。また、シーラント層７１は、好ましくは未延伸のフィルムからなる。なお「未延伸」とは、全く延伸されていないフィルムだけでなく、製膜の際に加えられる張力に起因してわずかに延伸されているフィルムも含む概念である。 (Second film)
The sealant film 70 includes at least a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30. As a material constituting the sealant layer 71, one or more resins selected from polyethylene such as low density polyethylene and linear low density polyethylene, and polypropylene can be used. The sealant layer 71 may be a single layer or a multilayer. The sealant layer 71 is preferably made of an unstretched film. “Unstretched” is a concept that includes not only a film that is not stretched at all, but also a film that is slightly stretched due to the tension applied during film formation.
　上述のように、積層体３０から構成された袋１０には、ボイル処理やレトルト処理などの殺菌処理が高温で施される。従って、シーラント層７１は、これらの高温での処理に耐える耐熱性を有するものが用いられる。 As described above, the bag 10 composed of the laminate 30 is subjected to sterilization treatment such as boil treatment and retort treatment at a high temperature. Therefore, as the sealant layer 71, a layer having heat resistance that can withstand processing at these high temperatures is used.
　シーラント層７１を構成する材料の融点は、１５０℃以上であることが好ましく、１６０℃以上であることがより好ましい。シーラント層７１の融点を高くすることにより、袋１０のレトルト処理を高温で実施することが可能になり、このため、レトルト処理に要する時間を短くすることができる。なお、シーラント層７１を構成する材料の融点は、基材４１を構成する樹脂の融点より低い。 The melting point of the material constituting the sealant layer 71 is preferably 150 ° C. or higher, and more preferably 160 ° C. or higher. By increasing the melting point of the sealant layer 71, the bag 10 can be retorted at a high temperature, and therefore the time required for the retort process can be shortened. The melting point of the material constituting the sealant layer 71 is lower than the melting point of the resin constituting the base material 41.
　レトルト処理の観点で考える場合、シーラント層７１を構成する材料として、プロピレンを主成分とする材料を用いることができる。ここで、プロピレンを「主成分とする」材料とは、プロピレンの含有率が９０質量％以上である材料を意味する。プロピレンを主成分とする材料としては、具体的には、プロピレン・エチレンブロック共重合体、プロピレン・エチレンランダム共重合体、ホモポリプロピレンなどのポリプロピレン、又はポリプロピレンとポリエチレンとを混合したものなどを挙げることができる。ここで、「プロピレン・エチレンブロック共重合体」とは、下記の式（Ｉ）に示される構造式を有する材料を意味する。また、「プロピレン・エチレンランダム共重合体」とは、下記の式（ＩＩ）に示される構造式を有する材料を意味する。また、「ホモポリプロピレン」とは、下記の式（ＩＩＩ）に示される構造式を有する材料を意味する。 When considering from the viewpoint of retort treatment, a material mainly composed of propylene can be used as the material constituting the sealant layer 71. Here, the material having “propylene as a main component” means a material having a propylene content of 90% by mass or more. Specific examples of the material mainly composed of propylene include propylene / ethylene block copolymer, propylene / ethylene random copolymer, polypropylene such as homopolypropylene, or a mixture of polypropylene and polyethylene. Can do. Here, the “propylene / ethylene block copolymer” means a material having a structural formula represented by the following formula (I). The “propylene / ethylene random copolymer” means a material having a structural formula represented by the following formula (II). “Homopolypropylene” means a material having the structural formula shown by the following formula (III).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　プロピレンを主成分とする材料として、ポリプロピレンとポリエチレンとを混合したものを用いる場合には、材料は、海島構造を有していてもよい。ここで、「海島構造」とは、ポリプロピレンが連続する領域の内に、ポリエチレンが不連続に分散している構造をいう。 In the case of using a mixture of polypropylene and polyethylene as a material mainly composed of propylene, the material may have a sea-island structure. Here, the “sea-island structure” means a structure in which polyethylene is discontinuously dispersed in a region where polypropylene is continuous.
　ボイル処理の観点で考える場合、シーラント層７１を構成する材料の例として、ポリエチレン、ポリプロピレン又はこれらの組み合わせなどを挙げることができる。ポリエチレンとしては、中密度ポリエチレン、直鎖状低密度ポリエチレン又はこれらの組み合わせなどを挙げることができる。例えば、上述のレトルト処理の観点からシーラント層を構成する材料として挙げた材料を用いることも可能である。シーラント層を構成する材料は、例えば１００℃以上、より好ましくは１０５℃以上、更に好ましくは１１０℃以上の融点を有する。シーラント層を構成する材料としてポリエチレンを用いる場合、１００℃以上の融点は、例えば、ポリエチレンの密度が０．９２０ｇ／ｃｍ３以上である場合に実現され得る。また、１００℃以上の融点を有するシーラント層を構成するためのシーラントフィルムの具体例としては、三井化学東セロ製ＴＵＸ－ＨＣ、東洋紡製Ｌ６１０１、出光ユニテック製ＬＳ７００Ｃ等を挙げることができる。１０５℃以上の融点を有するシーラント層を構成するためのシーラントフィルムの具体例としては、タマポリ製ＮＢ－１等を挙げることができる。１１０℃以上の融点を有するシーラント層を構成するためのシーラントフィルムの具体例としては、出光ユニテック製ＬＳ７６０Ｃ、三井化学東セロ製ＴＵＸ－ＨＺ等を挙げることができる。 When considered from the viewpoint of boil processing, examples of the material constituting the sealant layer 71 include polyethylene, polypropylene, or a combination thereof. Examples of polyethylene include medium density polyethylene, linear low density polyethylene, and combinations thereof. For example, it is also possible to use the materials mentioned as the material constituting the sealant layer from the viewpoint of the above retort processing. The material constituting the sealant layer has a melting point of, for example, 100 ° C. or higher, more preferably 105 ° C. or higher, and still more preferably 110 ° C. or higher. When polyethylene is used as the material constituting the sealant layer, a melting point of 100 ° C. or higher can be realized, for example, when the density of polyethylene is 0.920 g / cm 3 or higher. Specific examples of the sealant film for forming a sealant layer having a melting point of 100 ° C. or higher include TUX-HC manufactured by Mitsui Chemicals Tosero, L6101 manufactured by Toyobo, and LS700C manufactured by Idemitsu Unitech. Specific examples of the sealant film for forming a sealant layer having a melting point of 105 ° C. or higher include NB-1 manufactured by Tamapoly. Specific examples of the sealant film for forming a sealant layer having a melting point of 110 ° C. or higher include LS760C manufactured by Idemitsu Unitech, TUX-HZ manufactured by Mitsui Chemicals Tosero, and the like.
　好ましくは、シーラント層７１は、プロピレン・エチレンブロック共重合体を含む。例えば、シーラント層７１を含むシーラントフィルム７０は、プロピレン・エチレンブロック共重合体を主成分とする未延伸フィルムである。プロピレン・エチレンブロック共重合体を用いることにより、シーラントフィルム７０の耐衝撃性を高めることができ、これにより、落下時の衝撃により袋１０が破袋してしまうことを抑制することができる。また、積層体３０の耐突き刺し性を高めることができる。 Preferably, the sealant layer 71 includes a propylene / ethylene block copolymer. For example, the sealant film 70 including the sealant layer 71 is an unstretched film containing a propylene / ethylene block copolymer as a main component. By using the propylene / ethylene block copolymer, the impact resistance of the sealant film 70 can be increased, and thereby the bag 10 can be prevented from being broken due to the impact at the time of dropping. Moreover, the puncture resistance of the laminated body 30 can be improved.
　また、シーラント層７１は、熱可塑性エラストマーを更に含んでいてもよい。熱可塑性エラストマーを用いることにより、シーラントフィルム７０の耐衝撃性や耐突き刺し性を更に高めることができる。 The sealant layer 71 may further contain a thermoplastic elastomer. By using a thermoplastic elastomer, the impact resistance and puncture resistance of the sealant film 70 can be further enhanced.
　熱可塑性エラストマーは、例えば水添スチレン系熱可塑性エラストマーである。水添スチレン系熱可塑性エラストマーは、少なくとも１個のビニル芳香族化合物を主体とする重合体ブロックＡと少なくとも１個の水素添加された共役ジエン化合物を主体とする重合体ブロックＢからなる構造を有する。また、熱可塑性エラストマーは、エチレン・α－オレフィンエラストマーであってもよい。エチレン・α－オレフィンエラストマーは、低結晶性もしくは非晶性の共重合体エラストマーであり、主成分としての５０～９０質量％のエチレンと共重合モノマーとしてのα－オレフィンとのランダム共重合体である。 The thermoplastic elastomer is, for example, a hydrogenated styrene thermoplastic elastomer. The hydrogenated styrene-based thermoplastic elastomer has a structure comprising a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one hydrogenated conjugated diene compound. . The thermoplastic elastomer may be an ethylene / α-olefin elastomer. The ethylene / α-olefin elastomer is a low crystalline or amorphous copolymer elastomer, which is a random copolymer of 50 to 90% by mass of ethylene as a main component and α-olefin as a comonomer. is there.
　シーラント層７１におけるプロピレン・エチレンブロック共重合体の含有率は、例えば８０質量％以上であり、好ましくは９０質量％以上である。 The content of the propylene / ethylene block copolymer in the sealant layer 71 is, for example, 80% by mass or more, and preferably 90% by mass or more.
　プロピレン・エチレンブロック共重合体の製造方法としては、触媒を用いて原料であるプロピレンやエチレンなどを重合させる方法が挙げられる。触媒としては、チーグラー・ナッタ型やメタロセン触媒などを用いることができる。 Examples of the method for producing a propylene / ethylene block copolymer include a method of polymerizing propylene, ethylene, and the like as raw materials using a catalyst. As the catalyst, Ziegler-Natta type or metallocene catalyst can be used.
　シーラント層７１の厚みは、好ましくは３０μｍ以上であり、より好ましくは４０μｍ以上である。また、シーラント層７１の厚みは、好ましくは１００μｍ以下であり、より好ましくは８０μｍ以下である。 The thickness of the sealant layer 71 is preferably 30 μm or more, and more preferably 40 μm or more. The thickness of the sealant layer 71 is preferably 100 μm or less, and more preferably 80 μm or less.
　（接着剤層）
　接着剤層４５は、第１フィルム４０とシーラントフィルム７０とを接着するための接着剤を含む。接着剤層４５を構成する接着剤は、主剤及び溶剤を含む第１組成物と、硬化剤及び溶剤を含む第２組成物とを混合して作製した接着剤組成物から生成される。具体的には、接着剤は、接着剤組成物中の主剤と溶剤とが反応して生成された硬化物を含む。 (Adhesive layer)
The adhesive layer 45 includes an adhesive for bonding the first film 40 and the sealant film 70. The adhesive constituting the adhesive layer 45 is generated from an adhesive composition prepared by mixing a first composition containing a main agent and a solvent and a second composition containing a curing agent and a solvent. Specifically, an adhesive contains the hardened | cured material produced | generated by the reaction of the main ingredient and solvent in an adhesive composition.
　接着剤の例としては、エーテル系の二液反応型接着剤又はエステル系の二液反応型接着剤を挙げることができる。エーテル系の二液反応型接着剤としては、ポリエーテルポリウレタンなどを挙げることができる。ポリエーテルポリウレタンは、主剤としてのポリエーテルポリオールと、硬化剤としてのイソシアネート化合物とが反応することにより生成される硬化物である。エステル系の二液反応型接着剤としては、例えば、ポリエステルポリウレタンやポリエステルなどを挙げることができる。ポリエステルポリウレタンは、主剤としてのポリエステルポリオールと、硬化剤としてのイソシアネート化合物とが反応することにより生成される硬化物である。 Examples of adhesives include ether-based two-component reactive adhesives and ester-based two-component reactive adhesives. Examples of the ether-based two-component reactive adhesive include polyether polyurethane. The polyether polyurethane is a cured product produced by a reaction between a polyether polyol as a main agent and an isocyanate compound as a curing agent. Examples of the ester-based two-component reactive adhesive include polyester polyurethane and polyester. Polyester polyurethane is a cured product produced by a reaction between a polyester polyol as a main agent and an isocyanate compound as a curing agent.
　ポリエーテルポリオールやポリエステルポリオールなどのポリオールと反応して硬化物を生成するイソシアネート化合物としては、芳香族系イソシアネート化合物及び脂肪族系イソシアネート化合物が存在する。このうち芳香族系イソシアネート化合物は、加熱殺菌（レトルト処理）時などの高温環境下において、食品用途で使用できない成分を溶出させる。ところで、接着剤層４５は、図２及び図４に示すように、積層体３０の内面３０ｘを構成するシーラントフィルム７０に接している。このため、接着剤層４５が芳香族系イソシアネート化合物を含む場合、芳香族系イソシアネート化合物から溶出した成分が、積層体３０によって構成された袋１０の内容物に付着することがある。 As an isocyanate compound that reacts with a polyol such as polyether polyol or polyester polyol to produce a cured product, there are an aromatic isocyanate compound and an aliphatic isocyanate compound. Of these, the aromatic isocyanate compound elutes components that cannot be used in food applications in a high temperature environment such as during heat sterilization (retort treatment). Incidentally, as shown in FIGS. 2 and 4, the adhesive layer 45 is in contact with the sealant film 70 constituting the inner surface 30 x of the laminate 30. For this reason, when the adhesive layer 45 contains an aromatic isocyanate compound, a component eluted from the aromatic isocyanate compound may adhere to the contents of the bag 10 constituted by the laminate 30.
　このような課題を考慮し、接着剤層４５を構成する接着剤として、主剤としてのポリオールと、硬化剤としての脂肪族系イソシアネート化合物とが反応することにより生成される硬化物を用いる。これにより、接着剤層４５に起因する、食品用途で使用できない成分が内容物に付着することを防ぐことができる。脂肪族イソシアネートとしては、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）などが挙げられる。 In consideration of such a problem, a cured product generated by a reaction between a polyol as a main agent and an aliphatic isocyanate compound as a curing agent is used as an adhesive constituting the adhesive layer 45. Thereby, it can prevent that the component which cannot be used for the food use resulting from the adhesive bond layer 45 adheres to the content. Examples of the aliphatic isocyanate include hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI).
　一方、後述する実施例で示すように、硬化剤として脂肪族系イソシアネート化合物を用いる場合、第１フィルム４０とシーラントフィルム７０との間のラミネート強度が、芳香族系イソシアネート化合物を用いる場合に比べて低くなる。 On the other hand, as shown in the examples described later, when an aliphatic isocyanate compound is used as a curing agent, the laminate strength between the first film 40 and the sealant film 70 is higher than that when an aromatic isocyanate compound is used. Lower.
　特に、本実施の形態においては、第１フィルム４０において、基材４１のシーラントフィルム７０側に印刷層４２が設けられている。印刷層４２を構成するインキに含まれるバインダーは、接着剤層４５と同様に、主剤としてのポリオールと、硬化剤としてのイソシアネート化合物とが反応することにより生成される硬化物を含み、例えばポリウレタンを含む。イソシアネート化合物としては、食品用途で使用できない成分が溶出することを防ぐため、接着剤層４５と同様に脂肪族系イソシアネート化合物を用いる。また、印刷層４２を構成するインキは、ポリウレタンに加えて顔料を含む。顔料は、基材４１と印刷層４２との接着または／および印刷層４２と接着剤層４５との接着を阻害するように作用する。また、基材４１及び印刷層４２を含む第１フィルム４０を作製した後に第１フィルム４０をロール状に巻き取る際、重なり合う第１フィルム４０の表面と裏面とが密着することを抑制するためには、印刷層４２のバインダーにおける、主剤に対する硬化剤の比率が小さいことが求められる。従って、第１フィルム４０が印刷層４２を含むことは、第１フィルム４０とシーラントフィルム７０との間のラミネート強度を低下させるように作用する。顔料が白色である場合、顔料の寸法が大きく、このため、硬化物による接着が顔料によって阻害される度合いがより大きくなるので、ラミネート強度の低下の度合いがより大きくなる。 In particular, in the present embodiment, in the first film 40, the printing layer 42 is provided on the base material 41 on the sealant film 70 side. Like the adhesive layer 45, the binder contained in the ink constituting the printing layer 42 includes a cured product generated by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent. Including. As the isocyanate compound, an aliphatic isocyanate compound is used in the same manner as the adhesive layer 45 in order to prevent components that cannot be used in food applications from eluting. In addition, the ink constituting the printing layer 42 includes a pigment in addition to polyurethane. The pigment acts to inhibit adhesion between the substrate 41 and the printing layer 42 and / or adhesion between the printing layer 42 and the adhesive layer 45. In addition, when the first film 40 including the base material 41 and the printing layer 42 is produced and then wound up in a roll shape, the surface and the back surface of the overlapping first film 40 are prevented from coming into close contact with each other. Is required to have a small ratio of the curing agent to the main agent in the binder of the printing layer 42. Accordingly, the fact that the first film 40 includes the printing layer 42 acts to reduce the laminate strength between the first film 40 and the sealant film 70. When the pigment is white, the size of the pigment is large. For this reason, the degree to which adhesion by the cured product is inhibited by the pigment is increased, and thus the degree of decrease in the laminate strength is increased.
　このような課題を考慮し、本実施の形態においては、接着剤層４５を構成する主剤（ポリオール）と硬化剤（脂肪族イソシアネート化合物）において、主剤に対する硬化剤の比率を従来よりも大きくすることを提案する。例えば、主剤及び溶剤を含む第１組成物と、硬化剤及び溶剤を含む第２組成物との重量比は、従来は０．１程度である。これに対して、本実施の形態においては、主剤及び溶剤を含む第１組成物に対する、硬化剤及び溶剤を含む第２組成物の重量比を、０．１よりも大きく、例えば０．１５以上に、具体的には０．１５や０．２にする。主剤に対して硬化剤を増加することにより、主剤と硬化剤の反応を促進し、第１フィルム４０及びシーラントフィルム７０に対する接着剤層４５の密着性を高めることができる。このことにより、第１フィルム４０とシーラントフィルム７０との間のラミネート強度を高めることができる。これにより、例えば、積層体３０の引き裂き性を高めたり、積層体３０の耐衝撃性を高めたりすることができる。 Considering such problems, in the present embodiment, in the main agent (polyol) and the curing agent (aliphatic isocyanate compound) constituting the adhesive layer 45, the ratio of the curing agent to the main agent is made larger than before. Propose. For example, the weight ratio of the first composition containing the main agent and the solvent to the second composition containing the curing agent and the solvent is conventionally about 0.1. On the other hand, in the present embodiment, the weight ratio of the second composition containing the curing agent and the solvent to the first composition containing the main agent and the solvent is larger than 0.1, for example, 0.15 or more. Specifically, it is set to 0.15 or 0.2. By increasing the curing agent relative to the main agent, the reaction between the main agent and the curing agent can be promoted, and the adhesion of the adhesive layer 45 to the first film 40 and the sealant film 70 can be enhanced. Thereby, the laminate strength between the first film 40 and the sealant film 70 can be increased. Thereby, for example, the tearability of the stacked body 30 can be improved, and the impact resistance of the stacked body 30 can be increased.
　例えば、主剤（ポリオール）のヒドロキシ基に対する硬化剤（脂肪族イソシアネート化合物）のモル比は、従来は３程度である。本実施の形態において、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は、３．５以上であることが好ましく、４以上であることがより好ましく、４．５以上であることが更に好ましい。更に好ましくは、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は５よりも大きい。 For example, the molar ratio of the curing agent (aliphatic isocyanate compound) to the hydroxy group of the main agent (polyol) is conventionally about 3. In the present embodiment, the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol is preferably 3.5 or more, more preferably 4 or more, and 4.5 or more. Is more preferable. More preferably, the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol is greater than 5.
　一方、脂肪族系イソシアネート化合物は高価であり、脂肪族系イソシアネート化合物の量を増加させることは、製造コストの点で好ましくない。また、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比が大きくなるほど、接着剤組成物を硬化させるために必要な温度が高くなり、又は、時間が長くなる。これらの点を考慮し、ヒドロキシ基に対する脂肪族系イソシアネート基のモル比は、７以下であることが好ましく、６以下であることがより好ましい。 On the other hand, the aliphatic isocyanate compound is expensive, and increasing the amount of the aliphatic isocyanate compound is not preferable in terms of production cost. Further, as the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol increases, the temperature necessary for curing the adhesive composition increases or the time increases. Considering these points, the molar ratio of the aliphatic isocyanate group to the hydroxy group is preferably 7 or less, and more preferably 6 or less.
　なお、印刷層４２のバインダーにおける、ポリオールのヒドロキシ基に対する脂肪族系イソシアネートのイソシアネート基のモル比は、接着剤層４５における、ポリオールのヒドロキシ基に対する脂肪族系イソシアネートのイソシアネート基のモル比よりも小さくなる。このような場合であっても、上述のように、接着剤層４５におけるポリオールのヒドロキシ基に対する脂肪族イソシアネート化合物のイソシアネート基のモル比を３．５以上にすることにより、接着剤層４５中の脂肪族イソシアネート化合物を印刷層４２中へ移動させることができると考えられる。このことにより、第１フィルム４０とシーラントフィルム７０との間のラミネート強度を更に高めることができる。 Note that the molar ratio of the isocyanate group of the aliphatic isocyanate to the hydroxyl group of the polyol in the binder of the printing layer 42 is smaller than the molar ratio of the isocyanate group of the aliphatic isocyanate to the hydroxyl group of the polyol in the adhesive layer 45. Become. Even in such a case, as described above, by setting the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol in the adhesive layer 45 to be 3.5 or more, It is believed that the aliphatic isocyanate compound can be moved into the printing layer 42. Thereby, the laminate strength between the first film 40 and the sealant film 70 can be further increased.
　接着剤層４５は、接着剤組成物を第１フィルム４０又はシーラントフィルム７０に塗布し、その後、接着剤組成物が乾燥し、また、接着剤組成物中の主剤と溶剤とが反応して接着剤組成物が硬化することによって形成される。本実施の形態において、乾燥後の接着剤組成物の、単位面積当たりの重量は、例えば２ｇ／ｍ２以上且つ５ｇ／ｍ２以下とすることが好ましく、３ｇ／ｍ２以上且つ４ｇ／ｍ２以下である。また、接着剤層４５の厚みは、２μｍ以上且つ５μｍ以下とすることが好ましく、３μｍ以上且つ４μｍ以下とすることがより好ましい。 The adhesive layer 45 is formed by applying the adhesive composition to the first film 40 or the sealant film 70, and then drying the adhesive composition, and reacting with the main agent and the solvent in the adhesive composition. It is formed by curing the agent composition. In this embodiment, the adhesive composition after drying, the weight per unit area, for example, preferably to 2 g / m 2 or more and a 5 g / m 2 or less, 3 g / m 2 or more and 4g / m 2 It is as follows. Further, the thickness of the adhesive layer 45 is preferably 2 μm or more and 5 μm or less, and more preferably 3 μm or more and 4 μm or less.
　下部フィルムの層構成
　次に、下部フィルム１６の層構成について説明する。 Next, the layer structure of the lower film 16 will be described.
　表面フィルム１４の内面及び裏面フィルム１５の内面と接合可能な内面を有する限りにおいて、下部フィルム１６の層構成は任意である。例えば、表面フィルム１４及び裏面フィルム１５と同様に、下部フィルム１６として上述の積層体３０を用いてもよい。若しくは、内面がシーラント層によって構成され、且つ積層体３０とは異なる構成のフィルムを、下部フィルム１６として用いてもよい。 The layer structure of the lower film 16 is arbitrary as long as it has an inner surface that can be joined to the inner surface of the front film 14 and the inner surface of the back film 15. For example, similar to the front film 14 and the back film 15, the above-described laminate 30 may be used as the lower film 16. Alternatively, a film having an inner surface constituted by a sealant layer and a configuration different from that of the laminate 30 may be used as the lower film 16.
　第１フィルムの製造方法
　次に、第１フィルム４０の製造方法の一例について説明する。 Method for Manufacturing First Film Next, an example of a method for manufacturing the first film 40 will be described.
　まず、主成分としてＰＢＴを含む樹脂材料を準備する。続いて、キャスト法やチューブラー法などの溶融押出法で樹脂材料を押し出すことにより、フィルム状の基材４１を作製する。続いて、アルミニウム酸化物などの無機材料をフィルム状の基材４１に蒸着させて、透明蒸着層３６を形成してもよい。続いて、透明蒸着層３６上に透明ガスバリア性組成物を塗布して、透明ガスバリア性塗布膜３７を形成してもよい。その後、基材４１上又は透明ガスバリア性塗布膜３７上に印刷層４２を形成する。このようにして、基材４１と、印刷層４２とを備える第１フィルム４０、あるいは、基材４１と、透明蒸着層３６及び透明ガスバリア性塗布膜３７を含む透明ガスバリア層３５と、印刷層４２とを備える第１フィルム４０を得ることができる。 First, a resin material containing PBT as a main component is prepared. Subsequently, the film-like base material 41 is produced by extruding a resin material by a melt extrusion method such as a cast method or a tubular method. Subsequently, an inorganic material such as aluminum oxide may be vapor-deposited on the film-like base material 41 to form the transparent vapor deposition layer 36. Subsequently, a transparent gas barrier coating composition 37 may be formed by applying a transparent gas barrier composition on the transparent vapor deposition layer 36. Thereafter, the printing layer 42 is formed on the substrate 41 or the transparent gas barrier coating film 37. Thus, the 1st film 40 provided with the base material 41 and the printing layer 42, or the base material 41, the transparent gas barrier layer 35 containing the transparent vapor deposition layer 36 and the transparent gas barrier coating film 37, and the printing layer 42. The 1st film 40 provided with these can be obtained.
　積層体の製造方法
　次に、積層体３０の製造方法の一例について説明する。 Method for producing a laminate Next, an example of a method for producing a laminate 30.
