JP2018167573A - Laminate and bag composed of laminate - Google Patents

Abstract

To provide a laminate having strength and improved coloring resistance.SOLUTION: A laminate 30 at least has a first base material 41, a second base material 51 and a sealant layer 61 in the stated order. The second base material 51 contains 51 mass% or more of polyethylene terephthalate or 51 mass% or more of polybutylene terephthalate. If the second base material 51 contains 51 mass% or more of polyethylene terephthalate, the first base material 41 contains 51 mass% or more of polybutylene terephthalate. Preferably, the laminate 30 has a piercing strength of 13N or more. Preferably, the base material containing 51 mass% or more of polybutylene phthalate, out of the first base material 41 or second base material 51, has a multilayered structure made up of 10 or more layers, or has a single layered structure with an IV value of 1.10-1.35dl/g.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a laminate and a bag composed of the laminate.

  Conventionally, many cooked or semi-cooked liquids, viscous bodies, or contents in which liquid and solid are mixed are filled and sealed in bags made of plastic laminates. In the bag, the non-seal part to which the laminated bodies are not joined constitutes an accommodation part in which the contents are accommodated. Moreover, the sealing part to which the laminated bodies are joined has sealed the accommodating part. The contents are, for example, cooked foods such as curry, stew, and soup. The contents are heated by a hot water bath or the like while being contained in a bag.

  The laminated body which comprises a bag contains a plastic film as a base material. For example, Patent Document 1 proposes to use polyethylene terephthalate, polypropylene, nylon, or the like as a base material of a laminate. A base material contributes to the improvement of the intensity | strength of a laminated body.

JP 2014-94767 A

  Nylon is known as a material having high strength. However, when nylon is used for the base material, it is considered that the appearance of the bag is impaired because nylon is easily colored by the contents.

  An object of this invention is to provide the laminated body which can solve such a subject effectively.

  The present invention is a laminate, and includes at least a first base material, a second base material, and a sealant layer in this order, and the second base material includes 51% by mass or more of polyethylene terephthalate or 51% by mass or more of poly When it contains butylene terephthalate and the second substrate contains 51% by mass or more of polyethylene terephthalate, the first substrate is a laminate containing 51% by mass or more of polybutylene terephthalate.

  In the laminate according to the present invention, the piercing strength of the laminate may be 13 N or more.

  The laminated body by this invention WHEREIN: The base material containing 51 mass% or more of polybutylene terephthalates among the 1st base material and the said 2nd base material may have a multilayered structure part containing 10 layers or more.

  In the laminate according to the present invention, the base material containing 51% by mass or more of the first base material and the second base material has an IV value of 1.10 dl / g or more and 1.35 dl / g or less. It may consist of a single layer structure having

  In the laminate according to the present invention, the first base material may contain 51% by mass or more of polybutylene terephthalate, and the second base material may contain 51% by mass or more of polyethylene terephthalate.

  In the laminate according to the present invention, the first base material may include 51% by mass or more of polyethylene terephthalate, and the second base material may include 51% by mass or more of polybutylene terephthalate.

  In the laminate according to the present invention, the sealant layer may contain polypropylene.

  In the laminate according to the present invention, the content of propylene in the sealant layer may be 90% by mass or more.

  In the laminate according to the present invention, the sealant layer may include polyethylene having a melting point of 100 ° C. or higher.

  The laminate according to the present invention may further include a light-shielding print layer positioned between the first base material and the second base material.

  In the laminate according to the present invention, the thickness of the light-shielding print layer may be 2 μm or more.

  In the laminate according to the present invention, the light-shielding printing layer may contain chromatic ink.

  In the laminate according to the present invention, the light-shielding print layer may contain an achromatic ink.

  The laminate according to the present invention may further include a picture print layer positioned on the outer surface side of the laminate from the light-shielding print layer.

  In the laminate according to the present invention, the total light transmittance of the laminate may be 20% or less.

  In the laminate according to the present invention, at least a transparent vapor deposition layer provided between at least one of the first base material and the second base material between the first base material and the second base material. A barrier layer may be further included.

  In the laminate according to the present invention, the transparent vapor deposition layer contains aluminum oxide, and the transparent vapor deposition layer is provided with at least one of the first base material and the second base material provided with the transparent vapor deposition layer. A covalent bond between an aluminum atom and a carbon atom may be formed at the interface with the.

  In the laminate according to the present invention, the barrier layer may further include a gas barrier coating film provided on the surface of the transparent vapor deposition layer.

  The present invention is a bag, comprising a laminate including an outer surface and an inner surface, and a seal portion that joins the inner surfaces of the laminate, and the laminate is first in order from the outer surface side to the inner surface side. A base material, a second base material, and a sealant layer are provided at least in this order. The second base material contains 51% by mass or more of polyethylene terephthalate or 51% by mass or more of polybutylene terephthalate, and the second base material is 51 When the polyethylene terephthalate is contained in an amount of not less than 5% by mass, the first substrate is a bag containing 51% by mass or more of polybutylene terephthalate.

  The bag by this invention WHEREIN: The said laminated body may further be equipped with the light-shielding printing layer located between the 1st base material and the said 2nd base material.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has stab resistance and coloring resistance can be provided.

It is a front view which shows the bag in embodiment of this invention. It is sectional drawing which shows an example of the laminated constitution of the laminated body which comprises a bag. It is sectional drawing which shows the other example of the layer structure of the laminated body which comprises a bag. It is sectional drawing which shows an example of the laminated constitution of the 1st film of a laminated body. It is a figure which shows an example of the measuring method of piercing strength. It is a figure which shows the layer structure and evaluation result of Examples 1-4 and Comparative Examples 1 and 2. FIG. It is sectional drawing which shows the other example of the layer structure of the laminated body which comprises a bag. It is sectional drawing which shows the other example of the layer structure of the laminated body which comprises a bag. It is sectional drawing which shows the other example of the layer structure of the laminated body which comprises a bag. It is sectional drawing which shows the other example of the layer structure of the laminated body which comprises a bag. It is a figure which shows the layer structure and evaluation result of Examples 5-8 and Comparative Examples 3 and 4. FIG.

(First embodiment)
An embodiment of the present invention will be described with reference to FIGS. Note that, in the drawings attached to the present specification, for convenience of illustration and understanding, the scale and vertical / horizontal dimension ratios are appropriately changed and exaggerated from those of the actual ones.

  In addition, as used in this specification, the shape and geometric conditions and the degree thereof are specified, for example, terms such as “parallel”, “orthogonal”, “identical”, length and angle values, etc. are strictly Without being bound by meaning, it should be interpreted including the extent to which similar functions can be expected.

  First, a problem to be solved by this embodiment will be described. The laminated body constituting the bag may be required to have a high light shielding property in order to preserve the contents while preventing the contents from being altered. In order to solve these problems, for example, the above-mentioned Patent Document 1 proposes to provide a light-shielding print layer having a light-shielding property on a substrate containing a resin such as polyethylene terephthalate.

  In Patent Document 1, the light-shielding print layer is obtained by printing an ink containing a pigment and a binder on a substrate with a sufficient thickness. On the other hand, an ink component such as a pigment, a binder, and a residual solvent generates an unpleasant odor (hereinafter also referred to as a strange odor), and the strange odor may permeate the sealant layer and adhere to the contents. . Such off-flavors are particularly problematic when the contents are food.

  The purpose of this embodiment is to provide a laminate that can effectively solve such problems.

  Next, the bag 10 according to the present embodiment will be described. FIG. 1 is a front view showing a bag 10 according to the present embodiment. The bag 10 includes a storage portion 17 that stores the contents. In addition, in FIG. 1, the bag 10 of the state (state which is not filled with the content) before being filled with the content is shown. Bag 10 by this embodiment is constituted so that retort processing can be performed. Hereinafter, the configuration of the bag 10 will be described.

In the present embodiment, the bag 10 is a gusseted bag configured to be able to stand on its own. The bag 10 includes an upper portion 11, a lower portion 12, and a side portion 13, and has a substantially rectangular outline in a front view. It should be noted that names such as “upper”, “lower” and “side”, and terms such as “upper” and “lower” refer to a bag based on the state in which the bag 10 is self-supporting with the gusset portion down. It is only a relative representation of the position and direction of 10 and its components. The attitude | position at the time of transport of the bag 10 or use is not limited by the name and terminology in this specification.

  As shown in FIG. 1, the bag 10 includes a surface film 14 that constitutes the front surface, a back film 15 that constitutes the back surface, and a lower film 16 that constitutes the lower portion 12. The lower film 16 is disposed between the front film 14 and the back film 15 in a state where the lower film 16 is folded at the folded portion 16f.

  In addition, the term “surface film”, “back film” and “lower film” described above is merely a partition of each film according to the positional relationship, and the method of providing a film when manufacturing the bag 10 It is not limited by the above terms. For example, the bag 10 may be manufactured using one film in which the front film 14, the back film 15, and the lower film 16 are continuously provided, or one sheet in which the front film 14 and the lower film 16 are continuously provided. It may be manufactured using a total of two films, a film and one back film 15, and a total of three films, one surface film 14, one back film 15, and one lower film 16. May be used.

  As for the surface film 14, the back film 15, and the lower film 16, inner surfaces are joined by the seal part. In the plan view of the bag 10 shown in FIG. 1 and the like, the seal portion is hatched.

