JP2020066230A - Packaging material - Google Patents

Abstract

To provide a packaging material excellent in a COreduction effect while having rigidity.SOLUTION: A packaging material at least includes a first oriented plastic film, a second oriented plastic film, a third oriented plastic film and a sealant layer in this order. The packaging material further includes a metal deposition layer formed on the second oriented plastic film or the third oriented plastic film. At least one of the three oriented plastic films has ethylene glycol as a diol unit, and includes polyethylene terephthalate having terephthalic acid and isophthalic acid as a dicarboxylic acid unit. Another one of the three oriented plastic films includes a rigid film. The rigid film contains polyamide, polybutylene terephthalate, or polyester with loop stiffness of 0.0017 N or more in one direction.SELECTED DRAWING: Figure 1A

Description

  The present invention relates to a packaging material for forming a bag.

  BACKGROUND ART A bag made of a soft packaging material is used as a bag for containing a fluid content such as liquid or powder. The shape of the bag is defined by the seal portion formed by heat-sealing the soft packaging material.

  The packaging material that constitutes the soft packaging material includes a base material and a sealant layer that is laminated on the base material and melts by heat sealing. The layer structure of the packaging material is determined, for example, from the viewpoint of mechanical strength. For example, in Patent Document 1, the base material is made of nylon and the sealant layer is made of polyethylene. Nylon contributes to improving the mechanical strength of the packaging material such as puncture resistance.

JP, 10-218204, A

As a material constituting the base material of the packaging material, conventionally, a material produced from petroleum, which is a fossil resource, has been used. In recent years, with respect to such materials derived from fossil fuels, the use of fossil fuels in various applications has been reduced in consideration of the environment, and the movement to reduce CO ₂ emission has been increasing year by year.

  An object of the present invention is to provide a packaging material that can effectively solve such problems.

  The present invention is a packaging material comprising at least a first stretched plastic film, a second stretched plastic film, a third stretched plastic film, and a sealant layer in this order, wherein the packaging material is the second stretched plastic film. A film or a metal vapor deposition layer provided on the third stretched plastic film, wherein at least one of the first stretched plastic film, the second stretched plastic film or the third stretched plastic film comprises ethylene glycol as a diol unit. And polyethylene terephthalate containing terephthalic acid and isophthalic acid as dicarboxylic acid units, and at least one of the first stretched plastic film, the second stretched plastic film and the third stretched plastic film is a rigid flap. Comprises Lum, the rigid film comprises, or polyamide, or comprises or polybutylene terephthalate, or, in one direction comprises a polyester which has a more loop stiffness 0.0017N, a packaging material.

  In the packaging material according to the present invention, the sealant layer may include linear low density polyethylene.

  In the packaging material according to the present invention, the sealant layer may have a thickness of 50 μm or more.

  In the packaging material according to the present invention, one of the first stretched plastic film, the second stretched plastic film or the third stretched plastic film, which is not provided with the metal vapor deposition layer, has ethylene glycol as a diol unit and terephthalic acid. It may include polyethylene terephthalate containing isophthalic acid as a dicarboxylic acid unit, and the other one may include the rigid film.

  In the packaging material according to the present invention, the first stretched plastic film contains polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as a dicarboxylic acid unit, and the second stretched plastic film or the third stretched film. One of the plastic films may be provided with the metal vapor deposition layer, and the other may include the rigid film.

  In the packaging material according to the present invention, the rigid film may include polyamide.

  In the packaging material according to the present invention, the rigid film may include polybutylene terephthalate.

  In the packaging material according to the present invention, the rigid film has a loop stiffness of 0.0017 N or more in one direction and may include polyester.

  In the packaging material according to the present invention, the intrinsic viscosity of the polyethylene terephthalate may be 0.58 dl / g or more and 0.80 dl / g or less.

  The present invention is a packaging material comprising at least a first stretched plastic film, a second stretched plastic film, a third stretched plastic film, and a sealant layer in this order, wherein the packaging material is the first stretched plastic film. At least one of the first stretched plastic film, the second stretched plastic film or the third stretched plastic film, further comprising a transparent vapor deposition layer provided on the film, the second stretched plastic film or the third stretched plastic film. Includes polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as a dicarboxylic acid unit, and the first stretched plastic film, the second stretched plastic film or the third stretched plastic film The other one comprises a rigid film, which comprises a polyamide or a polybutylene terephthalate, or a polyester having a loop stiffness of 0.0017 N or more in one direction and a polyester, It is a packaging material.

According to the present invention, it is possible to provide a packaging material having excellent CO ₂ reduction effect and rigidity.

It is a schematic cross section which shows an example of the packaging material by this Embodiment. It is a schematic cross section which shows an example of the packaging material by this Embodiment. It is a schematic cross section which shows an example of the packaging material by this Embodiment. It is a schematic cross section which shows an example of the packaging material by this Embodiment. It is a schematic cross section which shows an example of the packaging material by this Embodiment. It is a schematic cross section which shows an example of the packaging material by this Embodiment. It is a schematic cross section which shows an example of the packaging material by this Embodiment. It is a schematic cross section which shows an example of the packaging material by this Embodiment. It is a schematic cross section which shows an example of a recycled film. It is a top view which shows an example of a loop stiffness measuring device. FIG. 6 is a cross-sectional view of the loop stiffness measuring instrument of FIG. 5, taken along line VI-VI. It is a figure for demonstrating the process of attaching a test piece to a loop stiffness measuring device. It is a figure for demonstrating the process of forming a loop part in a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece. It is a schematic front view which shows an example of a packaging bag. It is a schematic cross section which shows an example of the packaging material which comprises the lower film of the packaging bag of FIG. It is a schematic front view which shows an example of a packaging bag.

<Packaging material>
The packaging material according to the present embodiment includes at least a first stretched plastic film, a second stretched plastic film, and a sealant layer in this order. The packaging material may further include other layers such as an adhesive layer, a printing layer, a metal vapor deposition layer, and a transparent vapor deposition layer.

  The packaging material according to the present embodiment will be described with reference to the drawings. Examples of schematic cross-sectional views of the packaging material according to the present embodiment are shown in FIGS. 1A to 3B.

  The packaging material 10 shown in FIG. 1A includes a first stretched plastic film 11, a printing layer 21, a first adhesive layer 16, a second stretched plastic film 12, a second adhesive layer 17, and a metal vapor deposition layer. 22, a third stretched plastic film 13, a third adhesive layer 18, and a sealant layer 15 are provided in this order. In the packaging bag including the packaging material 10 shown in FIG. 1A, the sealant layer 15 constitutes the inner surface of the packaging bag. In the example shown in FIG. 1A, the metal vapor deposition layer 22 is provided on the outer surface side of the surface of the third stretched plastic film 13. Although not shown, the metal vapor deposition layer 22 may be provided on the inner surface of the surface of the third stretched plastic film 13.

  As shown in FIG. 1B, the packaging material 10 includes a first stretched plastic film 11, a printed layer 21, a first adhesive layer 16, a second stretched plastic film 12, a second adhesive layer 17, and a transparent material. The vapor deposition layer 23a, the third stretched plastic film 13, the third adhesive layer 18, and the sealant layer 15 may be provided at least in this order. That is, the packaging material 10 may include the transparent vapor deposition layer 23a instead of the metal vapor deposition layer 22 shown in FIG. 1A. In this case, the packaging material 10 may further include a gas barrier coating film 23b provided on the surface of the transparent vapor deposition layer 23a provided on the third stretched plastic film 13, as shown in FIG. 1C. . In the example shown in FIG. 1B and FIG. 1C, the transparent vapor deposition layer 23 a is provided on the outer surface side of the surface of the third stretched plastic film 13. Although not shown, the transparent vapor deposition layer 23a may be provided on the inner surface of the third stretched plastic film 13.

  The packaging material 10 shown in FIG. 2A includes a first stretched plastic film 11, a printing layer 21, a first adhesive layer 16, a metal vapor deposition layer 22, a second stretched plastic film 12, and a second adhesive layer. 17, a third stretched plastic film 13, a third adhesive layer 18, and a sealant layer 15 are provided in this order. In the packaging bag including the packaging material 10 shown in FIG. 2A, the sealant layer 15 constitutes the inner surface of the packaging bag. In the example shown in FIG. 2A, the metal vapor deposition layer 22 is provided on the outer surface of the second stretched plastic film 12. Although not shown, the metal vapor deposition layer 22 may be provided on the inner surface of the second stretched plastic film 12.

  As shown in FIG. 2B, the packaging material 10 includes a first stretched plastic film 11, a printing layer 21, a first adhesive layer 16, a transparent vapor deposition layer 23a, a second stretched plastic film 12, and a second adhesive. The agent layer 17, the third stretched plastic film 13, the third adhesive layer 18, and the sealant layer 15 may be provided in this order. That is, the packaging material 10 may include a transparent vapor deposition layer 23a instead of the metal vapor deposition layer 22 shown in FIG. 2A. In this case, the packaging material 10 may further include a gas barrier coating film 23b provided on the surface of the transparent vapor deposition layer 23a provided on the third stretched plastic film 13, as shown in FIG. 2C. . In the example shown in FIGS. 2B and 2C, the transparent vapor deposition layer 23a is provided on the outer surface of the second stretched plastic film 12. Although not shown, the transparent vapor deposition layer 23a may be provided on the inner surface of the second stretched plastic film 12.

  The packaging material 10 shown in FIG. 3A includes a first stretched plastic film 11, a transparent vapor deposition layer 23a, a printing layer 21, a first adhesive layer 16, a second stretched plastic film 12, and a second adhesive layer. 17, a third stretched plastic film 13, a third adhesive layer 18, and a sealant layer 15 are provided in this order. In the packaging bag including the packaging material 10 illustrated in FIG. 3A, the sealant layer 15 constitutes the inner surface of the packaging bag. In the example shown in FIG. 3A, the transparent vapor deposition layer 23a is provided on the inner surface side of the surface of the first stretched plastic film 11. Although not shown, the transparent vapor deposition layer 23a may be provided on the outer surface of the surface of the first stretched plastic film 11.

  As shown in FIG. 3B, the packaging material 10 may further include a gas barrier coating film 23b provided on the surface of the transparent vapor deposition layer 23a provided on the first stretched plastic film 11.

  Hereinafter, the films and layers that form the packaging material 10 will be described.