　まず、主剤及び溶剤を含む第１組成物と、硬化剤及び溶剤を含む第２組成物とを混合して接着剤組成物を作製する。続いて、接着剤組成物を第１フィルム４０又はシーラントフィルム７０に塗布する。例えば、第１フィルム４０の印刷層４２上に塗布する。続いて、塗布された接着剤組成物を乾燥させて溶剤を揮発させる。その後、乾燥後の接着剤組成物を介して第１フィルム４０とシーラントフィルム７０とを積層する。続いて、積層体を、例えば２０℃以上の環境下で２４時間以上にわたってエージングする。これにより、接着剤組成物を硬化させて、ポリオールと脂肪族系イソシアネート化合物との硬化物を含む接着剤を得る。このようにして、第１フィルム４０及びシーラントフィルム７０を備える積層体３０を得ることができる。 First, an adhesive composition is prepared by mixing a first composition containing a main agent and a solvent and a second composition containing a curing agent and a solvent. Subsequently, the adhesive composition is applied to the first film 40 or the sealant film 70. For example, it is applied on the printing layer 42 of the first film 40. Subsequently, the applied adhesive composition is dried to volatilize the solvent. Then, the 1st film 40 and the sealant film 70 are laminated | stacked through the adhesive composition after drying. Subsequently, the laminate is aged for 24 hours or more, for example, in an environment of 20 ° C. or higher. Thereby, an adhesive composition is hardened and the adhesive agent containing the hardened | cured material of a polyol and an aliphatic isocyanate compound is obtained. Thus, the laminated body 30 provided with the 1st film 40 and the sealant film 70 can be obtained.
　袋の製造方法
　上述の積層体３０からなる表面フィルム１４及び裏面フィルム１５を準備する。また、表面フィルム１４と裏面フィルム１５との間に、折り返した状態の下部フィルム１６を挿入する。続いて、各フィルムの内面同士をヒートシールして、下部シール部１２ａ、側部シール部１３ａなどのシール部を形成する。また、ヒートシールによって互いに接合されたフィルムを適切な形状に切断して、図１に示す袋１０を得る。続いて、上部１１の開口部１１ｂを介して内容物１８を袋１０に充填する。内容物１８は、例えば、カレー、シチュー、スープ等の、水分を含む調理済食品である。その後、上部１１をヒートシールして上部シール部を形成する。このようにして、内容物１８が収容され封止された袋１０を得ることができる。 Manufacturing method of bag The front film 14 and the back film 15 which consist of the above-mentioned laminated body 30 are prepared. In addition, the lower film 16 in a folded state is inserted between the front film 14 and the back film 15. Subsequently, the inner surfaces of the films are heat-sealed to form seal portions such as the lower seal portion 12a and the side seal portion 13a. Further, the films bonded to each other by heat sealing are cut into an appropriate shape to obtain a bag 10 shown in FIG. Subsequently, the contents 18 are filled into the bag 10 through the opening 11 b of the upper portion 11. The contents 18 are cooked foods containing moisture, such as curry, stew, and soup. Thereafter, the upper part 11 is heat-sealed to form an upper seal part. Thus, the bag 10 in which the contents 18 are accommodated and sealed can be obtained.
　（本実施の形態の効果）
　本実施の形態によれば、表面フィルム１４及び裏面フィルム１５を構成する積層体３０が、ＰＢＴを主成分とする基材４１を含むことにより、下記の効果を奏することができる。
　まず、ＰＢＴは、印刷適性に優れる。このため、ポリエチレンテレフタレートの場合と同様に、ＰＢＴを含む基材４１上に印刷層４２を設けることができる。
　また、ＰＢＴは、耐熱性に優れる。このため、袋１０にボイル処理やレトルト処理を施す際に基材４１が変形したり基材４１の強度が低下したりすることを抑制することができる。
　また、ＰＢＴは、高い強度を有する。このため、袋１０を構成する積層体がナイロンを含む場合と同様に、袋１０に耐突き刺し性を持たせることができる。袋１０を構成する積層体の耐突き刺し性は、１１Ｎ以上であることが好ましく、１３Ｎ以上であることがより好ましく、１５Ｎ以上であることがさらに好ましく、１７Ｎ以上であることが特に好ましい。突き刺し強度の測定方法については、後述する実施例Ａ１において説明する。
　また、ＰＢＴは、ナイロンに比べて水分を吸収しにくいという特性を有する。このため、ＰＢＴを含む基材４１を積層体３０の外面３０ｙに配置した場合であっても、基材４１が水分を吸収して積層体３０のラミネート強度が低下してしまうことを抑制することができる。 (Effect of this embodiment)
According to this Embodiment, when the laminated body 30 which comprises the surface film 14 and the back surface film 15 contains the base material 41 which has PBT as a main component, there can exist the following effect.
First, PBT is excellent in printability. For this reason, the printing layer 42 can be provided on the base material 41 containing PBT similarly to the case of polyethylene terephthalate.
Moreover, PBT is excellent in heat resistance. For this reason, it is possible to prevent the base material 41 from being deformed or the strength of the base material 41 from being lowered when the bag 10 is subjected to boil processing or retort processing.
PBT has high strength. For this reason, the stab resistance can be given to the bag 10 similarly to the case where the laminated body which comprises the bag 10 contains nylon. The puncture resistance of the laminate constituting the bag 10 is preferably 11N or more, more preferably 13N or more, further preferably 15N or more, and particularly preferably 17N or more. A method for measuring the piercing strength will be described in Example A1 described later.
PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 41 containing PBT is arrange | positioned on the outer surface 30y of the laminated body 30, it suppresses that the base material 41 absorbs a water | moisture content and the laminate strength of the laminated body 30 falls. Can do.
　また、本実施の形態において、第１フィルム４０とシーラントフィルム７０とを接合するための接着剤層４５は、従来に比べて多くの硬化剤を含む。例えば、接着剤層４５における、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比が、３．５以上である。このため、硬化剤として脂肪族系イソシアネート化合物を用いる場合であっても、主剤と硬化剤の反応を促進し、第１フィルム４０及びシーラントフィルム７０に対する接着剤層４５の密着性を高めることができる。このことにより、第１フィルム４０とシーラントフィルム７０との間のラミネート強度を高めることができる。また、硬化剤として脂肪族系イソシアネート化合物を用いるので、食品用途で使用できない成分が溶出することを防ぐことができる。 Moreover, in this Embodiment, the adhesive bond layer 45 for joining the 1st film 40 and the sealant film 70 contains many hardening | curing agents compared with the past. For example, the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol in the adhesive layer 45 is 3.5 or more. For this reason, even when an aliphatic isocyanate compound is used as the curing agent, the reaction between the main agent and the curing agent can be promoted, and the adhesion of the adhesive layer 45 to the first film 40 and the sealant film 70 can be enhanced. . Thereby, the laminate strength between the first film 40 and the sealant film 70 can be increased. Moreover, since an aliphatic isocyanate compound is used as a hardening | curing agent, it can prevent that the component which cannot be used for a food use elutes.
　また、本実施の形態によれば、第１フィルム４０とシーラントフィルム７０との間のラミネート強度を高くすることにより、袋１０の引き裂き性を高めることができる。以下、引き裂き性について説明する。 Moreover, according to the present embodiment, the tear strength of the bag 10 can be enhanced by increasing the laminate strength between the first film 40 and the sealant film 70. Hereinafter, the tearability will be described.
　シーラント層７１を含むシーラントフィルム７０は、基材４１を含む第１フィルム４０に比べて引張弾性率が小さく、このため伸びやすい。ところで、第１フィルム４０とシーラントフィルム７０との間のラミネート強度が低い場合、消費者が袋１０を引き裂く際にシーラントフィルム７０が第１フィルム４０から剥離することがある。この場合、消費者が袋１０に加える力が、第１フィルム４０から剥離したシーラントフィルム７０を伸ばす力として主に作用するので、袋１０を引き裂くことが困難になってしまう。 The sealant film 70 including the sealant layer 71 has a smaller tensile elastic modulus than the first film 40 including the base material 41, and thus is easily stretched. By the way, when the laminate strength between the first film 40 and the sealant film 70 is low, the sealant film 70 may peel from the first film 40 when the consumer tears the bag 10. In this case, the force applied to the bag 10 by the consumer mainly acts as a force for stretching the sealant film 70 peeled off from the first film 40, so that it becomes difficult to tear the bag 10.
　ここで本実施の形態においては、第１フィルム４０とシーラントフィルム７０との間のラミネート強度を高くすることにより、消費者が袋１０を引き裂く時にシーラントフィルム７０が第１フィルム４０から剥離することを抑制することができる。このため、消費者が袋１０に加える力が、第１フィルム４０とシーラントフィルム７０とが接合された積層体３０を直線的に引き裂くように作用し、袋１０をスムーズに開封することができる。従って、袋１０を構成する積層体３０が、第１フィルム４０及びシーラントフィルム７０という２つのフィルムで構成されている場合であっても、優れた引き裂き性を実現することができる。 Here, in the present embodiment, by increasing the laminate strength between the first film 40 and the sealant film 70, the sealant film 70 is peeled off from the first film 40 when the consumer tears the bag 10. Can be suppressed. For this reason, the force which a consumer applies to the bag 10 acts so that the laminated body 30 with which the 1st film 40 and the sealant film 70 were joined may be linearly torn, and the bag 10 can be opened smoothly. Therefore, even if the laminated body 30 constituting the bag 10 is composed of two films, the first film 40 and the sealant film 70, excellent tearability can be realized.
　積層体３０の、１５ｍｍ幅におけるラミネート強度は、５Ｎ以上であることが好ましく、６Ｎ以上であることがより好ましい。ラミネート強度の測定方法については、後述する実施例Ａ１において説明する。 The laminate strength of the laminate 30 at a width of 15 mm is preferably 5N or more, and more preferably 6N or more. A method for measuring the laminate strength will be described in Example A1 described later.
　また、本実施の形態において、第１フィルム４０の基材４１は、ＰＢＴを主成分として含んでいる。ＰＢＴは上述のように、耐熱性及び耐突き刺し性を有する。このため、基材４１を、積層体３０の外面３０ｙを構成する層として用いることができる。従って、本実施の形態によれば、第１フィルム４０とシーラントフィルム７０とが積層された２層構成の積層体３０を用いて、引き裂き性、耐熱性、及び耐突き刺し性が求められる袋１０を構成することができる。積層体３０を２層構成にすることにより、３層構成の場合に比べて、積層体３０及び袋１０に要するコスト、工数などを削減することができる。なお、基材４１とシーラント層７１で構成される２層構成の積層体３０においては、基材４１などの一定の硬さを有する層が積層体３０全体に対して占める厚みの比率が、３層構成の積層体（第１の基材／第２の基材／シーラント層）の場合に比べて低くなる。従って、引き裂き性に関して、ラミネート強度という点だけでなく、一定の硬さを有する層の比率という点でも、２層構成の方が３層構成に比べて不利である。これに対して、本実施の形態によれば、上述のように、接着剤層４５における、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比を高めることにより、２層構成であっても優れた引き裂き性を実現することができる。例えば、２層構成の場合、基材４１に対するシーラント層７１の厚み比は、２．５以上１０．０以下である。 Moreover, in this Embodiment, the base material 41 of the 1st film 40 contains PBT as a main component. As described above, PBT has heat resistance and puncture resistance. For this reason, the base material 41 can be used as a layer constituting the outer surface 30y of the laminate 30. Therefore, according to the present embodiment, using the laminate 30 having a two-layer structure in which the first film 40 and the sealant film 70 are laminated, the bag 10 that requires tearing, heat resistance, and puncture resistance is provided. Can be configured. By making the laminated body 30 into a two-layer structure, costs, man-hours, and the like required for the laminated body 30 and the bag 10 can be reduced as compared with the case of a three-layer structure. In the laminate 30 having a two-layer structure composed of the base material 41 and the sealant layer 71, the ratio of the thickness occupied by the layer having a certain hardness, such as the base material 41, to the entire laminate 30 is 3 It becomes lower than the case of a layered structure (first base material / second base material / sealant layer). Therefore, regarding tearability, the two-layer structure is disadvantageous compared to the three-layer structure in terms of not only the laminate strength but also the ratio of layers having a certain hardness. In contrast, according to the present embodiment, as described above, the adhesive layer 45 has a two-layer structure by increasing the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol. Even excellent tearability can be realized. For example, in the case of a two-layer configuration, the thickness ratio of the sealant layer 71 to the base material 41 is 2.5 or more and 10.0 or less.
　また、本実施の形態においては、シーラントフィルム７０のシーラント層７１が、プロピレン・エチレンブロック共重合体を含む。このため、シーラントフィルム７０及びシーラントフィルム７０を備える積層体３０の耐衝撃性を高めることができる。従って、２層構成の積層体３０（基材を１つのみ含む積層体３０）を用いて袋１０を構成する場合であっても、落下等の衝撃によって袋１０が破袋することを抑制することができる。 Further, in the present embodiment, the sealant layer 71 of the sealant film 70 includes a propylene / ethylene block copolymer. For this reason, the impact resistance of the laminate 30 including the sealant film 70 and the sealant film 70 can be enhanced. Therefore, even when the bag 10 is configured using the laminate 30 having a two-layer structure (a laminate 30 including only one base material), the bag 10 is prevented from being broken by an impact such as dropping. be able to.
　積層体３０の衝撃強度は、８００ｋＪ／ｍ以上であることが好ましく、９００ｋＪ／ｍ以上であることがより好ましく、１０００ｋＪ／ｍ以上であることが更に好ましく、１１００ｋＪ／ｍ以上であることが特に好ましい。衝撃強度の測定方法については、後述する実施例Ａ１において説明する。 The impact strength of the laminate 30 is preferably 800 kJ / m or more, more preferably 900 kJ / m or more, still more preferably 1000 kJ / m or more, and particularly preferably 1100 kJ / m or more. . A method for measuring the impact strength will be described in Example A1 described later.
　なお、上述した実施の形態に対して様々な変更を加えることが可能である。以下、必要に応じて図面を参照しながら、変形例について説明する。以下の説明および以下の説明で用いる図面では、上述した実施の形態と同様に構成され得る部分について、上述の実施の形態における対応する部分に対して用いた符号と同一の符号を用いることとし、重複する説明を省略する。また、上述した実施の形態において得られる作用効果が変形例においても得られることが明らかである場合、その説明を省略することもある。 Note that various modifications can be made to the above-described embodiment. Hereinafter, modified examples will be described with reference to the drawings as necessary. In the following description and the drawings used in the following description, the same reference numerals as those used for the corresponding parts in the above embodiment are used for the parts that can be configured in the same manner as in the above embodiment. A duplicate description is omitted. In addition, when it is clear that the operational effects obtained in the above-described embodiment can be obtained in the modified example, the description thereof may be omitted.
　（層構成の変形例）
　上述の本実施の形態においては、袋１０を構成する積層体３０の第１フィルム４０が、基材４１に加えて印刷層４２を有する例を示した。しかしながら、これに限られることはなく、第１フィルム４０は、印刷層４２を有していなくてもよい。従って、積層体３０の層構成として、外面側から内面側へ順に下記のような配列も可能である。
　　基材／接着剤層／シーラント層
　　基材／透明ガスバリア層／接着剤層／シーラント層 (Modification of layer structure)
In the above-described embodiment, the example in which the first film 40 of the laminate 30 constituting the bag 10 includes the printing layer 42 in addition to the base material 41 has been described. However, the present invention is not limited to this, and the first film 40 may not have the printing layer 42. Therefore, the following arrangement is possible in order from the outer surface side to the inner surface side as the layer configuration of the laminate 30.
Base material / adhesive layer / sealant layer Base material / transparent gas barrier layer / adhesive layer / sealant layer
　（ヒドロキシ基に対するイソシアネート基のモル比の変形例）
　上述の本実施の形態においては、接着剤層４５を構成するポリオール及び脂肪族イソシアネート化合物において、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比が３．５以上である例を示した。しかしながら、後述する実施例によって支持されるように、ヒドロキシ基に対するイソシアネート基のモル比を３．５以上にすることは、積層体３０の衝撃強度を８００ｋＪ／ｍ以上にする上での必須条件ではない。例えば、後述する実施例に示すように、プロピレン・エチレンブロック共重合体を含むシーラント層７１を用いることにより、ヒドロキシ基に対するイソシアネート基のモル比が３．５未満の場合であっても、積層体３０の衝撃強度を８００ｋＪ／ｍ以上に高めることができる。 (Modification of molar ratio of isocyanate group to hydroxy group)
In the present embodiment described above, in the polyol and the aliphatic isocyanate compound constituting the adhesive layer 45, an example in which the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol is 3.5 or more is shown. It was. However, as supported by the examples described later, setting the molar ratio of isocyanate groups to hydroxy groups to 3.5 or more is an essential condition for increasing the impact strength of the laminate 30 to 800 kJ / m or more. Absent. For example, as shown in the examples described later, by using a sealant layer 71 containing a propylene / ethylene block copolymer, even if the molar ratio of isocyanate groups to hydroxy groups is less than 3.5, the laminate The impact strength of 30 can be increased to 800 kJ / m or more.
　（シーラント層の変形例）
　上述の本実施の形態においては、積層体３０のシーラント層７１がプロピレン・エチレンブロック共重合体を含む例を示した。しかしながら、後述する実施例によって支持されるように、シーラント層７１の材料としてプロピレン・エチレンブロック共重合体を用いることは、積層体３０のラミネート強度を５Ｎ以上にする上での必須条件ではない。 (Modification of sealant layer)
In the above-described embodiment, an example in which the sealant layer 71 of the laminate 30 includes a propylene / ethylene block copolymer has been described. However, as supported by the examples described later, the use of a propylene / ethylene block copolymer as the material of the sealant layer 71 is not an essential condition for increasing the laminate strength of the laminate 30 to 5 N or more.
　第２の実施の形態
　次に、本発明の第２の実施の形態について説明する。本実施の形態においては、積層体３０の基材４１とシーラント層７１との間に金属箔４７が存在する例について説明する。本実施の形態において、第１の実施の形態と同一部分には同一符号を付して詳細な説明は省略する。また、第１の実施の形態において得られる作用効果が本実施の形態においても得られることが明らかである場合、その説明を省略することもある。 Second Embodiment Next, a second embodiment of the present invention will be described. In the present embodiment, an example in which a metal foil 47 exists between the base material 41 and the sealant layer 71 of the laminate 30 will be described. In the present embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Moreover, when it is clear that the effect obtained in the first embodiment can be obtained in the present embodiment, the description thereof may be omitted.
　まず、本実施の形態が解決しようとする課題について説明する。袋を構成するための積層体には、先端が尖った鋭利な部材が袋に接触した場合にも袋が破けてしまうことを抑制する特性、いわゆる耐突き刺し性が求められる。従来は、例えば特開２０１２－２２３９９２号公報に記載の積層体においては、蒸着フィルムに含まれるナイロンなどのポリアミド樹脂によって、耐突き刺し性が確保されている。一方、ナイロンは、水分を吸収し易く、且つ耐熱性に乏しい。特許文献１に記載の積層体においては、ナイロンの外面側に存在するポリエステル樹脂が、積層体の耐熱性に寄与していると考えられる。 First, problems to be solved by this embodiment will be described. The laminate for constituting the bag is required to have a characteristic that prevents the bag from being broken even when a sharp member with a sharp tip contacts the bag, so-called stab resistance. Conventionally, for example, in a laminate described in JP 2012-2231992 A, puncture resistance is ensured by a polyamide resin such as nylon contained in a deposited film. On the other hand, nylon is easy to absorb moisture and has poor heat resistance. In the laminated body of patent document 1, it is thought that the polyester resin which exists in the outer surface side of nylon has contributed to the heat resistance of a laminated body.
　ところで、樹脂材料の寸法は、大気中の水蒸気などの水分を吸収すること、すなわち吸湿によって変化することがある。また、吸湿の程度は、樹脂材料によって異なる。例えば、ポリアミド樹脂の寸法は、ポリエステル樹脂の寸法に比べて、吸湿によって変化し易い。このため、特開２０１２－２２３９９２号公報のようにポリエステル樹脂及びポリアミド樹脂の共押出し延伸フィルムを用いる場合、吸湿性の相違に基づいて、ポリアミド樹脂の寸法が相対的に大きく変化し、この結果、共押出し延伸フィルムに反りが生じてしまうことがある。この場合、共押出し延伸フィルムを搬送する際や、共押出し延伸フィルムとその他のフィルムとを積層させるラミネート工程の際に、反りを抑制したり解消させたりするための追加の設備や工程が必要になり、積層体の製造コストが増加してしまう。本実施の形態は、このような課題を効果的に解決し得る積層体を提供することを目的とする。 Incidentally, the dimensions of the resin material may change due to absorption of moisture such as water vapor in the atmosphere, that is, moisture absorption. Further, the degree of moisture absorption varies depending on the resin material. For example, the dimensions of the polyamide resin are more likely to change due to moisture absorption than the dimensions of the polyester resin. For this reason, when using a coextruded stretched film of a polyester resin and a polyamide resin as in JP 2012-2231992 A, the dimensions of the polyamide resin change relatively greatly based on the difference in hygroscopicity. Warpage may occur in the coextruded stretched film. In this case, when transporting the co-extrusion stretched film, or during the laminating process of laminating the co-extrusion stretched film and other films, additional equipment and processes for suppressing or eliminating the warp are required. As a result, the manufacturing cost of the laminate increases. The purpose of this embodiment is to provide a laminate that can effectively solve such problems.
　続いて、本実施の形態に係る積層体３０について説明する。図５は、本実施の形態における積層体３０の層構成の一例を示す断面図である。図５に示すように、積層体３０は、第１フィルム４０、金属箔４７及びシーラントフィルム７０をこの順で少なくとも含む。金属箔４７は、第１接着剤層４６を介して第１フィルム４０に接合されており、また、第２接着剤層４８を介してシーラントフィルム７０に接合されている。 Subsequently, the laminate 30 according to the present embodiment will be described. FIG. 5 is a cross-sectional view illustrating an example of the layer configuration of the stacked body 30 in the present embodiment. As shown in FIG. 5, the laminate 30 includes at least a first film 40, a metal foil 47, and a sealant film 70 in this order. The metal foil 47 is bonded to the first film 40 via the first adhesive layer 46, and is bonded to the sealant film 70 via the second adhesive layer 48.
　上述の第１の実施の形態の場合と同様に、第１フィルム４０は基材４１を含み、シーラントフィルム７０はシーラント層７１を含む。第１フィルム４０は、基材４１の内面３０ｘ側に設けられた印刷層４２を更に含んでいてもよい。従って、本実施の形態による積層体３０は、外面側から内面側へ順に
　　基材／第１接着剤層／金属箔／第２接着剤層／シーラント層、又は、
　　基材／印刷層／第１接着剤層／金属箔／第２接着剤層／シーラント層、
を備えている、と言える。なお、「／」は層と層の境界を表している。 As in the case of the first embodiment described above, the first film 40 includes the base material 41, and the sealant film 70 includes the sealant layer 71. The first film 40 may further include a printing layer 42 provided on the inner surface 30 x side of the base material 41. Therefore, the laminate 30 according to the present embodiment is, in order from the outer surface side to the inner surface side, base material / first adhesive layer / metal foil / second adhesive layer / sealant layer, or
Substrate / printing layer / first adhesive layer / metal foil / second adhesive layer / sealant layer,
It can be said that it has. Note that “/” represents a boundary between layers.
　以下、第１フィルム４０、第１接着剤層４６、金属箔４７、第２接着剤層４８及びシーラントフィルム７０についてそれぞれ詳細に説明する。 Hereinafter, each of the first film 40, the first adhesive layer 46, the metal foil 47, the second adhesive layer 48, and the sealant film 70 will be described in detail.
　（第１フィルム）
　第１フィルム４０の基材４１は、上述の第１の実施の形態と同様に、主成分としてポリブチレンテレフタレートを含む。例えば、第１基材５１は、５１質量％以上のＰＢＴを含む。ＰＢＴを含む第１基材５１の構成としては、上述の第１の実施の形態における基材４１に関して説明した第１の構成又は第２の構成のいずれを採用してもよい。 (First film)
The substrate 41 of the first film 40 includes polybutylene terephthalate as a main component, as in the first embodiment described above. For example, the 1st base material 51 contains 51 mass% or more PBT. As the configuration of the first base material 51 including PBT, any of the first configuration and the second configuration described with respect to the base material 41 in the first embodiment described above may be adopted.
　（第１接着剤層）
　第１接着剤層４６は、第１フィルム５０と金属箔４７とを接着するための第１接着剤を含む。第１接着剤の例としては、上述の第１の実施の形態における接着剤層４５の場合と同様に、エーテル系の二液反応型接着剤、エステル系の二液反応型接着剤などを挙げることができる。 (First adhesive layer)
The first adhesive layer 46 includes a first adhesive for bonding the first film 50 and the metal foil 47. Examples of the first adhesive include an ether-based two-component reactive adhesive, an ester-based two-component reactive adhesive, and the like, as in the case of the adhesive layer 45 in the first embodiment described above. be able to.
　好ましくは、第１接着剤層４６を構成する第１接着剤として、主剤としてのポリオールと、硬化剤としての芳香族系イソシアネート化合物とが反応することにより生成される硬化物を用いる。硬化剤として芳香族系イソシアネート化合物を用いることにより、第１フィルム４０と金属箔４７との間のラミネート強度をより高めることができる。なお、ポリオールとしては、ポリエーテルポリオールやポリエステルポリオールを用いることができるが、ポリエステルポリオールを用いることが好ましい。 Preferably, as the first adhesive constituting the first adhesive layer 46, a cured product generated by a reaction between a polyol as a main agent and an aromatic isocyanate compound as a curing agent is used. By using an aromatic isocyanate compound as a curing agent, the laminate strength between the first film 40 and the metal foil 47 can be further increased. In addition, although polyether polyol and polyester polyol can be used as polyol, it is preferable to use polyester polyol.
　第１接着剤層４６を構成する第１接着剤における、ポリオールのヒドロキシ基に対する芳香族系イソシアネート化合物のイソシアネート基のモル比は、例えば１～５の範囲内である。 The molar ratio of the isocyanate group of the aromatic isocyanate compound to the hydroxyl group of the polyol in the first adhesive constituting the first adhesive layer 46 is in the range of 1 to 5, for example.
　（金属箔）
　金属箔４７は、水蒸気や酸素に対するバリア性を高めるため、第１フィルム４０とシーラントフィルム７０との間に設けられている。金属箔４７を構成する金属材料は、例えばアルミニウムなどである。金属箔４７の厚みは、例えば５μｍ以上且つ１５μｍ以下である。 (Metal foil)
The metal foil 47 is provided between the first film 40 and the sealant film 70 in order to improve the barrier property against water vapor and oxygen. The metal material constituting the metal foil 47 is, for example, aluminum. The thickness of the metal foil 47 is, for example, not less than 5 μm and not more than 15 μm.