  As shown in FIG. 1, the seal portion has an outer edge seal portion that extends along the outer edge of the bag 10. The outer edge seal portion includes a lower seal portion 12 a extending in the lower portion 12 and a pair of side seal portions 13 a extending along the pair of side portions 13. In addition, in the bag 10 in a state before being filled with the contents, as shown in FIG. 1, the upper portion 11 of the bag 10 is an opening 11b. After the contents are stored in the bag 10, the inner surface of the front film 14 and the inner surface of the back film 15 are joined at the upper portion 11, whereby an upper seal portion is formed and the bag 10 is sealed.

  The side seal portion 13a and the upper seal portion described later are seal portions configured by joining the inner surface of the front film 14 and the inner surface of the back film 15. On the other hand, the lower seal portion 12a is formed by bonding the inner surface of the surface film 14 and the inner surface of the lower film 16, and by bonding the inner surface of the back film 15 and the inner surface of the lower film 16. Including a configured seal.

  As long as the opposing films can be bonded to each other and the bag 10 can be sealed, the method for forming the seal portion is not particularly limited. For example, the sealing portion may be formed by melting the inner surfaces of the film by heating or the like and welding the inner surfaces, that is, by heat sealing. Or you may form a seal | sticker part by adhere | attaching the inner surfaces of the opposing film using an adhesive agent etc.

Easy opening means The front film 14 and the back film 15 may be provided with easy opening means 25 for tearing the front film 14 and the back film 15 to open the bag 10. For example, as shown in FIG. 1, the easy-opening means 25 may include a notch 26 that is formed in the side seal portion 13 a of the bag 10 and serves as a starting point of tearing. Further, a half-cut line formed by laser processing, a cutter, or the like may be provided as the easy-opening means 25 in a portion that becomes a path when the bag 10 is torn.

  Moreover, although not shown, the easy-opening means 25 may include notches and scars formed in the area where the seal portion is formed in the front film 14 and the back film 15. The scar group may include, for example, a plurality of through holes formed so as to penetrate the front film 14 and / or the back film 15. Alternatively, the scar group may include a plurality of holes formed on the outer surface of the front film 14 and / or the back film 15 so as not to penetrate the front film 14 and / or the back film 15.

Next, the layer structure of the front film 14 and the back film 15 will be described. FIG. 2 is a cross-sectional view showing an example of a laminated body 30 constituting the front film 14 and the back film 15. FIG. 3 is a cross-sectional view showing another example of the laminate 30 that constitutes the front film 14 and the back film 15.

  As shown in FIG. 2, the laminate 30 includes at least a first film 40, a second film 50, and a third film 60 in this order. The first film 40 is located on the outer surface 30y side, and the third film 60 is located on the inner surface 30x side opposite to the outer surface 30y. The inner surface 30x is a surface located on the accommodating portion 17 side.

As shown in FIG. 2, the first film 40 includes at least a first base material 41 and a light-shielding print layer 42 provided on the surface of the first base material 41 on the second film 50 side. Moreover, the 1st film 40 may further contain the pattern printing layer 43 located between the 1st base material 41 and the light shielding printing layer 42, as shown in FIG. The second film 50 includes at least a second base material 51. The third film 60 includes at least a sealant layer 61. The first film 40 and the second film 50 are joined by a first adhesive layer 45, and the second film 50 and the third film 60 are joined by a second adhesive layer 55. Therefore, the laminate 30 according to the present embodiment has a first base material / light-shielding print layer / first adhesive layer / second base material / second adhesive layer / sealant layer in order from the outer surface side to the inner surface side.
Or
It can be said that the first substrate / the pattern printing layer / the light-shielding printing layer / the first adhesive layer / the second substrate / the second adhesive layer / the sealant layer. Note that “/” represents a boundary between layers.

  Hereinafter, the first film 40, the first adhesive layer 45, the second film 50, the second adhesive layer 55, and the third film 60 will be described in detail.

(First film)
In the example shown in FIG. 3, the first film 40 includes a first base material 41 constituting the outer surface 30 y of the laminate 30, a pattern printing layer 43 provided on the inner surface 30 x side of the first substrate 41, and pattern printing. A light-shielding print layer 42 provided on the inner surface 30x side of the layer 43. First, the light shielding printing layer 42 and the pattern printing layer 43 will be described.

[Shading printing layer]
The light shielding print layer 42 is a layer configured so that the stacked body 30 has a light shielding property. The light-shielding print layer 42 has an ink containing a pigment and a binder. Moreover, the thickness of the light-shielding printing layer 42 is 2 micrometers or more, for example, Preferably it is 3 micrometers or more, More preferably, it is 4 micrometers or more. Further, the thickness of the light-shielding print layer 42 is preferably 10 μm or less, more preferably 6 μm or less. The total light transmittance of the laminate 30 including the light-shielding print layer 42 is at least 20% or less, preferably 15% or less, and more preferably 10% or less. When the total light transmittance is 20% or less, visible light and ultraviolet rays made of external light having a wavelength range of 300 nm to 800 nm incident on the bag 10 under normal use conditions can be effectively blocked. It can suppress effectively that the content accommodated in 10 deteriorates with external light.

  The total light transmittance refers to the ratio of the total transmitted light amount that has passed through the laminate 30 to the total incident light amount of light incident on the test piece made of the laminate 30 including the light-shielding print layer 42. Since the test piece usually has light diffusibility, the total light transmittance is the sum of the parallel light transmittance and the diffuse transmittance. The total light transmittance is measured according to an optical property test method JIS-K7361-1 using an integrating sphere defined by JIS.

  The light-shielding print layer 42 has an achromatic layer including, for example, an achromatic color ink. An achromatic color is a color described only by lightness among the three-dimensional colors of hue, lightness, and saturation. Examples of achromatic colors include white, gray, and black. The thickness of the achromatic layer is, for example, 1 μm or more and 3 μm or less. The achromatic layer is preferably a single color layer extending over the entire surface of the first base material 41 in the same plane. In the following description, a printed layer having a region where the dot area ratio is 100% is also referred to as a solid layer. For example, a printed layer having a region in which the area ratio of white halftone dots is 100% is referred to as a white solid layer. Similarly, a printed layer having a region where the area ratio of black halftone dots is 100% is referred to as a black solid layer. The white solid layer is formed by solid printing white ink containing a white pigment on the first substrate 41. The black solid layer is formed by solid printing black ink containing a black pigment on the first base material 41. The light-shielding print layer 42 may include a plurality of achromatic layers stacked. Hereinafter, a specific layer configuration of the light-shielding print layer 42 will be described.

  The light-shielding print layer 42 may be composed of, for example, a black solid layer. In addition, when the pattern printing layer 43 is laminated | stacked on the outer surface 30y side of the light shielding printing layer 42, when the bag 10 is visually recognized from the outer surface 30y side of a laminated body, the light shielding printing layer 42 is observed as a background of the pattern printing layer 43. . For this reason, when the shading print layer 42 consists only of a black solid layer, it becomes difficult to visually recognize the pattern print layer 43. Therefore, when the laminate 30 includes the pattern print layer 43, the light-shielding print layer 42 is not black except the black solid layer, which is positioned on the outer surface 30 y side of the black solid layer as described below. It is preferable to further include a coloring layer.

The light-shielding print layer 42 may include a white solid layer and an achromatic layer that are sequentially stacked from the first base material 41 side to the inner surface 30x side. The achromatic layer may be a white solid layer or a black solid layer. The achromatic layer may be an ash solid layer formed by solid-printing gray ink on the first base material 41. The gray ink can be obtained, for example, by mixing a white ink containing a white pigment and a black ink containing a black pigment. The gray ink preferably has a white ink blending ratio higher than that of the black ink. By making the achromatic layer laminated on the inner surface 30x side of the white solid layer a gray solid layer, the color of the achromatic layer is a pattern compared to the case where the black solid layer is laminated on the inner surface 30x side of the white solid layer. The influence on the color of the print layer 43 can be suppressed.
Note that the number of achromatic layers is not limited to two. For example, the light-shielding print layer 42 may include three or four or more achromatic layers stacked. For example, the light-shielding print layer 42 may include a white solid layer, a white solid layer, and an ash solid layer that are sequentially stacked from the first base material 41 side to the inner surface 30x side.

  Further, the light-shielding print layer 42 may be a white solid layer. Even when the light-shielding print layer 42 does not include the above-described black solid layer or ash solid layer, the light-shielding print layer 42 can have sufficient light-shielding properties by increasing the thickness of the white solid layer.

  Further, the light-shielding print layer 42 may have a chromatic color layer containing chromatic color ink. A chromatic color means a color or color that includes all three dimensions of hue, lightness, and saturation. In other words, a chromatic color is a color other than an achromatic color. The thickness of the chromatic color layer is, for example, not less than 0.3 μm and not more than 2 μm. The chromatic color layer is preferably a single color layer extending over the entire surface of the first base material 41 in the same plane. The light-shielding print layer 42 may include a plurality of stacked chromatic color layers.

  The light shielding print layer 42 may include both an achromatic color layer and a chromatic color layer. For example, the light-shielding print layer 42 includes one or more achromatic layers and one or more chromatic layers located on the inner surface 30x side of the achromatic layer. Further, the light-shielding print layer 42 may include one or a plurality of chromatic color layers and one or a plurality of achromatic layers positioned closer to the inner surface 30x than the chromatic color layer. For example, the light-shielding print layer 42 may include a white solid layer and a chromatic color layer that are sequentially stacked from the first base material 41 side to the inner surface 30x side.