[Stretched plastic film]
The first stretched plastic film 11, the second stretched plastic film 12, and the third stretched plastic film 13 are all plastic films stretched in a predetermined direction. Each of the stretched plastic films 11, 12, 13 may be a uniaxially stretched film stretched in one predetermined direction or a biaxially stretched film stretched in two predetermined directions. The stretching direction of each stretched plastic film 11, 12, 13 is not particularly limited. For example, the stretched plastic films 11, 12, 13 may be stretched in the height direction of the packaging bag made of the packaging material 10 or may be stretched in the width direction of the packaging bag. The stretching directions of the stretched plastic films 11, 12, 13 may be the same or different. The stretch ratio of each stretched plastic film 11, 12, 13 is, for example, 1.05 times or more.

  At least one of the first stretched plastic film 11, the second stretched plastic film 12, and the third stretched plastic film 13 is a recycled film containing recycled PET, and the other at least one is a rigid film having rigidity.

  In the present embodiment, as described above, the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a is provided on the first stretched plastic film 11, the second stretched plastic film 12, or the third stretched plastic film 13. Therefore, among the first stretched plastic film 11, the second stretched plastic film 12, and the third stretched plastic film 13, there are two stretched plastic films in which the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a is not provided. One of the two stretched plastic films not provided with the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a may be a recycled film and the other may be a rigid film. In this case, the stretched plastic film provided with the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a may be a virgin film containing PET or biomass PET derived from fossil fuel.

  Further, two of the first stretched plastic film 11, the second stretched plastic film 12, and the third stretched plastic film 13 may be recycled films or rigid films. In this case, the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a may be provided on either the recycled film or the rigid film. That is, the recycled film or the rigid film provided with the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a may be the first stretched plastic film 11, the second stretched plastic film 12, or the third stretched plastic film 13.

Table 1 shows an example of a combination of the first stretched plastic film 11, the second stretched plastic film 12, and the third stretched plastic film 13, which are composed of the above-described recycled film, rigid film, virgin film, and the like. In Examples 1 to 12, the metal vapor deposition layer 22 may be directed to the outer surface side of the second stretched plastic film 12, or may be provided on the inner surface side of the second stretched plastic film 12. The surface may be provided on the outer surface side of the third stretched plastic film 13, or may be provided on the inner surface side of the third stretched plastic film 13.

  In Examples 1 to 12 of Table 1, the transparent vapor-deposited layer 23a may be directed to the outer surface side of the first stretched plastic film 11 and is provided on the inner surface side of the first stretched plastic film 11. May be directed to the outer surface of the second stretched plastic film 12, may be provided on the inner surface of the second stretched plastic film 12, or the outer surface of the third stretched plastic film 13. It may be provided on the side surface or on the inner surface side of the third stretched plastic film 13. A gas barrier coating film 23b may be provided on the surface of the transparent vapor deposition layer 23a.

  Hereinafter, the recycled film, the rigid film, and the virgin film will be described.

(Recycled film)
The recycled film contains polyethylene terephthalate (hereinafter, polyethylene terephthalate is also referred to as PET) recycled by mechanical recycling. Specifically, the recycled film contains PET obtained by recycling PET bottles by mechanical recycling. In this PET, the diol unit is ethylene glycol, and the dicarboxylic acid unit contains terephthalic acid and isophthalic acid. Here, mechanical recycling generally means crushing collected polyethylene terephthalate resin products such as PET bottles and washing with alkali to remove dirt and foreign substances on the surface of the PET resin products, and then drying at high temperature and reduced pressure for a certain period of time. Then, the contaminants remaining inside the PET resin are diffused for decontamination to remove stains on the resin product made of the PET resin and then returned to the PET resin. Hereinafter, polyethylene terephthalate obtained by recycling PET bottles is referred to as “recycled polyethylene terephthalate (hereinafter also referred to as recycled PET)”, and unrecycled polyethylene terephthalate is referred to as “virgin polyethylene terephthalate (hereinafter also referred to as virgin PET). ) ”.

  Among PET contained in the recycled film, the content of isophthalic acid is preferably 0.5 mol% or more and 5 mol% or less, and 1.0 mol% or more, with respect to all dicarboxylic acid units constituting PET. It is more preferably 2.5 mol% or less. If the content of isophthalic acid is less than 0.5 mol%, the flexibility may not be improved, while if it exceeds 5 mol%, the melting point of PET may be lowered and heat resistance may be insufficient. The PET may be biomass PET in addition to ordinary fossil fuel-derived PET. The "biomass PET" is one containing ethylene glycol derived from biomass as a diol unit and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit. This biomass PET may be formed of only PET having a biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit, or a biomass-derived ethylene glycol and a fossil fuel-derived diol as a unit. It may be formed of PET having a diol unit and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit.

  PET used in a PET bottle can be obtained by a conventionally known method in which the above-mentioned diol unit and dicarboxylic acid unit are polycondensed. Specifically, a general method of melt polymerization in which a polycondensation reaction is performed under reduced pressure after an esterification reaction and / or a transesterification reaction between the above diol unit and a dicarboxylic acid unit, or an organic solvent Can be produced by a known solution heating dehydration condensation method using

  The amount of the diol unit used in producing the PET is substantially equimolar with respect to 100 mol of the dicarboxylic acid or its derivative, but in general, esterification and / or transesterification reaction and / or polycondensation are conducted. Since there is distillation during the reaction, it is used in excess of 0.1 mol% or more and 20 mol% or less.

  The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and may be added at the time of charging the raw materials or at the start of depressurization.

  The PET recycled from the PET bottle is polymerized and solidified as described above, and is further subjected to solid phase polymerization as necessary to further increase the degree of polymerization or to remove oligomers such as cyclic trimers. You can go. Specifically, solid-phase polymerization is performed by forming PET into chips, drying the PET, and then heating at a temperature of 100 ° C. or higher and 180 ° C. or lower for about 1 to 8 hours to pre-crystallize the PET, and then 190 ° C. The heating is performed at a temperature of 230 ° C. or less and under an inert gas atmosphere or reduced pressure for 1 hour to several tens of hours.

  The PET contained in the recycled film preferably has an intrinsic viscosity of 0.58 dl / g or more and 0.80 dl / g or less. If the intrinsic viscosity is less than 0.58 dl / g, the mechanical properties required for the PET film as a base material may be insufficient. On the other hand, when the intrinsic viscosity exceeds 0.80 dl / g, the productivity in the film forming process may be impaired. The intrinsic viscosity is measured with an ortho-chlorophenol solution at 35 ° C.

  The recycled film preferably contains recycled PET in a proportion of 50% by weight or more and 95% by weight or less, and may contain virgin PET in addition to recycled PET. The PET content in the recycled film may be 80% by mass or more, 90% by mass or more, and 95% by mass or more. As the virgin PET, the diol unit as described above may be ethylene glycol, the dicarboxylic acid unit may be PET containing terephthalic acid and isophthalic acid, and the dicarboxylic acid unit may be PET containing no isophthalic acid. Good. Further, the recycled film may contain polyester other than PET. For example, the dicarboxylic acid unit may contain an aliphatic dicarboxylic acid or the like in addition to the aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 to 40 carbon atoms. Ingredients or cycloaliphatic dicarboxylic acids. Examples of the derivative of the aliphatic dicarboxylic acid include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of the above aliphatic dicarboxylic acid, and cyclic acid anhydrides of the above aliphatic dicarboxylic acid such as succinic anhydride. . Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable as the aliphatic dicarboxylic acid, and one containing succinic acid as a main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, the methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.

  The recycled film composed of such PET may be a single layer or a multilayer. FIG. 4 is a cross-sectional view showing an example of the recycled film 30. The recycled film 30 shown in FIG. 4 includes three layers of a first layer 31, a second layer 32, and a third layer 33. The third layer 33 is located on the sealant layer 15 side of the packaging material 10. In the example shown in FIG. 4, the second layer 32 is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 31 and the third layer 33 are composed only of virgin PET. It is preferable that the layer is a layer. Thus, by using only virgin PET for the first layer 31 and the third layer 33, it is possible to prevent the recycled PET from being exposed from the front surface or the back surface of the recycled film 30. Therefore, the hygiene of the packaging material 10 can be ensured. Further, the recycled film 30 may include two layers of the second layer 32 and the third layer 33, without including the first layer 31 shown in FIG. 4. Furthermore, the recycled film 30 may include two layers, that is, the first layer 31 and the second layer 32, without including the third layer 33 shown in FIG. Also in these cases, the second layer 32 is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 31 and the third layer 33 are layers composed only of virgin PET. It is preferable that

  When one layer is formed by mixing recycled PET and virgin PET, there are a method of supplying them separately to a molding machine and a method of supplying them after mixing them by dry blending. Among them, the method of mixing by dry blending is preferable from the viewpoint of easy operation.

  Various additives can be added to PET constituting the recycled film in the manufacturing process or after the manufacturing as long as the characteristics are not impaired. As an additive, for example, a plasticizer, an ultraviolet stabilizer, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a thread friction reducing agent, a release agent, an antioxidant, an ion. An exchange agent, a coloring pigment, etc. are mentioned. The additive is preferably added in the range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less with respect to the entire resin composition containing PET.

  The recycled film can be formed by using the above-mentioned PET and forming it into a film by, for example, the T-die method. Specifically, after drying the PET described above, it is supplied to a melt extruder heated to a temperature (Tm) higher than the melting point of PET to Tm + 70 ° C. to melt the resin composition, for example, a T-die. A film can be formed by extruding into a sheet form from a die such as, and rapidly quenching and solidifying the extruded sheet form with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

  The film obtained as described above is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded on the cooling drum as described above is subsequently heated by roll heating, infrared heating or the like, and stretched in the longitudinal direction to obtain a longitudinally stretched film. This stretching is preferably performed by utilizing the peripheral speed difference between two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 ° C or higher and 100 ° C or lower. The longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, though it depends on the required characteristics of the film application. If the stretching ratio is less than 2.5 times, it is difficult to obtain a good film because the PET film has large thickness unevenness.

  The longitudinally stretched film is subsequently subjected to the treatment steps of lateral stretching, heat setting and heat relaxation in order to obtain a biaxially stretched film. The transverse stretching is usually performed in a temperature range of 50 ° C or higher and 100 ° C or lower. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, though it depends on the characteristics required for this application. When it is less than 2.5 times, it is difficult to obtain a good film because the thickness unevenness of the film becomes large, and when it exceeds 5.0 times, breakage easily occurs during film formation.