　（第２接着剤層）
　第２接着剤層４８は、金属箔４７とシーラントフィルム７０とを接着するための第２接着剤を含む。第２接着剤の例としては、エーテル系の二液反応型接着剤を挙げることができる。エーテル系の二液反応型接着剤としては、第１接着剤の場合と同様に、ポリウレタンなどを挙げることができる。ポリウレタンは、主剤としてのポリオールと、硬化剤としてのイソシアネート化合物とが反応することにより生成される硬化物である。なお、ポリオールとしては、ポリエーテルポリオールやポリエステルポリオールを用いることができるが、ポリエステルポリオールを用いることが好ましい。 (Second adhesive layer)
The second adhesive layer 48 includes a second adhesive for bonding the metal foil 47 and the sealant film 70. Examples of the second adhesive include ether-based two-component reaction type adhesives. Examples of the ether-based two-component reaction type adhesive include polyurethane as in the case of the first adhesive. Polyurethane is a cured product produced by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent. In addition, although polyether polyol and polyester polyol can be used as polyol, it is preferable to use polyester polyol.
　イソシアネート化合物としては、上述のように、芳香族系イソシアネート化合物及び脂肪族系イソシアネート化合物が存在する。このうち芳香族系イソシアネート化合物は、加熱殺菌などの高温環境下において、食品用途で使用できない成分が溶出する。ところで、第２接着剤層４８は、図５に示すように、金属箔４７よりも内面３０ｘ側に位置する。このため、第２接着剤層４８が芳香族系イソシアネート化合物を含む場合、芳香族系イソシアネート化合物から溶出された成分が、積層体３０によって構成された袋１０の内容物に付着することがある。 As described above, aromatic isocyanate compounds and aliphatic isocyanate compounds exist as isocyanate compounds. Among these, aromatic isocyanate compounds elute components that cannot be used in food applications under high-temperature environments such as heat sterilization. By the way, the 2nd adhesive bond layer 48 is located in the inner surface 30x side rather than the metal foil 47, as shown in FIG. For this reason, when the 2nd adhesive bond layer 48 contains an aromatic isocyanate compound, the component eluted from the aromatic isocyanate compound may adhere to the content of the bag 10 comprised by the laminated body 30. FIG.
　このような課題を考慮し、第２接着剤層４８を構成する第２接着剤として、主剤としてのポリオールと、硬化剤としての脂肪族系イソシアネート化合物とが反応することにより生成される硬化物を用いることを提案する。これにより、第２接着剤層４８に起因する食品用途で使用できない成分が内容物に付着することを防止することができる。 In consideration of such problems, as a second adhesive constituting the second adhesive layer 48, a cured product produced by a reaction between a polyol as a main agent and an aliphatic isocyanate compound as a curing agent is used. Suggest to use. Thereby, it can prevent that the component which cannot be used for the food use resulting from the 2nd adhesive bond layer 48 adheres to the content.
　第２接着剤層４８を構成する第２接着剤における、ポリエーテルポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は、例えば１～５の範囲内である。 The molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxy group of the polyether polyol in the second adhesive constituting the second adhesive layer 48 is in the range of 1 to 5, for example.
　（シーラントフィルム）
　シーラントフィルム７０は、積層体３０の内面３０ｘを構成するシーラント層７１を少なくとも含む。シーラント層７１を構成する材料としては、上述の第１の実施の形態の場合と同様に、低密度ポリエチレン、直鎖状低密度ポリエチレンなどのポリエチレン、ポリプロピレンから選択される１種または２種以上の樹脂を用いることができる。 (Sealant film)
The sealant film 70 includes at least a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30. As the material constituting the sealant layer 71, as in the case of the first embodiment described above, one or two or more selected from polyethylene such as low density polyethylene and linear low density polyethylene, and polypropylene are used. Resin can be used.
　積層体の製造方法
　次に、積層体３０の製造方法の一例について説明する。 Method for producing a laminate Next, an example of a method for producing a laminate 30.
　まず、上述の第１フィルム４０及び金属箔４７を準備する。続いて、ドライラミネート法により、第１フィルム４０と金属箔４７とを、第１接着剤層４６を介して積層する。その後、ドライラミネート法により、第１フィルム４０及び金属箔４７を含む積層体と、シーラントフィルム７０とを、第２接着剤層４８を介して積層する。これによって、第１フィルム４０、金属箔４７及びシーラントフィルム７０を備える積層体３０を得ることができる。 First, the first film 40 and the metal foil 47 described above are prepared. Subsequently, the first film 40 and the metal foil 47 are laminated via the first adhesive layer 46 by a dry laminating method. Thereafter, the laminate including the first film 40 and the metal foil 47 and the sealant film 70 are laminated via the second adhesive layer 48 by a dry laminating method. Thereby, the laminated body 30 provided with the 1st film 40, the metal foil 47, and the sealant film 70 can be obtained.
　若しくは、まず金属箔４７とシーラントフィルム７０とを第２接着剤層４８を介して積層し、その後、第１フィルム４０と、金属箔４７及びシーラントフィルム７０を含む積層体とを第１接着剤層４６を介して積層することにより、積層体３０を製造してもよい。 Alternatively, the metal foil 47 and the sealant film 70 are first laminated via the second adhesive layer 48, and then the first film 40 and the laminate including the metal foil 47 and the sealant film 70 are laminated to the first adhesive layer. The stacked body 30 may be manufactured by stacking via 46.
　本実施の形態によれば、第１フィルム４０の基材４１は、主成分としてＰＢＴを含む。第１の構成に係る基材４１において、各層４１ａの組成は同一であるため、基材４１を含む第１フィルム４０に反りが生じることを抑制することができる。また、第２の構成に係る基材４１において、組成は同一であるため、例えば基材４１はＰＢＴ及び添加剤のみで構成される単層のフィルムであるため、基材４１を含む第１フィルム４０に反りが生じることを抑制することができる。このことにより、積層体３０を効率良く製造することができる。 According to the present embodiment, the base material 41 of the first film 40 includes PBT as a main component. In the base material 41 which concerns on a 1st structure, since the composition of each layer 41a is the same, it can suppress that the 1st film 40 containing the base material 41 warp. Moreover, since the composition is the same in the base material 41 which concerns on a 2nd structure, for example, since the base material 41 is a single layer film comprised only by PBT and an additive, the 1st film containing the base material 41 40 can be prevented from warping. Thereby, the laminated body 30 can be manufactured efficiently.
　以下、本実施の形態に係る積層体３０が奏する効果について説明する。 Hereinafter, effects produced by the laminate 30 according to the present embodiment will be described.
　本実施の形態においては、袋１０の表面フィルム１４及び裏面フィルム１５を構成する積層体３０が、ＰＢＴを主成分とする基材４１を含むことにより、下記の効果を奏することができる。
　まず、ＰＢＴは、印刷適性に優れる。このため、ポリエチレンテレフタレートの場合と同様に、ＰＢＴを含む基材４１上に印刷層４２を設けることができる。
　また、ＰＢＴは、耐熱性に優れる。このため、袋１０にボイル処理やレトルト処理を施す際に基材４１が変形したり基材４１の強度が低下したりすることを抑制することができる。
　また、ＰＢＴは、高い強度を有する。このため、袋１０を構成する積層体がナイロンを含む場合と同様に、積層体３０及び袋１０の突き刺し強度を高めることができる。積層体３０の突き刺し強度は、１３Ｎ以上であることが好ましく、１５Ｎ以上であることがより好ましく、１７Ｎ以上であることがさらに好ましい。
　また、ＰＢＴは、ナイロンに比べて水分を吸収しにくいという特性を有する。このため、ＰＢＴを含む基材４１を積層体３０の外面３０ｙに配置した場合であっても、基材４１が水分を吸収して積層体３０のラミネート強度が低下してしまうことを抑制することができる。 In this Embodiment, when the laminated body 30 which comprises the surface film 14 and the back surface film 15 of the bag 10 contains the base material 41 which has PBT as a main component, there can exist the following effect.
First, PBT is excellent in printability. For this reason, the printing layer 42 can be provided on the base material 41 containing PBT similarly to the case of polyethylene terephthalate.
Moreover, PBT is excellent in heat resistance. For this reason, it is possible to prevent the base material 41 from being deformed or the strength of the base material 41 from being lowered when the bag 10 is subjected to boil processing or retort processing.
PBT has high strength. For this reason, the puncture strength of the laminated body 30 and the bag 10 can be increased similarly to the case where the laminated body constituting the bag 10 includes nylon. The puncture strength of the laminate 30 is preferably 13N or more, more preferably 15N or more, and further preferably 17N or more.
PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 41 containing PBT is arrange | positioned on the outer surface 30y of the laminated body 30, it suppresses that the base material 41 absorbs a water | moisture content and the laminate strength of the laminated body 30 falls. Can do.
　また、本実施の形態によれば、袋１０の表面フィルム１４及び裏面フィルム１５を構成する積層体３０が、金属箔４７を含む。このため、袋１０の外部の水蒸気や酸素が袋１０の内部に透過することを抑制することができるので、内容物が劣化することを抑制することができる。 Further, according to the present embodiment, the laminate 30 constituting the front film 14 and the back film 15 of the bag 10 includes the metal foil 47. For this reason, since it can suppress that the water vapor | steam and oxygen of the exterior of the bag 10 permeate | transmit the inside of the bag 10, it can suppress that a content deteriorates.
　また、本実施の形態によれば、袋１０の表面フィルム１４及び裏面フィルム１５を構成する積層体３０のシーラント層７１が、プロピレン・エチレンブロック共重合体を含む。このため、袋１０の耐衝撃性や耐突き刺し性を高めることができる。 Moreover, according to this Embodiment, the sealant layer 71 of the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains a propylene-ethylene block copolymer. For this reason, the impact resistance and puncture resistance of the bag 10 can be enhanced.
　第３の実施の形態
　次に、本発明の第３の実施の形態について説明する。上述の第１の実施の形態においては、積層体の基材を構成するプラスチックフィルムが１つのみである例を示した。本実施の形態においては、積層体の基材を構成するプラスチックフィルムが２つ存在する例について説明する。本実施の形態において、第１の実施の形態と同一部分には同一符号を付して詳細な説明は省略する。また、第１の実施の形態において得られる作用効果が本実施の形態においても得られることが明らかである場合、その説明を省略することもある。 Third Embodiment Next, a third embodiment of the present invention will be described. In the above-described first embodiment, an example in which there is only one plastic film constituting the base material of the laminated body has been shown. In the present embodiment, an example in which two plastic films constituting the base material of the laminate are present will be described. In the present embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Moreover, when it is clear that the effect obtained in the first embodiment can be obtained in the present embodiment, the description thereof may be omitted.
　まず、本実施の形態が解決しようとする課題について説明する。従来から、耐突き刺し性などの積層体の強度を高めるために、２つのプラスチックフィルムを用いて積層体を構成することが知られている。例えば、従来の積層体は、ＰＥＴフィルム、ナイロンフィルム及びシーラントフィルムを備える。ナイロンは、高い強度を有する一方で、水分を吸収し易いという特性を有するので、ナイロンフィルムは、ＰＥＴフィルムとシーラントフィルムとの間に配置される。しかしながら、この場合、ナイロンが袋の内容物によって着色されやすいので、袋の外観が損なわれてしまうことがある。本実施の形態は、このような課題を効果的に解決し得る積層体を提供することを目的とする。 First, problems to be solved by this embodiment will be described. Conventionally, in order to increase the strength of a laminated body such as puncture resistance, it is known to form a laminated body using two plastic films. For example, a conventional laminate includes a PET film, a nylon film, and a sealant film. Nylon has the property of being easy to absorb moisture while having high strength, so the nylon film is disposed between the PET film and the sealant film. However, in this case, since the nylon is easily colored by the contents of the bag, the appearance of the bag may be impaired. The purpose of this embodiment is to provide a laminate that can effectively solve such problems.
　続いて、本実施の形態に係る積層体３０について説明する。図６は、第３の実施の形態における積層体３０の層構成の一例を示す断面図である。図６に示すように、積層体３０は、第１フィルム５０、第２フィルム６０及びシーラントフィルム７０をこの順で少なくとも含む。第１フィルム５０は、外面３０ｙ側に位置しており、シーラントフィルム７０は、外面３０ｙの反対側の内面３０ｘ側に位置している。 Subsequently, the laminate 30 according to the present embodiment will be described. FIG. 6 is a cross-sectional view illustrating an example of a layer configuration of the stacked body 30 according to the third embodiment. As shown in FIG. 6, the laminate 30 includes at least a first film 50, a second film 60, and a sealant film 70 in this order. The first film 50 is located on the outer surface 30y side, and the sealant film 70 is located on the inner surface 30x side opposite to the outer surface 30y.
　第１フィルム５０は、第１基材５１を少なくとも含む。第２フィルム６０は、第２基材６１を少なくとも含む。シーラントフィルム７０は、シーラント層７１を少なくとも含む。また、第１フィルム５０と第２フィルム６０とは第１接着剤層５５によって接合されており、第２フィルム６０とシーラントフィルム７０とは第２接着剤層６５によって接合されている。従って、本実施の形態による積層体３０は、外面側から内面側へ順に
　　第１基材／第１接着剤層／第２基材／第２接着剤層／シーラント層
を備えている、と言える。なお、「／」は層と層の境界を表している。図示はしないが、第１基材５１と第２基材６１との間において印刷層が第１基材５１又は第２基材６１に設けられていてもよい。 The first film 50 includes at least a first base material 51. The second film 60 includes at least a second base material 61. The sealant film 70 includes at least a sealant layer 71. The first film 50 and the second film 60 are joined by a first adhesive layer 55, and the second film 60 and the sealant film 70 are joined by a second adhesive layer 65. Therefore, it can be said that the laminate 30 according to the present embodiment includes the first base material / first adhesive layer / second base material / second adhesive layer / sealant layer in order from the outer surface side to the inner surface side. . Note that “/” represents a boundary between layers. Although not shown, a printing layer may be provided on the first base material 51 or the second base material 61 between the first base material 51 and the second base material 61.
　以下、第１フィルム５０、第１接着剤層５５、第２フィルム６０、第２接着剤層６５及びシーラントフィルム７０についてそれぞれ詳細に説明する。 Hereinafter, each of the first film 50, the first adhesive layer 55, the second film 60, the second adhesive layer 65, and the sealant film 70 will be described in detail.
　（第１フィルム）
　第１フィルム５０の第１基材５１は、積層体３０の外面３０ｙを構成する第１基材５１を含む。第１基材５１は、上述の第１の実施の形態における基材４１と同様に、主成分としてポリブチレンテレフタレートを含む。例えば、第１基材５１は、５１質量％以上のＰＢＴを含む。ＰＢＴを含む第１基材５１の構成としては、上述の第１の実施の形態における基材４１に関して説明した第１の構成又は第２の構成のいずれを採用してもよい。 (First film)
The first substrate 51 of the first film 50 includes the first substrate 51 that constitutes the outer surface 30 y of the laminate 30. The 1st base material 51 contains polybutylene terephthalate as a main ingredient like base material 41 in the above-mentioned 1st embodiment. For example, the 1st base material 51 contains 51 mass% or more PBT. As the configuration of the first base material 51 including PBT, any of the first configuration and the second configuration described with respect to the base material 41 in the first embodiment described above may be adopted.
　（第１接着剤層）
　第１接着剤層５５は、第１フィルム５０と第２フィルム６０とを接着するための第１接着剤を含む。第１接着剤の例としては、上述の第１の実施の形態における接着剤層４５の場合と同様に、エーテル系の二液反応型接着剤、エステル系の二液反応型接着剤などを挙げることができる。 (First adhesive layer)
The first adhesive layer 55 includes a first adhesive for bonding the first film 50 and the second film 60. Examples of the first adhesive include an ether-based two-component reactive adhesive, an ester-based two-component reactive adhesive, and the like, as in the case of the adhesive layer 45 in the first embodiment described above. be able to.
　（第２フィルム）
　第２フィルム６０は、第２基材６１を少なくとも含む。第２基材６１は、主成分としてＰＥＴを含む。例えば、第２基材６１は、５１質量％以上のＰＥＴを含む。第２基材６１がＰＥＴを含むことにより、第２基材６１が耐熱性を有することができる。例えば、第２基材６１がナイロンを含む場合に比べて、第２基材６１の融点が高くなり、また、第２基材６１の吸湿性が低くなる。これにより、袋１０を加熱するとき、過熱された水などに起因して第２基材６１に穴が開いてしまうことを抑制することができる。また、ＰＥＴの耐熱性は、ＰＢＴの耐熱性よりも高い。このため、本実施の形態によれば、第２基材６１がＰＢＴからなる場合に比べても、積層体３０の耐熱性を高めることができる。これにより、例えば、袋１０を電子レンジで加熱して内容物の温度が高くなった時に積層体３０がダメージを受けて積層体３０の性能が低下することを抑制することができる。 (Second film)
The second film 60 includes at least a second base material 61. The 2nd base material 61 contains PET as a main component. For example, the 2nd base material 61 contains 51 mass% or more of PET. The 2nd base material 61 can have heat resistance because the 2nd base material 61 contains PET. For example, compared with the case where the 2nd base material 61 contains nylon, melting | fusing point of the 2nd base material 61 becomes high, and the hygroscopic property of the 2nd base material 61 becomes low. Thereby, when heating the bag 10, it can suppress that a hole opens in the 2nd base material 61 resulting from the overheated water. Moreover, the heat resistance of PET is higher than the heat resistance of PBT. For this reason, according to this Embodiment, compared with the case where the 2nd base material 61 consists of PBT, the heat resistance of the laminated body 30 can be improved. Thereby, for example, when the bag 10 is heated with a microwave oven and the temperature of the contents becomes high, it is possible to prevent the laminated body 30 from being damaged and the performance of the laminated body 30 from being deteriorated.
　第２基材６１の厚みは、好ましくは９μｍ以上であり、より好ましくは１２μｍ以上である。また、第２基材６１の厚みは、好ましくは２５μｍ以下であり、より好ましくは２０μｍ以下である。第２基材６１の厚みを９μｍ以上にすることにより、第２基材６１が十分な強度を有するようになる。また、第２基材６１の厚みを２５μｍ以下にすることにより、第２基材６１が優れた成形性を示すようになる。このため、積層体３０を加工して袋１０を製造する工程を効率的に実施することができる。 The thickness of the second substrate 61 is preferably 9 μm or more, more preferably 12 μm or more. Moreover, the thickness of the 2nd base material 61 becomes like this. Preferably it is 25 micrometers or less, More preferably, it is 20 micrometers or less. By setting the thickness of the second substrate 61 to 9 μm or more, the second substrate 61 has sufficient strength. Moreover, the 2nd base material 61 comes to show the outstanding moldability by the thickness of the 2nd base material 61 being 25 micrometers or less. For this reason, the process which processes the laminated body 30 and manufactures the bag 10 can be implemented efficiently.
　（第２接着剤層）
　第２接着剤層６５は、第２フィルム６０とシーラントフィルム７０とを接着するための第２接着剤を含む。第２接着剤の例としては、エーテル系の二液反応型接着剤を挙げることができる。エーテル系の二液反応型接着剤としては、第１接着剤の場合と同様に、ポリウレタンなどを挙げることができる。ポリウレタンは、主剤としてのポリオールと、硬化剤としてのイソシアネート化合物とが反応することにより生成される硬化物である。なお、ポリオールとしては、ポリエーテルポリオールやポリエステルポリオールを用いることができるが、ポリエステルポリオールを用いることが好ましい。 (Second adhesive layer)
The second adhesive layer 65 includes a second adhesive for bonding the second film 60 and the sealant film 70. Examples of the second adhesive include ether-based two-component reaction type adhesives. Examples of the ether-based two-component reaction type adhesive include polyurethane as in the case of the first adhesive. Polyurethane is a cured product produced by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent. In addition, although polyether polyol and polyester polyol can be used as polyol, it is preferable to use polyester polyol.
　イソシアネート化合物としては、上述のように、芳香族系イソシアネート化合物及び脂肪族系イソシアネート化合物が存在する。このうち芳香族系イソシアネート化合物は、加熱殺菌などの高温環境下において、食品用途で使用できない成分が溶出する。ところで、第２接着剤層６５は、図６に示すように、シーラントフィルム７０に接している。このため、第２接着剤層６５が芳香族系イソシアネート化合物を含む場合、芳香族系イソシアネート化合物から溶出された成分が、積層体３０によって構成された袋１０の内容物に付着することがある。 As described above, aromatic isocyanate compounds and aliphatic isocyanate compounds exist as isocyanate compounds. Among these, aromatic isocyanate compounds elute components that cannot be used in food applications under high-temperature environments such as heat sterilization. Incidentally, the second adhesive layer 65 is in contact with the sealant film 70 as shown in FIG. For this reason, when the 2nd adhesive bond layer 65 contains an aromatic isocyanate compound, the component eluted from the aromatic isocyanate compound may adhere to the content of the bag 10 comprised by the laminated body 30. FIG.
　このような課題を考慮し、第２接着剤層６５を構成する第２接着剤として、主剤としてのポリオールと、硬化剤としての脂肪族系イソシアネート化合物とが反応することにより生成される硬化物を用いることを提案する。これにより、第２接着剤層６５に起因する食品用途で使用できない成分が内容物に付着することを防止することができる。 In consideration of such problems, as a second adhesive constituting the second adhesive layer 65, a cured product produced by a reaction between a polyol as a main agent and an aliphatic isocyanate compound as a curing agent is used. Suggest to use. Thereby, it can prevent that the component which cannot be used for the food use resulting from the 2nd adhesive bond layer 65 adheres to the contents.
　なお、第２フィルム６０がガスバリア性などのバリア性を有さない場合であって、且つ上述の第１接着剤層５５が芳香族系イソシアネート化合物を含む場合、芳香族系イソシアネート化合物から溶出された成分が内容物に付着することも考えられる。この場合、第２接着剤層６５の場合と同様に、第１接着剤層５５を構成する第１接着剤として、主剤としてのポリオールと、硬化剤としての脂肪族系イソシアネート化合物とが反応することにより生成される硬化物を用いることが好ましい。 In addition, when the second film 60 does not have a barrier property such as a gas barrier property, and the first adhesive layer 55 includes an aromatic isocyanate compound, the second film 60 was eluted from the aromatic isocyanate compound. It is also conceivable that components adhere to the contents. In this case, as in the case of the second adhesive layer 65, the polyol as the main agent and the aliphatic isocyanate compound as the curing agent react as the first adhesive constituting the first adhesive layer 55. It is preferable to use a cured product produced by the above.
　（シーラントフィルム）
　シーラントフィルム７０は、積層体３０の内面３０ｘを構成するシーラント層７１を少なくとも含む。シーラント層７１を構成する材料としては、上述の第１の実施の形態の場合と同様に、低密度ポリエチレン、直鎖状低密度ポリエチレンなどのポリエチレン、ポリプロピレンから選択される１種または２種以上の樹脂を用いることができる。 (Sealant film)
The sealant film 70 includes at least a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30. As the material constituting the sealant layer 71, as in the case of the first embodiment described above, one or two or more selected from polyethylene such as low density polyethylene and linear low density polyethylene, and polypropylene are used. Resin can be used.
　積層体の製造方法
　次に、積層体３０の製造方法の一例について説明する。 Method for producing a laminate Next, an example of a method for producing a laminate 30.
　まず、上述の第１フィルム５０、及び第２フィルム６０を準備する。続いて、ドライラミネート法により、第１フィルム５０と第２フィルム６０とを、第１接着剤層５５を介して積層する。その後、ドライラミネート法により、第１フィルム５０及び第２フィルム６０を含む積層体と、シーラントフィルム７０とを、第２接着剤層６５を介して積層する。これによって、第１フィルム５０、第２フィルム６０及びシーラントフィルム７０を備える積層体３０を得ることができる。 First, the first film 50 and the second film 60 described above are prepared. Subsequently, the first film 50 and the second film 60 are laminated via the first adhesive layer 55 by a dry laminating method. Thereafter, the laminate including the first film 50 and the second film 60 and the sealant film 70 are laminated via the second adhesive layer 65 by a dry laminating method. Thereby, the laminated body 30 provided with the 1st film 50, the 2nd film 60, and the sealant film 70 can be obtained.
　若しくは、まず第２フィルム６０とシーラントフィルム７０とを第２接着剤層６５を介して積層し、その後、第１フィルム５０と、第２フィルム６０及びシーラントフィルム７０を含む積層体とを第１接着剤層５５を介して積層することにより、積層体３０を製造してもよい。 Alternatively, the second film 60 and the sealant film 70 are first laminated through the second adhesive layer 65, and then the first film 50 and the laminate including the second film 60 and the sealant film 70 are first bonded. The laminated body 30 may be manufactured by laminating via the agent layer 55.
　以下、本実施の形態に係る積層体３０が奏する効果について説明する。 Hereinafter, effects produced by the laminate 30 according to the present embodiment will be described.
　本実施の形態においては、袋１０の表面フィルム１４及び裏面フィルム１５を構成する積層体３０が、ＰＢＴを主成分とする第１基材５１を含むことにより、下記の効果を奏することができる。
　まず、ＰＢＴは、耐熱性に優れる。このため、袋１０にレトルト処理やボイル処理などを施す際に第１基材５１が変形したり第１基材５１の強度が低下したりすることを抑制することができる。
　また、ＰＢＴは、高い強度を有する。このため、袋１０を構成する積層体がナイロンを含む場合と同様に、積層体３０及び袋１０の突き刺し強度を高めることができる。積層体３０の突き刺し強度は、１３Ｎ以上であることが好ましく、１５Ｎ以上であることがより好ましく、１７Ｎ以上であることがさらに好ましい。
　また、ＰＢＴは、ナイロンに比べて水分を吸収しにくいという特性を有する。このため、ＰＢＴを含む第１基材５１を積層体３０の外面３０ｙに配置した場合であっても、第１基材５１が水分を吸収して積層体３０のラミネート強度が低下してしまうことを抑制することができる。 In this Embodiment, when the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains the 1st base material 51 which has PBT as a main component, there can exist the following effect.
First, PBT is excellent in heat resistance. For this reason, when performing the retort process, the boil process, etc. to the bag 10, it can suppress that the 1st base material 51 deform | transforms or the intensity | strength of the 1st base material 51 falls.
PBT has high strength. For this reason, the puncture strength of the laminated body 30 and the bag 10 can be increased similarly to the case where the laminated body constituting the bag 10 includes nylon. The puncture strength of the laminate 30 is preferably 13N or more, more preferably 15N or more, and further preferably 17N or more.
PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the 1st substrate 51 containing PBT is arranged on outer surface 30y of layered product 30, the 1st substrate 51 absorbs moisture, and the lamination strength of layered product 30 will fall. Can be suppressed.
　また、本実施の形態においては、積層体３０が、ＰＥＴを主成分とする第２基材６１を含むことにより、第２基材６１がナイロンからなる場合に比べて、第２基材６１が内容物によって着色されてしまうことを抑制することができる。これにより、袋１０の外観が損なわれることを抑制することができる。また、第２基材６１がナイロンからなる場合に比べて、第２基材６１が吸収した水分に起因して発泡が生じ、袋１０の外観が損なわれてしまうことを抑制することができる。この点でも、袋１０の外観が損なわれることを抑制することができる。 Moreover, in this Embodiment, the laminated body 30 contains the 2nd base material 61 which has PET as a main component, Compared with the case where the 2nd base material 61 consists of nylon, the 2nd base material 61 is. It can suppress coloring with the contents. Thereby, it can suppress that the external appearance of the bag 10 is impaired. Moreover, it can suppress that foaming arises due to the water | moisture content which the 2nd base material 61 absorbed, and the external appearance of the bag 10 is impaired compared with the case where the 2nd base material 61 consists of nylon. Also in this respect, it is possible to suppress the appearance of the bag 10 from being damaged.
　仮に、第２基材６１がナイロンを含む場合には、ナイロンから、ナイロンの原料であり、厚生省告示第３７０号「器具及び容器包装」にて溶出基準が定められているカプロラクタムなどが溶出し、内容物に混入するおそれがある。これに対して、本実施の形態によれば、第２基材６１をＰＥＴで構成することにより、カプロラクタムなどが溶出するおそれを低減することができる。 If the second base material 61 contains nylon, caprolactam, etc., which is a raw material of nylon from nylon and whose elution standard is defined in Ministry of Health and Welfare Notification No. 370 “Apparatus and Containers and Packaging”, There is a risk of mixing with the contents. On the other hand, according to this Embodiment, the possibility that caprolactam etc. elute can be reduced by comprising the 2nd base material 61 with PET.
　また、袋１０の表面フィルム１４及び裏面フィルム１５を構成する積層体３０が、ＰＥＴを主成分とする第２基材６１を含むことにより、第２基材６１がＰＢＴからなる場合に比べて、積層体３０の耐熱性を高めることができる。これにより、例えば、袋１０を加熱して内容物の温度が高くなった時に表面フィルム１４及び裏面フィルム１５がダメージを受けて表面フィルム１４及び裏面フィルム１５の性能が低下することを抑制することができる。 Moreover, the laminated body 30 which comprises the surface film 14 and the back surface film 15 of the bag 10 contains the 2nd base material 61 which has PET as a main component, compared with the case where the 2nd base material 61 consists of PBT, The heat resistance of the laminate 30 can be increased. Thereby, for example, when the bag 10 is heated and the temperature of the contents is increased, the surface film 14 and the back film 15 are damaged and the performance of the surface film 14 and the back film 15 is prevented from being deteriorated. it can.
　なお、上述した実施の形態に対して様々な変更を加えることが可能である。以下、必要に応じて図面を参照しながら、変形例について説明する。以下の説明および以下の説明で用いる図面では、上述した実施の形態と同様に構成され得る部分について、上述の実施の形態における対応する部分に対して用いた符号と同一の符号を用いることとし、重複する説明を省略する。また、上述した実施の形態において得られる作用効果が変形例においても得られることが明らかである場合、その説明を省略することもある。 Note that various modifications can be made to the above-described embodiment. Hereinafter, modified examples will be described with reference to the drawings as necessary. In the following description and the drawings used in the following description, the same reference numerals as those used for the corresponding parts in the above embodiment are used for the parts that can be configured in the same manner as in the above embodiment. A duplicate description is omitted. In addition, when it is clear that the operational effects obtained in the above-described embodiment can be obtained in the modified example, the description thereof may be omitted.
　（層構成の変形例）
　上述の本実施の形態においては、第１基材５１が５１質量％以上のＰＢＴを含み、第２基材６１が５１質量％以上のＰＥＴを含むことによって積層体３０の耐突き刺し性及び耐熱性を高める例を示した。しかしながら、これに限られることはなく、第１基材５１が５１質量％以上のＰＥＴを含み、第２基材６１が５１質量％以上のＰＢＴを含むことによって積層体３０の耐突き刺し性及び耐熱性を高めてもよい。第２基材６１のＰＢＴとしては、上述の第１の実施の形態で説明した第１の構成に係るＰＢＴ又は第２の構成に係るＰＢＴを用いることができる。 (Modification of layer structure)
In the present embodiment described above, the first substrate 51 includes 51 mass% or more of PBT, and the second substrate 61 includes 51 mass% or more of PET, whereby the stab resistance and heat resistance of the laminate 30. The example which raises is shown. However, the present invention is not limited to this, and the first substrate 51 includes 51% by mass or more of PET, and the second substrate 61 includes 51% by mass or more of PBT. You may increase the nature. As the PBT of the second substrate 61, the PBT according to the first configuration described in the first embodiment or the PBT according to the second configuration can be used.
　第２基材６１が５１質量％以上のＰＢＴを含み、第１基材５１が５１質量％以上のＰＥＴを含むことは、積層体３０の寸法安定性、印刷適性の向上にも寄与する。 The fact that the second base material 61 contains 51% by mass or more of PBT and the first base material 51 contains 51% by mass or more of PET contributes to the improvement of the dimensional stability and printability of the laminate 30.
　また、第１基材５１及び第２基材６１の両方が、５１質量％以上のＰＢＴを含んでいてもよい。この場合のＰＢＴとしても、上述の第１の構成に係るＰＢＴ又は第２の構成に係るＰＢＴを用いることができる。 Moreover, both the 1st base material 51 and the 2nd base material 61 may contain 51 mass% or more of PBT. As the PBT in this case, the PBT according to the first configuration described above or the PBT according to the second configuration can be used.
　第１基材５１及び第２基材６１を構成する材料の組み合わせの例をまとめて表１に示す。なお、表１において、「ＰＢＴ」という表記は、第１基材５１又は第２基材６１のフィルムを構成する樹脂中に５１質量％以上のＰＢＴが含まれることを意味する。また、表１において、「ＰＥＴ」という表記は、第１基材５１又は第２基材６１のフィルムを構成する樹脂中に５１質量％以上のＰＥＴが含まれることを意味する。
Figure JPOXMLDOC01-appb-T000004
 Table 1 summarizes examples of combinations of materials constituting the first base member 51 and the second base member 61. In Table 1, the notation “PBT” means that 51 mass% or more of PBT is contained in the resin constituting the film of the first base material 51 or the second base material 61. In Table 1, the expression “PET” means that 51% by mass or more of PET is contained in the resin constituting the film of the first base material 51 or the second base material 61.
Figure JPOXMLDOC01-appb-T000004
　なお、第１基材５１がＰＥＴを含むか、ＰＢＴを含むかを選択可能な場合には、ヒートシール性の観点からは、第１基材５１がＰＥＴを含むことが好ましい。ＰＥＴは、ＰＢＴよりも比較的高い融点を有する。このため、第１基材５１がＰＥＴを含む場合、積層体３０の外面３０ｙの耐熱性がより向上する。従って、袋１０のシール部をヒートシールによって形成する場合に、より高温にてヒートシールを行うことが可能となる。 In addition, when it can be selected whether the 1st base material 51 contains PET or PBT, it is preferable that the 1st base material 51 contains PET from a viewpoint of heat-sealability. PET has a relatively higher melting point than PBT. For this reason, when the 1st base material 51 contains PET, the heat resistance of the outer surface 30y of the laminated body 30 improves more. Therefore, when the seal part of the bag 10 is formed by heat sealing, the heat sealing can be performed at a higher temperature.
　また、第１基材５１と第２基材６１との間の位置において、第１基材５１又は／及び第２基材６１に、透明性を有する無機材料からなる透明蒸着層３６が設けられていてもよい。透明蒸着層３６は、図７に示すように、第１基材５１の内面３０ｘ側の面に設けられていてもよく、図８に示すように、第２基材６１の外面３０ｙ側の面に設けられていてもよい。また、透明蒸着層３６の上に、透明性を有する透明ガスバリア性塗布膜３７が設けられていてもよい。透明蒸着層３６及び透明ガスバリア性塗布膜３７の具体的な構成は、上述の第１の実施の形態の場合と同様である。 Moreover, the transparent vapor deposition layer 36 which consists of an inorganic material which has transparency in the position between the 1st base material 51 and the 2nd base material 61 in the 1st base material 51 or / and the 2nd base material 61 is provided. It may be. The transparent vapor deposition layer 36 may be provided on the surface on the inner surface 30x side of the first base material 51 as shown in FIG. 7, and the surface on the outer surface 30y side of the second base material 61 as shown in FIG. May be provided. A transparent gas barrier coating film 37 having transparency may be provided on the transparent vapor deposition layer 36. Specific configurations of the transparent vapor deposition layer 36 and the transparent gas barrier coating film 37 are the same as those in the first embodiment.
　透明蒸着層３６と第１基材５１又は第２基材６１との界面には、金属原子と炭素原子の共有結合が形成されていてもよい。例えば、透明蒸着層３６が酸化アルミニウムを含む場合、第１基材５１又は第２基材６１と透明蒸着層３６との界面には、アルミニウム原子と炭素原子の共有結合が形成されていてもよい。共有結合は、ＸＰＳ測定によって検出され得る。 A covalent bond between a metal atom and a carbon atom may be formed at the interface between the transparent vapor deposition layer 36 and the first substrate 51 or the second substrate 61. For example, when the transparent deposition layer 36 includes aluminum oxide, a covalent bond between an aluminum atom and a carbon atom may be formed at the interface between the first substrate 51 or the second substrate 61 and the transparent deposition layer 36. . Covalent bonds can be detected by XPS measurements.
　また、透明蒸着層３６においては、アルミニウム原子と炭素原子の共有結合の存在比率が、ＸＰＳ測定により透明蒸着層３６と第１基材５１又は第２基材６１との界面を測定した場合に観察される炭素原子を含む全結合のうちの０.３％以上且つ３０％以下の範囲内であることが好ましい。これにより、透明蒸着層３６と第１基材５１又は第２基材６１との密着性が強化され、透明性も優れ、ガスバリア性の蒸着フィルムとしてバランスのよい性能のものが得られる。 Moreover, in the transparent vapor deposition layer 36, the existence ratio of the covalent bond of an aluminum atom and a carbon atom is observed when the interface between the transparent vapor deposition layer 36 and the first substrate 51 or the second substrate 61 is measured by XPS measurement. It is preferable that it is within the range of 0.3% or more and 30% or less of all the bonds containing carbon atoms. Thereby, the adhesiveness of the transparent vapor deposition layer 36 and the 1st base material 51 or the 2nd base material 61 is strengthened, transparency is excellent, and the thing of the performance with sufficient balance as a gas barrier property vapor deposition film is obtained.
　アルミニウム原子と炭素原子の共有結合の存在比率が０.３％未満であると、透明蒸着層３６の密着性の改善が不十分であり、バリア性を安定して維持することが困難になる。 If the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is less than 0.3%, the adhesion of the transparent vapor-deposited layer 36 is not sufficiently improved, and it is difficult to stably maintain the barrier property.
　さらに、酸化アルミニウムを主成分とする透明蒸着層３６の、ＡＬ（アルミニウム）／Ｏ（酸素）比が、第１基材５１又は第２基材６１と透明蒸着層３６との界面から、第１基材５１又は第２基材６１とは反対側の透明蒸着層３６の表面に向かって３ｎｍまでの範囲内において、１.０以下であることが好ましい。
　透明蒸着層３６と第１基材５１又は第２基材６１との界面から、第１基材５１又は第２基材６１とは反対側の透明蒸着層３６の表面に向かう範囲内において、ＡＬ／Ｏの比が１.０を超えると、第１基材５１又は第２基材６１と透明蒸着層３６との間の密着性が不十分となり、かつアルミニウムの割合が高まり、透明蒸着層３６の透明性が低下する。 Furthermore, the AL (aluminum) / O (oxygen) ratio of the transparent vapor-deposited layer 36 mainly composed of aluminum oxide is such that the first substrate 51 or the second substrate 61 and the interface between the transparent vapor-deposited layer 36 are the first. In the range up to 3 nm toward the surface of the transparent vapor deposition layer 36 on the side opposite to the base material 51 or the second base material 61, it is preferably 1.0 or less.
In the range from the interface between the transparent deposition layer 36 and the first substrate 51 or the second substrate 61 toward the surface of the transparent deposition layer 36 on the side opposite to the first substrate 51 or the second substrate 61, AL When the ratio of / O exceeds 1.0, the adhesion between the first base material 51 or the second base material 61 and the transparent vapor deposition layer 36 becomes insufficient, and the ratio of aluminum increases, so that the transparent vapor deposition layer 36 The transparency of the is reduced.
　第１基材５１又は第２基材６１に透明蒸着層３６を形成する場合、第１基材５１又は第２基材６１の面に予めコロナ放電処理、フレーム処理、プラズマ処理などの前処理を施しておいてもよい。特に、透明蒸着層３６と第１基材５１又は第２基材６１との界面に、金属原子と炭素原子の共有結合を形成する場合には、透明蒸着層３６を形成しようとする第１基材５１又は第２基材６１の面に対し前処理を施すことが好ましい。前処理がプラズマ処理である場合、前処理装置により、０．１Ｐａ以上１００Ｐａ以下の減圧環境下において、第１基材５１又は第２基材６１の面に対してプラズマを供給する。プラズマは、アルゴン等の不活性ガス単独又は酸素、窒素、炭酸ガス及びそれらの１種以上のガスとの混合ガスをプラズマ原料ガスとして用い、高周波電圧等による電位差によって、プラズマ原料ガスを励起状態にすることにより、発生させることができる。 When forming the transparent vapor deposition layer 36 on the 1st base material 51 or the 2nd base material 61, it pre-processes, such as a corona discharge process, a flame process, and a plasma process, to the surface of the 1st base material 51 or the 2nd base material 61 previously. You may give it. In particular, when a covalent bond between a metal atom and a carbon atom is formed at the interface between the transparent vapor deposition layer 36 and the first base material 51 or the second base material 61, the first group on which the transparent vapor deposition layer 36 is to be formed. The surface of the material 51 or the second base 61 is preferably pretreated. When the pretreatment is plasma treatment, plasma is supplied to the surface of the first base material 51 or the second base material 61 in a reduced pressure environment of 0.1 Pa or more and 100 Pa or less by the pretreatment apparatus. Plasma uses an inert gas such as argon alone or a mixed gas of oxygen, nitrogen, carbon dioxide and one or more of them as a plasma source gas, and the plasma source gas is excited by a potential difference due to a high-frequency voltage or the like. By doing so, it can be generated.
　前処理により、第１基材５１又は第２基材６１の表面近傍にプラズマを閉じ込めることができる。これにより、第１基材５１又は第２基材６１の表面の形状や、化学的な結合状態や官能基を変化させ、第１基材５１又は第２基材６１の表面の化学的性状を変化させることができる。このことにより、第１基材５１又は第２基材６１と透明蒸着層３６との密着性を向上させることが可能となる。 The plasma can be confined in the vicinity of the surface of the first substrate 51 or the second substrate 61 by the pretreatment. Thereby, the shape of the surface of the 1st substrate 51 or the 2nd substrate 61, a chemical bond state, and a functional group are changed, and the chemical property of the surface of the 1st substrate 51 or the 2nd substrate 61 is changed. Can be changed. This makes it possible to improve the adhesion between the first substrate 51 or the second substrate 61 and the transparent vapor deposition layer 36.
　第４の実施の形態
　次に、本発明の第４の実施の形態について説明する。本実施の形態においては、第３の実施の形態で説明した、２つのプラスチックフィルムを備える積層体３０が、遮光性を有する印刷層（以下、遮光印刷層と称する）を更に備える例について説明する。本実施の形態において、第３の実施の形態と同一部分には同一符号を付して詳細な説明は省略する。また、第３の実施の形態において得られる作用効果が本実施の形態においても得られることが明らかである場合、その説明を省略することもある。 Fourth Embodiment Next, a fourth embodiment of the present invention will be described. In the present embodiment, an example will be described in which the laminate 30 including two plastic films described in the third embodiment further includes a printing layer having a light shielding property (hereinafter referred to as a light shielding printing layer). . In the present embodiment, the same parts as those in the third embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Moreover, when it is clear that the effect obtained in the third embodiment can be obtained in the present embodiment, the description thereof may be omitted.
　まず、本実施の形態が解決しようとする課題について説明する。袋を構成する積層体には、内容物の変質を防止しながら内容物を保存するために、高い遮光性が求められることがある。これらの課題を解決するため、例えば上述の特許文献１は、ポリエチレンテレフタレートなどの樹脂を含む基材に遮光性を有する遮光印刷層を設けることを提案している。 First, problems to be solved by this embodiment will be described. The laminated body constituting the bag may be required to have a high light shielding property in order to preserve the contents while preventing the contents from being altered. In order to solve these problems, for example, the above-mentioned Patent Document 1 proposes to provide a light-shielding printing layer having a light-shielding property on a base material containing a resin such as polyethylene terephthalate.
　特許文献１において、遮光印刷層は、顔料及びバインダーを含むインキを基材に十分な厚さで印刷することによって得られる。一方、顔料、バインダー、残留溶媒などのインキ成分からは、人が不快に感じる臭い（以下、異臭とも称する）が発生し、異臭がシーラント層を透過して内容物に付着してしまうことがある。このような異臭は、内容物が食品の場合に特に問題になる。本実施の形態は、このような課題を効果的に解決し得る積層体を提供することを目的とする。 In Patent Document 1, the light-shielding print layer is obtained by printing an ink containing a pigment and a binder on a substrate with a sufficient thickness. On the other hand, an ink component such as a pigment, a binder, and a residual solvent generates an unpleasant odor (hereinafter also referred to as a strange odor), and the strange odor may permeate the sealant layer and adhere to the contents. . Such off-flavors are particularly problematic when the contents are food. The purpose of this embodiment is to provide a laminate that can effectively solve such problems.
　続いて、本実施の形態に係る積層体３０について説明する。図９は、第４の実施の形態における積層体３０の層構成の一例を示す断面図である。また、図１０は、第４の実施の形態における積層体３０の層構成のその他の例を示す断面図である。積層体３０は、第３の実施の形態の場合と同様に、第１フィルム５０、第２フィルム６０及びシーラントフィルム７０をこの順で少なくとも含む。 Subsequently, the laminate 30 according to the present embodiment will be described. FIG. 9 is a cross-sectional view illustrating an example of a layer configuration of the stacked body 30 according to the fourth embodiment. Moreover, FIG. 10 is sectional drawing which shows the other example of the layer structure of the laminated body 30 in 4th Embodiment. As in the case of the third embodiment, the laminate 30 includes at least the first film 50, the second film 60, and the sealant film 70 in this order.
　第１フィルム５０は、図９に示すように、第１基材５１と、第１基材５１の面のうち第２フィルム６０側の面に設けられた遮光印刷層５２と、を少なくとも含む。また、第１フィルム５０は、図１０に示すように、第１基材５１と遮光印刷層５２との間に位置する絵柄印刷層５３を更に含んでいてもよい。第２フィルム６０は、第２基材６１を少なくとも含む。シーラントフィルム７０は、シーラント層７１を少なくとも含む。また、第１フィルム５０と第２フィルム６０とは第１接着剤層５５によって接合されており、第２フィルム６０とシーラントフィルム７０とは第２接着剤層６５によって接合されている。従って、本実施の形態による積層体３０は、外面側から内面側へ順に
　　第１基材／遮光印刷層／第１接着剤層／第２基材／第２接着剤層／シーラント層、
　または、
　　第１基材／絵柄印刷層／遮光印刷層／第１接着剤層／第２基材／第２接着剤層／シーラント層
を備えている、と言える。なお、「／」は層と層の境界を表している。 As shown in FIG. 9, the first film 50 includes at least a first substrate 51 and a light-shielding print layer 52 provided on the surface of the first substrate 51 on the second film 60 side. Moreover, the 1st film 50 may further contain the pattern printing layer 53 located between the 1st base material 51 and the light shielding printing layer 52, as shown in FIG. The second film 60 includes at least a second base material 61. The sealant film 70 includes at least a sealant layer 71. The first film 50 and the second film 60 are joined by a first adhesive layer 55, and the second film 60 and the sealant film 70 are joined by a second adhesive layer 65. Therefore, the laminate 30 according to the present embodiment has a first base material / light-shielding print layer / first adhesive layer / second base material / second adhesive layer / sealant layer in order from the outer surface side to the inner surface side.
Or
It can be said that the first substrate / the pattern printing layer / the light-shielding printing layer / the first adhesive layer / the second substrate / the second adhesive layer / the sealant layer. Note that “/” represents a boundary between layers.
　次に、遮光印刷層５２及び絵柄印刷層５３について説明する。なお、第１基材５１、第１接着剤層５５、第２基材６１、第２接着剤層６５及びシーラント層７１の構成は、第３の実施の形態の場合と同一であるので、説明を省略する。 Next, the light shielding printing layer 52 and the pattern printing layer 53 will be described. The configurations of the first base material 51, the first adhesive layer 55, the second base material 61, the second adhesive layer 65, and the sealant layer 71 are the same as in the case of the third embodiment. Is omitted.
　〔遮光印刷層〕
　遮光印刷層５２は、積層体３０が遮光性を有するように構成された層である。遮光印刷層５２は、顔料及びバインダーを含むインクを有する。また、遮光印刷層５２の厚みは、例えば２μｍ以上であり、好ましくは３μｍ以上であり、より好ましくは４μｍ以上である。また、遮光印刷層５２の厚みは、好ましくは１０μｍ以下、より好ましくは６μｍ以下である。遮光印刷層５２を含む積層体３０の全光線透過率は、少なくとも２０％以下であり、好ましくは１５％以下であり、更に好ましくは１０％以下である。全光線透過率が２０％以下である場合、通常の使用条件下において袋１０に入射する３００ｎｍから８００ｎｍの波長域の外光からなる可視光と紫外線とを効果的に遮断することができ、袋１０に収容した内容物が外光によって劣化することを効果的に抑制することができる。 [Shading printing layer]
The light shielding print layer 52 is a layer configured so that the laminate 30 has a light shielding property. The light-shielding print layer 52 has an ink containing a pigment and a binder. Further, the thickness of the light-shielding print layer 52 is, for example, 2 μm or more, preferably 3 μm or more, and more preferably 4 μm or more. Further, the thickness of the light-shielding printing layer 52 is preferably 10 μm or less, more preferably 6 μm or less. The total light transmittance of the laminate 30 including the light-shielding print layer 52 is at least 20% or less, preferably 15% or less, and more preferably 10% or less. When the total light transmittance is 20% or less, visible light and ultraviolet rays made of external light having a wavelength range of 300 nm to 800 nm incident on the bag 10 under normal use conditions can be effectively blocked. It can suppress effectively that the content accommodated in 10 deteriorates with external light.
　全光線透過率とは、遮光印刷層５２を含む積層体３０からなる試験片に入射する光の全入射光量に対する、積層体３０を通過した全透過光量の割合をいう。試験片は通常は光拡散性を有するため、全光線透過率は、平行光線透過率と拡散透過率の和となる。全光線透過率は、ＪＩＳで規定される積分球を使用する光学的特性試験方法ＪＩＳ－Ｋ７３６１－１に準拠して測定される。 The total light transmittance refers to the ratio of the total transmitted light amount that has passed through the laminate 30 to the total incident light amount of light incident on the test piece made of the laminate 30 including the light-shielding print layer 52. Since the test piece usually has light diffusibility, the total light transmittance is the sum of the parallel light transmittance and the diffuse transmittance. The total light transmittance is measured according to an optical characteristic test method JIS-K7361-1 using an integrating sphere defined by JIS.
　遮光印刷層５２は、例えば無彩色のインキを含む無彩色層を有する。無彩色とは、色相、明度及び飽和度という色の三次元のうち、明度のみによって記述される色のことである。無彩色の例としては、白色、灰色、黒色を挙げることができる。無彩色層の厚みは、例えば１μｍ以上且つ３μｍ以下である。無彩色層は、好ましくは、同一平面内において第１基材５１の面の全域にわたって広がる単一の色の層である。以下の説明において、網点の面積率が１００％である領域を有する印刷層のことを、ベタ層とも称する。例えば、白色の網点の面積率が１００％である領域を有する印刷層のことを、白ベタ層と称する。同様に、黒色の網点の面積率が１００％である領域を有する印刷層のことを、黒ベタ層と称する。白ベタ層は、白色系顔料を含む白色インキを第１基材５１にベタ印刷することによって形成される。また、黒ベタ層は、黒色系顔料を含む黒色インキを第１基材５１にベタ印刷することによって形成される。遮光印刷層５２は、積層された複数の無彩色層を含んでいてもよい。以下、遮光印刷層５２の具体的な層構成について説明する。 The light-shielding print layer 52 has an achromatic layer containing, for example, an achromatic color ink. An achromatic color is a color described only by lightness among the three-dimensional colors of hue, lightness, and saturation. Examples of achromatic colors include white, gray, and black. The thickness of the achromatic layer is, for example, 1 μm or more and 3 μm or less. The achromatic layer is preferably a single color layer extending over the entire surface of the first substrate 51 in the same plane. In the following description, a printed layer having a region where the dot area ratio is 100% is also referred to as a solid layer. For example, a printed layer having a region in which the area ratio of white halftone dots is 100% is referred to as a white solid layer. Similarly, a printed layer having a region where the area ratio of black halftone dots is 100% is referred to as a black solid layer. The white solid layer is formed by solid printing white ink containing a white pigment on the first substrate 51. The black solid layer is formed by solid printing black ink containing a black pigment on the first substrate 51. The light-shielding print layer 52 may include a plurality of stacked achromatic layers. Hereinafter, a specific layer configuration of the light-shielding print layer 52 will be described.