[Pattern printing layer]
The pattern printing layer 43 is a layer provided by printing in order to show product information or impart aesthetics to the bag 10. The picture print layer 43 expresses characters, numbers, symbols, figures, pictures, and the like. In the pattern print layer 43, a plurality of color layers are spread in the same plane. As a material constituting the pattern printing layer 43, gravure printing ink or flexographic printing ink can be used. As a specific example of the ink for gravure printing, FINAT manufactured by DIC Graphics Corporation can be given.

[First base material]
The first base material 41 includes polybutylene terephthalate (hereinafter also referred to as PBT) as a main component. For example, the first base material 41 includes 51% by mass or more of PBT. Hereinafter, advantages of the first base material 41 including PBT will be described.

  PBT is excellent in dimensional stability, and therefore excellent in printability. For this reason, as in the case of polyethylene terephthalate (hereinafter also referred to as PET), the light-shielding print layer 42 can be provided on the first base material 41 containing PBT.

  Moreover, PBT is excellent in heat resistance. For this reason, it is possible to prevent the first base material 41 from being deformed or the strength of the first base material 41 from being reduced when the bag 10 is subjected to a sterilization process such as a boil process or a retort process. The retort process is a process of heating the bag 10 in a pressurized state after filling the bag 10 with the contents and sealing the bag 10. The temperature of retort processing is 120 degreeC or more, for example. The boil process is a process of filling the bag 10 with the contents and sealing the bag 10 and then bathing the bag 10 under atmospheric pressure. The temperature of boil processing is 90 degreeC or more and 100 degrees C or less, for example.

  PBT has high strength. For this reason, the stab resistance can be given to the bag 10 similarly to the case where the laminated body 30 which comprises the bag 10 contains nylon.

  PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, it can suppress that the 1st base material 41 absorbs a water | moisture content and the laminate strength of the laminated body 30 falls.

  Hereinafter, the structure of the 1st base material 41 containing PBT is demonstrated in detail. In the present embodiment, as the configuration of the first base material 41 including PBT, any of the following first configuration or second configuration may be adopted.

[First Configuration of Substrate]
The content of PBT in the first base material 41 according to the first configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further 70% by mass or more, and particularly preferably 75% by mass or more. Preferably it is 80 mass% or more. By setting the content of PBT to 51% by mass or more, the first film 40 can have excellent impact strength and pinhole resistance.

  PBT used as a main constituent component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, most preferably 100 mol% or more of terephthalic acid as a dicarboxylic acid component. Mol%. 1,4-butanediol as the glycol component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and most preferably 1,4-butanediol during polymerization. It is not included except by-products generated by the ether bond of butanediol.

The first base material 41 may contain a polyester resin other than PBT. Thereby, for example, the film formability when the film-like first base material 41 is biaxially stretched and the dynamic characteristics of the first base material 41 can be adjusted.
Polyester resins other than PBT include polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polypropylene terephthalate (PPT), as well as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid. , Cyclohexanedicarboxylic acid, adipic acid, azelaic acid, PBT resin copolymerized with dicarboxylic acid such as sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, polycarbonate diol Min can be mentioned copolymerized PBT resin.

  The amount of the polyester resin other than PBT is preferably 49% by mass or less, and more preferably 40% by mass or less. If the addition amount of the polyester resin other than PBT exceeds 49% by mass, the mechanical properties as PBT may be impaired, and impact strength, pinhole resistance, and drawability may be insufficient.

  The 1st base material 41 may contain the polyester-type and polyamide-type elastomer which copolymerized at least any one of the flexible polyether component, the polycarbonate component, and the polyester component as an additive. Thereby, the pinhole resistance at the time of bending can be improved. The additive amount of the additive is, for example, 20% by mass. When the additive amount exceeds 20% by mass, the effect as the additive may be saturated, or the transparency of the first base material 41 may be reduced.

  An example of a method for producing the film-like first base material 41 according to the first configuration will be described. Here, a method for producing the film-like first base material 41 by a casting method will be described. More specifically, a method of casting a resin having the same composition in multiple layers during casting will be described.

Since PBT has a high crystallization speed, crystallization proceeds even during casting. At this time, when cast as a single layer without being multi-layered, there is no barrier that can suppress the growth of the crystal, so the crystal grows to a large size, and the resulting unstretched original fabric is obtained. The yield stress of becomes higher. For this reason, it becomes easy to fracture when the unstretched original fabric is biaxially stretched. Moreover, it is possible that the yield stress of the obtained biaxially stretched film becomes high and the moldability of the biaxially stretched film becomes insufficient.
On the other hand, if the same resin is multilayered at the time of casting, the stretching stress of the unstretched sheet can be reduced. For this reason, stable biaxial stretching is possible, and the yield stress of the obtained biaxially stretched film is reduced. Thereby, a flexible and high breaking strength film can be obtained.

  FIG. 4 is a cross-sectional view showing an example of the layer configuration of the first film. When the first substrate 41 is produced by casting the resin in multiple layers, as shown in FIG. 4, the first substrate 41 of the first film 40 is composed of a multilayer structure including a plurality of layers 41a. . Each of the plurality of layers 41a includes PBT as a main component. For example, each of the plurality of layers 41a preferably includes 51% by mass or more of PBT, and more preferably includes 60% by mass or more of PBT. In the plurality of layers 41a, the (n + 1) th layer 41a is directly stacked on the nth layer 41a. That is, no adhesive layer or adhesive layer is interposed between the plurality of layers 41a.

  The reason why the characteristics of the PBT film are improved by the multilayering is estimated as follows. When the resins are laminated, even if the resin composition is the same, a layer interface exists, and crystallization is accelerated by the interface. On the other hand, the growth of large crystals beyond the layer thickness is suppressed. For this reason, it is considered that the size of the crystal (spherulite) becomes small.

  As a specific method for reducing the size of spherulites by multilayering, a general multilayering apparatus (multilayer feedblock, static mixer, multilayer multimanifold, etc.) can be used. For example, a method of laminating thermoplastic resins sent from different flow paths using two or more extruders in multiple layers using a feed block, a static mixer, a multi-manifold die, or the like can be used. In addition, when multilayering resin of the same composition, it is also possible to introduce the above multilayering apparatus into the melt line from the extruder to the die using only one extruder.

  The first substrate 41 is composed of a multilayer structure including at least 10 layers, preferably 60 layers or more, more preferably 250 layers or more, and still more preferably 1000 layers or more. By increasing the number of layers, the size of spherulites in the unstretched raw PBT can be reduced, and the subsequent biaxial stretching can be carried out stably. Moreover, the yield stress of PBT in the state of a biaxially stretched film can be made small. Preferably, the diameter of the spherulite in the unstretched raw PBT is 500 nm or less.

  The stretching temperature (hereinafter also referred to as MD stretching temperature) in the longitudinal stretching direction (hereinafter referred to as MD) when producing a biaxially stretched film by biaxially stretching the unstretched raw material of PBT is preferably 40 ° C. or higher. Yes, more preferably 45 ° C or higher. By setting the MD stretching temperature to 40 ° C. or higher, the film can be prevented from being broken. Moreover, MD extending | stretching temperature becomes like this. Preferably it is 100 degrees C or less, More preferably, it is 95 degrees C or less. The phenomenon that the orientation of the biaxially stretched film does not occur can be suppressed by setting the MD stretching temperature to 100 ° C. or lower.

  The draw ratio in MD (hereinafter also referred to as MD draw ratio) is preferably 2.5 times or more. Thereby, a biaxially stretched film can be oriented and a favorable mechanical characteristic and uniform thickness can be implement | achieved. MD stretch ratio is 5 times or less, for example.

  The stretching temperature (hereinafter also referred to as TD stretching temperature) in the transverse stretching direction (hereinafter also referred to as TD) is preferably 40 ° C. or higher. By setting the TD stretching temperature to 40 ° C. or higher, the film can be prevented from being broken. The TD stretching temperature is preferably 100 ° C. or lower. By setting the TD stretching temperature to 100 ° C. or lower, the phenomenon that the orientation of the biaxially stretched film does not occur can be suppressed.

  The draw ratio in TD (hereinafter also referred to as TD draw ratio) is preferably 2.5 times or more. Thereby, a biaxially stretched film can be oriented and a favorable mechanical characteristic and uniform thickness can be implement | achieved. MD stretch ratio is 5 times or less, for example.

  The TD relaxation rate is preferably 0.5% or more. Thereby, it can suppress that a fracture | rupture arises at the time of heat setting of the biaxially stretched film of PBT. The TD relaxation rate is preferably 10% or less. Thereby, sagging etc. arise in a biaxially stretched film of PBT, and it can control that thickness unevenness generate | occur | produces.

The thickness of the layer 41a of the first base material 41 shown in FIG. 4 is preferably 3 nm or more, more preferably 10 nm or more. The thickness of the layer 41a is preferably 200 nm or less, and more preferably 100 nm or less.
Further, the thickness of the first base material 41 is preferably 9 μm or more, and more preferably 12 μm or more. Further, the thickness of the first base material 41 is preferably 25 μm or less, and more preferably 20 μm or less. By setting the thickness of the first base material 41 to 9 μm or more, the first base material 41 has sufficient strength. Moreover, the 1st base material 41 comes to show the moldability which was excellent by making the thickness of the 1st base material 41 into 25 micrometers or less. For this reason, the process which processes the laminated body 30 containing the 1st base material 41 and manufactures the bag 10 can be implemented efficiently.