  After transverse stretching, heat setting treatment is subsequently carried out, but the preferable temperature range for heat setting is Tg + 70 to Tm−10 ° C. of PET. The heat setting time is preferably 1 second or more and 60 seconds or less. Furthermore, for applications requiring a low heat shrinkage, heat relaxation treatment may be carried out as necessary.

The thickness of the recycled film obtained as described above is arbitrary depending on the application, but is usually about 5 μm or more and 100 μm or less, preferably 5 μm or more and 25 μm or less. Further, the breaking strength of the recycled film, the MD direction 5 kg / mm ² or more 40 kg / mm ² or less, at 35 kg / mm ² or less 5 kg / mm ² or more in the TD direction, elongation at break in MD direction 50 % To 350%, and 50% to 300% in the TD direction. Further, the shrinkage ratio when left for 30 minutes in a temperature environment of 150 ° C. is 0.1% or more and 5% or less.

  The virgin PET may be fossil fuel polyethylene terephthalate (hereinafter also referred to as fossil fuel PET) or biomass PET. Here, the “fossil fuel PET” means a diol derived from fossil fuel as a diol unit and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit. The recycled PET may be obtained by recycling a PET resin product formed using fossil fuel PET, or may be obtained by recycling a PET resin product formed using biomass PET. It may be.

(Rigid film)
The rigid film is a film for imparting strength such as puncture resistance to the packaging material 10. As the rigid film, any of the following stretched plastic films (1) to (3) can be used.
(1) Stretched plastic film containing polyamide as a main component (hereinafter, also referred to as polyamide film)
(2) Stretched plastic film containing polybutylene terephthalate (hereinafter, also referred to as PBT) as a main component (hereinafter, also referred to as PBT film)
(3) A stretched plastic film having a loop stiffness of 0.0017 N or more in at least one direction and containing polyester as a main component (hereinafter, also referred to as a high stiffness film).
By forming the rigid film using any of the stretched plastic films of (1) to (3), the puncture strength of the rigid film can be increased, and can be, for example, 10 N or more. Thereby, it is possible to impart rigidity to the bag formed of the packaging material 10 including the rigid film to prevent the bag from being broken even when a sharp member having a sharp tip comes into contact with the bag.

  The stretched plastic films (1) to (3) will be described below. First, the polyamide film will be described. The polyamide film contains 51% by mass or more of polyamide. The polyamide content in the polyamide film may be 80% by mass or more, 90% by mass or more, and 95% by mass or more. Examples of polyamide-based materials include aliphatic polyamides and aromatic polyamides. Examples of the aliphatic polyamide include nylon such as nylon-6, nylon-6,6, and a copolymer of nylon 6 and nylon 6,6. As the aromatic polyamide, polymethaxylene adipamide ( MXD6) and the like.

  The thickness of the polyamide film is preferably 12 μm or more, more preferably 15 μm or more. The thickness of the polyamide film is preferably 30 μm or less, more preferably 25 μm or less.

  The polyamide film may be composed of a single layer or may be composed of a plurality of layers. When the polyamide film includes a plurality of layers, the polyamide film is, for example, a co-extrusion film produced by co-extrusion. The polyamide film produced by co-extrusion includes, for example, a first layer made of polyester such as PET, a second layer made of polyamide such as nylon, and a third layer made of polyester such as PET, which are sequentially laminated. When the mass of the second layer made of polyamide such as nylon is 51% or more of the mass of the entire polyamide film, it can be said that the main component of the polyamide film produced by coextrusion is polyamide.

  Next, the PBT film will be described. The PBT film contains 51% by mass or more of PBT. The content of PBT in the PBT film may be 60% by mass or more, 70% by mass or more, 80% by mass or more, and 90% by mass or more, 95 It may be mass% or more. As the structure of the PBT film, either of the following first structure or second structure may be adopted.

  The PBT film having the first structure is produced by, for example, as disclosed in International Publication No. WO 2015/178390 pamphlet, by layering and casting a resin having the same composition. In this case, the PBT film is composed of a multilayer structure part including at least 10 layers or more, preferably 60 layers or more, more preferably 250 layers or more, and further preferably 1000 layers or more. Each of the plurality of layers preferably contains 51% by mass or more of PBT, and more preferably 60% by mass or more of PBT. In the plurality of layers, the (n + 1) th layer is directly laminated on the nth layer. That is, no adhesive layer or adhesive layer is interposed between the plurality of layers. The thickness of each layer is preferably 3 nm or more, more preferably 10 nm or more. The thickness of each layer is preferably 200 nm or less, more preferably 100 nm or less, and further preferably 75 nm or less.

  The total thickness of the PBT film is preferably 9 μm or more, more preferably 12 μm or more. The total thickness of the PBT film having the first structure is preferably 25 μm or less, more preferably 20 μm or less. When the thickness of the PBT film is 9 μm or more, the PBT film has sufficient strength. Further, by setting the thickness of the PBT film to 25 μm or less, the PBT film comes to exhibit excellent moldability. Therefore, the process of manufacturing the packaging bag by processing the packaging material 10 including the PBT film can be efficiently performed.

  When the PBT film is composed of the multilayer structure part including a plurality of layers as described above, some of the plurality of layers may contain a polyester resin other than PBT as a main component. For example, the PBT film of the first structure may be composed of a plurality of layers containing PBT as a main component and a layer containing, for example, PET as a main component, which is located between two PBT layers. That is, the PBT film having the first configuration may be configured by alternately stacking layers containing PBT as a main component and layers containing, for example, PET as a main component.

Preferably, the value obtained by dividing the tensile strength of the PBT film of the first constitution by the tensile elongation in at least one direction is 2.0 [MPa /%] or more. For example, the value obtained by dividing the tensile strength of the PBT film in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa /%] or more, more preferably 2.2 [MPa /%] or more. is there.
The tensile strength and the tensile elongation can be measured according to JIS K7127. As a measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co. can be used. As the test piece, a PBT film cut into a rectangular film having a width of 15 mm and a length of 150 mm can be used. The interval at the start of measurement between the pair of chucks holding the test piece was 100 mm, and the pulling speed was 300 mm / min. The length of the test piece can be adjusted as long as the test piece can be held by the pair of chucks. In the present application, unless otherwise specified, the environmental temperature during the test is 25 ° C., and the relative humidity is 50%.

  The PBT film having the second structure is composed of a single layer film containing polyester containing butylene terephthalate as a main repeating unit, as disclosed in, for example, JP-A-2014-133332. For example, a PBT film contains 1,4-butanediol as a glycol component or an ester-forming derivative thereof as a main component and terephthalic acid as an dibasic acid component or an ester-forming derivative thereof as a main component and condenses them. The resulting homo or copolymer type polyester is included. The content of PBT in the PBT film 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 It is 90 mass% or more. Further, the PBT film according to the second structure is preferably composed only of polybutylene terephthalate and the additive.

  In order to impart mechanical strength to the PBT film of the second structure, PBT having a melting point of 200 ° C. or higher and 250 ° C. or lower and an IV value of 1.10 dl / g or higher and 1.35 dl / g or lower is required. Is preferred. Further, those having a melting point of 215 ° C. or higher and 225 ° C. or lower and an IV value of 1.15 dl / g or higher and 1.30 dl / g or lower are particularly preferable. These IV values may be met by the entire material that makes up the PBT film. The IV value can be calculated based on JIS K 7367-5: 2000.

  The PBT film according to the second configuration may include a polyester resin such as PET other than PBT in a range of 30% by mass or less. When the PBT film contains PET in addition to PBT, crystallization of PBT can be suppressed and the stretchability of the PBT film can be improved. As the PET compounded in the PBT of the PBT film, polyester having ethylene terephthalate as a main repeating unit can be used. For example, a homotype containing ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component as a main component can be preferably used. In order to impart good mechanical strength characteristics, PET having a melting point of 240 ° C. or higher and 265 ° C. or lower and an IV value of 0.55 dl / g or higher and 0.90 dl / g or lower is preferable. Further, 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.

  Next, the high stiffness film will be described. The high stiffness film contains polyester as a main component and has a loop stiffness of 0.0017 N or more in at least one direction. The high stiffness film has, for example, a loop stiffness of 0.0017 N or more in at least one of the machine direction (MD) and the vertical direction (TD). The high stiffness film may have a loop stiffness of 0.0017 N or more, for example, in both the machine direction (MD) and the vertical direction (TD).

  The loop stiffness is a parameter indicating the strength of the film. Hereinafter, a method for measuring loop stiffness will be described with reference to FIGS. The measuring method described below can be used not only for a single-layer film such as a stretched plastic film but also for a film including a plurality of layers such as a vapor deposition film and a laminated film. The vapor deposition film is a film including a single layer film such as a stretched plastic film and a vapor deposition layer formed on the single layer film. A laminated film is a film including a plurality of laminated films, such as the packaging material 10.

  5 is a plan view showing the test piece 60 and the loop stiffness measuring instrument 65, and FIG. 6 is a cross-sectional view of the test piece 60 and the loop stiffness measuring instrument 65 of FIG. 5 taken along the line V-V. The test piece 60 is a rectangular film having long sides and short sides. In the present application, the long side length L1 of the test piece 60 is 150 mm, and the short side length L2 is 15 mm. As the loop stiffness measuring device 65, for example, No. manufactured by Toyo Seiki Co., Ltd. 581 LOOP STIFFNESS TESTER DA type can be used. The length L1 of the long side of the test piece 60 can be adjusted as long as the test piece 60 can be gripped by a pair of chuck portions 66 described later.

  The loop stiffness measuring instrument 65 has a pair of chuck portions 66 for gripping a pair of end portions of the test piece 60 in the long side direction, and a support member 67 that supports the chuck portion 66. The chuck unit 66 includes a first chuck 661 and a second chuck 662. In the state shown in FIGS. 5 and 6, the test piece 60 is arranged on the pair of first chucks 661, and the second chuck 662 still grips the test piece 60 with the first chuck 661. Not not. As will be described later, the test piece 60 is gripped between the first chuck 661 and the second chuck 662 of the chuck portion 66 during measurement. The second chuck 662 may be connected to the first chuck 661 via a hinge mechanism.