　遮光印刷層５２は、例えば、黒ベタ層からなっていてもよい。なお、遮光印刷層５２の外面３０ｙ側に絵柄印刷層５３が積層されている場合、積層体の外面３０ｙ側から袋１０を視認すると、絵柄印刷層５３の背景として遮光印刷層５２が観察される。このため、遮光印刷層５２が黒ベタ層のみからなる場合、絵柄印刷層５３を視認することが困難になる。従って、積層体３０が絵柄印刷層５３を含む場合、遮光印刷層５２が、黒ベタ層に加えて、以下に説明するように、黒ベタ層よりも外面３０ｙ側に位置する、黒色以外の無彩色層を更に含むことが好ましい。 The light-shielding print layer 52 may be composed of, for example, a black solid layer. In addition, when the pattern printing layer 53 is laminated | stacked on the outer surface 30y side of the light shielding printing layer 52, when the bag 10 is visually recognized from the outer surface 30y side of a laminated body, the light shielding printing layer 52 is observed as a background of the pattern printing layer 53. . For this reason, when the shading print layer 52 consists only of a black solid layer, it becomes difficult to visually recognize the pattern print layer 53. Therefore, when the laminate 30 includes the pattern print layer 53, the light-shielding print layer 52 is located in the outer surface 30y side of the black solid layer, as described below, in addition to the black solid layer. It is preferable to further include a coloring layer.
　遮光印刷層５２は、第１基材５１側から内面３０ｘ側へ順に積層された白ベタ層及び無彩色層を含んでいてもよい。無彩色層は、白ベタ層であってもよく、黒ベタ層であってもよい。また、無彩色層は、灰色のインキを第１基材５１にベタ印刷することによって形成される灰ベタ層であってもよい。灰色のインキは、例えば、白色系顔料を含む白色インキ及び黒色系顔料を含む黒色インキを混合することによって得られる。灰色のインキは、白インキの配合比率が黒インキの配合比率よりも高いことが好ましい。白ベタ層の内面３０ｘ側に積層される無彩色層を灰ベタ層とすることにより、白ベタ層の内面３０ｘ側に黒ベタ層を積層する場合に比べて、無彩色層の色味が絵柄印刷層５３の色味に影響を及ぼすことを抑制することができる。
　なお、無彩色層の数が２層に限られることはない。例えば、遮光印刷層５２は、積層された３層又は４層以上の無彩色層を含んでいてもよい。例えば、遮光印刷層５２は、第１基材５１側から内面３０ｘ側へ順に積層された白ベタ層、白ベタ層及び灰ベタ層を含んでいてもよい。 The light-shielding print layer 52 may include a white solid layer and an achromatic layer that are sequentially stacked from the first base material 51 side to the inner surface 30x side. The achromatic layer may be a white solid layer or a black solid layer. The achromatic layer may be an ash solid layer formed by solid printing gray ink on the first base material 51. The gray ink can be obtained, for example, by mixing a white ink containing a white pigment and a black ink containing a black pigment. The gray ink preferably has a white ink blending ratio higher than that of the black ink. By making the achromatic layer laminated on the inner surface 30x side of the white solid layer a gray solid layer, the color of the achromatic layer is a pattern compared to the case where the black solid layer is laminated on the inner surface 30x side of the white solid layer. The influence on the color of the print layer 53 can be suppressed.
Note that the number of achromatic layers is not limited to two. For example, the light-shielding print layer 52 may include three or four or more achromatic layers stacked. For example, the light-shielding print layer 52 may include a white solid layer, a white solid layer, and an ash solid layer that are sequentially stacked from the first base material 51 side to the inner surface 30x side.
　また、遮光印刷層５２は、白ベタ層からなっていてもよい。遮光印刷層５２が上述の黒ベタ層や灰ベタ層を含まない場合であっても、白ベタ層の厚みを大きくすることにより、遮光印刷層５２に十分な遮光性を持たせることができる。 Further, the light-shielding print layer 52 may be composed of a white solid layer. Even when the light-shielding print layer 52 does not include the above-described black solid layer or ash solid layer, the light-shielding print layer 52 can have sufficient light-shielding properties by increasing the thickness of the white solid layer.
　また、遮光印刷層５２は、有彩色のインキを含む有彩色層を有していてもよい。有彩色とは、色相、明度及び飽和度という色の三次元を全て含む色又は色彩を意味する。言い換えると、有彩色とは、無彩色以外の色である。有彩色層の厚みは、例えば０．３μｍ以上且つ２μｍ以下である。有彩色層は、好ましくは、同一平面内において第１基材５１の面の全域にわたって広がる単一の色の層である。遮光印刷層５２は、積層された複数の有彩色層を含んでいてもよい。 Further, the light-shielding print layer 52 may have a chromatic color layer containing chromatic ink. A chromatic color means a color or color that includes all three dimensions of hue, lightness, and saturation. In other words, a chromatic color is a color other than an achromatic color. The thickness of the chromatic color layer is, for example, not less than 0.3 μm and not more than 2 μm. The chromatic color layer is preferably a single color layer extending over the entire surface of the first substrate 51 in the same plane. The light-shielding print layer 52 may include a plurality of stacked chromatic color layers.
　遮光印刷層５２は、無彩色層及び有彩色層の両方を含んでいてもよい。例えば、遮光印刷層５２は、１つ又は複数の無彩色層と、無彩色層よりも内面３０ｘ側に位置する１つ又は複数の有彩色層と、を有する。また、遮光印刷層５２は、１つ又は複数の有彩色層と、有彩色層よりも内面３０ｘ側に位置する１つ又は複数の無彩色層と、を有していてもよい。例えば、遮光印刷層５２は、第１基材５１側から内面３０ｘ側へ順に積層された白ベタ層及び有彩色層を含んでいてもよい。 The light-shielding print layer 52 may include both an achromatic color layer and a chromatic color layer. For example, the light-shielding print layer 52 includes one or more achromatic layers and one or more chromatic layers located on the inner surface 30x side of the achromatic layer. Further, the light-shielding print layer 52 may include one or more chromatic color layers and one or more achromatic layers positioned on the inner surface 30x side of the chromatic color layer. For example, the light-shielding print layer 52 may include a white solid layer and a chromatic color layer that are sequentially stacked from the first base material 51 side to the inner surface 30x side.
　〔絵柄印刷層〕
　絵柄印刷層５３は、袋１０に製品情報を示したり美感を付与したりするために印刷によって設けられた層である。絵柄印刷層５３は、文字、数字、記号、図形、絵柄などを表現する。絵柄印刷層５３においては、複数の色の層が、同一平面内において広がっている。絵柄印刷層５３を構成する材料としては、グラビア印刷用のインキやフレキソ印刷用のインキを用いることができる。グラビア印刷用のインキの具体例としては、ＤＩＣグラフィックス株式会社製のフィナートを挙げることができる。 [Pattern printing layer]
The pattern print layer 53 is a layer provided by printing in order to show product information or impart aesthetics to the bag 10. The picture print layer 53 expresses characters, numbers, symbols, figures, pictures, and the like. In the pattern print layer 53, a plurality of color layers spreads in the same plane. As a material constituting the pattern printing layer 53, gravure printing ink or flexographic printing ink can be used. As a specific example of the ink for gravure printing, FINAT manufactured by DIC Graphics Corporation can be given.
　以下、本実施の形態に係る積層体３０が奏する効果について説明する。 Hereinafter, effects produced by the laminate 30 according to the present embodiment will be described.
　本実施の形態においては、袋１０の表面フィルム１４及び裏面フィルム１５を構成する積層体３０が、ＰＢＴを主成分とする第１基材５１を含むことにより、下記の効果を奏することができる。
　まず、ＰＢＴは、印刷適性に優れる。このため、ポリエチレンテレフタレートの場合と同様に、ＰＢＴを含む第１基材５１上に遮光印刷層５２や絵柄印刷層５３を設けることができる。
　また、ＰＢＴは、耐熱性に優れる。このため、袋１０にレトルト処理やボイル処理などを施す際に第１基材５１が変形したり第１基材５１の強度が低下したりすることを抑制することができる。
　また、ＰＢＴは、高い強度を有する。このため、袋１０を構成する積層体がナイロンを含む場合と同様に、積層体３０及び袋１０の突き刺し強度を高めることができる。積層体３０の突き刺し強度は、１３Ｎ以上であることが好ましく、１５Ｎ以上であることがより好ましく、１７Ｎ以上であることがさらに好ましい。
　また、ＰＢＴは、ナイロンに比べて水分を吸収しにくいという特性を有する。このため、ＰＢＴを含む第１基材５１を積層体３０の外面３０ｙに配置した場合であっても、第１基材５１が水分を吸収して積層体３０のラミネート強度が低下してしまうことを抑制することができる。 In this Embodiment, when the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains the 1st base material 51 which has PBT as a main component, there can exist the following effect.
First, PBT is excellent in printability. For this reason, as in the case of polyethylene terephthalate, the light-shielding print layer 52 and the pattern print layer 53 can be provided on the first substrate 51 containing PBT.
Moreover, PBT is excellent in heat resistance. For this reason, when performing the retort process, the boil process, etc. to the bag 10, it can suppress that the 1st base material 51 deform | transforms or the intensity | strength of the 1st base material 51 falls.
PBT has high strength. For this reason, the puncture strength of the laminated body 30 and the bag 10 can be increased similarly to the case where the laminated body constituting the bag 10 includes nylon. The puncture strength of the laminate 30 is preferably 13N or more, more preferably 15N or more, and further preferably 17N or more.
PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the 1st substrate 51 containing PBT is arranged on outer surface 30y of layered product 30, the 1st substrate 51 absorbs moisture, and the lamination strength of layered product 30 will fall. Can be suppressed.
　また、本実施の形態においては、積層体３０が、第１基材５１と第２基材６１との間に位置する遮光印刷層５２を備える。このため、外光が積層体３０を透過して内容物に照射されてしまうことを抑制することができ、これにより、内容物が外光によって劣化することを抑制することができる。 Further, in the present embodiment, the laminated body 30 includes a light-shielding print layer 52 positioned between the first base material 51 and the second base material 61. For this reason, it can suppress that external light permeate | transmits the laminated body 30, and is irradiated to a content, and can suppress that a content deteriorates by external light by this.
　また、本実施の形態においては、積層体３０が、ＰＥＴ又はＰＢＴを主成分とする第２基材６１を含むことにより、第２基材６１がナイロンからなる場合に比べて、遮光印刷層５２で発生した異臭が第２フィルム６０及びシーラントフィルム７０を透過して内容物に付着してしまうことを抑制することができる。また、第２基材６１がＰＢＴからなる場合に比べて、積層体３０の耐熱性を高めることができる。これにより、例えば、袋１０を加熱した時に表面フィルム１４及び裏面フィルム１５がダメージを受けて表面フィルム１４及び裏面フィルム１５の性能が低下することを抑制することができる。 Moreover, in this Embodiment, the laminated body 30 contains the 2nd base material 61 which has PET or PBT as a main component, Compared with the case where the 2nd base material 61 consists of nylon, the light shielding printing layer 52. It is possible to prevent the off-flavor generated in step S from passing through the second film 60 and the sealant film 70 and adhering to the contents. Moreover, compared with the case where the 2nd base material 61 consists of PBT, the heat resistance of the laminated body 30 can be improved. Thereby, for example, when the bag 10 is heated, it is possible to prevent the front film 14 and the back film 15 from being damaged and the performance of the front film 14 and the back film 15 from being deteriorated.
　なお、上述した実施の形態に対して様々な変更を加えることが可能である。以下、必要に応じて図面を参照しながら、変形例について説明する。以下の説明および以下の説明で用いる図面では、上述した実施の形態と同様に構成され得る部分について、上述の実施の形態における対応する部分に対して用いた符号と同一の符号を用いることとし、重複する説明を省略する。また、上述した実施の形態において得られる作用効果が変形例においても得られることが明らかである場合、その説明を省略することもある。 Note that various modifications can be made to the above-described embodiment. Hereinafter, modified examples will be described with reference to the drawings as necessary. In the following description and the drawings used in the following description, the same reference numerals as those used for the corresponding parts in the above embodiment are used for the parts that can be configured in the same manner as in the above embodiment. A duplicate description is omitted. In addition, when it is clear that the operational effects obtained in the above-described embodiment can be obtained in the modified example, the description thereof may be omitted.
　本実施の形態に係る、遮光印刷層５２を備える積層体３０は、第３の実施の形態の場合と同様に、透明蒸着層３６や、透明蒸着層３６上に位置する透明ガスバリア性塗布膜３７を更に備えていてもよい。
　透明蒸着層３６は、第１基材５１の内面３０ｘ側の面に設けられていてもよい。この場合、積層体３０は、外面側から内面側へ順に
　　第１基材／透明蒸着層／透明ガスバリア性塗布膜／遮光印刷層／第１接着剤層／第２基材／第２接着剤層／シーラント層
を備えている、と言える。
　また、透明蒸着層３６は、第２基材６１の外面３０ｙ側の面に設けられていてもよい。この場合、積層体３０は、外面側から内面側へ順に
　　第１基材／第１接着剤層／遮光印刷層／透明ガスバリア性塗布膜／透明蒸着層／第２基材／第２接着剤層／シーラント層
を備えている、と言える。 As in the case of the third embodiment, the laminate 30 including the light-shielding print layer 52 according to the present embodiment is a transparent vapor deposition layer 36 or a transparent gas barrier coating film 37 positioned on the transparent vapor deposition layer 36. May be further provided.
The transparent vapor deposition layer 36 may be provided on the surface on the inner surface 30 x side of the first base material 51. In this case, the laminated body 30 is, in order from the outer surface side to the inner surface side, first substrate / transparent vapor deposition layer / transparent gas barrier coating film / light-shielding printing layer / first adhesive layer / second substrate / second adhesive layer. / It can be said that it has a sealant layer.
The transparent vapor deposition layer 36 may be provided on the surface of the second base 61 on the outer surface 30y side. In this case, the laminated body 30 is in order from the outer surface side to the inner surface side. First substrate / first adhesive layer / light-shielding printing layer / transparent gas barrier coating film / transparent vapor deposition layer / second substrate / second adhesive layer / It can be said that it has a sealant layer.
　（袋の変形例）
　上述の各実施の形態においては、袋１０がガセット式の袋である例を示したが、袋１０の具体的な構成が特に限定されることはない。例えば、袋１０は、１枚の積層体が筒状になるように背貼りシール部を形成することによって作製される、いわゆるピロー袋であってもよい。また、袋１０は、四方シール袋や三方シール袋であってもよい。 (Bag variant)
In each above-mentioned embodiment, although the bag 10 showed the example which is a gusset type bag, the specific structure of the bag 10 is not specifically limited. For example, the bag 10 may be a so-called pillow bag produced by forming a back-sealed seal portion so that a single laminate is formed into a cylindrical shape. The bag 10 may be a four-side sealed bag or a three-side sealed bag.
　次に、本発明を実施例により更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例の記載に限定されるものではない。 Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.
　以下に説明する実施例Ａ１～Ａ５及び比較例Ａ１～Ａ３は、第１の実施の形態において説明した、積層体の基材を構成するプラスチックフィルムが１つのみである場合に関する例である。また、実施例Ｂ１～Ｂ３及び比較例Ｂ１～Ｂ３は、第２の実施の形態において説明した、積層体が、基材とシーラント層との間に位置する金属箔を備える場合に関する例である。また、実施例Ｃ１～Ｃ６及び比較例Ｃ１，Ｃ２は、第３の実施の形態において説明した、積層体の基材を構成するプラスチックフィルムが２つ存在する場合に関する例である。また、実施例Ｄ１～Ｄ４及び比較例Ｄ１，Ｄ２は、第４の実施の形態において説明した、積層体の基材を構成するプラスチックフィルムが２つ存在し、積層体が遮光印刷層を更に備える場合に関する例である。まず、実施例Ａ１～Ａ４及び比較例Ａ１，Ａ２について説明する。 Examples A1 to A5 and Comparative Examples A1 to A3 described below are examples relating to the case where there is only one plastic film constituting the base material of the laminate described in the first embodiment. Examples B1 to B3 and Comparative Examples B1 to B3 are examples related to the case where the laminate includes a metal foil positioned between the base material and the sealant layer described in the second embodiment. Examples C1 to C6 and Comparative Examples C1 and C2 are examples relating to the case where there are two plastic films constituting the base material of the laminate described in the third embodiment. In Examples D1 to D4 and Comparative Examples D1 and D2, there are two plastic films constituting the base material of the laminate described in the fourth embodiment, and the laminate further includes a light-shielding print layer. An example of the case. First, Examples A1 to A4 and Comparative Examples A1 and A2 will be described.
　（実施例Ａ１）
　〔積層体の作製〕
　上述の第１の構成で説明した、複数の層４１ａを含み、キャスト法で作製された、フィルム状の基材４１を準備した。各層４１ａにおけるＰＢＴの含有率は８０％であり、層４１ａの層数は１０２４であり、基材４１の厚みは１５μｍであった。続いて、フィルム状の基材４１上にグラビア印刷によって印刷層４２を形成した。印刷層４２を形成するためのインキとしては、大日精化工業製の白色インキ　ラミックＦＢを用いた。このようにして、基材４１及び印刷層４２を有する第１フィルム４０を作製した。印刷層４２の厚みは１μｍであった。 (Example A1)
(Production of laminate)
A film-like base material 41 including a plurality of layers 41a described in the first configuration and manufactured by a casting method was prepared. The content of PBT in each layer 41a was 80%, the number of layers 41a was 1024, and the thickness of the base material 41 was 15 μm. Subsequently, the printing layer 42 was formed on the film-like substrate 41 by gravure printing. As an ink for forming the printing layer 42, white ink ceramic FB manufactured by Dainichi Seika Kogyo was used. Thus, the 1st film 40 which has the base material 41 and the printing layer 42 was produced. The thickness of the printing layer 42 was 1 μm.
　次に、主剤及び溶剤を含む第１組成物と、硬化剤及び溶剤を含む第２組成物とを混合して接着剤組成物を作製した。主剤及び溶剤を含む第１組成物としては、ロックペイント株式会社製のＲＵ－４０を用いた。ＲＵ－４０は、ポリエステルポリオールを含む。硬化剤及び溶剤を含む第２組成物としては、ロックペイント株式会社製のＨ－４を用いた。Ｈ－４は、脂肪族系イソシアネート化合物を含む。第１組成物に対する第２組成物の重量比は０．１５とした。また、接着剤組成物における、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は４．５であった。 Next, an adhesive composition was prepared by mixing a first composition containing a main agent and a solvent and a second composition containing a curing agent and a solvent. RU-40 manufactured by Rock Paint Co., Ltd. was used as the first composition containing the main agent and the solvent. RU-40 contains a polyester polyol. H-4 manufactured by Rock Paint Co., Ltd. was used as the second composition containing a curing agent and a solvent. H-4 contains an aliphatic isocyanate compound. The weight ratio of the second composition to the first composition was 0.15. Moreover, the molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxy group of the polyol in the adhesive composition was 4.5.
　次に、接着剤組成物を第１フィルム４０の印刷層４２上に塗布した。続いて、第１フィルム４０上に塗布された接着剤組成物を乾燥させて溶剤を揮発させた。その後、乾燥後の接着剤組成物を介して第１フィルム４０とシーラントフィルム７０とを積層した。続いて、積層体を、４０℃の環境下で９６時間にわたって加熱した。これにより、接着剤組成物を硬化させて、ポリオールと脂肪族系イソシアネート化合物との硬化物を含む接着剤層４５を得た。接着剤層４５の厚みは、３μｍであった。 Next, the adhesive composition was applied on the printing layer 42 of the first film 40. Subsequently, the adhesive composition applied on the first film 40 was dried to volatilize the solvent. Then, the 1st film 40 and the sealant film 70 were laminated | stacked through the adhesive composition after drying. Subsequently, the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive composition was cured to obtain an adhesive layer 45 containing a cured product of a polyol and an aliphatic isocyanate compound. The thickness of the adhesive layer 45 was 3 μm.
　次に、シーラント層７１を含むシーラントフィルム７０を準備した。シーラント層７１としては、東レフィルム加工株式会社製の未延伸ポリプロピレンフィルム　ＺＫ９３ＦＭを用いた。シーラント層７１の厚みは７０μｍであった。 Next, a sealant film 70 including a sealant layer 71 was prepared. As the sealant layer 71, an unstretched polypropylene film ZK93FM manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the sealant layer 71 was 70 μm.
　〔ラミネート強度の評価〕
　続いて、積層体３０の第１フィルム４０とシーラントフィルム７０との間のラミネート強度を測定した。測定器としては、Ａ＆Ｄ製のテンシロン万能材料試験機ＲＴＣ－１３１０を用いた。具体的には、まず、積層体３０を切り出して、図１１に示すように、第１フィルム４０とシーラントフィルム７０とを長辺方向において１５ｍｍ剥離させた矩形状の試験片８０を準備した。試験片８０の幅（短辺の長さ）は１５ｍｍとした。その後、図１２に示すように、第１フィルム４０及びシーラントフィルム７０のうち既に剥離されている部分をそれぞれ、測定器のつかみ具８１及びつかみ具８２で把持した。また、つかみ具８１，８２をそれぞれ、第１フィルム４０とシーラントフィルム７０とがまだ積層されている部分の面方向に対して直交する方向において互いに逆向きに、５０ｍｍ／分の速度で引っ張り、安定領域（図１３参照）における引張応力の平均値を測定した。引っ張りを開始する際の、つかみ具８１，８２間の間隔Ｓは３０ｍｍとし、引っ張りを終了する際の、つかみ具８１，８２間の間隔Ｓは６０ｍｍとした。図１３は、つかみ具８１，８２間の間隔Ｓに対する引張応力の変化を示す図である。図１３に示すように、間隔Ｓに対する引張応力の変化は、第１領域を経て、第１領域よりも変化率の小さい第２領域（安定領域）に入る。 [Evaluation of laminate strength]
Subsequently, the laminate strength between the first film 40 and the sealant film 70 of the laminate 30 was measured. As a measuring instrument, Tensilon universal material testing machine RTC-1310 manufactured by A & D was used. Specifically, first, the laminate 30 was cut out, and as shown in FIG. 11, a rectangular test piece 80 in which the first film 40 and the sealant film 70 were peeled by 15 mm in the long side direction was prepared. The width (length of short side) of the test piece 80 was 15 mm. Thereafter, as shown in FIG. 12, the already peeled portions of the first film 40 and the sealant film 70 were respectively held by the gripping tool 81 and the gripping tool 82 of the measuring instrument. Further, each of the grips 81 and 82 is pulled at a speed of 50 mm / min in a direction opposite to each other in the direction orthogonal to the surface direction of the portion where the first film 40 and the sealant film 70 are still laminated. The average value of tensile stress in the region (see FIG. 13) was measured. The spacing S between the gripping tools 81 and 82 when starting the pulling was 30 mm, and the spacing S between the gripping tools 81 and 82 when finishing the pulling was 60 mm. FIG. 13 is a diagram illustrating a change in tensile stress with respect to the distance S between the gripping tools 81 and 82. As shown in FIG. 13, the change of the tensile stress with respect to the interval S enters the second region (stable region) having a smaller change rate than the first region through the first region.
　５個の試験片８０について、安定領域における引張応力の平均値を測定し、その平均値を積層体３０のラミネート強度とした。測定時の環境は、温度２３℃、相対湿度５０％とした。結果、１５ｍｍ幅におけるラミネート強度は６．７Ｎであった。 For the five test pieces 80, the average value of the tensile stress in the stable region was measured, and the average value was taken as the laminate strength of the laminate 30. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. As a result, the laminate strength at a width of 15 mm was 6.7 N.
　〔引き裂き性の評価〕
　長尺状の積層体３０を、図１４に示すように、幅Ｗ１が１５ｍｍ、長さＷ２が１００ｍｍとなるように切り出して、試験片９０を作製した。試験片９０の幅Ｗ１は、図１に示す袋１０の高さＳ１の方向に平行である。また、試験片９０の長さＷ２は、基材４１を成膜する際の流れ方向に平行であり、また、図１に示す袋１０の幅Ｓ２の方向に平行である。続いて、図１４に示すように、試験片９０の幅Ｗ１の方向における中央に切れ込み２８を形成した。続いて、切れ込み２８を起点として、長さＷ２の方向において試験片９０を手で引き裂いた。結果、途中で積層体３０のシーラントフィルム７０が伸びることなく、試験片９０を長さＷ２の方向で引き裂くことができた。 [Evaluation of tearability]
As shown in FIG. 14, the long laminate 30 was cut out so that the width W1 was 15 mm and the length W2 was 100 mm, and the test piece 90 was produced. The width W1 of the test piece 90 is parallel to the direction of the height S1 of the bag 10 shown in FIG. Further, the length W2 of the test piece 90 is parallel to the flow direction when the base material 41 is formed, and is parallel to the direction of the width S2 of the bag 10 shown in FIG. Subsequently, as shown in FIG. 14, a cut 28 was formed at the center of the test piece 90 in the width W1 direction. Subsequently, the test piece 90 was manually torn in the direction of the length W2 starting from the notch 28. As a result, the test piece 90 could be torn in the direction of the length W2 without the sealant film 70 of the laminated body 30 extending along the way.
　〔耐衝撃性の評価〕
　続いて、２枚の積層体３０を重ねて１９０℃で１秒間にわたって加熱し、積層体３０の内面３０ｘ同士をヒートシールした。次に、ヒートシールされた２枚の積層体３０を１５ｍｍ幅で切り出して、試験片１００を作製した。図１５は、試験片１００を示す平面図であり、図１６は、図１５の試験片９０の断面図である。試験片９０は、幅Ｗ３が１５ｍｍで長さＷ４が５０ｍｍであり、一方の端部から１０ｍｍの長さＷ５に亘ってシール部１０１が形成され、他方の端部から４０ｍｍの長さに亘ってシール部が形成されていないものである。続いて、図１７に示すように、一方の積層体３０のシールされていない部分と他方の積層体３０のシールされていない部分をシール部１０１の面方向に対して直交する方向において互いに逆向きになるように、すなわちＴ字状になるようにした後、一方の積層体３０のシールされていない部分の端部と他方の積層体３０のシールされていない部分の端部をそれぞれ治具１０２，１０３に固定した。このとき、シール部１０１の面方向に対して直交する方向における治具１０２，１０３間の距離Ｔは４０ｍｍとした。続いて、一方の治具１０２に対して、一方の積層体３０の第１フィルム４０側の面からハンマー１０４で叩いて、一方の積層体３０と他方の積層体３０とが分離する際の衝撃強度を測定した。測定器としては、株式会社東洋精機製作所製のデジタルインパクトテスターを用いて評価した。試験片１００に衝撃を加えるためのハンマーとしては、２Ｊのものを用いた。結果、衝撃強度は１０５６ｋＪ／ｍであった。 [Evaluation of impact resistance]
Subsequently, the two laminates 30 were stacked and heated at 190 ° C. for 1 second, and the inner surfaces 30x of the laminate 30 were heat-sealed. Next, the heat-sealed two laminated bodies 30 were cut out with a width of 15 mm, and the test piece 100 was produced. 15 is a plan view showing the test piece 100, and FIG. 16 is a cross-sectional view of the test piece 90 of FIG. The test piece 90 has a width W3 of 15 mm and a length W4 of 50 mm, a seal portion 101 is formed over a length W5 of 10 mm from one end, and a length of 40 mm from the other end. The seal portion is not formed. Subsequently, as shown in FIG. 17, the unsealed portion of one laminate 30 and the unsealed portion of the other laminate 30 are opposite to each other in a direction perpendicular to the surface direction of the seal portion 101. In other words, the end of the unsealed portion of one laminated body 30 and the end of the unsealed portion of the other laminated body 30 are respectively connected to the jig 102. , 103. At this time, the distance T between the jigs 102 and 103 in the direction orthogonal to the surface direction of the seal portion 101 was 40 mm. Subsequently, the impact when the one laminate 30 and the other laminate 30 are separated by hitting one jig 102 with the hammer 104 from the surface of the one laminate 30 on the first film 40 side. The strength was measured. Evaluation was performed using a digital impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd. As the hammer for applying an impact to the test piece 100, a 2J hammer was used. As a result, the impact strength was 1056 kJ / m.