[Second Configuration of Base Material]
The 1st base material 41 concerning the 2nd composition consists of a single layer film containing polyester which makes butylene terephthalate the main repeating unit. For example, the first base material 41 is mainly composed of 1,4-butanediol as a glycol component, or an ester-forming derivative thereof, and terephthalic acid as a dibasic acid component, or an ester-forming derivative thereof. Includes homo- or copolymer-type polyesters obtained by condensation. The content of PBT in the first base material 41 according to the second configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 80% by mass or more, Most preferably, it is 90 mass% or more. Moreover, it is preferable that the 1st base material 41 which concerns on a 2nd structure is comprised only with the polybutylene terephthalate and the additive.

  In order to impart mechanical strength to the first base material 41, PBT having a melting point of 200 ° C. or more and 250 ° C. or less and an IV value of 1.10 dl / g or more and 1.35 dl / g or less is preferable. . Furthermore, those having a melting point of 215 ° C. or more and 225 ° C. or less and an IV value of 1.15 dl / g or more and 1.30 dl / g or less are particularly preferable. These IV values may be satisfied by the entire material constituting the first base material 41. The IV value can be calculated based on JIS K 7367-5: 2000.

The 1st base material 41 concerning the 2nd composition may contain polyester resins other than PBT, such as PET, in the range of 30 mass% or less. When the 1st base material 41 contains PET in addition to PBT, PBT crystallization can be suppressed and the extending | stretching workability of a PBT film can be improved. As PET mix | blended with PBT of the 1st base material 41, polyester which uses ethylene terephthalate as the main repeating unit can be used. For example, a homotype mainly composed of ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component can be preferably used. In order to impart good mechanical strength characteristics, among PET, those having a melting point of 240 ° C. or more and 265 ° C. or less and an IV value of 0.55 dl / g or more and 0.90 dl / g or less are preferable. Furthermore, those having a melting point of 245 ° C. or more and 260 ° C. or less and an IV value of 0.60 dl / g or more and 0.80 dl / g or less are particularly preferable.
By setting the blending amount of PET to 30% by mass or less, it is possible to suppress the unstretched raw fabric and the stretched film from becoming too rigid. Thereby, a stretched film becomes brittle and it can suppress that the pressure resistance strength, impact strength, puncture strength, etc. of a stretched film fall. Moreover, it is possible to suppress the occurrence of stretching failure when the unstretched raw fabric is stretched.

  The first base material 41 is made of a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a colorant, a crystallization inhibitor, and a crystallization as necessary. Additives such as accelerators may be included. Further, the polyester resin pellet used as a raw material of the first base material 41 has a moisture content of 0.05% by weight or less, preferably 0.01% by weight before heating and melting in order to avoid a decrease in viscosity due to hydrolysis during heating and melting. It is preferable to use after sufficiently pre-drying so as to be not more than%.

  An example of a method for producing the film-like first base material 41 according to the second configuration will be described.

  In order to stably produce the film of the first base material 41 having the above-described configuration, it is important to suppress the crystal growth in the unstretched raw fabric state. Specifically, when forming the film by cooling the extruded PBT melt, the crystallization temperature region of the polymer is cooled at a certain rate or more, that is, the raw fabric cooling rate is an important factor. The raw fabric cooling rate is, for example, 200 ° C./second or more, preferably 250 ° C./second or more, particularly preferably 350 ° C./second or more. Since the unstretched original film formed at a high cooling rate maintains a low crystalline state, the stability of the bubbles during stretching is improved. Furthermore, since film formation at high speed is possible, film productivity is also improved. When the cooling rate is less than 200 ° C./sec, it is considered that the crystallinity of the obtained unstretched original fabric is increased and the stretchability is lowered. In extreme cases, the stretching bubble may burst and stretching may not continue.

  The unstretched original fabric containing PBT as a main component is preferably transported to a space where biaxial stretching is performed while maintaining the atmospheric temperature at 25 ° C. or lower, preferably 20 ° C. or lower. Thereby, even if it is a case where residence time becomes long, the crystallinity of the unstretched original fabric immediately after film-forming can be maintained.

  The biaxial stretching method for obtaining a stretched film by stretching an unstretched raw fabric is not particularly limited. For example, the longitudinal direction and the lateral direction may be simultaneously stretched by the tubular method or the tenter method, or the longitudinal direction and the lateral direction may be sequentially stretched. Among these, the tubular method can obtain a stretched film having a good balance of physical properties in the circumferential direction, and is particularly preferably employed.

  In the tubular method, the unstretched raw material guided to the stretching space is inserted between a pair of low-speed nip rolls, and then heated by a stretching heater while air is pressed into the unstretched raw fabric. After stretching, air is blown onto the stretched film by a cooling shoulder air ring. The stretching ratio is preferably 2.7 times or more and 4.5 times or less for MD and TD, respectively, in consideration of stretching stability, strength physical properties of the stretched film, transparency, and thickness uniformity. By setting the draw ratio to 2.7 times or more, it is possible to sufficiently ensure the tensile elastic modulus and impact strength of the stretched film. In addition, by setting the draw ratio to 4.5 times or less, it is possible to suppress the occurrence of excessive molecular chain distortion due to stretching, and to suppress the occurrence of breakage and puncture during the stretching process, so that the stretched film can be stabilized. Can be produced.

  The stretching temperature is preferably 40 ° C. or higher and 80 ° C. or lower, and particularly preferably 45 ° C. or higher and 65 ° C. or lower. Since the unstretched original fabric produced at the above-described high cooling rate has low crystallinity, the unstretched original fabric can be stably stretched even when the stretching temperature is relatively low. Further, by setting the stretching temperature to 80 ° C. or less, it is possible to suppress stretching bubble shaking and obtain a stretched film with good thickness accuracy. In addition, by setting the stretching temperature to 40 ° C. or higher, it is possible to suppress the occurrence of excessive stretch-oriented crystallization due to low-temperature stretching, thereby preventing whitening of the film.

  The 1st base material 41 produced as mentioned above is comprised by the single layer containing polyester which makes butylene terephthalate the main repeating unit, for example. According to the above-described production method, since the unstretched raw film is formed at a high cooling rate, even when the unstretched raw fabric is constituted by a single layer, a low crystalline state can be maintained, For this reason, an unstretched original fabric can be extended | stretched stably.

(First adhesive layer)
The first adhesive layer 45 includes a first adhesive for bonding the first film 40 and the second film 50. Examples of the first adhesive include ether-based two-component reactive adhesives and ester-based two-component reactive adhesives.

  Examples of the ether-based two-component reactive adhesive include polyether polyurethane. The polyether polyurethane is a cured product produced by a reaction between a polyether polyol as a main agent and an isocyanate compound as a curing agent. As isocyanate compounds, aromatic isocyanate compounds such as tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), etc. Aliphatic isocyanate compounds, or adducts or multimers of the above-mentioned various isocyanate compounds can be used.

  Examples of the ester-based two-component reactive adhesive include polyester polyurethane and polyester. Polyester polyurethane is a cured product produced by a reaction between a polyester polyol as a main agent and an isocyanate compound as a curing agent. Examples of the isocyanate compound are the same as in the case of the ether-based adhesive described above.

(Second film)
The second film 50 includes at least a second base material 51. The 2nd base material 51 contains PET as a main component. For example, the 2nd base material 51 contains 51 mass% or more of PET. The 2nd base material 51 can have heat resistance because the 2nd base material 51 contains PET. For example, compared with the case where the 2nd base material 51 contains nylon, melting | fusing point of the 2nd base material 51 becomes high, and the hygroscopic property of the 2nd base material 51 becomes low. Thereby, when heating the bag 10, it can suppress that a hole opens in the 2nd base material 51 resulting from the overheated water. Moreover, the heat resistance of PET is higher than the heat resistance of PBT. For this reason, according to this Embodiment, compared with the case where the 2nd base material 51 consists of PBT, the heat resistance of the laminated body 30 can be improved. Thereby, for example, when the bag 10 is heated, it is possible to prevent the laminated body 30 from being damaged and the performance of the laminated body 30 from being deteriorated.

  The thickness of the second substrate 51 is preferably 9 μm or more, and more preferably 12 μm or more. The thickness of the second substrate 51 is preferably 25 μm or less, more preferably 20 μm or less. By setting the thickness of the second base material 51 to 9 μm or more, the second base material 51 has sufficient strength. Moreover, the 2nd base material 51 comes to show the outstanding moldability by the thickness of the 2nd base material 51 being 25 micrometers or less. For this reason, the process which processes the laminated body 30 and manufactures the bag 10 can be implemented efficiently.

(Second adhesive layer)
The second adhesive layer 55 includes a second adhesive for bonding the second film 50 and the third film 60. Examples of the second adhesive include ether-based two-component reaction type adhesives. Examples of the ether-based two-component reaction type adhesive include polyurethane as in the case of the first adhesive. Polyurethane is a cured product produced by a reaction between a polyol as a main agent and an isocyanate compound as a curing agent. In addition, although polyether polyol and polyester polyol can be used as polyol, it is preferable to use polyester polyol.