  When a film to be measured such as a stretched plastic film, a vapor-deposited film or a laminated film is available in a state before the film is processed into a packaging product, the test piece 60 is produced by cutting the film to be measured. May be. Further, the test piece 60 may be produced by cutting a packaged product made of the packaging material 10, such as a packaging bag, and taking out the film to be measured. For example, the test piece may be prepared by cutting the front surface film 74 or the back surface film 75 of the packaging bag 70 as shown by a dotted line with reference numeral 60A or 60B in FIGS. 11 and 13 described later. When measuring the loop stiffness of the packaging material 10 in the flow direction, as shown by reference numeral 60A in FIGS. 11 and 13, the front surface film 74 or the back surface of the packaging bag 70 is arranged so that the long side direction of the test piece coincides with the flow direction. The film 75 is cut to produce a test piece. When measuring the loop stiffness of the packaging material 10 in the vertical direction, as shown by reference numeral 60B in FIGS. 11 and 13, the surface film 74 or the back surface of the packaging bag 70 is arranged so that the long side direction of the test piece coincides with the vertical direction. The film 75 is cut to produce a test piece.

  A method of measuring the loop stiffness of the test piece 60 using the loop stiffness measuring device 65 will be described. First, as shown in FIGS. 5 and 6, the test piece 60 is placed on the first chucks 661 of the pair of chuck portions 66 that are arranged with a gap L3 therebetween. In the present application, the interval L3 is set so that the length of the loop portion 61 (hereinafter, also referred to as loop length), which will be described later, is 60 mm. The test piece 60 includes an inner surface 60x located on the first chuck 661 side and an outer surface 60y located on the opposite side of the inner surface 60x. When the test piece 60 is made of the packaging material 10, the inner surface 60x and the outer surface 60y of the test piece 60 coincide with the inner surface and the outer surface of the packaging material 10. When forming the loop portion 61 described later on the test piece 60, the inner surface 60x is located inside the loop portion 61 and the outer surface 60y is located outside the loop portion 61. Subsequently, as shown in FIG. 7, the second chuck 662 is arranged on the test piece 60 so as to hold the end of the test piece 60 in the long side direction between the first chuck 661 and the first chuck 661.

  Subsequently, as shown in FIG. 8, at least one of the pair of chuck portions 66 is slid on the support member 67 in the direction in which the distance between the pair of chuck portions 66 is reduced. Thereby, the loop portion 61 can be formed on the test piece 60. The test piece 60 shown in FIG. 8 includes a loop portion 61, a pair of intermediate portions 62, and a pair of fixing portions 63. The pair of fixing portions 63 are portions of the test piece 60 that are held by the pair of chuck portions 66. The pair of intermediate portions 62 are portions of the test piece 60 that are located between the loop portion 61 and the pair of intermediate portions 62. As shown in FIG. 8, the chuck portion 66 is slid on the support member 67 until the inner surfaces 60x of the pair of intermediate portions 62 come into contact with each other. Thereby, the loop part 61 having a loop length of 60 mm can be formed. The loop length of the loop portion 61 is the position P1 where the surface of the second chuck 662 on the side of the loop portion 61 and the test piece 60 intersect, and the surface of the second chuck 662 on the side of the loop portion 61 and the test piece 60. It is the length of the test piece 60 between the position P2 where the points intersect. When the thickness of the test piece 60 is ignored, the above-mentioned distance L3 is a value obtained by adding 2 × t to the length of the loop portion 61. t is the thickness of the second chuck 662 of the chuck portion 66.

  After that, as shown in FIG. 9, the posture of the chuck portion 66 is adjusted so that the protruding direction Y of the loop portion 61 with respect to the chuck portion 66 is horizontal. For example, the posture of the chuck portion 66 supported by the support member 67 is adjusted by moving the support member 67 so that the normal line direction of the support member 67 faces the horizontal direction. In the example shown in FIG. 9, the protruding direction Y of the loop portion 61 matches the thickness direction of the chuck portion. Further, the load cell 68 is prepared at a position separated from the second chuck 662 by the distance Z1 in the protruding direction Y of the loop portion 61. In the present application, the distance Z1 is set to 50 mm. Subsequently, the load cell 68 is moved toward the loop portion 61 of the test piece 60 at the speed V by the distance Z2 shown in FIG. As shown in FIGS. 9 and 10, the distance Z2 is set so that the load cell 68 contacts the loop portion 61 and then the load cell 68 pushes the loop portion 61 toward the chuck portion 66 side. In the present application, the distance Z2 is 40 mm. In this case, the distance Z3 between the load cell 68 and the second chuck 662 of the chuck portion 66 when the load cell 68 pushes the loop portion 61 toward the chuck portion 66 side is 10 mm. The speed V at which the load cell 68 was moved was 3.3 mm / sec.

  Subsequently, as shown in FIG. 10, the load cell 68 is moved to the chuck portion 66 side by the distance Z2, and the load cell 68 is being pushed into the loop portion 61 of the test piece 60, and is added to the load cell 68 from the loop portion 61. After the load value stabilizes, record the load value. The value of the load thus obtained is adopted as the loop stiffness of the film forming the test piece 60. In the present application, unless otherwise specified, the environment at the time of measuring loop stiffness is a temperature of 23 ° C. and a relative humidity of 50%.

  By using a high-stiffness film having a loop stiffness of 0.0017 N or more in at least one direction as the stretched plastic film, the piercing strength of the stretched plastic film can be increased. Thereby, in the packaging material 10 provided with the high stiffness film, the puncture strength of the packaging material 10 can be, for example, 13 N or more, more preferably 14 N or more, and further preferably 15 N or more or 16 N or more. be able to.

  Examples of the high stiffness film include a high stiffness PET film containing 51% by mass or more of PET. The PET content in the high-stiffness PET film may be 80% by mass or more, 90% by mass or more, and 95% by mass or more. The thickness of the high stiffness film is preferably 5 μm or more, more preferably 7 μm or more. The thickness of the high stiffness film may be 10 μm or more, or 14 μm or more. The thickness of the high stiffness film is preferably 30 μm or less, 25 μm or less, or 20 μm or less.

The preferable mechanical properties of the high stiffness film will be further described.
The puncture strength of the high stiffness film is preferably 10 N or more, more preferably 11 N or more.
The tensile strength of the high stiffness film in at least one direction is preferably 250 MPa or more, more preferably 280 MPa or more. For example, the tensile strength of the high-stiffness film in the flow direction is preferably 250 MPa or more, more preferably 280 MPa or more. The tensile strength of the high stiffness film in the vertical direction is preferably 250 MPa or more, more preferably 280 MPa or more.
The tensile elongation of the high stiffness film in at least one direction is preferably 130% or less, more preferably 120% or less. For example, the tensile elongation of the high stiffness film in the machine direction is preferably 130% or less, more preferably 120% or less. The tensile elongation of the high stiffness film in the vertical direction is preferably 120% or less, more preferably 110% or less.
Preferably, the value obtained by dividing the tensile strength of the high stiffness film by the tensile elongation in at least one direction is 2.0 [MPa /%] or more. For example, the value obtained by dividing the tensile strength of the high stiffness film in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa /%] or more, more preferably 2.2 [MPa /%] or more. Is. The value obtained by dividing the tensile strength of the high stiffness film in the machine direction (MD) by the tensile elongation is preferably 1.8 [MPa /%] or more, and more preferably 2.0 [MPa /%] or more. .

The heat shrinkage ratio of the high stiffness film in at least one direction is preferably 0.7% or less, more preferably 0.5% or less. For example, the heat shrinkage rate of the high stiffness film in the flow direction is preferably 0.7% or less, and more preferably 0.5% or less. The heat shrinkage rate of the high stiffness film in the vertical direction is preferably 0.7% or less, and more preferably 0.5% or less. The heating temperature when measuring the heat shrinkage is 100 ° C., and the heating time is 40 minutes.
The Young's modulus of the high stiffness film in at least one direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more. For example, the Young's modulus of the high-stiffness film in the flow direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more. The Young's modulus of the high stiffness film in the vertical direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more.

  The Young's modulus can be measured according to JIS K7127, like the tensile strength and the tensile elongation. As a measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co. can be used. As the test piece, a high-stiffness film cut into a rectangular film having a width of 15 mm and a length of 150 mm can be used. The interval at the start of measurement between the pair of chucks holding the test piece was 100 mm, and the pulling speed was 300 mm / min. The length of the test piece can be adjusted as long as the test piece can be held by the pair of chucks. In the present application, unless otherwise specified, the environment at the time of measuring the Young's modulus is a temperature of 25 ° C. and a relative humidity of 50%.

  In the packaging material 10 including the high-stiffness film, the high-stiffness film may be provided with the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a as described above. In this case, the high stiffness film provided with the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a may have mechanical properties equivalent to those of a single high stiffness film. For example, the high stiffness film provided with the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a may have a loop stiffness of 0.0017 N or more in at least one direction.

  As described above, the gas barrier coating film 23b may be provided on the transparent vapor deposition layer 23a. In this case, the high-stiffness film provided with the transparent vapor-deposited layer 23a and the gas barrier coating film 23b may have mechanical properties equivalent to those of a single high-stiffness film. For example, the high stiffness film provided with the transparent vapor deposition layer 23a and the gas barrier coating film 23b may have a loop stiffness of 0.0017 N or more in at least one direction.

  In the manufacturing process of a high stiffness film, for example, first, a plastic film obtained by melting and molding polyester is subjected to 3 to 4.5 times at 90 ° C. to 145 ° C. in the flow direction and the vertical direction, respectively. A first stretching step of stretching is performed. Subsequently, a second stretching step is performed in which the plastic film is stretched 1.1 times to 3.0 times at 100 ° C. to 145 ° C. in the flow direction and the vertical direction, respectively. Then, heat fixation is performed at a temperature of 190 ° C to 220 ° C. Subsequently, in the flow direction and the vertical direction, a relaxation treatment (a treatment for reducing the film width) of about 0.2% to 2.5% is performed at a temperature of 100 ° C to 190 ° C. In these steps, a high stiffness film having the above-mentioned mechanical properties can be obtained by adjusting the stretching ratio, stretching temperature, heat setting temperature, and relaxation treatment rate.