　続いて、積層体３０の突き刺し強度を、ＪＩＳ　Ｚ１７０７　７．４に準拠して測定した。測定器としては、Ａ＆Ｄ製のテンシロン万能材料試験機ＲＴＣ－１３１０を用いた。具体的には、図１８に示すように、固定されている状態の積層体３０の試験片に対して、外面３０ｙ側から、直径１．０ｍｍ、先端形状半径０．５ｍｍの半円形の針１１０を、５０ｍｍ／分（１分あたり５０ｍｍ）の速度で突き刺し、針１１０が積層体３０を貫通するまでの応力の最大値を測定した。５個以上の試験片について、応力の最大値を測定し、その平均値を積層体３０の突き刺し強度とした。測定時の環境は、温度２３℃、相対湿度５０％とした。結果、突き刺し強度は１５Ｎであった。 Subsequently, the piercing strength of the laminate 30 was measured according to JIS Z1707 7.4. As a measuring instrument, Tensilon universal material testing machine RTC-1310 manufactured by A & D was used. Specifically, as shown in FIG. 18, a semicircular needle 110 having a diameter of 1.0 mm and a tip shape radius of 0.5 mm from the outer surface 30y side with respect to the test piece of the laminated body 30 in a fixed state. Was stabbed at a speed of 50 mm / min (50 mm per minute), and the maximum value of stress until the needle 110 penetrated the laminate 30 was measured. About five or more test pieces, the maximum value of stress was measured, and the average value was defined as the piercing strength of the laminate 30. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. As a result, the piercing strength was 15N.
　〔落下強度の評価〕
　続いて、２枚の積層体３０を重ねて１９０℃で１秒間にわたって加熱し、積層体３０の内面３０ｘ同士をヒートシールするとともに、内容物として２００ｇの水を充填して、４方シール袋１０を作製した。袋１０の高さＳ１は１８０ｍｍとし、幅Ｓ２は１３０ｍｍとした。 (Evaluation of drop strength)
Subsequently, the two laminates 30 are overlapped and heated at 190 ° C. for 1 second to heat seal the inner surfaces 30x of the laminate 30 and fill with 200 g of water as the contents to fill the four-side sealed bag 10. Was made. The height S1 of the bag 10 was 180 mm, and the width S2 was 130 mm.
　水が収容された状態の袋１０を３℃の環境下で一晩保管した後、表面フィルム１４及び裏面フィルム１５が水平になるように保持した袋１０を、１２０ｃｍの高さから落下させて、袋１０が破袋するか否かを検査した。袋１０を繰り返し５回落下させたが、破袋は見られなかった。 After storing the bag 10 containing water overnight in an environment of 3 ° C., the bag 10 holding the front film 14 and the back film 15 so as to be horizontal is dropped from a height of 120 cm, It was inspected whether the bag 10 was broken. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
　（実施例Ａ２）
　接着剤組成物を作製する際の、第１組成物に対する第２組成物の重量比を０．２としたこと以外は、実施例Ａ１の場合と同様にして、積層体３０を作製した。接着剤組成物における、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は６であった。 (Example A2)
A laminate 30 was produced in the same manner as in Example A1, except that the weight ratio of the second composition to the first composition was 0.2 when producing the adhesive composition. The molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxy group of the polyol in the adhesive composition was 6.
　また、実施例Ａ１の場合と同様にして、積層体３０のラミネート強度を評価した。結果、１５ｍｍ幅におけるラミネート強度は７．１Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０の引き裂き性を評価した。結果、途中で積層体３０のシーラントフィルム７０が伸びることなく、試験片９０を長さＷ２の方向で引き裂くことができた。また、実施例Ａ１の場合と同様にして、２枚の積層体３０の内面３０ｘ同士をヒートシールした積層体の耐衝撃性を評価した。結果、積層体の衝撃強度は１１３７ｋＪ／ｍであった。また、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１５Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０を用いて構成した袋１０の落下強度を評価した。袋１０を繰り返し５回落下させたが、破袋は見られなかった。 Further, the laminate strength of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the laminate strength at a width of 15 mm was 7.1 N. Further, the tearability of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the test piece 90 could be torn in the direction of the length W2 without the sealant film 70 of the laminated body 30 extending along the way. Further, in the same manner as in Example A1, the impact resistance of the laminate in which the inner surfaces 30x of the two laminates 30 were heat-sealed was evaluated. As a result, the impact strength of the laminate was 1137 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 15N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
　（実施例Ａ３）
　各層４１ａにおけるＰＢＴの含有率が７０％である基材４１を用いたこと以外は、実施例Ａ１の場合と同様にして、積層体３０を作製した。また、実施例Ａ１の場合と同様にして、積層体３０のラミネート強度を評価した。結果、１５ｍｍ幅におけるラミネート強度は６．５Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０の引き裂き性を評価した。結果、途中で積層体３０のシーラントフィルム７０が伸びることなく、試験片９０を長さＷ２の方向で引き裂くことができた。また、実施例Ａ１の場合と同様にして、２枚の積層体３０の内面３０ｘ同士をヒートシールした積層体の耐衝撃性を評価した。結果、積層体の衝撃強度は９１２ｋＪ／ｍであった。また、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１３Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０を用いて構成した袋１０の落下強度を評価した。袋１０を繰り返し５回落下させたが、破袋は見られなかった。 (Example A3)
A laminate 30 was produced in the same manner as in Example A1, except that the base material 41 having a PBT content of 70% in each layer 41a was used. Further, the laminate strength of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the laminate strength at a width of 15 mm was 6.5 N. Further, the tearability of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the test piece 90 could be torn in the direction of the length W2 without the sealant film 70 of the laminated body 30 extending along the way. Further, in the same manner as in Example A1, the impact resistance of the laminate in which the inner surfaces 30x of the two laminates 30 were heat-sealed was evaluated. As a result, the impact strength of the laminate was 912 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 13N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
　（比較例Ａ１）
　接着剤組成物を作製する際の、第１組成物に対する第２組成物の重量比を０．１としたこと以外は、実施例Ａ１の場合と同様にして、積層体３０を作製した。接着剤組成物における、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は３であった。 (Comparative Example A1)
A laminate 30 was produced in the same manner as in Example A1, except that the weight ratio of the second composition to the first composition was 0.1 when producing the adhesive composition. The molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol in the adhesive composition was 3.
　また、実施例Ａ１の場合と同様にして、積層体３０のラミネート強度を評価した。結果、１５ｍｍ幅におけるラミネート強度は４．２Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０の引き裂き性を評価した。結果、途中で積層体３０のシーラントフィルム７０が伸びてしまい、このため、試験片９０を長さＷ２の方向で引き裂くことができなかった。また、実施例Ａ１の場合と同様にして、２枚の積層体３０の内面３０ｘ同士をヒートシールした積層体の耐衝撃性を評価した。結果、積層体の衝撃強度は７５８ｋＪ／ｍであった。また、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１５Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０を用いて構成した袋１０の落下強度を評価した。結果、４回目の落下で袋１０が破袋した。 Further, the laminate strength of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the laminate strength at a width of 15 mm was 4.2 N. Further, the tearability of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the sealant film 70 of the laminate 30 was stretched on the way, and therefore the test piece 90 could not be torn in the direction of the length W2. Further, in the same manner as in Example A1, the impact resistance of the laminate in which the inner surfaces 30x of the two laminates 30 were heat sealed was evaluated. As a result, the impact strength of the laminate was 758 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 15N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. As a result, the bag 10 was broken by the fourth drop.
　（実施例Ａ４）
　外面側から内面側へ順に基材４１／接着剤層４５／シーラント層７１を備える積層体３０を作製した。基材４１としては、実施例Ａ１の場合と同様に、複数の層４１ａを含み、キャスト法で作製された、フィルム状の基材４１を用いた。接着剤層４５を構成するための接着剤組成物としては、実施例Ａ１の場合と同様に、ＲＵ－４０を含む第１組成物とＨ－４を含む第２組成物とによって構成されたものを用いた。第１組成物に対する第２組成物の重量比は、比較例Ａ１の場合と同様に０．１０とした。接着剤組成物における、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は３であった。シーラント層７１としては、東レフィルム加工株式会社製の未延伸ポリプロピレンフィルム　ＺＫ５００を用いた。ＺＫ５００は、上述のプロピレン・エチレンブロック共重合体及びエラストマーを含む。シーラント層７１の厚みは７０μｍであった。
　実施例Ａ４の積層体３０は、比較例Ａ１の積層体３０から印刷層４２を削除し、且つ、シーラント層７１をＺＫ５００に置換したものであると言える。 (Example A4)
The laminated body 30 provided with the base material 41 / adhesive layer 45 / sealant layer 71 in this order from the outer surface side to the inner surface side was produced. As the base material 41, as in Example A1, a film-like base material 41 including a plurality of layers 41a and manufactured by a casting method was used. As in the case of Example A1, the adhesive composition for constituting the adhesive layer 45 is composed of the first composition containing RU-40 and the second composition containing H-4. Was used. The weight ratio of the second composition to the first composition was 0.10 as in Comparative Example A1. The molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol in the adhesive composition was 3. As the sealant layer 71, an unstretched polypropylene film ZK500 manufactured by Toray Film Processing Co., Ltd. was used. ZK500 contains the above-mentioned propylene / ethylene block copolymer and elastomer. The thickness of the sealant layer 71 was 70 μm.
It can be said that the laminated body 30 of Example A4 is obtained by deleting the printed layer 42 from the laminated body 30 of Comparative Example A1 and replacing the sealant layer 71 with ZK500.
　実施例Ａ１の場合と同様にして、２枚の積層体３０の内面３０ｘ同士をヒートシールして試験片１００を作製し、衝撃強度を測定した。結果、衝撃強度は９４６ｋＪ／ｍであった。また、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１５Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０を用いて構成した袋１０の落下強度を評価した。袋１０を繰り返し５回落下させたが、破袋は見られなかった。 In the same manner as in Example A1, the inner surfaces 30x of the two laminates 30 were heat sealed to produce a test piece 100, and the impact strength was measured. As a result, the impact strength was 946 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 15N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
　（実施例Ａ５）
　基材４１として、ＰＢＴを含み、チューブラー法で作製されたフィルム状の基材４１を用いたこと以外は、実施例Ａ４の場合と同様にして、積層体３０を作製した。基材４１はＰＢＴ及び添加剤のみで構成される単層のフィルムであり、基材４１の厚みは１５μｍであった。 (Example A5)
A laminate 30 was produced in the same manner as in Example A4, except that a film-like substrate 41 containing PBT and produced by a tubular method was used as the substrate 41. The base material 41 was a single layer film composed only of PBT and an additive, and the thickness of the base material 41 was 15 μm.
　実施例Ａ１の場合と同様にして、２枚の積層体３０の内面３０ｘ同士をヒートシールして試験片１００を作製し、衝撃強度を測定した。結果、衝撃強度は８３８ｋＪ／ｍであった。また、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１５Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０を用いて構成した袋１０の落下強度を評価した。袋１０を繰り返し５回落下させたが、破袋は見られなかった。 In the same manner as in Example A1, the inner surfaces 30x of the two laminates 30 were heat sealed to produce a test piece 100, and the impact strength was measured. As a result, the impact strength was 838 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 15N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. The bag 10 was repeatedly dropped 5 times, but no broken bag was seen.
　（比較例Ａ２）
　シーラント層７１として、東レフィルム加工株式会社製の未延伸ポリプロピレンフィルム　ＺＫ９３ＦＭを用いたこと以外は、実施例Ａ４の場合と同様にして、積層体３０を作製した。シーラント層７１の厚みは７０μｍであった。 (Comparative Example A2)
A laminate 30 was produced in the same manner as in Example A4 except that an unstretched polypropylene film ZK93FM manufactured by Toray Film Processing Co., Ltd. was used as the sealant layer 71. The thickness of the sealant layer 71 was 70 μm.
　実施例Ａ１の場合と同様にして、２枚の積層体３０の内面３０ｘ同士をヒートシールして試験片１００を作製し、衝撃強度を測定した。結果、衝撃強度は５０２ｋＪ／ｍであった。また、実施例Ａ１の場合と同様にして、積層体３０を用いて構成した袋１０の落下強度を評価した。結果、４回目の落下で袋１０が破袋した。 In the same manner as in Example A1, the inner surfaces 30x of the two laminates 30 were heat sealed to produce a test piece 100, and the impact strength was measured. As a result, the impact strength was 502 kJ / m. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. As a result, the bag 10 was broken by the fourth drop.
　（比較例Ａ３）
　基材４１として東洋紡製のＰＥＴフィルム　Ｅ５１００（厚み１２μｍ）を用いたこと以外は、比較例Ａ２の場合と同様にして、積層体３０を作製した。また、実施例Ａ１の場合と同様にして、積層体３０のラミネート強度を評価した。結果、１５ｍｍ幅におけるラミネート強度は３．８Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０の引き裂き性を評価した。結果、途中で積層体３０のシーラントフィルム７０が伸びてしまい、このため、試験片９０を長さＷ２の方向で引き裂くことができなかった。また、実施例Ａ１の場合と同様にして、２枚の積層体３０の内面３０ｘ同士をヒートシールした積層体の耐衝撃性を評価した。結果、積層体の衝撃強度は５３７ｋＪ／ｍであった。また、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１０Ｎであった。また、実施例Ａ１の場合と同様にして、積層体３０を用いて構成した袋１０の落下強度を評価した。結果、４回目の落下で袋１０が破袋した。 (Comparative Example A3)
A laminate 30 was produced in the same manner as in Comparative Example A2, except that Toyobo PET film E5100 (thickness 12 μm) was used as the substrate 41. Further, the laminate strength of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the laminate strength at a width of 15 mm was 3.8N. Further, the tearability of the laminate 30 was evaluated in the same manner as in Example A1. As a result, the sealant film 70 of the laminate 30 was stretched on the way, and therefore the test piece 90 could not be torn in the direction of the length W2. Further, in the same manner as in Example A1, the impact resistance of the laminate in which the inner surfaces 30x of the two laminates 30 were heat-sealed was evaluated. As a result, the impact strength of the laminate was 537 kJ / m. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 10N. Moreover, the drop strength of the bag 10 configured using the laminate 30 was evaluated in the same manner as in Example A1. As a result, the bag 10 was broken by the fourth drop.
　実施例Ａ１～Ａ５及び比較例Ａ１～Ａ３の積層体３０の層構成及び評価結果を、図１９にまとめて示す。実施例Ａ１～Ａ５と比較例Ａ１，Ａ２の比較から分かるように、８００ｋＪ／ｍ以上の衝撃強度を有する積層体３０を用いて袋１０を構成することにより、５回の落下でも破袋しない程度の落下強度を袋１０に持たせることができた。 FIG. 19 shows the layer configuration and evaluation results of the laminates 30 of Examples A1 to A5 and Comparative Examples A1 to A3. As can be seen from the comparison between Examples A1 to A5 and Comparative Examples A1 and A2, by forming the bag 10 using the laminate 30 having an impact strength of 800 kJ / m or more, the bag does not break even when dropped five times. It was possible to give the bag 10 the drop strength.
　実施例Ａ４，Ａ５と比較例Ａ１、Ａ２との比較から分かるように、積層体３０の衝撃強度を高める上では、シーラント層７１がプロピレン・エチレンブロック共重合体を含むことや、エラストマーを含むことが好ましいと言える。また、実施例Ａ１，Ａ２，Ａ３と比較例Ａ１，Ａ３との比較から分かるように、積層体３０の衝撃強度を高める上では、接着剤組成物における、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比が高いことが好ましいと言える。 As can be seen from the comparison between Examples A4 and A5 and Comparative Examples A1 and A2, in order to increase the impact strength of the laminate 30, the sealant layer 71 contains a propylene / ethylene block copolymer or contains an elastomer. Can be said to be preferable. Further, as can be seen from the comparison between Examples A1, A2, A3 and Comparative Examples A1, A3, in order to increase the impact strength of the laminate 30, an aliphatic isocyanate compound for the hydroxyl group of the polyol in the adhesive composition. It can be said that it is preferable that the molar ratio of the isocyanate groups is high.
　実施例Ａ１、Ａ２、Ａ３と比較例Ａ１、Ａ３の比較から分かるように、硬化剤として脂肪族系イソシアネート化合物を用いた場合であっても、接着剤層４５における硬化剤の構成比率を高めることにより、積層体３０のラミネート強度を高くすることができた。これにより、積層体３０に良好な引き裂き性を持たせることができた。また、積層体３０の衝撃強度を高くすることもできた。なお、引き裂き性に関して、実施例Ａ１、Ａ２、Ａ３においては、試験片９０を長さＷ２の方向で全域にわたってスムーズに引き裂くことができたので、評価結果を「ｇｏｏｄ」とした。一方、比較例Ａ１、Ａ３においては、途中で積層体３０のシーラントフィルム７０が伸びてしまい、このため、試験片９０を長さＷ２の方向で全域にわたってスムーズに引き裂くことができなかったので、評価結果を「ｂａｄ」とした。 As can be seen from the comparison between Examples A1, A2, and A3 and Comparative Examples A1 and A3, the composition ratio of the curing agent in the adhesive layer 45 is increased even when an aliphatic isocyanate compound is used as the curing agent. Thus, the laminate strength of the laminate 30 could be increased. Thereby, it was possible to give the laminate 30 good tearability. In addition, the impact strength of the laminate 30 could be increased. Regarding the tearability, in Examples A1, A2, and A3, the test piece 90 could be smoothly torn across the entire area in the direction of the length W2, and thus the evaluation result was “good”. On the other hand, in Comparative Examples A1 and A3, the sealant film 70 of the laminate 30 was stretched in the middle, and therefore, the test piece 90 could not be smoothly torn across the entire area in the direction of the length W2, and thus evaluation was performed. The result was “bad”.
　また、比較例Ａ３に示すように、基材４１がＰＥＴフィルムからなる場合、積層体３０の突き刺し強度が１０Ｎ以下であった。一方、実施例Ａ１～Ａ５に示すように、基材４１がＰＢＴを主成分として含むフィルムからなる場合、積層体３０の突き刺し強度を１１Ｎ以上にすることができ、より具体的には１３Ｎ以上にすることができた。 Moreover, as shown in Comparative Example A3, when the base material 41 was made of a PET film, the puncture strength of the laminate 30 was 10 N or less. On the other hand, as shown in Examples A1 to A5, when the base material 41 is made of a film containing PBT as a main component, the puncture strength of the laminate 30 can be 11 N or more, more specifically 13 N or more. We were able to.
　次に、第２の実施の形態において説明した、積層体が、基材とシーラント層との間に位置する金属箔を備える場合に関する実施例Ｂ１、Ｂ２及び比較例Ｂ１、Ｂ２について説明する。 Next, Examples B1 and B2 and Comparative Examples B1 and B2 related to the case where the laminate described in the second embodiment includes a metal foil positioned between the base material and the sealant layer will be described.
　（実施例Ｂ１）
　実施例Ａ１の場合と同様にして、上述の第１の構成で説明した、複数の層を含み、キャスト法で作製されたフィルム状の第１基材５１を準備した。各層におけるＰＢＴの含有率は８０％であり、層の層数は１０２４であり、第１基材５１の厚みは１５μｍであった。また、シーラント層７１を含むシーラントフィルム７０を準備した。シーラント層７１としては、東レフィルム加工株式会社製の未延伸ポリプロピレンフィルム　ＺＫ９９Ｓを用いた。シーラント層７１の厚みは７０μｍであった。また、金属箔４７として、厚み７μｍのアルミニウム箔を準備した。 (Example B1)
In the same manner as in Example A1, a film-like first base material 51 including a plurality of layers and manufactured by a casting method described in the first configuration was prepared. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the first base material 51 was 15 μm. Further, a sealant film 70 including a sealant layer 71 was prepared. As the sealant layer 71, an unstretched polypropylene film ZK99S manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the sealant layer 71 was 70 μm. Further, an aluminum foil having a thickness of 7 μm was prepared as the metal foil 47.
　基材４１からなる第１フィルム４０における反りを評価した。具体的には、まず、第１フィルム４０を切り出して、一辺１０ｃｍの正方形状の試験片を作製した。続いて、正方形状の試験片の４隅においてそれぞれ、反りの高さを測定した。結果、４隅における反りの高さの最大値は、０ｍｍであった。なお、第１フィルム４０をその長手方向に沿って搬送する際に第１フィルム４０の幅方向の端部に反りや折れなどが生じるのを抑制する上では、試験片の４隅における反りの高さの最大値が５ｍｍ以下であることが好ましく、３ｍｍ以下であることがより好ましい。 The curvature in the 1st film 40 which consists of base materials 41 was evaluated. Specifically, first, the first film 40 was cut out to produce a square test piece having a side of 10 cm. Subsequently, the height of warpage was measured at each of the four corners of the square test piece. As a result, the maximum value of the height of warpage at the four corners was 0 mm. It should be noted that when the first film 40 is transported along the longitudinal direction thereof, the warp and the crease at the end in the width direction of the first film 40 are suppressed, so that the height of the warp at the four corners of the test piece is high. The maximum value is preferably 5 mm or less, and more preferably 3 mm or less.
　次に、第１接着剤層４６を介して第１フィルム４０と金属箔４７とをドライラミネート法により積層する第１ラミネート工程を実施した。具体的には、まず、第１フィルム４０に溶剤を含む接着剤を塗布した後、接着剤を乾燥させることにより溶剤を揮発させて、未硬化状態の第１接着剤層４６を形成した。接着剤は、主剤として東洋モートン株式会社製のＴＭ－５５６Ｓ、硬化剤として東洋モートン株式会社製のＣＡＴ－５６を用いた。ＴＭ－５５６Ｓは、ポリエステルポリオールを含む。ＣＡＴ－５６は、芳香族系イソシアネート化合物を含む。また、ポリオールのヒドロキシ基に対する芳香族系イソシアネート化合物のイソシアネート基のモル比は３であった。続いて、第１接着剤層４６が形成された第１フィルム４０及び金属箔４７を、両者を積層するためのラミロールに向けて搬送した。その後、ラミロールを用いて金属箔４７を第１フィルム４０に圧着させ、第１フィルム４０及び金属箔４７の積層体を作製した。続いて、積層体を、４０℃の環境下で９６時間にわたって加熱した。これにより、接着剤を硬化させて、ポリオールと芳香族系イソシアネート化合物との硬化物を含む第１接着剤層４６を得た。第１接着剤層４６の厚みは、３μｍであった。 Next, a first laminating step of laminating the first film 40 and the metal foil 47 through the first adhesive layer 46 by a dry laminating method was performed. Specifically, first, an adhesive containing a solvent was applied to the first film 40, and then the solvent was volatilized by drying the adhesive to form an uncured first adhesive layer 46. As the adhesive, TM-556S manufactured by Toyo Morton Co., Ltd. was used as the main agent, and CAT-56 manufactured by Toyo Morton Co., Ltd. was used as the curing agent. TM-556S contains polyester polyol. CAT-56 contains an aromatic isocyanate compound. The molar ratio of the isocyanate group of the aromatic isocyanate compound to the hydroxyl group of the polyol was 3. Then, the 1st film 40 in which the 1st adhesive bond layer 46 was formed, and metal foil 47 were conveyed toward the lami roll for laminating both. Then, the metal foil 47 was press-bonded to the first film 40 using a lami roll, and a laminate of the first film 40 and the metal foil 47 was produced. Subsequently, the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a first adhesive layer 46 containing a cured product of a polyol and an aromatic isocyanate compound. The thickness of the first adhesive layer 46 was 3 μm.
　第１ラミネート工程において第１フィルム４０を搬送する際、第１フィルム４０の端部に反りや折れなどは観察されなかった。このため、反りや折れなどを解消するために第１フィルム４０に加える張力を調整する作業は不要であった。 When the first film 40 was transported in the first laminating step, no warp or breakage was observed at the end of the first film 40. For this reason, the operation | work which adjusts the tension | tensile_strength added to the 1st film 40 in order to eliminate a curvature, a bend, etc. was unnecessary.