  As described above, aromatic isocyanate compounds and aliphatic isocyanate compounds exist as isocyanate compounds. Among these, aromatic isocyanate compounds elute components that cannot be used in food applications under high-temperature environments such as heat sterilization. By the way, the 2nd adhesive bond layer 55 is in contact with the 3rd film 60, as shown in FIG.2 and FIG.3. For this reason, when the 2nd adhesive bond layer 55 contains an aromatic isocyanate compound, the component eluted from the aromatic isocyanate compound may adhere to the content of the bag 10 comprised by the laminated body 30. FIG.

  In consideration of such problems, as a second adhesive constituting the second adhesive layer 55, a cured product generated by a reaction between a polyol as a main agent and an aliphatic isocyanate compound as a curing agent is used. Suggest to use. Thereby, it can prevent that the component which cannot be used for the food use resulting from the 2nd adhesive bond layer 55 adheres to the content.

(Third film)
The third film 60 includes at least a sealant layer 61 that constitutes the inner surface 30 x of the laminate 30. As a material constituting the sealant layer 61, one or two or more resins selected from polyethylene such as low density polyethylene and linear low density polyethylene, and polypropylene can be used. The sealant layer 61 may be a single layer or a multilayer. The sealant layer 61 is preferably made of an unstretched film.

  The melting point of the material constituting the sealant layer 61 is preferably 150 ° C. or higher, and more preferably 160 ° C. or higher. By increasing the melting point of the sealant layer 61, the bag 10 can be retorted at a high temperature, and the time required for the retort process can be shortened. The melting point of the material constituting the sealant layer 61 is lower than the melting point of the resin constituting the first base member 41 and the melting point of the resin constituting the second base member 51.

  Preferably, the sealant layer 61 includes a propylene / ethylene block copolymer. For example, the third film 60 including the sealant layer 61 is an unstretched film containing a propylene / ethylene block copolymer as a main component. By using the propylene / ethylene block copolymer, the impact resistance of the third film 60 can be increased, and thereby the bag 10 can be prevented from being broken due to the impact at the time of dropping. Moreover, the puncture resistance of the laminated body 30 can be improved.

  The sealant layer 61 may further contain a thermoplastic elastomer. By using the thermoplastic elastomer, the impact resistance and puncture resistance of the third film 60 can be further improved.

  The thermoplastic elastomer is, for example, a hydrogenated styrene thermoplastic elastomer. The hydrogenated styrene-based thermoplastic elastomer has a structure comprising a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one hydrogenated conjugated diene compound. . The thermoplastic elastomer may be an ethylene / α-olefin elastomer. The ethylene / α-olefin elastomer is a low crystalline or amorphous copolymer elastomer, and is a random copolymer of 50 to 90% by mass of ethylene as a main component and α-olefin as a copolymerization monomer. is there.

  The content of the propylene / ethylene block copolymer in the sealant layer 61 is, for example, 80% by mass or more, and preferably 90% by mass or more.

  Examples of the method for producing a propylene / ethylene block copolymer include a method of polymerizing propylene, ethylene, and the like as raw materials using a catalyst. As the catalyst, Ziegler-Natta type or metallocene catalyst can be used.

  The thickness of the sealant layer 61 is preferably 30 μm or more, more preferably 40 μm or more. Moreover, the thickness of the sealant layer 61 is preferably 100 μm or less, and more preferably 80 μm or less.

Next, the layer structure of the lower film 16 will be described.

  As long as it has the inner surface which can be joined with the inner surface of the surface film 14 and the inner surface of the back surface film 15, the layer structure of the lower film 16 is arbitrary. For example, similar to the front film 14 and the back film 15, the above-described laminate 30 may be used as the lower film 16. Alternatively, a film having an inner surface constituted by a sealant layer and a configuration different from that of the laminate 30 may be used as the lower film 16.

Method for Manufacturing First Film Next, an example of a method for manufacturing the first film 40 will be described.

  First, a resin material containing PBT as a main component is prepared. Then, the film-form 1st base material 41 is produced by extruding resin material by melt extrusion methods, such as a cast method and a tubular method. Subsequently, the pattern printing layer 43 and the light shielding printing layer 42 are formed on the first base material 41. Thus, the 1st film 40 provided with the 1st base material 41, the shading printing layer 42, and the pattern printing layer 43 can be obtained.

Method for producing a laminate Next, an example of a method for producing a laminate 30.

  First, the first film 40 and the second film 50 described above are prepared. Subsequently, the first film 40 and the second film 50 are laminated via the first adhesive layer 45 by a dry laminating method. Thereafter, the laminate including the first film 40 and the second film 50 and the third film 60 are laminated via the second adhesive layer 55 by a dry laminating method. Thereby, the laminated body 30 provided with the 1st film 40, the 2nd film 50, and the 3rd film 60 can be obtained.

  Alternatively, first, the second film 50 and the third film 60 are laminated via the second adhesive layer 55, and then the first film 40 and the laminate including the second film 50 and the third film 60 are first laminated. The laminated body 30 may be manufactured by laminating via one adhesive layer 45.

Manufacturing method of bag The front film 14 and the back film 15 which consist of the above-mentioned laminated body 30 are prepared. In addition, the lower film 16 in a folded state is inserted between the front film 14 and the back film 15. Subsequently, the inner surfaces of the films are heat-sealed to form seal portions such as the lower seal portion 12a and the side seal portion 13a. Further, the films bonded to each other by heat sealing are cut into an appropriate shape to obtain a bag 10 shown in FIG. Subsequently, the bag 10 is filled with the contents through the opening 11 b of the upper portion 11. The contents are, for example, cooked foods such as curry, stew, and soup. In addition to food, items that can be heated by hot water can be stored in the bag 10 as contents. Thereafter, the upper part 11 is heat-sealed to form an upper seal part. Thus, the bag 10 in which the contents are accommodated and sealed can be obtained.

  Hereinafter, advantages of the bag 10 according to the present embodiment will be described.

In this Embodiment, when the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains the 1st base material 41 which has PBT as a main component, there can exist the following effect.
First, PBT is excellent in printability. For this reason, as in the case of polyethylene terephthalate (hereinafter also referred to as PET), the light-shielding print layer 42 and the pattern print layer 43 can be provided on the first base material 41 containing PBT.
Moreover, PBT is excellent in heat resistance. For this reason, when performing the retort process, the boil process, etc. to the bag 10, it can suppress that the 1st base material 41 deform | transforms or the intensity | strength of the 1st base material 41 falls.
PBT has high strength. For this reason, the puncture strength of the laminated body 30 and the bag 10 can be increased similarly to the case where the laminated body constituting the bag 10 includes nylon. The puncture strength of the laminate 30 is preferably 13N or more, more preferably 15N or more, and further preferably 17N or more. A method for measuring the piercing strength will be described in Example 1 described later.
PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the 1st substrate 41 containing PBT is arranged on the outer surface 30y of layered product 30, the first substrate 41 will absorb moisture and the laminate strength of layered product 30 will fall. Can be suppressed.

  Further, in the present embodiment, the laminate 30 includes a light-shielding print layer 42 positioned between the first base material 41 and the second base material 51. For this reason, it can suppress that external light permeate | transmits the laminated body 30, and is irradiated to a content, and can suppress that a content deteriorates by external light by this.

  Further, in the present embodiment, the laminate 30 includes the second base material 51 containing PET as a main component, so that it occurs in the light-shielding print layer 42 as compared with the case where the second base material 51 is made of nylon. It is possible to suppress the odor that has been transmitted through the second film 50 and the third film 60 and adhere to the contents. Moreover, the heat resistance of the laminated body 30 can be improved compared with the case where the 2nd base material 51 consists of PBT. Thereby, for example, when the bag 10 is heated, it is possible to prevent the front film 14 and the back film 15 from being damaged and the performance of the front film 14 and the back film 15 from being deteriorated.

  Moreover, according to this Embodiment, the sealant layer 61 of the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains a propylene and ethylene block copolymer. For this reason, the impact resistance and puncture resistance of the bag 10 can be enhanced.

  Note that various modifications can be made to the above-described embodiment. Hereinafter, modified examples will be described with reference to the drawings as necessary. In the following description and the drawings used in the following description, the same reference numerals as those used for the corresponding parts in the above embodiment are used for the parts that can be configured in the same manner as in the above embodiment. A duplicate description is omitted. In addition, when it is clear that the operational effects obtained in the above-described embodiment can be obtained in the modified example, the description thereof may be omitted.

(Modification of layer structure)
In the present embodiment described above, the first base material 41 includes 51% by mass or more of PBT, and the second base material 51 includes 51% by mass or more of PET, whereby the stab resistance and heat resistance of the stacked body 30. The example which raises is shown. However, the present invention is not limited to this, and the first substrate 41 includes 51% by mass or more of PET, and the second substrate 51 includes 51% by mass or more of PBT. You may increase the nature. As the PBT of the second base material 51, the PBT according to the first configuration described in the first base material 41 or the PBT according to the second configuration can be used.

  The fact that the second base material 51 contains 51% by mass or more of PBT and the first base material 41 contains 51% by mass or more of PET contributes to the improvement of the dimensional stability and printability of the laminate 30.

  Moreover, both the 1st base material 41 and the 2nd base material 51 may contain 51 mass% or more of PBT. Also as PBT in this case, PBT which concerns on the 1st structure demonstrated with the above-mentioned 1st base material 41, or PBT which concerns on a 2nd structure can be used.