(Virgin film)
Virgin film is a film made of non-recycled resin. The virgin film includes, for example, PET derived from fossil fuel and biomass PET. When the virgin film contains PET such as fossil fuel PET or biomass PET as a main component, the PET content in the virgin film may be 80% by mass or more, 90% by mass or more, and 95% by mass. % Or more. The puncture strength of the virgin film is lower than the puncture strength of the rigid film described above, and is, for example, less than 10N. Also, the loop stiffness of the virgin film is lower than the loop stiffness of the high stiffness film described above, for example, less than 0.0017 N in the machine direction (MD) and the vertical direction (TD). The thickness of the virgin film is arbitrary depending on its application, but is usually about 5 μm or more and 100 μm or less, preferably 5 μm or more and 25 μm or less.

[Metal vapor deposition layer]
Next, the metal vapor deposition layer 22 provided on the second stretched plastic film 12 or the third stretched plastic film 13 will be described. The metal vapor deposition layer 22 is a layer formed of a metal vapor deposition film that can be formed by a conventionally known vapor deposition method. By providing the metal vapor deposition layer 22, a metallic luster can be imparted to the packaging bag, so that the designability can be improved. Further, it is possible to impart or improve the light blocking property of blocking the transmission of visible light and ultraviolet rays. In addition, it can also contribute to a gas barrier property that prevents permeation of oxygen gas, water vapor and the like.

  Examples of the material forming the metal vapor deposition layer 22 include aluminum (Al), magnesium (Mg), tin (Sn), sodium (Na), titanium (Ti), lead (Pb), zirconium (Zr), yttrium ( One or more metal materials selected from the group consisting of Y), gold (Au) and chromium (Cr) can be used. Particularly, for a packaging bag, it is preferable that the metal vapor deposition layer 22 includes an aluminum vapor deposition layer.

  The metal vapor deposition layer 22 may be composed of a single layer or may be composed of a plurality of layers. Each of the single layer and the plurality of layers includes one or more metal materials selected from the above group. When the metal vapor deposition layer 22 includes a plurality of layers, each layer may include the same metal material or different metal materials.

  The thickness of the metal vapor deposition layer 22 varies depending on the type of metal used and the like, but is arbitrarily selected within the range of, for example, 50 Å or more and 2000 Å or less, preferably 100 Å or more and 1000 Å or less. More specifically, in the case of an aluminum vapor deposition layer, the thickness is preferably 300 Å or more and 1000 Å or less, and more preferably 350 Å or more and 900 Å or less.

[Transparent deposition layer]
Next, the transparent vapor deposition layer 23a provided on the first stretched plastic film 11, the second stretched plastic film 12, or the third stretched plastic film 13 will be described. The transparent vapor deposition layer 23a is a layer made of a transparent vapor deposition film that can be formed by a conventionally known vapor deposition method. The transparent vapor deposition layer 23a can contribute to the gas barrier property of blocking the permeation of oxygen gas, water vapor, and the like.

  The material forming the transparent vapor deposition layer 23a is, for example, one selected from the group consisting of a transparent metal oxide such as aluminum oxide (aluminum oxide) and a transparent inorganic compound such as silicon oxide. Alternatively, two or more kinds of materials can be used.

  The transparent vapor deposition layer 23a may be composed of a single layer or may be composed of a plurality of layers. Each of the single layer and the plurality of layers contains one or more materials selected from the above group. When the transparent vapor deposition layer 23a includes a plurality of layers, each layer may include the same material or different materials.

The transparent vapor deposition layer 23a may be a non-crystalline thin film of aluminum oxide. Specifically, the transparent vapor deposition layer 23a is a non-crystalline 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). May be. As the transparent vapor deposition layer 23a, an amorphous thin film of aluminum oxide whose X value decreases in the depth direction from the film surface to the inner surface can also be used. The amorphous thin film of aluminum oxide is represented by the formula AlO _x (wherein X represents a number in the range of 0.5 to 1.5), and is formed in the depth direction from the thin film surface to the inner surface. It is preferred that the value of X is increasing toward. As the value of X in the above formula, it is basically possible to use a value of X = 0.5 or more, but if X = less than 1.0, the coloring is intense and transparent. It is preferable that X = 1.0 or more is used because it is inferior in properties. Further, when X = 1.5, since Al and oxygen are completely oxidized, it is possible to use those up to X = 1.5 as the upper limit. When the value of X in the above formula is 0, the substance is a complete inorganic substance (pure substance) and is not transparent.

  The rate of decrease in the value of X is determined by using a surface analyzer such as an X-ray photoelectron spectrometer (XPS) or a secondary ion mass spectrometer (SIMS) in the depth direction. This can be confirmed by performing elemental analysis of the transparent vapor-deposited layer by utilizing a method of analyzing by ion etching.

  The thickness of the transparent vapor deposition layer is preferably 3 nm or more and 50 nm or less, preferably 8 nm or more and 30 nm or less.

  Examples of the method for forming the metal vapor deposition layer 22 and the transparent vapor deposition layer 23a include 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 method. Examples thereof include chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as a vapor phase growth method, a thermochemical vapor phase growth method, and a photochemical vapor phase growth method.

  On the surface of the first stretched plastic film 11, the second stretched plastic film 12 or the third stretched plastic film 13 on which the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a is provided, the first stretched plastic film 11 and the second stretched plastic film The metal vapor-deposited layer 22 or the transparent vapor-deposited layer 23a may be subjected to a treatment for improving the adhesiveness to the 12 or the third stretched plastic film 13, or a layer for enhancing the adhesiveness may be formed. For example, plasma treatment using plasma may be applied to the surface of the first stretched plastic film 11, the second stretched plastic film 12, or the third stretched plastic film 13.

[Coated film with gas barrier property]
Next, the gas barrier coating film 23b provided on the surface of the transparent vapor deposition layer 23a will be described.

The gas barrier coating film 23b has a general formula R ¹ _n M (OR ² ) _m (wherein 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 at least one alkoxide represented by the above, and the polyvinyl alcohol as described above. A transparent gas barrier composition containing a 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. To be The gas barrier coating film 23b is preferably transparent.

As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one kind of alkoxide partial hydrolyzate and alkoxide hydrolyzate condensate can be used. Further, the partial hydrolyzate of the above alkoxide does not need to have all the alkoxy groups hydrolyzed, and may be one or more of which are hydrolyzed, or a mixture thereof. As the hydrolyzed condensate of the alkoxide, a partially hydrolyzed alkoxide dimer or more, specifically, a dimer to hexamer is used.

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. Preferred metals include, for example, silicon and titanium. Further, in the present embodiment, the alkoxide may be used alone or as a mixture of two or more different metal atom alkoxides in the same solution.

In the alkoxide represented by the above 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, methyl group, ethyl group, n-propyl group, i. Examples include -propyl group, n-butyl group, sec-butyl group, and the like. In addition, these alkyl groups may be the same or different in the same molecule.

  When preparing the above transparent gas barrier composition, for example, a silane coupling agent or the like may be added. As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used. In particular, an organoalkoxysilane having an epoxy group is preferably used, and specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be used. The silane coupling agents as described above may be used alone or in combination of two or more.

[Sealant layer]
The sealant layer 15 is arranged on the contents side of the packaging bag when the packaging material 10 is manufactured and has a function of sealing the packaging materials 10 to each other. The sealant layer 15 includes a polyethylene resin such as low density polyethylene or linear low density polyethylene, or a polyolefin resin such as polypropylene. However, the sealant layer 15 is a linear low density polyethylene from the viewpoints of adhesion, manufacturing cost and the like. It is preferable to include. The sealant layer 15 is preferably made of a non-stretched film.

  Linear low-density polyethylene is obtained by polymerizing ethylene and a small amount of α-olefin by a low pressure polymerization method (gas phase polymerization method using Ziegler-Natta catalyst or liquid phase polymerization method using metallocene catalyst). is there. The linear low-density polyethylene has many short molecular chains in its molecular chain and is excellent in sealing performance.

Linear low density polyethylene is less than 0.93 g / cm ^3, preferably 0.91 g / cm ³ or more 0.93 g / cm less than ^3, more preferably 0.912 g / cm ³ or more 0.928 g / cm ³ or less More preferably, it has a density of 0.915 g / cm ³ or more and 0.925 g / cm ³ or less. The density of the linear low-density polyethylene is a value measured according to the method defined in Method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. When the linear low-density polyethylene has a density of 0.91 g / cm ³ or more, the rigidity of the sealant layer 15 containing the linear low-density polyethylene can be increased, and the linear low-density polyethylene can be suitably used as the inner layer of the packaging bag. Further, if the linear low-density polyethylene has a density of less than 0.93 g / cm ³ , the mechanical strength of the sealant layer 15 can be increased and it can be suitably used as the inner layer of the packaging bag.

  The linear low-density polyethylene is 0.1 g / 10 minutes or more and 10 g / 10 minutes or less, preferably 0.2 g / 10 minutes or more and 9 g / 10 minutes or less, more preferably 1 g / 10 minutes or more and 8.5 g / 10 minutes. It has the following melt flow rate (MFR). The melt flow rate is a value measured by Method A under the conditions of temperature 190 ° C. and load 21.18 N in the method specified in JIS K7210-1995. If the MFR of the linear low-density polyethylene is 0.1 g / 10 minutes or more, the extrusion load during molding can be reduced. If the MFR of the linear low-density polyethylene is 10 g / 10 minutes or less, the mechanical strength of the sealant layer 15 can be increased.

The sealant layer 15 may further contain low density polyethylene in addition to the linear low density polyethylene. Thereby, the tearability of the packaging material 10 can be improved. When the sealant layer 15 contains both linear low-density polyethylene and low-density polyethylene, the content (% by weight) of the linear low-density polyethylene is preferably larger than the content (% by weight) of the low-density polyethylene. . When the sealant layer 15 contains both linear low density polyethylene and low density polyethylene, the density of the sealant layer 15 is, for example, 0.912 g / cm ³ or more and 0.930 g / cm ³ or less, and more preferably 0. .915g / cm ³ or more and 0.925 g / cm ³ or less.