　続いて、金属箔４７に溶剤を含む接着剤を塗布した後、接着剤を乾燥させることにより溶剤を揮発させて、未硬化状態の第２接着剤層４８を形成した。接着剤は、主剤としてロックペイント株式会社製のＲＵ－４０、硬化剤としてロックペイント株式会社製のＨ－４を用いた。ＲＵ－４０は、ポリエステルポリオールを含む。Ｈ－４は、脂肪族系イソシアネート化合物を含む。また、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は３であった。その後、第２接着剤層４８を介して第１フィルム４０及び金属箔４７の積層体とシーラントフィルム７０とをドライラミネート法により積層する第２ラミネート工程を実施した。このようにして、外面３０ｙ側から内面３０ｘ側へ順に第１フィルム４０、金属箔４７及びシーラントフィルム７０を備える積層体３０を作製した。続いて、積層体３０を、４０℃の環境下で９６時間にわたって加熱した。これにより、接着剤を硬化させて、ポリオールと脂肪族系イソシアネート化合物との硬化物を含む第２接着剤層４８を得た。第２接着剤層４８の厚みは、３μｍであった。積層体３０の層構成は、下記のように表される。
　ＰＢＴ（多層）／第１接着剤層／アルミニウム箔／第２接着剤層／ポリプロピレン Subsequently, after applying an adhesive containing a solvent to the metal foil 47, the solvent was volatilized by drying the adhesive to form an uncured second adhesive layer 48. As the adhesive, RU-40 manufactured by Rock Paint Co., Ltd. was used as the main agent, and H-4 manufactured by Rock Paint Co., Ltd. was used as the curing agent. RU-40 contains a polyester polyol. H-4 contains an aliphatic isocyanate compound. The molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol was 3. Then, the 2nd laminating process which laminates | stacks the laminated body of the 1st film 40 and the metal foil 47, and the sealant film 70 through the 2nd adhesive bond layer 48 by the dry laminating method was implemented. Thus, the laminated body 30 provided with the 1st film 40, the metal foil 47, and the sealant film 70 in order from the outer surface 30y side to the inner surface 30x side was produced. Subsequently, the laminate 30 was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a second adhesive layer 48 containing a cured product of a polyol and an aliphatic isocyanate compound. The thickness of the second adhesive layer 48 was 3 μm. The layer configuration of the stacked body 30 is expressed as follows.
PBT (multilayer) / first adhesive layer / aluminum foil / second adhesive layer / polypropylene
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１９Ｎであった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 19N.
　（実施例Ｂ２）
　基材４１として、ＰＢＴを含み、チューブラー法で作製されたフィルム状の基材４１を用いたこと以外は、実施例Ｂ１の場合と同様にして、積層体３０を作製した。基材４１はＰＢＴ及び添加剤のみで構成される単層のフィルムであり、基材４１の厚みは１５μｍであった。また、実施例Ｂ１の場合と同様にして、第１フィルム４０における反りを評価した。結果、反りの高さの最大値は、０ｍｍであった。また、第１フィルム４０を搬送する際、第１フィルム４０の端部に反りや折れなどは観察されなかった。 (Example B2)
A laminate 30 was produced in the same manner as in Example B1, except that a film-like substrate 41 containing PBT and produced by a tubular method was used as the substrate 41. The base material 41 was a single layer film composed only of PBT and an additive, and the thickness of the base material 41 was 15 μm. Moreover, the curvature in the 1st film 40 was evaluated similarly to the case of Example B1. As a result, the maximum warp height was 0 mm. Moreover, when conveying the 1st film 40, the curvature of the edge part of the 1st film 40, a bending, etc. were not observed.
積層体３０の層構成は、下記のように表される。
　ＰＢＴ（単層）／第１接着剤層／アルミニウム箔／第２接着剤層／ポリプロピレン
続いて、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１８Ｎであった。 The layer configuration of the stacked body 30 is expressed as follows.
PBT (single layer) / first adhesive layer / aluminum foil / second adhesive layer / polypropylene Subsequently, the piercing strength of the laminate 30 was measured. As a result, the piercing strength was 18N.
　（実施例Ｂ３）
　各層４１ａにおけるＰＢＴの含有率が５５％である基材４１を用いたこと以外は、実施例Ｂ１の場合と同様にして、基材４１からなる第１フィルム４０における反りを評価した。結果、反りの高さの最大値は、０ｍｍであった。また、ＰＢＴの含有率が５５％である基材４１を用いて、実施例Ｂ１の場合と同様に積層体３０を作製した。積層体３０を作製する工程において基材４１からなる第１フィルム４０を搬送する際、第１フィルム４０の端部に反りや折れなどは観察されなかった。また、積層体３０の突き刺し強度は１３Ｎであった。 (Example B3)
The warpage of the first film 40 made of the base material 41 was evaluated in the same manner as in Example B1 except that the base material 41 having a PBT content of 55% in each layer 41a was used. As a result, the maximum warp height was 0 mm. Moreover, the laminated body 30 was produced similarly to the case of Example B1 using the base material 41 whose PBT content rate is 55%. When the first film 40 made of the base material 41 was transported in the step of producing the laminate 30, no warp or breakage was observed at the end of the first film 40. Moreover, the puncture strength of the laminated body 30 was 13N.
　（比較例Ｂ１）
　基材４１として、厚み１５μｍのヘプタックスＨＢＮ（グンゼ株式会社製）を用いたこと以外は、実施例Ｂ１の場合と同様にして、積層体３０を作製した。ヘプタックスＨＢＮは、ＰＥＴとナイロンとを共押出しすることによって作製された２層共押しフィルムである。また、実施例Ｂ１の場合と同様にして、第１フィルム４０における反りを評価した。結果、反りの程度が大きすぎて試験片の４隅が丸まってしまい、反りの高さを測定することができなかった。また、第１フィルム４０を搬送する際、第１フィルム４０の幅方向における端部に折れが生じていたので、折れを解消するために第１フィルム４０に加える張力を調整した。 (Comparative Example B1)
A laminate 30 was produced in the same manner as in Example B1, except that 15 μm thick Heptax HBN (manufactured by Gunze Co., Ltd.) was used as the base material 41. Heptax HBN is a two-layer co-pressed film made by co-extrusion of PET and nylon. Moreover, the curvature in the 1st film 40 was evaluated similarly to the case of Example B1. As a result, the degree of warpage was too large, and the four corners of the test piece were rounded, and the height of warpage could not be measured. Moreover, when the 1st film 40 was conveyed, since the edge part in the width direction of the 1st film 40 had broken, the tension | tensile_strength added to the 1st film 40 was adjusted in order to eliminate a break.
　積層体３０の層構成は、下記のように表される。
　ヘプタックスＨＢＮ／第１接着剤層／アルミニウム箔／第２接着剤層／ポリプロピレン
続いて、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１２Ｎであった。 The layer configuration of the stacked body 30 is expressed as follows.
Heptax HBN / first adhesive layer / aluminum foil / second adhesive layer / polypropylene Subsequently, the piercing strength of the laminate 30 was measured. As a result, the piercing strength was 12N.
　（比較例Ｂ２）
　基材として、厚み１２μｍのＰＥＴフィルムと厚み１５μｍのナイロンフィルムを準備した。また、実施例Ｂ１の場合と同様にして、ＰＥＴフィルムにおける反りを評価した。結果、反りの高さの最大値は、０ｍｍであった。 (Comparative Example B2)
As a substrate, a PET film having a thickness of 12 μm and a nylon film having a thickness of 15 μm were prepared. Further, the warpage in the PET film was evaluated in the same manner as in Example B1. As a result, the maximum warp height was 0 mm.
　続いて、ＰＥＴフィルムに溶剤を含む接着剤を塗布した後、接着剤を乾燥させることにより溶剤を揮発させて、未硬化状態の第１接着剤層を形成した。接着剤は、主剤として東洋モートン株式会社製のＴＭ－５５６Ｓ、硬化剤として東洋モートン株式会社製のＣＡＴ－５６を用いた。また、ポリオールのヒドロキシ基に対する芳香族系イソシアネート化合物のイソシアネート基のモル比は３であった。ＰＥＴフィルムを搬送する際、ＰＥＴフィルムの端部に反りや折れなどは観察されなかった。続いて、ＰＥＴフィルムにナイロンフィルムを圧着させ、ＰＥＴフィルム及びナイロンフィルムの積層体を作製した。続いて、積層体を、４０℃の環境下で９６時間にわたって加熱した。これにより、接着剤を硬化させて、ポリオールと芳香族系イソシアネート化合物との硬化物を含む第１接着剤層を得た。第１接着剤層の厚みは、３μｍであった。 Subsequently, an adhesive containing a solvent was applied to the PET film, and then the solvent was evaporated by drying the adhesive to form an uncured first adhesive layer. As the adhesive, TM-556S manufactured by Toyo Morton Co., Ltd. was used as the main agent, and CAT-56 manufactured by Toyo Morton Co., Ltd. was used as the curing agent. The molar ratio of the isocyanate group of the aromatic isocyanate compound to the hydroxyl group of the polyol was 3. When the PET film was transported, no warp or breakage was observed at the end of the PET film. Subsequently, a nylon film was pressure-bonded to the PET film to produce a laminate of the PET film and the nylon film. Subsequently, the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a first adhesive layer containing a cured product of a polyol and an aromatic isocyanate compound. The thickness of the first adhesive layer was 3 μm.
　続いて、ナイロンフィルムに溶剤を含む接着剤を塗布した後、接着剤を乾燥させることにより溶剤を揮発させて、未硬化状態の第２接着剤層を形成した。接着剤は、主剤として東洋モートン株式会社製のＴＭ－５５６Ｓ、硬化剤として東洋モートン株式会社製のＣＡＴ－５６を用いた。また、ポリオールのヒドロキシ基に対する芳香族系イソシアネート化合物のイソシアネート基のモル比は３であった。続いて、ナイロンフィルムに厚み７μｍのアルミニウム箔を圧着させ、ＰＥＴフィルムとナイロンフィルムとアルミニウム箔の積層体を作製した。続いて、積層体を、４０℃の環境下で９６時間にわたって加熱した。これにより、接着剤を硬化させて、ポリオールと芳香族系イソシアネート化合物との硬化物を含む第２接着剤層を得た。第２接着剤層の厚みは、３μｍであった。 Subsequently, after applying an adhesive containing a solvent to the nylon film, the solvent was evaporated by drying the adhesive to form an uncured second adhesive layer. As the adhesive, TM-556S manufactured by Toyo Morton Co., Ltd. was used as the main agent, and CAT-56 manufactured by Toyo Morton Co., Ltd. was used as the curing agent. The molar ratio of the isocyanate group of the aromatic isocyanate compound to the hydroxyl group of the polyol was 3. Subsequently, an aluminum foil having a thickness of 7 μm was pressure-bonded to the nylon film to produce a laminate of a PET film, a nylon film, and an aluminum foil. Subsequently, the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a second adhesive layer containing a cured product of a polyol and an aromatic isocyanate compound. The thickness of the second adhesive layer was 3 μm.
　続いて、アルミニウム箔に溶剤を含む接着剤を塗布した後、接着剤を乾燥させることにより溶剤を揮発させて、未硬化状態の第３接着剤層を形成した。接着剤は、主剤としてロックペイント株式会社製のＲＵ－４０、硬化剤としてロックペイント株式会社製のＨ－４を用いた。また、ポリオールのヒドロキシ基に対する脂肪族系イソシアネート化合物のイソシアネート基のモル比は３であった。続いて、アルミニウム箔にポリプロピレンフィルムを圧着させ、積層体を作製した。ポリプロピレンフィルムとしては、東レフィルム加工株式会社製の未延伸ポリプロピレンフィルム　ＺＫ９９Ｓを用いた。続いて、積層体を、４０℃の環境下で９６時間にわたって加熱した。これにより、接着剤を硬化させて、ポリオールと脂肪族系イソシアネート化合物との硬化物を含む第３接着剤層を得た。第３接着剤層の厚みは、３μｍであった。 Subsequently, after applying an adhesive containing a solvent to the aluminum foil, the solvent was evaporated by drying the adhesive to form an uncured third adhesive layer. As the adhesive, RU-40 manufactured by Rock Paint Co., Ltd. was used as the main agent, and H-4 manufactured by Rock Paint Co., Ltd. was used as the curing agent. The molar ratio of the isocyanate group of the aliphatic isocyanate compound to the hydroxyl group of the polyol was 3. Subsequently, a polypropylene film was pressure-bonded to the aluminum foil to prepare a laminate. As the polypropylene film, unstretched polypropylene film ZK99S manufactured by Toray Film Processing Co., Ltd. was used. Subsequently, the laminate was heated in an environment of 40 ° C. for 96 hours. Thereby, the adhesive was cured to obtain a third adhesive layer containing a cured product of a polyol and an aliphatic isocyanate compound. The thickness of the third adhesive layer was 3 μm.
積層体の層構成は、下記のように表される。
　ＰＥＴ／第１接着剤層／ナイロン／第２接着剤層／アルミニウム箔／第３接着剤層／ポリプロピレン
続いて、積層体の突き刺し強度を測定した。結果、突き刺し強度は１９Ｎであった。 The layer structure of the laminate is expressed as follows.
PET / first adhesive layer / nylon / second adhesive layer / aluminum foil / third adhesive layer / polypropylene Subsequently, the piercing strength of the laminate was measured. As a result, the piercing strength was 19N.
　（比較例Ｂ３）
　基材４１として、厚み１２μｍのＰＥＴフィルム（東洋紡製　Ｅ５１００）を用いたこと以外は、実施例Ｂ１の場合と同様にして、基材４１からなる第１フィルム４０における反りを評価した。結果、反りの高さの最大値は、０ｍｍであった。 (Comparative Example B3)
The warpage in the first film 40 made of the base material 41 was evaluated in the same manner as in Example B1, except that a PET film having a thickness of 12 μm (Toyobo E5100) was used as the base material 41. As a result, the maximum warp height was 0 mm.
　また、ＰＥＴフィルムからなる基材４１を用いて、実施例Ｂ１の場合と同様に積層体３０を作製した。積層体３０を作製する工程において基材４１からなる第１フィルム４０を搬送する際、第１フィルム４０の端部に反りや折れなどは観察されなかった。 Moreover, the laminated body 30 was produced similarly to the case of Example B1 using the base material 41 which consists of PET films. When the first film 40 made of the base material 41 was transported in the step of producing the laminate 30, no warp or breakage was observed at the end of the first film 40.
　積層体の層構成は、下記のように表される。
　ＰＥＴ／第１接着剤層／アルミニウム箔／第２接着剤層／ポリプロピレン
続いて、積層体の突き刺し強度を測定した。結果、突き刺し強度は１１Ｎであった。 The layer structure of the laminate is expressed as follows.
PET / first adhesive layer / aluminum foil / second adhesive layer / polypropylene Subsequently, the piercing strength of the laminate was measured. As a result, the puncture strength was 11N.
　実施例Ｂ１～Ｂ３及び比較例Ｂ１～Ｂ３の積層体の層構成及び評価結果を、図２０にまとめて示す。図２０において、「層構成」の欄には、接着剤層を除く積層体の構成要素を、外面側の層から順に上から記載している。また、「ラミネート工程」の欄に関して、実施例Ｂ１～Ｂ３及び比較例Ｂ２，Ｂ３においては、フィルムの端部に反りや折れなどが観察されなかったので、評価結果を「ｇｏｏｄ」とした。一方、比較例Ｂ１においては、フィルムの端部に折れが観察され、第１フィルム４０と金属箔４７をラミネートするときの張力を調整する作業が必要であったので、評価結果を「ｂａｄ」とした。 FIG. 20 shows the layer structure and evaluation results of the laminates of Examples B1 to B3 and Comparative Examples B1 to B3. In FIG. 20, in the “layer configuration” column, the components of the laminate excluding the adhesive layer are described in order from the outer surface side layer. Further, regarding the column of “laminate process”, in Examples B1 to B3 and Comparative Examples B2 and B3, no warp or breakage was observed at the edge of the film, so the evaluation result was “good”. On the other hand, in Comparative Example B1, folds were observed at the end of the film, and the work of adjusting the tension when laminating the first film 40 and the metal foil 47 was necessary, so the evaluation result was “bad”. did.
　図２０からわかるように、実施例Ｂ１～Ｂ３によれば、ＰＢＴを用いて第１フィルム４０の基材４１を構成することにより、第１フィルム４０に反りが生じることを抑制することができた。このため、積層体３０を効率良く製造することができた。また、１３Ｎ以上の突き刺し強度を実現することができた。 As can be seen from FIG. 20, according to Examples B1 to B3, it was possible to suppress the warp of the first film 40 by forming the base material 41 of the first film 40 using PBT. . For this reason, the laminated body 30 was able to be manufactured efficiently. Moreover, the puncture strength of 13N or more was able to be realized.
　次に、第３の実施の形態において説明した、積層体の基材を構成するプラスチックフィルムが２つ存在する場合に関する実施例Ｃ１～Ｃ６及び比較例Ｃ１、Ｃ２について説明する。 Next, Examples C1 to C6 and Comparative Examples C1 and C2 relating to the case where there are two plastic films constituting the base material of the laminate described in the third embodiment will be described.
　（実施例Ｃ１）
　実施例Ａ１の場合と同様にして、上述の第１の構成で説明した、複数の層を含み、キャスト法で作製されたフィルム状の第１基材５１を準備した。各層におけるＰＢＴの含有率は８０％であり、層の層数は１０２４であり、第１基材５１の厚みは１５μｍであった。また、第２基材６１を含むフィルム状の第２フィルム６０を準備した。第２基材６１としては、１００質量％のＰＥＴを含むものを用いた。第２基材６１の厚みは１２μｍであった。また、シーラント層７１を含むシーラントフィルム７０を準備した。シーラント層７１としては、東レフィルム加工株式会社製の未延伸ポリプロピレンフィルム　ＺＫ２０７を用いた。シーラント層７１の厚みは６０μｍであった。 (Example C1)
In the same manner as in Example A1, a film-like first base material 51 including a plurality of layers and manufactured by a casting method described in the first configuration was prepared. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the first base material 51 was 15 μm. Moreover, the film-like 2nd film 60 containing the 2nd base material 61 was prepared. As the 2nd base material 61, what contains 100 mass% PET was used. The thickness of the second substrate 61 was 12 μm. Further, a sealant film 70 including a sealant layer 71 was prepared. As the sealant layer 71, an unstretched polypropylene film ZK207 manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the sealant layer 71 was 60 μm.
　次に、第１接着剤層５５を介して第１フィルム５０と第２フィルム６０とをドライラミネート法により積層した。第１接着剤層５５としては、ロックペイント株式会社製の２液型ポリウレタン系接着剤（主剤：ＲＵ－４０、硬化剤：Ｈ－４）を用いた。ＲＵ－４０は、ポリエステルポリオールを含む。Ｈ－４は、脂肪族系イソシアネート化合物を含む。第１接着剤層５５の厚みは、３μｍであった。 Next, the first film 50 and the second film 60 were laminated by the dry laminating method through the first adhesive layer 55. As the first adhesive layer 55, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used. RU-40 contains a polyester polyol. H-4 contains an aliphatic isocyanate compound. The thickness of the first adhesive layer 55 was 3 μm.
　次に、第１フィルム５０及び第２フィルム６０の積層体とシーラントフィルム７０とを、第２接着剤層６５を介してドライラミネート法により積層し、積層体３０を得た。第２接着剤層６５としては、第１接着剤層５５と同様に、ロックペイント株式会社製の２液型ポリウレタン系接着剤（主剤：ＲＵ－４０、硬化剤：Ｈ－４）を用いた。第２接着剤層６５の厚みは、３μｍであった。 Next, the laminate of the first film 50 and the second film 60 and the sealant film 70 were laminated by the dry laminating method through the second adhesive layer 65 to obtain the laminate 30. As the second adhesive layer 65, similarly to the first adhesive layer 55, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used. The thickness of the second adhesive layer 65 was 3 μm.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１７Ｎであった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N.
　続いて、積層体３０の耐着色性を評価した。具体的には、２枚の積層体３０の内面３０ｘ同士をシールして、内容物として市販のカレーが収容された袋を作製した。続いて、袋にレトルト処理を施した後、袋を開封して、袋を構成する積層体３０が着色されているか否かを目視で評価した。２枚の積層体３０の寸法はそれぞれ、縦１００ｍｍ、横１００ｍｍであった。袋の形状は、四方シール袋とした。袋のレトルト処理は、１２１℃で３０分間、熱水式にて行った。結果、着色は観察されなかった。 Subsequently, the coloration resistance of the laminate 30 was evaluated. Specifically, the inner surfaces 30x of the two laminates 30 were sealed to produce a bag containing a commercially available curry as the contents. Subsequently, after the bag was retorted, the bag was opened, and it was visually evaluated whether or not the laminate 30 constituting the bag was colored. The dimensions of the two laminates 30 were 100 mm in length and 100 mm in width, respectively. The shape of the bag was a four-side sealed bag. The bag was retorted by a hot water method at 121 ° C. for 30 minutes. As a result, coloring was not observed.
　（実施例Ｃ２）
　第１フィルム５０の第１基材５１として、上述の第２の構成で説明した、１００質量％のＰＢＴを含み、ＰＢＴの融点が２２４℃、ＩＶ値が１．２６ｄｌ／ｇであり、チューブラー法で作製された単層フィルムを用いたこと以外は、実施例Ｃ１の場合と同様にして、積層体３０を作製した。第１基材５１はＰＢＴ及び添加剤のみで構成される単層のフィルムであり、第１基材５１の厚みは１５μｍであった。 (Example C2)
As the 1st base material 51 of the 1st film 50, it contains 100 mass% PBT explained by the above-mentioned 2nd composition, Melting | fusing point of PBT is 224 degreeC, IV value is 1.26 dl / g, Tubular A laminate 30 was produced in the same manner as in Example C1, except that the single-layer film produced by the method was used. The first base 51 was a single layer film composed only of PBT and additives, and the thickness of the first base 51 was 15 μm.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１７Ｎであった。また、実施例Ｃ１の場合と同様にして、積層体３０の耐着色性を評価した。結果、着色は観察されなかった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
　（実施例Ｃ３）
　各層におけるＰＢＴの含有率が５５％である第１基材５１を用いたこと以外は、実施例Ｃ１の場合と同様にして、積層体３０を作製した。また、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１３Ｎであった。また、実施例Ｃ１の場合と同様にして、積層体３０の耐着色性を評価した。結果、着色は観察されなかった。 (Example C3)
A laminate 30 was produced in the same manner as in Example C1, except that the first base material 51 having a PBT content of 55% in each layer was used. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 13N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
　（実施例Ｃ４）
　実施例Ｃ１の第１基材５１を構成するＰＢＴを第２基材６１として用い、実施例Ｃ１の第２基材６１を構成するＰＥＴを第１基材５１として用いたこと以外は、実施例Ｃ１の場合と同様にして、積層体３０を作製した。 (Example C4)
Example except that PBT constituting the first substrate 51 of Example C1 was used as the second substrate 61 and PET constituting the second substrate 61 of Example C1 was used as the first substrate 51 The laminated body 30 was produced like the case of C1.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１６Ｎであった。また、実施例Ｃ１の場合と同様にして、積層体３０の耐着色性を評価した。結果、着色は観察されなかった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 16N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
　（実施例Ｃ５）
　実施例Ｃ２の第１基材５１を構成するＰＢＴを第２基材６１として用い、実施例Ｃ２の第２基材６１を構成するＰＥＴを第１基材５１として用いたこと以外は、実施例Ｃ１の場合と同様にして、積層体３０を作製した。 (Example C5)
Example except that PBT constituting the first substrate 51 of Example C2 was used as the second substrate 61 and PET constituting the second substrate 61 of Example C2 was used as the first substrate 51 The laminated body 30 was produced like the case of C1.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１６Ｎであった。また、実施例Ｃ１の場合と同様にして、積層体３０の耐着色性を評価した。結果、着色は観察されなかった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 16N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
　（実施例Ｃ６）
　各層におけるＰＢＴの含有率が５５％である第２基材６１を用いたこと以外は、実施例Ｃ４の場合と同様にして、積層体３０を作製した。また、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１３Ｎであった。また、実施例Ｃ１の場合と同様にして、積層体３０の耐着色性を評価した。結果、着色は観察されなかった。 (Example C6)
A laminate 30 was produced in the same manner as in Example C4 except that the second base material 61 having a PBT content of 55% in each layer was used. Further, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 13N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
　（比較例Ｃ１）
　第１フィルム５０の第１基材５１として、１００質量％のＰＥＴを含む基材を用いたこと以外は、実施例Ｃ１の場合と同様にして、積層体３０を作製した。第１基材５１の厚みは１２μｍであった。 (Comparative Example C1)
A laminate 30 was produced in the same manner as in Example C1, except that a substrate containing 100% by mass of PET was used as the first substrate 51 of the first film 50. The thickness of the first base material 51 was 12 μm.
　続いて、実施例Ｃ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１１Ｎであった。また、実施例Ｃ１の場合と同様にして、積層体３０の耐着色性を評価した。結果、着色は観察されなかった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example C1. As a result, the puncture strength was 11N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was not observed.
　（比較例Ｃ２）
　第２フィルム６０の第２基材６１として、厚み１５μｍのナイロンフィルム（興人ホールディングス株式会社製　ボニールＷ）を用いたこと以外は、比較例Ｃ１の場合と同様にして、積層体３０を作製した。 (Comparative Example C2)
A laminate 30 was produced in the same manner as in Comparative Example C1, except that a nylon film having a thickness of 15 μm (bonile W manufactured by Kojin Holdings Co., Ltd.) was used as the second substrate 61 of the second film 60. .
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１７Ｎであった。また、実施例Ｃ１の場合と同様にして、積層体３０の耐着色性を評価した。結果、着色が観察された。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example C1. As a result, coloring was observed.
　実施例Ｃ１～Ｃ６及び比較例Ｃ１，Ｃ２の積層体の層構成及び評価結果を、図２１にまとめて示す。図２１において、「層構成」の欄には、接着剤層を除く積層体の構成要素を、外面側の層から順に上から記載している。実施例Ｃ１～Ｃ６と比較例Ｃ１の比較から分かるように、第１基材５１又は第２基材６１がＰＢＴを含むことにより、第１基材５１及び第２基材６１の両方がＰＥＴを含む場合に比べて高い突き刺し強度を、具体的には１３Ｎ以上の突き刺し強度を実現することができた。また、実施例Ｃ１～Ｃ６と比較例Ｃ２の比較から分かるように、第２基材６１としてナイロン以外の材料、具体的にはＰＢＴ又はＰＥＴを用いることにより、第２基材６１がナイロンを含む場合に比べて、良好な耐着色性を実現することができた。 The layer configuration and evaluation results of the laminates of Examples C1 to C6 and Comparative Examples C1 and C2 are collectively shown in FIG. In FIG. 21, in the “layer configuration” column, the components of the laminate excluding the adhesive layer are described from the top in order from the outer surface side layer. As can be seen from the comparison between Examples C1 to C6 and Comparative Example C1, the first substrate 51 or the second substrate 61 contains PBT, so that both the first substrate 51 and the second substrate 61 are made of PET. Compared with the case where it contains, the piercing intensity | strength higher, specifically, the piercing intensity | strength of 13N or more was realizable. Further, as can be seen from the comparison between Examples C1 to C6 and Comparative Example C2, by using a material other than nylon, specifically PBT or PET, as the second base material 61, the second base material 61 contains nylon. Compared to the case, it was possible to realize better coloring resistance.