Table 1 summarizes examples of combinations of materials constituting the first base material 41 and the second base material 51. In Table 1, the notation “PBT” means that 51 mass% or more of PBT is contained in the resin constituting the film of the first base material 41 or the second base material 51. In Table 1, the expression “PET” means that 51% by mass or more of PET is contained in the resin constituting the film of the first base material 41 or the second base material 51.

In the above-described embodiment, an example in which the light-shielding print layer 42 and the pattern print layer 43 are provided on the inner surface 30x side of the first base material 41 has been described, but the present invention is not limited thereto. When the light-shielding print layer 42 is located between the first base material 41 and the second base material 51 and the pattern print layer 43 is provided, the pattern print layer 43 is located on the outer surface 30y side of the light-shielding print layer 42. As long as it does, arrangement | positioning of each layer is arbitrary. For example, the light shielding printing layer 42 and the pattern printing layer 43 may be provided on the outer surface 30 y side of the second base material 51. Alternatively, the light shielding print layer 42 may be provided on the outer surface 30 y side of the second base material 51, and the pattern print layer 43 may be provided on the inner surface 30 x side of the first base material 41. Examples of the arrangement of each layer are listed below.
Arrangement example 1: first substrate / light-shielding printing layer / first adhesive layer / second substrate / second adhesive layer / sealant layer Arrangement example 2: first substrate / pattern printing layer / light-shielding printing layer / first 1 adhesive layer / second base material / second adhesive layer / sealant layer Arrangement example 3: first base material / first adhesive layer / light-shielding printing layer / second base material / second adhesive layer / sealant layer Arrangement Example 4: First Base Material / First Adhesive Layer / Picture Printing Layer / Light-shielding Printing Layer / Second Base Material / Second Adhesive Layer / Sealant Layer Arrangement Example 5: First Substrate / Picture Printing Layer / First 1 adhesive layer / light-shielding printing layer / second substrate / second adhesive layer / sealant layer

(Bag variant)
In the above-described embodiment, an example in which the bag 10 is a gusset type bag has been shown, but the specific configuration of the bag 10 is not particularly limited. For example, the bag 10 may be a so-called four-side sealed bag formed by joining the inner surfaces of the front film 14 and the back film 15 made of the laminate 30 at the upper part 11, the lower part 12 and the side part 13.

(Laminated body according to the second embodiment)
In the first embodiment described above, the configuration in which the stacked body 30 includes the light-shielding print layer 42 has been described, but the scope of the present invention is not limited thereto. FIG. 7 is a cross-sectional view showing an example of a laminated body 30 according to the second embodiment. The laminated body 30 shown in FIG. 7 is different only in that the light-shielding print layer 42 is not provided, and the other configuration is substantially the same as the laminated body 30 according to the first embodiment shown in FIG. 2 or FIG. Are the same. In the laminate 30 according to the second embodiment, the same parts as those in the laminate 30 according to the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. In addition, when it is clear that the effects obtained in the first embodiment can be obtained in the second embodiment, the description thereof may be omitted.

  As shown in FIG. 7, the laminate 30 includes at least a first film 40, a second film 50, and a third film 60 in this order. The first film 40 is located on the outer surface 30y side, and the third film 60 is located on the inner surface 30x side opposite to the outer surface 30y. The inner surface 30x is a surface located on the accommodating portion 17 side.

As shown in FIG. 7, the first film 40 includes at least a first base material 41. The second film 50 includes at least a second base material 51. The third film 60 includes at least a sealant layer 61. The first film 40 and the second film 50 are joined by a first adhesive layer 45, and the second film 50 and the third film 60 are joined by a second adhesive layer 55. Therefore, the laminated body 30 according to the second embodiment includes, in order from the outer surface side to the inner surface side, the first base material / first adhesive layer / second base material / second adhesive layer / sealant layer,
It can be said that it has. Note that “/” represents a boundary between layers. Although not shown, the above-described pattern printing layer 43 may be provided on the first base material 41 or the second base material 51 between the first base material 41 and the second base material 51.

  Also in the present embodiment, as in the case of the first embodiment described above, at least one of the first base material 41 and the second base material 51 includes 51% by mass or more of PBT. Thereby, the puncture resistance and heat resistance of the laminated body 30 can be improved.

  Also in the present embodiment, as in the case of the first embodiment described above, the second base material 51 includes 51% by mass or more of PBT or 51% by mass or more of PET. Hereinafter, the effect by which the 2nd substrate 51 contains PBT or PET is explained. Here, an effect is demonstrated based on the comparison with the case where the 2nd base material 51 contains nylon.

  Nylon is prone to penetration of the components of the contents. For this reason, when the 2nd base material 51 which opposes the sealant layer 61 contains nylon, it is possible that the 2nd base material 51 will be colored with the content. Such coloring tends to occur when high-temperature processing such as retort processing or boil processing is performed on the contents. On the other hand, the penetration of the components of the contents hardly occurs in PET and PBT. For this reason, it can suppress that the 2nd base material 51 is colored with the content by comprising the 2nd base material 51 which opposes the sealant layer 61 by PBT or PET. Thereby, it can suppress that the external appearance of the bag 10 is impaired.

  Nylon has high hygroscopicity. For this reason, when the 2nd substrate 51 contains nylon, the 2nd substrate 51 tends to contain moisture. For this reason, when the bag 10 is heated, it is considered that foaming occurs due to moisture contained in the second base material 51 and the appearance of the bag 10 is impaired. Such foaming is particularly likely to occur in the lower seal portion 12a and the side seal portion 13a where the front film 14 and the back film 15 are overlapped and joined. In contrast, the hygroscopicity of PBT and PET is lower than that of nylon. For this reason, it can suppress that the 2nd base material 51 contains a water | moisture content by comprising the 2nd base material 51 by PBT or PET. Thereby, it can suppress that foaming arises in the bag 10, and can suppress that the external appearance of the bag 10 is impaired.

  In addition, when the second base material 51 includes nylon, caprolactam or the like, which is a raw material of nylon from the nylon, and whose elution standard is defined in the Ministry of Health and Welfare Notification No. 370 “Equipment and Container Packaging”, is eluted. There is a risk of mixing with the contents. On the other hand, according to this Embodiment, the possibility that caprolactam etc. elute can be reduced by comprising the 2nd base material 51 by PBT or PET.

  In addition, the effect regarding suppression of coloring, suppression of foaming, and suppression of the elution of the substance to the contents is an effect which arises by comprising the 2nd base material 51 by PBT or PET, and the above-mentioned 1st Embodiment. Of course, this can occur.

  The combination of the material which comprises the 1st base material 41 in the 2nd embodiment and the 2nd base material 51 can be made to be the same as the combination shown in the above-mentioned 1st Embodiment and a modification. For example, the combinations shown in Table 1 can be used.

  When it is possible to select whether the first base material 41 includes PET or PBT, it is preferable that the first base material 41 includes PET from the viewpoint of heat sealability. PET has a relatively higher melting point than PBT. Therefore, the heat resistance of the 1st base material 41 improves more because the 1st base material 41 which is a base material located in the outer surface 30y side of bag 10 contains PET. As described above, when the seal portion of the bag 10 is formed by heat sealing, it becomes possible to perform heat sealing at a higher temperature.

  Next, the sealant layer 61 will be described. As described above, the bag 10 composed of the laminate 30 is subjected to sterilization treatment such as boil treatment and retort treatment at a high temperature. Therefore, as the sealant layer 61, a layer having heat resistance that can withstand processing at these high temperatures is used.

  When considering from the viewpoint of retort processing, a material mainly composed of propylene can be used as the material constituting the sealant layer 61. Here, the material having “propylene as a main component” means a material having a propylene content of 90% by mass or more. As a material mainly composed of propylene, specifically, in addition to the propylene / ethylene block copolymer described as the material constituting the sealant layer 61 in the first embodiment, a propylene / ethylene random copolymer, Examples thereof include polypropylene such as homopolypropylene, or a mixture of polypropylene and polyethylene. Here, the “propylene / ethylene block copolymer” means a material having a structural formula represented by the following formula (I). The “propylene / ethylene random copolymer” means a material having a structural formula represented by the following formula (II). “Homopolypropylene” means a material having the structural formula shown by the following formula (III).

  When a material containing propylene as a main component and a mixture of polypropylene and polyethylene is used, the material may have a sea-island structure. Here, the “sea-island structure” means a structure in which polyethylene is discontinuously dispersed in a region where polypropylene is continuous.

When considered from the viewpoint of boil processing, examples of the material constituting the sealant layer 61 include polyethylene, polypropylene, or a combination thereof. Examples of polyethylene include medium density polyethylene, linear low density polyethylene, and combinations thereof. For example, it is also possible to use the materials mentioned as the material constituting the sealant layer from the viewpoint of the above retort processing. The material constituting the sealant layer has a melting point of, for example, 100 ° C. or higher, more preferably 105 ° C. or higher, and still more preferably 110 ° C. or higher. When polyethylene is used as the material constituting the sealant layer, a melting point of 100 ° C. or higher can be realized, for example, when the density of polyethylene is 0.920 g / cm ³ or higher. Specific examples of the sealant film for forming a sealant layer having a melting point of 100 ° C. or higher include TUX-HC manufactured by Mitsui Chemicals Tosero, L6101 manufactured by Toyobo, and LS700C manufactured by Idemitsu Unitech. As a specific example of the sealant film for constituting a sealant layer having a melting point of 105 ° C. or higher, NB-1 manufactured by Tamapoli can be cited. Specific examples of the sealant film for forming a sealant layer having a melting point of 110 ° C. or higher include LS760C manufactured by Idemitsu Unitech, TUX-HZ manufactured by Mitsui Chemicals Tosero, and the like.