  From the viewpoint of further reducing the environmental load, polyethylene derived from biomass can be used. Biomass polyethylene is a monomer polymer containing ethylene derived from biomass. Since ethylene derived from biomass is used as a raw material monomer, the polymerized polyolefin is derived from biomass. The content of biomass-derived ethylene in the raw material monomer does not need to be 100% by mass, and is, for example, preferably 50% or more, more preferably 80% or more. The raw material monomer may contain fossil fuel-derived ethylene, or may contain an α-olefin monomer such as butylene, hexene, and octene. Even in such a case, the obtained polymer is called biomass polyethylene. By including the α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, so that it can be more flexible than a simple linear one.

  For example, biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. Particularly, it is preferable to use biomass-derived fermented ethanol obtained from a plant raw material. The plant raw material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beets, and manioc can be mentioned. The biomass-derived fermented ethanol refers to ethanol that has been purified after the ethanol-producing microorganism or a crushed product-derived product is brought into contact with a culture solution containing a carbon source obtained from a plant raw material. For the purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method of adding benzene, cyclohexane or the like to carry out azeotropic distillation, or removing water by membrane separation or the like can be mentioned.

As the biomass polyethylene, a linear low density polyethylene derived from biomass manufactured by Braskem Co., Ltd. (trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1.0 g / 10 min, biomass degree 87%), Braschem Co. Linear low-density polyethylene derived from Biomass (trade name: SLL318, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min, biomass degree 87%), linear derived from biomass produced by Braskem Low density polyethylene (trade name: SLH218, density: 0.916 g / cm ³ , MFR: 2.3 g / 10 minutes, biomass degree 87%) and the like.

  For the linear low-density polyethylene derived from biomass, for example, one using sugar cane as a raw material is produced. The degree of dispersion of such straight chain low density polyethylene derived from sugar cane can be 4 or more and 7 or less. On the other hand, the degree of dispersion of fossil-derived linear low-density polyethylene is usually 1.5 or more and 3.5 or less.

  The sealant layer 15 may be a single layer or a multilayer. When the linear low density polyethylene derived from biomass as described above is used for the sealant layer 15, a sealant layer having three layers of an inner layer, an intermediate layer, and an outer layer may be used. In that case, it is preferable that the intermediate layer is a linear low-density polyethylene derived from biomass, and the inner layer and the outer layer are linear low-density polyethylene derived from a conventionally known fossil fuel.

  The thickness of the sealant layer 15 is preferably 50 μm or more, more preferably 80 μm or more. The thickness of the sealant layer 15 is preferably 170 μm or less, more preferably 120 μm or less. When the thickness of the sealant layer 15 is in the above range, sufficient sealability can be imparted when the packaging bag is manufactured.

[Adhesive layer]
The first adhesive layer 16 is formed by applying an adhesive to the surface of the film including the first stretched plastic film 11 and the film including the second stretched plastic film 12 on the side to be laminated and drying the applied adhesive. It is a layer to be. The second adhesive layer 17 is formed by applying an adhesive to the surface of the film including the second stretched plastic film 12 and the film including the third stretched plastic film 13 on the side to be laminated and drying the applied adhesive. It is a layer to be. The third adhesive layer 18 is a layer formed by applying an adhesive to the surface of the film of the film containing the third stretched plastic film 13 and the film of the film containing the sealant layer 15 on the side to be laminated and then drying. Is. As the adhesive constituting the adhesive layers such as the first adhesive layer 16, the second adhesive layer 17, and the third adhesive layer 18, for example, one-component type or two-component type curable or non-curable vinyl is used. A solvent-based, water-based, or emulsion-based adhesive such as a system-based (meth) acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, or the like can be used. As the two-component curing type adhesive, a cured product of a polyol and an isocyanate compound can be used. As a method for coating the above-mentioned laminating adhesive, for example, direct gravure roll coating method, gravure roll coating method, kiss coating method, reverse roll coating method, Fonten method, transfer roll coating method, or the like can be applied .

  The adhesive layers such as the first adhesive layer 16, the second adhesive layer 17, and the third adhesive layer 18 may include a biomass-derived component. For example, when the adhesive layer contains a cured product of a polyol and an isocyanate compound, at least one of the polyol and the isocyanate compound may contain a biomass-derived component.

[Print layer]
The printing layer 21 includes characters, numbers, pictures, figures, symbols, patterns, etc. for decoration, display of contents, display of shelf life, display of manufacturers, sellers, etc. and addition of aesthetics. Is a layer that forms any desired printed pattern. The printing layer 21 can be provided as needed, and can be provided, for example, between the first stretched plastic film 11 and the first adhesive layer 16. The printing layer 21 may be provided on the entire surface of the first stretched plastic film 11 or may be provided on a part thereof. The printed layer 21 can be formed using a conventionally known pigment or dye, and the forming method is not particularly limited.

  The printing layer 21 preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and further preferably 1 μm or more and 3 μm or less.

  The printed layer 21 may include a biomass-derived component. For example, when the printed layer 21 contains a cured product of a polyol and an isocyanate compound, at least one of the polyol and the isocyanate compound may contain a biomass-derived component.

In the present embodiment, the packaging material 10 is provided with the recycled film containing recycled PET in a ratio of, for example, 50% by weight or more and 95% by weight or less, as described above. Therefore, it is possible to provide the packaging material 10 that is more excellent in the CO ₂ reduction effect than the packaging material that does not contain recycled PET. Moreover, since the packaging material 10 is provided with a rigid film such as a polyamide film, a PBT film, or a high stiffness film, it is possible to impart strength such as puncture resistance to the packaging material 10. Further, the packaging material 10 includes the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a provided on the first stretched plastic film 11, the second stretched plastic film 12, or the third stretched plastic film 13, so that the packaging bag has a gas barrier property. Can be increased. Further, when the metal vapor deposition layer 22 is provided, the packaging bag can be provided with metallic luster, so that the designability can be improved.

<Method of manufacturing packaging material>
Next, an example of a method of manufacturing the packaging material 10 will be described.

  First, the above-mentioned first stretched plastic film 11 and second stretched plastic film 12 are prepared. The printed layer 21 may be provided in advance on the first stretched plastic film 11. Further, the first stretched plastic film 11 or the second stretched plastic film 12 may be provided with a metal vapor deposition layer 22 or a transparent vapor deposition layer 23a in advance. A gas barrier coating film 23b may be provided on the surface of the transparent vapor deposition layer 23a.

  Subsequently, the first stretched plastic film 11 and the second stretched plastic film 12 are laminated via the first adhesive layer 16 by the dry laminating method. Then, the laminated body including the first stretched plastic film 11 and the second stretched plastic film 12 and the third stretched plastic film 13 are laminated via the second adhesive layer 17 by a dry laminating method. When the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a is not provided on the first stretched plastic film 11 and the second stretched plastic film 12, the metal vapor deposition layer 22 or the transparent vapor deposition layer 23a is previously provided on the third stretched plastic film 13. It may be provided. A gas barrier coating film 23b may be provided on the surface of the transparent vapor deposition layer 23a.

  After that, the laminate including the first stretched plastic film 11, the second stretched plastic film 12, and the third stretched plastic film 13 and the sealant layer 15 are laminated via the third adhesive layer 18. Thereby, the packaging material 10 including the first stretched plastic film 11, the second stretched plastic film 12, the third stretched plastic film 13, and the sealant layer 15 can be obtained.

  The order in which the first stretched plastic film 11, the second stretched plastic film 12, the third stretched plastic film 13, and the sealant layer 15 are laminated by the dry lamination method is not limited to the above order. For example, a first laminate including the first stretched plastic film 11 and the second stretched plastic film 12 and a second laminate including the third stretched plastic film 13 and the sealant layer 15 are laminated by a dry lamination method. The packaging material 10 may be manufactured according to.

  In the dry laminating method, first, the adhesive composition is applied to one of the two laminated films. Then, the applied adhesive composition is dried to volatilize the solvent. Then, the two films are laminated via the adhesive composition after drying. Subsequently, the two laminated films are wound and aged for 24 hours or more in an environment of 20 ° C. or more, for example.

  For the purpose of imparting chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. to the packaging material 10. It is also possible to carry out secondary processing. Examples of secondary processing include embossing, painting, bonding, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.) and the like. Further, the packaging material 10 may be subjected to lamination processing (dry lamination or extrusion lamination), bag-making processing, and other post-treatment processing to produce a molded product.

<Packaging bag>
The packaging material 10 is used as a material for forming a packaging bag. For example, the packaging material 10 is folded back, or two pieces of the packaging material 10 are prepared, and the sealant layer 15 of the packaging material 10 on the front side and the sealant layer 15 of the packaging material 10 on the back side are overlapped with each other, and further the periphery thereof. For example, the end part is a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope sticking seal type, a seal sticking seal type (pillow seal type), a pleated seal type, a flat bottom seal type, a square bottom seal By heat-sealing in a heat-sealing mode such as a mold, various types of packaging bags can be manufactured. It is also possible to manufacture a gusset type packaging bag by heat-sealing with the folded packaging material 10 inserted between the front packaging material 10 and the back packaging material 10. Note that not all of the packaging materials that make up the packaging bag may be the packaging material 10 according to the present invention. That is, at least a part of the packaging material forming the packaging bag may be the packaging material 10 including the recycled film and the rigid film, and the other portion of the packaging material forming the packaging bag does not include the recycled film and the rigid film. It may be a packaging material.

  As a method of heat sealing, for example, a known method such as bar sealing, rotating roll sealing, belt sealing, impulse sealing, high frequency sealing or ultrasonic sealing can be used.

  The packaging bag formed by using the packaging material 10 is, for example, food and drink, fruit juice, juice, drinking water, liquor, cooked food, seafood paste, frozen food, meat product, stewed food, rice cake, pot soup, etc. Can be suitably used for packaging various food and drink products such as liquid soaps and seasonings, cosmetics such as liquid detergents, shampoos, rinses and conditioners, hygiene products, daily necessities and chemical products.

  FIG. 11 is a diagram showing an example of a packaging bag 70 including the packaging material 10. The packaging bag 70 includes a front surface film 74 forming a front surface, a back surface film 75 forming a back surface, and a lower film 76 forming a lower portion 72. The lower film 76 is arranged between the front surface film 74 and the back surface film 75 in a state of being folded back at the folding back portion 76f. As described above, the packaging bag 70 shown in FIG. 11 is a self-standing standing pouch whose lower portion is configured as a gusset portion.