　次に、第４の実施の形態において説明した、積層体の基材を構成するプラスチックフィルムが２つ存在し、積層体が遮光印刷層を更に備える場合に関する実施例Ｄ１～Ｄ４及び比較例Ｄ１、Ｄ２について説明する。 Next, Examples D1 to D4 and Comparative Example D1 related to the case where there are two plastic films constituting the base material of the laminate described in the fourth embodiment, and the laminate further includes a light-shielding print layer, D2 will be described.
　（実施例Ｄ１）
　実施例Ａ１の場合と同様にして、上述の第１の構成で説明した、複数の層を含み、キャスト法で作製されたフィルム状の第１基材５１を準備した。各層におけるＰＢＴの含有率は８０％であり、層の層数は１０２４であり、第１基材５１の厚みは１５μｍであった。続いて、フィルム状の第１基材５１上に、ＤＩＣグラフィックス株式会社製のフィナートを用いて絵柄印刷層５３を形成した。続いて、絵柄印刷層５３上に遮光印刷層５２を形成した。遮光印刷層５２は、絵柄印刷層５３上に順に積層された白ベタ層及び灰ベタ層を含む。 (Example D1)
In the same manner as in Example A1, a film-like first base material 51 including a plurality of layers and manufactured by a casting method described in the first configuration was prepared. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the first base material 51 was 15 μm. Then, the pattern printing layer 53 was formed on the film-form 1st base material 51 using the final made by DIC graphics. Subsequently, a light shielding printing layer 52 was formed on the pattern printing layer 53. The light-shielding print layer 52 includes a white solid layer and an ash solid layer that are sequentially stacked on the pattern print layer 53.
　白ベタ層は、グラビア印刷にて基材に白インキを２回ベタ印刷することによって形成した。１層目の白ベタ層は、白インキ（東洋インキ社製、製品名「ファインスター６８１ＡＴ」）を絵柄印刷層５３上にベタ印刷することにより形成した。２層目の白ベタ層は、白インキ（東洋インキ社製、製品名「ＮＫＦＳ　Ｒ６９Ｋ」）を１層目の白ベタ層上にベタ印刷することにより形成した。１層目の白ベタ層の厚みは１μｍであり、２層目の白ベタ層の厚みは１．５μｍであった。白ベタ層の形成には、版深２８μｍ、版胴の線数１７５である版胴を用いた。
　灰ベタ層は、白インキ（東洋インキ社製、製品名「Ｒ６３１ＡＴ」）と黒インキ（東洋インキ社製、製品名「Ｎ８００ＬＰＧＴスミ」）とを６対４の配合比率で配合した灰色インキを、白ベタ層上に１回ベタ印刷することにより形成した。灰ベタ層の形成には、版深２２μｍ、版胴の線数１７５である版胴を用いた。灰ベタ層の厚みは１．５μｍであった。 The white solid layer was formed by printing solid white ink twice on the substrate by gravure printing. The first white solid layer was formed by solid printing white ink (manufactured by Toyo Ink Co., Ltd., product name “Fine Star 681AT”) on the pattern printing layer 53. The second white solid layer was formed by solid printing white ink (manufactured by Toyo Ink Co., Ltd., product name “NKFS R69K”) on the first white solid layer. The thickness of the first white solid layer was 1 μm, and the thickness of the second white solid layer was 1.5 μm. For the formation of the white solid layer, a plate cylinder having a plate depth of 28 μm and a plate cylinder line number of 175 was used.
The gray solid layer is a gray ink in which white ink (manufactured by Toyo Ink, product name “R631AT”) and black ink (manufactured by Toyo Ink, product name “N800LPGT Sumi”) are blended at a blending ratio of 6: 4. It was formed by solid printing once on the white solid layer. For forming the solid ash layer, a plate cylinder having a plate depth of 22 μm and a plate cylinder line number of 175 was used. The thickness of the ash solid layer was 1.5 μm.
　また、第２基材６１を含むフィルム状の第２フィルム６０を準備した。第２基材６１としては、１００質量％のＰＥＴを含むものを用いた。第２基材６１の厚みは１２μｍであった。また、シーラント層７１を含むシーラントフィルム７０を準備した。シーラント層７１としては、東レフィルム加工株式会社製の未延伸ポリプロピレンフィルム　ＺＫ２０７を用いた。シーラント層７１の厚みは６０μｍであった。 Further, a film-like second film 60 including the second substrate 61 was prepared. As the 2nd base material 61, what contains 100 mass% PET was used. The thickness of the second substrate 61 was 12 μm. Further, a sealant film 70 including a sealant layer 71 was prepared. As the sealant layer 71, an unstretched polypropylene film ZK207 manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the sealant layer 71 was 60 μm.
　次に、第１接着剤層５５を介して第１フィルム５０と第２フィルム６０とをドライラミネート法により積層した。第１接着剤層５５としては、ロックペイント株式会社製の２液型ポリウレタン系接着剤（主剤：ＲＵ－４０、硬化剤：Ｈ－４）を用いた。ＲＵ－４０は、ポリエステルポリオールを含む。Ｈ－４は、脂肪族系イソシアネート化合物を含む。第１接着剤層５５の厚みは、３μｍであった。 Next, the first film 50 and the second film 60 were laminated by the dry laminating method through the first adhesive layer 55. As the first adhesive layer 55, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used. RU-40 contains a polyester polyol. H-4 contains an aliphatic isocyanate compound. The thickness of the first adhesive layer 55 was 3 μm.
　次に、第１フィルム５０及び第２フィルム６０の積層体とシーラントフィルム７０とを、第２接着剤層６５を介してドライラミネート法により積層し、積層体３０を得た。第２接着剤層６５としては、第１接着剤層５５と同様に、ロックペイント株式会社製の２液型ポリウレタン系接着剤（主剤：ＲＵ－４０、硬化剤：Ｈ－４）を用いた。第２接着剤層６５の厚みは、３μｍであった。 Next, the laminate of the first film 50 and the second film 60 and the sealant film 70 were laminated by the dry laminating method through the second adhesive layer 65 to obtain the laminate 30. As the second adhesive layer 65, similarly to the first adhesive layer 55, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used. The thickness of the second adhesive layer 65 was 3 μm.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１７Ｎであった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N.
　続いて、積層体３０の遮光性を評価した。具体的には、積層体３０の外面３０ｙから光を入射させた場合の、積層体３０の全光線透過率を測定した。測定器としては、村上色彩技術研究所社製の全光線透過率測定装置であるヘーズメーターＨＭ－１５０を用いた。結果、全光線透過率は９％であった。 Subsequently, the light shielding properties of the laminate 30 were evaluated. Specifically, the total light transmittance of the laminate 30 when light was incident from the outer surface 30y of the laminate 30 was measured. As a measuring instrument, a haze meter HM-150, which is a total light transmittance measuring device manufactured by Murakami Color Research Laboratory Co., Ltd., was used. As a result, the total light transmittance was 9%.
　続いて、積層体３０の異臭バリア性を評価した。具体的には、２枚の積層体３０の内面３０ｘ同士をシールして袋を形成し、袋を加熱した後、袋を開封して、異臭を感じるか否かを評価した。２枚の積層体３０の寸法はそれぞれ、縦１００ｍｍ、横１００ｍｍであった。袋の形状は、四方シール袋とした。袋の加熱は、４０℃に制御されたオーブンを用いて１分間行った。結果、異臭を感じなかった。 Subsequently, the odor barrier property of the laminate 30 was evaluated. Specifically, the inner surfaces 30x of the two laminates 30 were sealed to form a bag, the bag was heated, the bag was then opened, and whether or not a strange odor was felt was evaluated. The dimensions of the two laminates 30 were 100 mm in length and 100 mm in width, respectively. The shape of the bag was a four-side sealed bag. The bag was heated for 1 minute using an oven controlled at 40 ° C. As a result, no nasty smell was felt.
　（実施例Ｄ２）
　第１フィルム５０の第１基材５１として、上述の第２の構成で説明した、１００質量％のＰＢＴを含み、ＰＢＴの融点が２２４℃、ＩＶ値が１．２６ｄｌ／ｇであり、チューブラー法で作製された単層フィルムを用いたこと以外は、実施例Ｄ１の場合と同様にして、積層体３０を作製した。第１基材５１はＰＢＴ及び添加剤のみで構成される単層のフィルムであり、第１基材５１の厚みは１５μｍであった。 (Example D2)
As the 1st base material 51 of the 1st film 50, it contains 100 mass% PBT explained by the above-mentioned 2nd composition, Melting | fusing point of PBT is 224 degreeC, IV value is 1.26 dl / g, Tubular A laminate 30 was produced in the same manner as in Example D1, except that the single-layer film produced by the method was used. The first base 51 was a single layer film composed only of PBT and additives, and the thickness of the first base 51 was 15 μm.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１７Ｎであった。また、実施例Ｄ１の場合と同様にして、積層体３０の全光線透過率を測定した。結果、全光線透過率は９％であった。また、実施例Ｄ１の場合と同様にして、積層体３０の異臭バリア性を評価した。結果、異臭を感じなかった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 9%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, no nasty smell was felt.
　（実施例Ｄ３）
　実施例Ｄ１の第１基材５１を構成するＰＢＴを第２基材６１として用い、実施例Ｄ１の第２基材６１を構成するＰＥＴを第１基材５１として用いたこと以外は、実施例Ｄ１の場合と同様にして、積層体３０を作製した。 (Example D3)
Example except that PBT constituting the first substrate 51 of Example D1 was used as the second substrate 61 and PET constituting the second substrate 61 of Example D1 was used as the first substrate 51 The laminated body 30 was produced like the case of D1.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１７Ｎであった。また、実施例Ｄ１の場合と同様にして、積層体３０の全光線透過率を測定した。結果、全光線透過率は９％であった。また、実施例Ｄ１の場合と同様にして、積層体３０の異臭バリア性を評価した。結果、異臭を感じなかった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 9%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, no nasty smell was felt.
　（実施例Ｄ４）
　実施例Ｄ２の第１基材５１を構成するＰＢＴを第２基材６１として用い、実施例Ｄ２の第２基材６１を構成するＰＥＴを第１基材５１として用いたこと以外は、実施例Ｄ１の場合と同様にして、積層体３０を作製した。 (Example D4)
Example except that PBT constituting the first base material 51 of Example D2 was used as the second base material 61 and PET constituting the second base material 61 of Example D2 was used as the first base material 51 The laminated body 30 was produced like the case of D1.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１７Ｎであった。また、実施例Ｄ１の場合と同様にして、積層体３０の全光線透過率を測定した。結果、全光線透過率は９％であった。また、実施例Ｄ１の場合と同様にして、積層体３０の異臭バリア性を評価した。結果、異臭を感じなかった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 9%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, no nasty smell was felt.
　（比較例Ｄ１）
　第１フィルム５０の第１基材５１として、１００質量％のＰＥＴを含む基材を用いたこと以外は、実施例Ｄ１の場合と同様にして、積層体３０を作製した。第１基材５１の厚みは１２μｍであった。 (Comparative Example D1)
The laminated body 30 was produced like the case of Example D1 except having used the base material containing 100 mass% PET as the 1st base material 51 of the 1st film 50. FIG. The thickness of the first base material 51 was 12 μm.
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１２Ｎであった。また、実施例Ｄ１の場合と同様にして、積層体３０の全光線透過率を測定した。結果、全光線透過率は１０％であった。また、実施例Ｄ１の場合と同様にして、積層体３０の異臭バリア性を評価した。結果、異臭を感じなかった。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 12N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 10%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, no nasty smell was felt.
　（比較例Ｄ２）
　第２フィルム６０の第２基材６１として、厚み１５μｍのナイロンフィルム（興人ホールディングス株式会社製　ボニールＷ）を用いたこと以外は、比較例Ｄ１の場合と同様にして、積層体３０を作製した。 (Comparative Example D2)
A laminate 30 was produced in the same manner as in Comparative Example D1 except that a 15 μm-thick nylon film (Bonil W manufactured by Kojin Holdings Co., Ltd.) was used as the second substrate 61 of the second film 60. .
　続いて、実施例Ａ１の場合と同様にして、積層体３０の突き刺し強度を測定した。結果、突き刺し強度は１７Ｎであった。また、実施例Ｄ１の場合と同様にして、積層体３０の全光線透過率を測定した。結果、全光線透過率は１０％であった。また、実施例Ｄ１の場合と同様にして、積層体３０の異臭バリア性を評価した。結果、異臭を感じた。 Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example D1. As a result, the total light transmittance was 10%. Moreover, the off-flavor barrier property of the laminated body 30 was evaluated in the same manner as in Example D1. As a result, a nasty smell was felt.
　実施例Ｄ１～Ｄ４及び比較例Ｄ１，Ｄ２の積層体の層構成及び評価結果を、図２２にまとめて示す。図２２において、「層構成」の欄には、接着剤層を除く積層体の構成要素を、外面側の層から順に上から記載している。実施例Ｄ１～Ｄ４と比較例Ｄ１の比較から分かるように、第１基材５１又は第２基材６１がＰＢＴを含むことにより、第１基材５１及び第２基材６１の両方がＰＥＴを含む場合に比べて、高い突き刺し強度を実現することができた。また、実施例Ｄ１～Ｄ４と比較例Ｄ２の比較から分かるように、第２基材６１としてナイロン以外の材料、具体的にはＰＢＴ又はＰＥＴを用いることにより、第２基材６１がナイロンを含む場合に比べて、良好な遮光性及び異臭バリア性を実現することができた。 The layer configuration and evaluation results of the laminates of Examples D1 to D4 and Comparative Examples D1 and D2 are collectively shown in FIG. In FIG. 22, in the column “layer configuration”, the components of the laminate excluding the adhesive layer are listed from the top in order from the outer surface side layer. As can be seen from the comparison between Examples D1 to D4 and Comparative Example D1, the first base material 51 or the second base material 61 contains PBT, so that both the first base material 51 and the second base material 61 contain PET. Compared to the case of inclusion, a high piercing strength could be realized. Further, as can be seen from the comparison between Examples D1 to D4 and Comparative Example D2, by using a material other than nylon, specifically, PBT or PET as the second base material 61, the second base material 61 contains nylon. Compared to the case, it was possible to achieve better light-shielding properties and odor barrier properties.
１０　袋
１１　上部
１２　下部
１２ａ　下部シール部
１３　側部
１３ａ　側部シール部
１４　表面フィルム
１５　裏面フィルム
１６　下部フィルム
１７　収容部
１８　内容物
２５　易開封性手段
２６　ノッチ
３０　積層体
３５　透明ガスバリア層
３６　透明蒸着層
３７　透明ガスバリア性塗布膜
４０　第１フィルム
４１　基材
４１ａ　層
４２　印刷層
４５　接着剤層
４６　第１接着剤層
４７　金属箔
４８　第２接着剤層
５０　第１フィルム
５１　第１基材
５２　遮光印刷層
５５　第１接着剤層
６０　第２フィルム
６１　第２基材
６５　第２接着剤層
７０　シーラントフィルム
７１　シーラント層 DESCRIPTION OF SYMBOLS 10 Bag 11 Upper part 12 Lower part 12a Lower seal part 13 Side part 13a Side part seal part 14 Surface film 15 Back surface film 16 Lower film 17 Storage part 18 Contents 25 Easy-opening means 26 Notch 30 Laminate body 35 Transparent gas barrier layer 36 Transparent vapor deposition Layer 37 Transparent gas barrier coating film 40 First film 41 Base 41a Layer 42 Print layer 45 Adhesive layer 46 First adhesive layer 47 Metal foil 48 Second adhesive layer 50 First film 51 First base 52 Light-shielding printing Layer 55 First adhesive layer 60 Second film 61 Second substrate 65 Second adhesive layer 70 Sealant film 71 Sealant layer

Claims (18)

  1. 　積層体であって、
    　５１質量％以上のポリブチレンテレフタレートを含む基材と、
    　直鎖状低密度ポリエチレン又はポリプロピレンのいずれかを少なくとも含み、前記積層体の内面を構成するシーラント層と、を備える、積層体。     A laminate,
    A substrate containing 51% by weight or more of polybutylene terephthalate;
    A laminate comprising at least either linear low-density polyethylene or polypropylene, and a sealant layer constituting the inner surface of the laminate.
  2. 　ポリブチレンテレフタレートを含む前記基材は、１０層以上を含む多層構造部を有する、請求項１に記載の積層体。 The laminate according to claim 1, wherein the base material containing polybutylene terephthalate has a multilayer structure part including 10 layers or more.
  3. 　ポリブチレンテレフタレートを含む前記基材は、１．１０ｄｌ／ｇ以上且つ１．３５ｄｌ／ｇ以下のＩＶ値を有する単層構造からなる、請求項１に記載の積層体。 The laminate according to claim 1, wherein the base material containing polybutylene terephthalate has a single layer structure having an IV value of 1.10 dl / g or more and 1.35 dl / g or less.
  4. 　前記シーラント層は、９０質量％以上のポリプロピレンを含む、請求項１乃至３のいずれか一項に記載の積層体。 The laminate according to any one of claims 1 to 3, wherein the sealant layer contains 90% by mass or more of polypropylene.
  5. 　前記シーラント層が、１００℃以上の融点を有する直鎖状低密度ポリエチレンを含む、請求項１乃至４のいずれか一項に記載の積層体。 The laminate according to any one of claims 1 to 4, wherein the sealant layer contains linear low-density polyethylene having a melting point of 100 ° C or higher.
  6. 　前記シーラント層の外面側に設けられ、ポリオールと脂肪族系イソシアネート化合物との硬化物を含む接着剤層を更に備え、
    　前記ポリオールのヒドロキシ基に対する前記脂肪族系イソシアネート化合物のイソシアネート基のモル比が、３．５以上である、請求項１乃至５のいずれか一項に記載の積層体。     Provided on the outer surface side of the sealant layer, further comprising an adhesive layer containing a cured product of a polyol and an aliphatic isocyanate compound;
    The laminate according to any one of claims 1 to 5, wherein a molar ratio of an isocyanate group of the aliphatic isocyanate compound to a hydroxy group of the polyol is 3.5 or more.
  7. 　前記積層体は、
    　基材／接着剤層／シーラント層、
    　基材／印刷層／接着剤層／シーラント層、
    　基材／透明蒸着層／透明ガスバリア性塗布膜／印刷層／接着剤層／シーラント層、又は
    　基材／透明蒸着層／透明ガスバリア性塗布膜／接着剤層／シーラント層、をこの順で含む、請求項１乃至６のいずれか一項に記載の積層体。     The laminate is
    Substrate / adhesive layer / sealant layer,
    Substrate / printing layer / adhesive layer / sealant layer,
    Substrate / transparent deposition layer / transparent gas barrier coating film / printing layer / adhesive layer / sealant layer, or base material / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer in this order, The laminated body as described in any one of Claims 1 thru | or 6.
  8. 　前記積層体は、
    　基材／透明蒸着層／透明ガスバリア性塗布膜／印刷層／接着剤層／シーラント層、又は
    　基材／透明蒸着層／透明ガスバリア性塗布膜／接着剤層／シーラント層、をこの順で含み、
    　前記透明蒸着層は、酸化アルミニウムを含み、
    　前記基材と前記透明蒸着層との界面に、アルミニウム原子と炭素原子の共有結合が形成されている、請求項７に記載の積層体。     The laminate is
    Substrate / transparent deposition layer / transparent gas barrier coating film / printing layer / adhesive layer / sealant layer, or substrate / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer in this order,
    The transparent vapor deposition layer includes aluminum oxide,
    The laminate according to claim 7, wherein a covalent bond of an aluminum atom and a carbon atom is formed at an interface between the base material and the transparent vapor deposition layer.
  9. 　前記積層体の衝撃強度が８００ｋＪ／ｍ以上である、請求項７又は８に記載の積層体。 The laminate according to claim 7 or 8, wherein the impact strength of the laminate is 800 kJ / m or more.
  10. 　前記積層体の突き刺し強度が１１Ｎ以上である、請求項７乃至９のいずれか一項に記載の積層体。 The laminate according to any one of claims 7 to 9, wherein the puncture strength of the laminate is 11 N or more.
  11. 　前記積層体は、
    　基材／第１接着剤層／金属箔／第２接着剤層／シーラント層、又は
    　基材／印刷層／第１接着剤層／金属箔／第２接着剤層／シーラント層、をこの順で含み、
    　前記第２接着剤層は、ポリオール及び脂肪族系イソシアネート化合物の硬化物を含む、請求項１乃至６のいずれか一項に記載の積層体。     The laminate is
    Substrate / first adhesive layer / metal foil / second adhesive layer / sealant layer, or substrate / print layer / first adhesive layer / metal foil / second adhesive layer / sealant layer in this order Including
    The laminate according to any one of claims 1 to 6, wherein the second adhesive layer contains a cured product of a polyol and an aliphatic isocyanate compound.
  12. 　前記積層体は、第１基材、第２基材及びシーラント層をこの順で少なくとも含み、
    　前記第２基材は、５１質量％以上のポリエチレンテレフタレート又は５１質量％以上のポリブチレンテレフタレートを含み、
    　前記第２基材が５１質量％以上のポリエチレンテレフタレートを含む場合、前記第１基材は、５１質量％以上のポリブチレンテレフタレートを含む、請求項１乃至６のいずれか一項に記載の積層体。     The laminate includes at least a first base material, a second base material, and a sealant layer in this order,
    The second base material includes 51% by mass or more of polyethylene terephthalate or 51% by mass or more of polybutylene terephthalate,
    The laminate according to any one of claims 1 to 6, wherein when the second base material contains 51% by mass or more of polyethylene terephthalate, the first base material contains 51% by mass or more of polybutylene terephthalate. .
  13. 　前記積層体は、前記第１基材と前記第２基材との間において前記第１基材又は前記第２基材に設けられた透明蒸着層と、前記透明蒸着層上に設けられた透明ガスバリア性塗布膜と、を更に含む、請求項１２に記載の積層体。 The laminate includes a transparent vapor deposition layer provided on the first base material or the second base material between the first base material and the second base material, and a transparent material provided on the transparent vapor deposition layer. The laminate according to claim 12, further comprising a gas barrier coating film.
  14. 　前記透明蒸着層は、酸化アルミニウムを含み、
    　前記第１基材又は前記第２基材と前記透明蒸着層との界面に、アルミニウム原子と炭素原子の共有結合が形成されている、請求項１３に記載の積層体。     The transparent vapor deposition layer includes aluminum oxide,
    The laminated body of Claim 13 in which the covalent bond of the aluminum atom and the carbon atom is formed in the interface of the said 1st base material or the said 2nd base material, and the said transparent vapor deposition layer.
  15. 　前記積層体は、前記第１基材と前記第２基材との間に位置する遮光印刷層を更に含み、
    　前記積層体の全光線透過率が２０％以下である、請求項１２乃至１４のいずれか一項に記載の積層体。     The laminate further includes a light-shielding print layer positioned between the first base material and the second base material,
    The laminated body as described in any one of Claims 12 thru | or 14 whose total light transmittance of the said laminated body is 20% or less.
  16. 　前記第１基材が、ポリブチレンテレフタレートを含み、
    　前記第２基材が、ポリエチレンテレフタレートを含む、請求項１２乃至１５のいずれか一項に記載の積層体。     The first substrate comprises polybutylene terephthalate;
    The laminate according to any one of claims 12 to 15, wherein the second base material contains polyethylene terephthalate.
  17. 　前記第１基材が、ポリエチレンテレフタレートを含み、
    　前記第２基材が、ポリブチレンテレフタレートを含む、請求項１２乃至１５のいずれか一項に記載の積層体。     The first substrate comprises polyethylene terephthalate;
    The laminate according to any one of claims 12 to 15, wherein the second base material contains polybutylene terephthalate.
  18. 　前記積層体の突き刺し強度が１３Ｎ以上である、請求項１１乃至１７のいずれか一項に記載の積層体。 The laminate according to any one of claims 11 to 17, wherein the puncture strength of the laminate is 13 N or more.
PCT/JP2017/035078 2016-09-30 2017-09-27 Laminated body WO2018062331A1 (en)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP2016-194994 2016-09-30
JP2016194988 2016-09-30
JP2016-195007 2016-09-30
JP2016-194988 2016-09-30
JP2016194994 2016-09-30
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JP2017065959 2017-03-29
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JP2018058356A (en) * 2016-09-30 2018-04-12 大日本印刷株式会社 Laminate and bag composed of the laminate
JP2018058357A (en) * 2016-09-30 2018-04-12 大日本印刷株式会社 Laminate and bag composed of the laminate and method for producing laminate
JP2021050014A (en) * 2019-09-24 2021-04-01 大日本印刷株式会社 Packaging material and package product with packaging material
JP2021054419A (en) * 2019-09-26 2021-04-08 大日本印刷株式会社 Packaging material and pouch
WO2021257294A1 (en) * 2020-06-19 2021-12-23 Proampac Holdings Inc. Recycle-ready retortable laminated polyester-based gusseted pouches
JP7443834B2 (en) 2019-03-06 2024-03-06 大日本印刷株式会社 pouch

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JP2018058356A (en) * 2016-09-30 2018-04-12 大日本印刷株式会社 Laminate and bag composed of the laminate
JP2018058357A (en) * 2016-09-30 2018-04-12 大日本印刷株式会社 Laminate and bag composed of the laminate and method for producing laminate
JP7033266B2 (en) 2016-09-30 2022-03-10 大日本印刷株式会社 A method for manufacturing a laminated body, a bag composed of the laminated body, and the laminated body.
JP7124285B2 (en) 2016-09-30 2022-08-24 大日本印刷株式会社 Laminate and bag composed of the laminate
JP7443834B2 (en) 2019-03-06 2024-03-06 大日本印刷株式会社 pouch
JP2021050014A (en) * 2019-09-24 2021-04-01 大日本印刷株式会社 Packaging material and package product with packaging material
JP2021054419A (en) * 2019-09-26 2021-04-08 大日本印刷株式会社 Packaging material and pouch
JP7408978B2 (en) 2019-09-26 2024-01-09 大日本印刷株式会社 Packaging materials and pouches
WO2021257294A1 (en) * 2020-06-19 2021-12-23 Proampac Holdings Inc. Recycle-ready retortable laminated polyester-based gusseted pouches
US11738542B2 (en) 2020-06-19 2023-08-29 Proampac Holdings Inc. Recycle-ready retortable laminated polyester-based gusseted pouches

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