  The sealant layer 61 may be a single layer or a multilayer as in the case of the first embodiment. Moreover, the material of the above-mentioned sealant layer 61 can also be applied to the sealant layer 61 of the laminate 30 according to the above-described first embodiment.

(Laminated body according to the third embodiment)
Next, the laminated body 30 in 3rd Embodiment is demonstrated. The layered product 30 according to the third embodiment is different only in that it further includes a barrier layer 80 provided on at least one of the first base material 41 and the second base material 51. 7 is substantially the same as the laminate 30 according to the second embodiment shown in FIG. In the stacked body 30 according to the third embodiment, the same parts as those of the stacked body 30 according to the second embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Moreover, when it is clear that the effects obtained in the first embodiment or the second embodiment can be obtained also in the third embodiment, the description thereof may be omitted.

FIG. 8 is a cross-sectional view illustrating an example of the stacked body 30 in the third embodiment. In the example illustrated in FIG. 8, the stacked body 30 includes a barrier layer 80 provided on the surface on the inner surface 30 x side of the first base material 41. FIG. 9 is a cross-sectional view showing another example of the laminate 30 that constitutes the front film 14 and the back film 15 in the third embodiment. In the example illustrated in FIG. 9, the stacked body 30 includes a barrier layer 80 provided on the outer surface 30 y side of the second base material 51. Therefore, the laminated body 30 according to the third embodiment includes, in order from the outer surface side to the inner surface side, the first base material / barrier layer / first adhesive layer / second base material / second adhesive layer / sealant layer,
Or
It can be said that the first substrate / first adhesive layer / barrier layer / second substrate / second adhesive layer / sealant layer are provided. Note that “/” represents a boundary between layers. Although not shown, the above-mentioned pattern printing layer 43 may be provided between the barrier layer and the first adhesive layer.

[Barrier layer]
Hereinafter, the barrier layer 80 will be described.

(Transparent deposition layer)
As shown in FIGS. 8 and 9, the barrier layer 80 includes at least a transparent vapor deposition layer 81. The transparent vapor deposition layer 81 is provided on the first base material 41 as shown in FIG. 8, or is provided on the second base material 51 as shown in FIG. The transparent vapor deposition layer 81 is a layer formed of a vapor deposition layer that can be formed by a conventionally known method. By providing the transparent vapor deposition layer 81, the gas barrier property which prevents permeation | transmission of oxygen gas, water vapor | steam, etc. can be provided thru | or improved. Note that the barrier layer 80 may include two or more transparent vapor deposition layers 81. When the barrier layer 80 includes two or more transparent vapor deposition layers 81, each may have the same composition or a different composition.

  The transparent vapor deposition layer 81 is made of an inorganic oxide vapor deposition layer. Examples of the transparent deposition layer 81 include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium. An evaporated layer of an oxide such as (Ti), lead (Pb), zirconium (Zr), or yttrium (Y) can be used. In particular, it is preferable to provide a vapor deposition layer of aluminum oxide or silicon oxide.

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1.5 for boron (B), titanium (Ti) Can take values ranging from 0 to 2, lead (Pb) from 0 to 2, zirconium (Zr) from 0 to 2, and yttrium (Y) from 0 to 1.5. In the above, when X = 0, it is a complete inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are suitably used for the packaging material, silicon (Si) is in the range of 1.0 to 2.0, and aluminum (Al) is in the range of 0.5 to 1.5. Can be used.

  The transparent vapor deposition layer 81 may be a layer made of a mixture of inorganic compounds containing a covalent bond between an aluminum atom and a carbon atom. In this case, the transparent vapor deposition layer 81 uses an X-ray photoelectron spectrometer (measuring conditions: X-ray source AlKα, X-ray output 120 W) and shares aluminum atoms and carbon atoms at the peak measured by ion etching in the depth direction. It may have a gas barrier property that indicates the presence of a bond and has transparency and prevents permeation of oxygen, water vapor, and the like.

  A covalent bond between a metal atom and a carbon atom may be formed at the interface between the transparent vapor deposition layer 81 and the first base material 41 or the second base material 51. For example, when the transparent vapor deposition layer 81 contains aluminum oxide, a covalent bond between an aluminum atom and a carbon atom is formed at the interface between the first base material 41 or the second base material 51 and the transparent vapor deposition layer 81. can do. The covalent bond can be detected by measurement by X-ray photoelectron spectroscopy (hereinafter referred to as “XPS measurement” for short).

  Moreover, in the transparent vapor deposition layer 81, the carbon atom observed when the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is measured when the interface with the first base material 41 or the second base material 51 is measured by XPS measurement. It is preferable that it is within the range of 0.3% or more and 30% or less of all the bonds included. Thereby, the adhesiveness of the transparent vapor deposition layer 81 and the 1st base material 41 or the 2nd base material 51 is strengthened, transparency is excellent, and the thing of the performance with the balance as a gas barrier property vapor deposition film is obtained.

  When the ratio of the covalent bond between the aluminum atom and the carbon atom is less than 0.3%, the adhesion of the transparent vapor deposition layer 81 is not sufficiently improved, and it becomes difficult to stably maintain the barrier property.

Furthermore, the AL (aluminum) / O (oxygen) ratio of the transparent vapor-deposited layer 81 containing aluminum oxide as the main component is the first base 41 or the second base 51 from the interface between the transparent vapor-deposited layer 81 and It is preferable that it is 1.0 or less in the range up to 3 nm toward the surface of the transparent vapor deposition layer 81 on the opposite side to the base material 41 or the second base material 51.
AL / O within a range from the interface between the transparent vapor deposition layer 81 and the first base material 41 or the second base material 51 toward the surface of the transparent vapor deposition layer 81 opposite to the first base material 41 or the second base material 51. If the ratio exceeds 1.0, the adhesiveness between the surface of the first base material 41 or the second base material 51 on the transparent vapor deposition layer 81 side and the transparent vapor deposition layer 81 becomes insufficient, and the proportion of aluminum increases. The transparency of the transparent vapor deposition layer 81 falls.

  The thickness of the transparent vapor-deposited layer 81 varies depending on the type of inorganic oxide to be used and the like. For example, it is desirable to arbitrarily select and form within 50 to 2000 mm, preferably 100 to 1000 mm. . For example, in the case of a vapor deposition layer of aluminum oxide or silicon oxide, the layer thickness is preferably 50 to 500 mm, more preferably 100 to 300 mm.

  The transparent vapor deposition layer 81 can be formed on the first base material 41 or the second base material 51 using the following forming method. As a method for forming a vapor deposition layer, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, a plasma chemical vapor deposition method, a thermochemistry, or the like. Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method. Specifically, a vapor deposition layer can be formed on a film formation roller using a roller-type vapor deposition film forming apparatus.

  In particular, when a covalent bond between a metal atom and a carbon atom is formed at the interface between the transparent vapor deposition layer 81 and the first base material 41 or the second base material 51, the first is to form the transparent vapor deposition layer 81. Pretreatment is performed on the surface of the substrate 41 or the second substrate 51. The pretreatment can be performed by supplying plasma to the surface of the first substrate 41 or the second substrate 51 in a reduced pressure environment of 0.1 Pa or more and 100 Pa or less by a pretreatment apparatus. Plasma uses an inert gas such as argon alone or a mixed gas of oxygen, nitrogen, carbon dioxide and one or more of them as a plasma source gas, and the plasma source gas is excited by a potential difference due to a high-frequency voltage or the like. By doing so, it can be generated.

  By the pretreatment, the plasma can be confined in the vicinity of the surface of the first base material 41 or the second base material 51. Thereby, the shape of the surface of a base material, a chemical bonding state, and a functional group can be changed, and the chemical property of the surface of a base material can be changed. This makes it possible to improve the adhesion between the first base material 41 or the second base material 51 and the transparent vapor deposition layer 81 when forming the vapor deposition layer.

[Gas barrier coating film]
The barrier layer 80 may further include a gas barrier coating film 82. The gas barrier coating film 82 is provided on the surface of the transparent vapor deposition layer 81. The gas barrier coating film 82 is a coating film that functions as a layer that suppresses permeation of oxygen gas, water vapor, and the like. The gas barrier coating film 82 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, 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.), a polyvinyl alcohol-based resin, and / or Alternatively, it is obtained by a gas barrier composition containing 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.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one kind of a partial hydrolyzate of alkoxide and a condensate of hydrolysis of alkoxide can be used. Moreover, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which 1 or more was hydrolyzed, and its mixture may be sufficient. As the condensate of hydrolysis of alkoxide, a dimer or more of partially hydrolyzed alkoxide, specifically, a 2 to 6 mer 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. In the present embodiment, examples of preferable metals include silicon and titanium. In the present invention, alkoxides may be used alone or in combination of two or more different metal atom alkoxides in the same solution.

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, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group, and the like. These alkyl groups in the same molecule may be the same or different.

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

(Effect of this embodiment)
In the present embodiment, the laminate 30 includes a barrier layer 80 provided on at least one of the first base material 41 and the second base material 51. For this reason, the gas barrier property of the bag 10 comprised from the laminated body 30 can be improved.