  Inner surfaces of the front surface film 74, the rear surface film 75, and the lower film 76 are joined by a seal portion. In the front view of the packaging bag 70 shown in FIG. 11 and the like, the seal portion is hatched. As shown in FIG. 11, the seal portion has an outer edge seal portion extending along the outer edge of the packaging bag 70. The outer edge seal portion includes a lower seal portion 72a extending to the lower portion 72 and a pair of side seal portions 73a extending along the pair of side portions 73. In addition, in the packaging bag 70 in the state before being filled with the contents (the state in which the contents are not filled), the upper portion 71 of the packaging bag 70 is an opening 71b as shown in FIG. After the contents are accommodated in the packaging bag 70, the inner surface of the front surface film 74 and the inner surface of the back surface film 75 are joined at the upper portion 71 to form an upper seal portion and seal the packaging bag 70.

  The terms “front surface film”, “back surface film”, and “lower film” described above are merely partitions of each film according to the positional relationship, and provide the packaging material 10 when manufacturing the packaging bag 70. The method is not limited by the above terms. For example, the packaging bag 70 may be manufactured by using one piece of the packaging material 10 in which the front surface film 74, the back surface film 75, and the lower film 76 are continuously arranged, and the front surface film 74 and the lower film 76 are continuously arranged. It may be manufactured using a total of two packaging materials 10 of one packaging material 10 and one back film 75, one front film 74, one back film 75 and one lower film 76. It may be manufactured using a total of three packaging materials 10.

  As shown in FIG. 11, the packaging bag 70 may include a spout 85. The spout 85 is a part through which the contents are stored when the contents stored in the storage 79 are taken out. In this case, the content is a fluid liquid or the like. The width of the spout portion 85 is narrower than the width of the accommodation portion 79. Therefore, the user can accurately determine the pouring direction of the content pouring out from the packaging bag 70 through the pouring portion 85.

  In the example shown in FIG. 11, the spout 85 is composed of the front film 74 and a part of the back film 75. For example, the spout portion 85 includes a spout sealing portion 86 that joins the front surface film 74 and the back surface film 75 to define the spout portion 85 having a width narrower than that of the storage portion 79. The packaging bag 70 provided with such a spout 85 is suitably used as a refillable pouch that stores contents such as detergent, shampoo, and rinse that can be refilled in a bottle.

  At least one of the front surface film 74, the back surface film 75, and the lower film 76 is constituted by the above-mentioned packaging material 10 including three stretched plastic films including a recycled film and a rigid film. For example, the front surface film 74 and the back surface film 75 can be made of the packaging material 10 described above. By using the packaging material 10 including the recycled film and the rigid film, it is possible to reduce the amount of fossil fuel used and to reduce the environmental load as compared with the conventional case. Further, even when a sharp member having a sharp tip contacts the packaging bag 70, the packaging bag 70 can be prevented from being broken.

  Note that the structure of the spout 85 is not limited to the structure shown in FIG. 11 as long as the contents can be appropriately discharged. For example, the spout 85 may be a member such as a spout other than the front film 74 and the back film 75.

  The lower film 76 may be made of the packaging material 10 described above that includes three stretched plastic films including a recycled film and a rigid film, or may be made of the packaging material 40 shown in FIG. Hereinafter, the packaging material 40 will be described with reference to FIG. Note that, in the packaging material 40 shown in FIG. 12, the same reference numerals as those used for the packaging material 10 are used for the parts that can be configured in the same manner as the packaging material 10, and redundant description will be omitted.

  The packaging material 40 shown in FIG. 12 includes a first stretched plastic film 41, a printed layer 21, a first adhesive layer 46, a second stretched plastic film 42, a second adhesive layer 47, and a sealant layer 15. And in this order. In the packaging bag including the packaging material 10 shown in FIG. 12, the sealant layer 15 constitutes the inner surface of the packaging bag.

  Both the first stretched plastic film 41 and the second stretched plastic film 42 are stretched in a predetermined direction, like the above-mentioned first stretched plastic film 11, second stretched plastic film 12, and third stretched plastic film 13. It is a plastic film.

  One of the first stretched plastic film 41 and the second stretched plastic film 42 is a recycled film containing recycled PET, and the other is a rigid film having rigidity. For example, the first stretched plastic film 41 may be a rigid film and the second stretched plastic film 42 may be a recycled film. Further, the first stretched plastic film 41 may be a recycled film and the second stretched plastic film 42 may be a rigid film.

  FIG. 13 is a diagram showing another example of the packaging bag 70 including the packaging material 10. The packaging bag 70 shown in FIG. 13 is a pillow pouch formed by joining the inner surfaces of a film 77 folded back in a tubular shape at an upper portion 71, a lower portion 72, and a palm portion 78. The upper part 71 and the lower part 72 include an upper seal part 71a and a lower seal part 72a. Further, the palm-sealing portion 78 includes a palm-sealing seal portion 78a extending from the upper seal portion 71a to the lower seal portion 72a.

  Also in the packaging bag 70 shown in FIG. 13, the film 77 is made of the packaging material 10 including a recycled film and a rigid film. As a result, the amount of fossil fuel used can be reduced and the environmental load can be reduced as compared with the conventional case. Further, even when a sharp member having a sharp tip contacts the packaging bag 70, the packaging bag 70 can be prevented from being broken.

  Although not shown, the packaging bag 70 may be a three-way seal pouch or a four-way seal pouch formed by joining the front surface film 74 and the back surface film 75 along the outer edge at three sides or four sides. .

  Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the description of the following examples unless it exceeds the gist.

[Example 1]
The packaging material 10 (hereinafter, also referred to as a packaging material for the body portion) that configures the front surface film 74 and the back surface film 75, and the packaging material 40 (hereinafter, also referred to as a lower packaging material) that configures the lower film 76 described above. ) And prepared. Subsequently, the body packaging material 10 and the lower packaging material 40 were heat-sealed to produce a packaging bag 70 shown in FIG. 11.

  First, the packaging material 10 for the body will be described.

  As the first stretched plastic film 11, a biaxially stretched recycled PET film containing PET recycled by mechanical recycling was prepared. The recycled PET film contains 90% by mass or more of PET. The thickness of the recycled PET film was 12 μm. Further, the printing layer 21 was formed on the recycled PET film.

  As the second stretched plastic film 12, a biaxially stretched nylon film derived from fossil fuel was prepared. The nylon film contains 90% by mass or more of polyamide. The thickness of the nylon film can be selected within the range of 15 μm or more and 25 μm or less, but here it is set to 15 μm.

  As the third stretched plastic film 13, a biaxially stretched recycled PET film containing PET recycled by mechanical recycling was prepared. The recycled PET film contains 90% by mass or more of PET. The thickness of the recycled PET film was 12 μm. Further, a metal vapor deposition layer 22 made of aluminum and having a thickness of 450 Å was formed on the recycled PET film.

  Subsequently, the adhesive was applied onto the printed layer 21 provided on the recycled PET film of the first stretched plastic film 11, and dried to obtain the first adhesive layer 16. Subsequently, the recycled PET film of the first stretched plastic film 11 and the nylon film of the second stretched plastic film 12 were bonded together via the first adhesive layer 16.

  Then, a laminated body including the recycled PET film of the first stretched plastic film 11 and the nylon film of the second stretched plastic film 12 and the recycled PET film of the third stretched plastic film 13 are placed via the second adhesive layer 17. And laminated by the dry lamination method. At this time, the third stretched plastic film 13 was laminated so that the metal vapor deposition layer 22 provided on the recycled PET film faced the nylon film side.

As the sealant layer 15, a polyethylene film produced as described below was used. First, fossil fuel-derived linear low-density polyethylene (density: 0.918 g / cm ³ , MFR: 3.8 g / 10 min) and fossil fuel-derived low-density polyethylene (density: 0.924 g / cm ³ , MFR: 2.0 g / 10 minutes) was melt-kneaded to obtain a resin composition. The ratio of the linear low-density polyethylene derived from fossil fuel and the low-density polyethylene derived from fossil fuel can be selected within the ranges of 70 to 90 parts by mass and 10 to 30 parts by mass, for example, 90 parts by mass and 10 parts by mass. It is a department. Next, the obtained resin composition was formed into a film by a top-blown air-cooled inflation coextrusion film forming machine to obtain a single-layer polyethylene film for a sealant layer. The thickness of the polyethylene film can be selected within the range of 50 μm or more and 150 μm or less, but here it is set to 80 μm.

  Subsequently, the laminated body including the recycled PET film, the nylon film, and the recycled PET film was bonded to the polyethylene film via the third adhesive layer 18 by a dry lamination method. In this way, the packaging material 10 for the body was manufactured.

The layer structure of the packaging material 10 for the body of this example is expressed as follows.
Recycled PET12 / mark / contact / nylon 15 / contact / vapor deposition / recycled PET12 / contact / PE80
"Recycled PET" refers to recycled PET film. The “mark” represents the print layer. "Contact" represents an adhesive layer. “Nylon” refers to a nylon film. "Deposition" refers to a metal deposition layer. "PE" means the polyethylene film described above. The numbers mean the thickness of the layer (unit is μm).
As described in the above embodiment, the rigid film of the second stretched plastic film 12 may be a biaxially stretched PBT film or a biaxially stretched high stiffness film instead of the nylon film. Good. As the biaxially stretched high stiffness film, a high stiffness PET film containing 90% by mass or more of PET can be preferably used. The thickness of the high stiffness PET film is 14 μm or more, for example, 16 μm. The same applies to Examples 2 to 8 described later.

  Next, the packaging material 40 for the lower portion will be described.

  As the first stretched plastic film 41, a biaxially stretched nylon film derived from fossil fuel was prepared. The nylon film contains 90% by mass or more of polyamide. The thickness of the nylon film can be selected within the range of 15 μm or more and 25 μm or less, but here it is set to 15 μm. Further, the printing layer 21 was formed on the nylon film.

  As the second stretched plastic film 42, a biaxially stretched recycled PET film containing PET recycled by mechanical recycling was prepared. The recycled PET film contains 90% by mass or more of PET. The thickness of the recycled PET film was 12 μm.

  Subsequently, the adhesive was applied onto the printing layer 21 provided on the nylon film and dried to obtain the first adhesive layer 46. Then, the nylon film and the recycled PET film were bonded together via the first adhesive layer 46.

  As the sealant layer 15, the same polyethylene film as the case of the sealant layer 15 of the packaging material for the body was prepared. The thickness of the polyethylene film can be selected within the range of 50 μm or more and 150 μm or less, but here it is set to 80 μm.

  Subsequently, the laminated body including the nylon film and the recycled PET film and the polyethylene film were attached to each other via the second adhesive layer 47 by a dry laminating method. In this way, the lower packaging material 40 was produced.

The layer structure of the packaging material 40 for the lower part of the present embodiment is expressed as follows.
Nylon 15 / mark / contact / recycled PET12 / contact / PE80
As described in the above embodiment, as the rigid film of the first stretched plastic film 41, a PBT film or a high stiffness film may be used instead of the nylon film.

[Example 2]
In the same manner as in Example 1, the body packaging material 10 and the lower packaging material 40 were heat-sealed to produce the packaging bag 70 shown in FIG. 11. The body packaging material 10 was biaxially stretched, containing PET derived from fossil fuel instead of the recycled PET film as the first stretched plastic film 11 in the body packaging material 10 of Example 1. The thing which adopted the PET film was used. The fossil fuel-derived PET film contains 90% by mass or more of PET. The thickness of the PET film derived from fossil fuel was 12 μm. As the packaging material 40 for the lower part, the same one as in the case of Example 1 was used.

The layer structure of the packaging material 10 for the body of this example is expressed as follows.
Fossil PET12 / mark / contact / nylon 15 / contact / vapor deposition / recycled PET12 / contact / PE80
“Fossil PET” refers to a PET film containing PET derived from fossil fuels.
As described in the above embodiment, the rigid film of the second stretched plastic film 12 may be a biaxially stretched PBT film or a biaxially stretched high stiffness film instead of the nylon film. Good.

[Example 3]
In the same manner as in Example 1, the body packaging material 10 and the lower packaging material 40 were heat-sealed to produce the packaging bag 70 shown in FIG. 11. As the body packaging material 10, a biaxially stretched nylon film was used instead of the recycled PET film as the first stretched plastic film 11 in the body packaging material 10 of Example 1. I was there. The nylon film contains 90% by mass or more of polyamide. The thickness of the nylon film was 15 μm. As the packaging material 40 for the lower part, the same one as in the case of Example 1 was used.

The layer structure of the packaging material 10 for the body of this example is expressed as follows.
Nylon 15 / mark / contact / nylon 15 / contact / vapor deposition / recycled PET12 / contact / PE80
As described in the above embodiment, the rigid films of the first stretched plastic film 11 and the second stretched plastic film 12 were biaxially stretched PBT film or biaxially stretched instead of the nylon film. High stiffness films may be used.

[Example 4]
In the same manner as in Example 1, the body packaging material 10 and the lower packaging material 40 were heat-sealed to produce the packaging bag 70 shown in FIG. 11. The packaging material 10 for the body was biaxially stretched, containing PET derived from fossil fuel instead of the recycled PET film as the third stretched plastic film 13 in the packaging material 10 for the body of Example 1. The thing which adopted the PET film was used. The fossil fuel-derived PET film contains 90% by mass or more of PET. The thickness of the PET film derived from fossil fuel was 12 μm. As the packaging material 40 for the lower part, the same one as in the case of Example 1 was used.

The layer structure of the packaging material 10 for the body of this example is expressed as follows.
Recycled PET12 / mark / contact / nylon 15 / contact / vapor deposition / fossil PET12 / contact / PE80
As described in the above embodiment, the rigid film of the second stretched plastic film 12 may be a biaxially stretched PBT film or a biaxially stretched high stiffness film instead of the nylon film. Good.

[Example 5]
In the same manner as in Example 1, the body packaging material 10 and the lower packaging material 40 were heat-sealed to produce the packaging bag 70 shown in FIG. 11. As the packaging material 10 for the body part, the nylon film described in Example 1 constitutes the third stretched plastic film 13, and the recycled PET film described in Example 1 on which the metal vapor deposition layer 22 is formed is used as the second. A stretched plastic film 12 was used. As the packaging material 40 for the lower part, the same one as in the case of Example 1 was used.

The layer structure of the packaging material 10 for the body of this example is expressed as follows.
Recycled PET12 / mark / contact / vapor deposition / recycled PET12 / contact / nylon 15 / contact / PE80
As described in the above embodiment, as the rigid film of the third stretched plastic film 13, a biaxially stretched PBT film or a biaxially stretched high stiffness film may be used instead of the nylon film. Good.

[Example 6]
In the same manner as in Example 5, the body packaging material 10 and the lower packaging material 40 were heat-sealed to produce the packaging bag 70 shown in FIG. 11. The body packaging material 10 was biaxially stretched, containing PET derived from fossil fuel instead of the recycled PET film as the first stretched plastic film 11 in the body packaging material 10 of Example 5. The thing which adopted the PET film was used. The fossil fuel-derived PET film contains 90% by mass or more of PET. The thickness of the PET film derived from fossil fuel was 12 μm. As the packaging material 40 for the lower part, the same one as in the case of Example 5 was used.

The layer structure of the packaging material 10 for the body of this example is expressed as follows.
Fossil PET12 / mark / contact / vapor deposition / recycled PET12 / contact / nylon 15 / contact / PE80
As described in the above embodiment, as the rigid film of the third stretched plastic film 13, a biaxially stretched PBT film or a biaxially stretched high stiffness film may be used instead of the nylon film. Good.

[Example 7]
In the same manner as in Example 5, the body packaging material 10 and the lower packaging material 40 were heat-sealed to produce the packaging bag 70 shown in FIG. 11. As the body packaging material 10, a biaxially stretched nylon film was used instead of the recycled PET film as the first stretched plastic film 11 in the body packaging material 10 of Example 5. I was there. The nylon film contains 90% by mass or more of polyamide. The thickness of the nylon film was 15 μm. As the packaging material 40 for the lower part, the same one as in the case of Example 5 was used.

The layer structure of the packaging material 10 for the body of this example is expressed as follows.
Nylon 15 / mark / contact / vapor deposition / recycled PET12 / contact / nylon 15 / contact / PE80
As described in the above embodiment, as the rigid film of the first stretched plastic film 11 and the third stretched plastic film 13, a biaxially stretched PBT film or a biaxially stretched film was used instead of the nylon film. High stiffness films may be used.

[Example 8]
In the same manner as in Example 5, the body packaging material 10 and the lower packaging material 40 were heat-sealed to produce the packaging bag 70 shown in FIG. 11. The body packaging material 10 was biaxially stretched, containing fossil fuel-derived PET instead of the recycled PET film as the second stretched plastic film 12 in the body packaging material 10 of Example 5. The thing which adopted the PET film was used. The fossil fuel-derived PET film contains 90% by mass or more of PET. The thickness of the PET film derived from fossil fuel was 12 μm. As the packaging material 40 for the lower part, the same one as in the case of Example 5 was used.

The layer structure of the packaging material 10 for the body of this example is expressed as follows.
Recycled PET12 / mark / contact / vapor deposition / fossil PET12 / contact / nylon 15 / contact / PE80
As described in the above embodiment, as the rigid film of the third stretched plastic film 13, a biaxially stretched PBT film or a biaxially stretched high stiffness film may be used instead of the nylon film. Good.

The layer structure of the packaging material 10 for the body in Examples 1 to 8 is summarized in Table 2 below. The fossil PET of Examples 2, 4, 6 and 8 can be replaced with biaxially stretched biomass PET.

10 Packaging Material 11 First Stretched Plastic Film 12 Second Stretched Plastic Film 13 Third Stretched Plastic Film 15 Sealant Layer 16 First Adhesive Layer 17 Second Adhesive Layer 18 Third Adhesive Layer 21 Printing Layer 22 Metallized Layer 23a Transparent vapor deposition layer 23b Gas barrier coating film 30 Recycled film 31 First layer 32 Second layer 33 Third layer 40 Packaging material

Claims (10)

A packaging material comprising at least a first stretched plastic film, a second stretched plastic film, a third stretched plastic film, and a sealant layer in this order,
The packaging material further comprises a metal vapor deposition layer provided on the second stretched plastic film or the third stretched plastic film,
At least one of the first stretched plastic film, the second stretched plastic film, or the third stretched plastic film contains polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as a dicarboxylic acid unit,
The other one of the first stretched plastic film, the second stretched plastic film or the third stretched plastic film comprises a rigid film,
A packaging material, wherein the rigid film comprises a polyamide, or a polybutylene terephthalate, or has a loop stiffness of 0.0017 N or more in one direction and a polyester.   The packaging material according to claim 1, wherein the sealant layer includes linear low-density polyethylene.   The packaging material according to claim 1, wherein the sealant layer has a thickness of 50 μm or more.   One of the first stretched plastic film, the second stretched plastic film, or the third stretched plastic film that is not provided with the metal vapor-deposited layer has ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as a dicarboxylic acid unit. The packaging material according to any one of claims 1 to 3, further comprising polyethylene terephthalate, wherein the other comprises the rigid film. The first stretched plastic film contains polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as a dicarboxylic acid unit,
The packaging material according to claim 4, wherein one of the second stretched plastic film and the third stretched plastic film is provided with the metal vapor deposition layer, and the other includes the rigid film.   The packaging material according to any one of claims 1 to 5, wherein the rigid film contains polyamide.   The packaging material according to claim 1, wherein the rigid film contains polybutylene terephthalate.   The packaging material according to any one of claims 1 to 5, wherein the rigid film has a loop stiffness of 0.0017 N or more in one direction and contains polyester.   The packaging material according to any one of claims 1 to 8, wherein the polyethylene terephthalate has an intrinsic viscosity of 0.58 dl / g or more and 0.80 dl / g or less. A packaging material comprising at least a first stretched plastic film, a second stretched plastic film, a third stretched plastic film, and a sealant layer in this order,
The packaging material further comprises a transparent vapor deposition layer provided on the first stretched plastic film, the second stretched plastic film or the third stretched plastic film,
At least one of the first stretched plastic film, the second stretched plastic film, or the third stretched plastic film contains polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as a dicarboxylic acid unit,
The other one of the first stretched plastic film, the second stretched plastic film or the third stretched plastic film comprises a rigid film,
A packaging material, wherein the rigid film comprises a polyamide, or a polybutylene terephthalate, or has a loop stiffness of 0.0017 N or more in one direction and a polyester.