(Laminated body according to the fourth embodiment)
In the second embodiment, the layered structure 30 includes the layer configuration including the light-shielding print layer 42, and in the third embodiment, the stacked body 30 includes the barrier configuration including the barrier layer 80. It is also possible to apply in combination. FIG. 10 is a cross-sectional view illustrating an example of the stacked body 30 according to the fourth embodiment. The laminated body 30 by 4th Embodiment is the 1st base material / barrier layer / light-shielding printing layer / first adhesive layer / second base material / second adhesive layer / sealant layer in order from the outer surface side to the inner surface side. It can be said that it has. Note that “/” represents a boundary between layers. Although not shown, the above-mentioned pattern printing layer may be provided between the barrier layer and the light-shielding printing layer.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

  First, according to Examples 1 to 4 and Comparative Examples 1 and 2, the puncture strength, total light transmittance, and odor barrier property of the laminate 30 in the present invention were evaluated.

Example 1
A film-like first base material 41 including a plurality of layers 41a described in the first configuration and manufactured by a casting method was prepared. The content of PBT in each layer 41a was 80%, the number of layers 41a was 1024, and the thickness of the first base material 41 was 15 μm. Then, the pattern printing layer 43 was formed on the film-form 1st base material 41 using the finart made from DIC graphics. Subsequently, a light shielding printing layer 42 was formed on the pattern printing layer 43. The light-shielding print layer 42 includes a white solid layer and an ash solid layer that are sequentially laminated on the pattern print layer 43.

The white solid layer was formed by printing solid white ink twice on the substrate by gravure printing. The first white solid layer was formed by solid printing white ink (manufactured by Toyo Ink, product name “Fine Star 681AT”) on the pattern printing layer 43. The second white solid layer was formed by solid printing white ink (manufactured by Toyo Ink Co., Ltd., product name “NKFS R69K”) on the first white solid layer. The thickness of the first white solid layer was 1 μm, and the thickness of the second white solid layer was 1.5 μm. For the formation of the white solid layer, a plate cylinder having a plate depth of 28 μm and a plate cylinder line number of 175 was used.
The gray solid layer is a gray ink in which white ink (manufactured by Toyo Ink, product name “R631AT”) and black ink (manufactured by Toyo Ink, product name “N800LPGT Sumi”) are blended at a blending ratio of 6: 4. It was formed by solid printing once on the white solid layer. For forming the solid ash layer, a plate cylinder having a plate depth of 22 μm and a plate cylinder line number of 175 was used. The thickness of the ash solid layer was 1.5 μm.

  Moreover, the film-like 2nd film 50 containing the 2nd base material 51 was prepared. As the 2nd base material 51, what contains 100 mass% PET was used. The thickness of the second substrate 51 was 12 μm.

  A film-like third film 60 including the sealant layer 61 was prepared. As the sealant layer 61, an unstretched polypropylene film ZK207 manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the sealant layer 61 was 60 μm.

  Next, the first film 40 and the second film 50 were laminated by the dry laminating method through the first adhesive layer 45. As the first adhesive layer 45, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used. RU-40 contains a polyester polyol. H-4 contains an aliphatic isocyanate compound. The thickness of the first adhesive layer 45 was 3 μm.

  Next, the laminated body of the 1st film 40 and the 2nd film 50, and the 3rd film 60 were laminated | stacked by the dry lamination method, and the laminated body 30 was obtained. As the second adhesive layer 55, similarly to the first adhesive layer 45, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used. The thickness of the second adhesive layer 55 was 3 μm.

  Subsequently, the piercing strength of the laminate 30 was measured in accordance with JIS Z1707 7.4. As a measuring device, Tensilon universal material testing machine RTC-1310 manufactured by A & D was used. Specifically, as shown in FIG. 5, a semicircular needle 70 having a diameter of 1.0 mm and a tip shape radius of 0.5 mm from the outer surface 30y side with respect to the test piece of the laminated body 30 in a fixed state. Was stabbed at a speed of 50 mm / min (50 mm per minute), and the maximum value of the stress until the needle 70 penetrated the laminate 30 was measured. About five or more test pieces, the maximum value of stress was measured, and the average value was defined as the piercing strength of the laminate 30. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. As a result, the piercing strength was 17N.

  Subsequently, the light shielding property of the laminate 30 was evaluated. Specifically, the total light transmittance of the laminate 30 when light was incident from the outer surface 30y of the laminate 30 was measured. A haze meter HM-150, which is a total light transmittance measuring device manufactured by Murakami Color Research Laboratory Co., Ltd., was used as a measuring instrument. As a result, the total light transmittance was 9%.

  Subsequently, the bad odor barrier property of the laminate 30 was evaluated. Specifically, the inner surfaces 30x of the two laminates 30 were sealed to form a bag, the bag was heated, the bag was then opened, and whether or not a strange odor was felt was evaluated. The dimensions of the two laminates 30 were 100 mm in length and 100 mm in width, respectively. The shape of the bag was a four-side sealed bag. The bag was heated for 1 minute using an oven controlled at 40 ° C. As a result, no nasty smell was felt.

(Example 2)
As the first base material 41 of the first film 40, the PBT containing 100% by mass described in the second configuration is included, the melting point of the PBT is 224 ° C., the IV value is 1.26 dl / g, and the tubular A laminate 30 was produced in the same manner as in Example 1 except that the single-layer film produced by the method was used. The first substrate 41 was a single layer film composed only of PBT and additives, and the thickness of the first substrate 41 was 15 μm.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example 1. As a result, the total light transmittance was 9%. Further, the odor barrier property of the laminate 30 was evaluated in the same manner as in Example 1. As a result, no nasty smell was felt.

(Example 3)
Example 1 except that PBT constituting the first base material 41 of Example 1 was used as the second base material 51 and PET constituting the second base material 51 of Example 1 was used as the first base material 41 The laminated body 30 was produced like the case of 1. FIG.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example 1. As a result, the total light transmittance was 9%. Further, the odor barrier property of the laminate 30 was evaluated in the same manner as in Example 1. As a result, no nasty smell was felt.

Example 4
Example except that PBT constituting the first base material 41 of Example 2 was used as the second base material 51 and PET constituting the second base material 51 of Example 2 was used as the first base material 41 The laminated body 30 was produced like the case of 1. FIG.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example 1. As a result, the total light transmittance was 9%. Further, the odor barrier property of the laminate 30 was evaluated in the same manner as in Example 1. As a result, no nasty smell was felt.

(Comparative Example 1)
The laminated body 30 was produced like the case of Example 1 except having used the base material containing 100 mass% PET as the 1st base material 41 of the 1st film 40. FIG. The thickness of the first base material 41 was 12 μm.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 12N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example 1. As a result, the total light transmittance was 10%. Further, the odor barrier property of the laminate 30 was evaluated in the same manner as in Example 1. As a result, no nasty smell was felt.

(Comparative Example 2)
The laminated body 30 was produced like the case of the comparative example 1 except having used the 15-micrometer-thick nylon film (Konjin Holdings Co., Ltd. Bonile W) as the 2nd base material 51 of the 2nd film 50. .

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 17N. Further, the total light transmittance of the laminate 30 was measured in the same manner as in Example 1. As a result, the total light transmittance was 10%. Further, the odor barrier property of the laminate 30 was evaluated in the same manner as in Example 1. As a result, a nasty smell was felt.

  The layer structure and evaluation result of the laminated body of Examples 1-4 and Comparative Examples 1 and 2 are collectively shown in FIG. In FIG. 6, in the “layer configuration” column, the components of the laminate excluding the adhesive layer are described from the top in order from the outer surface side layer. As can be seen from the comparison between Examples 1 to 4 and Comparative Example 1, when the first base material 41 or the second base material 51 contains PBT, both the first base material 41 and the second base material 51 are made of PET. Compared to the case of inclusion, a high piercing strength could be realized. Moreover, as can be seen from the comparison between Examples 1 to 4 and Comparative Example 2, the second substrate 51 contains nylon by using a material other than nylon, specifically PBT or PET, as the second substrate 51. Compared to the case, it was possible to achieve better light-shielding properties and odor barrier properties.

  Next, according to Examples 5 to 8 and Comparative Examples 3 and 4, the puncture strength and color resistance of the laminate 30 in the present invention were evaluated.

(Example 5)
A laminate 30 was produced in the same manner as in Example 1 except that the light-shielding print layer 42 and the pattern print layer 43 were not provided.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 17N.

  Subsequently, the coloring resistance of the laminate 30 was evaluated. Specifically, the inner surfaces 30x of the two laminates 30 were sealed to produce a bag containing a commercially available curry as the contents. Subsequently, after the bag was retorted, the bag was opened, and it was visually evaluated whether or not the laminate 30 constituting the bag was colored. The dimensions of the two laminates 30 were 100 mm in length and 100 mm in width, respectively. The shape of the bag was a four-side sealed bag. The bag was retorted by a hot water method at 121 ° C. for 30 minutes. As a result, coloring was not observed.

(Example 6)
As the first base material 41 of the first film 40, the PBT containing 100% by mass described in the second configuration is included, the melting point of the PBT is 224 ° C., the IV value is 1.26 dl / g, and the tubular A laminate 30 was produced in the same manner as in Example 5 except that the single-layer film produced by the method was used. The first substrate 41 was a single layer film composed only of PBT and additives, and the thickness of the first substrate 41 was 15 μm.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 17N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example 5. As a result, coloring was not observed.

(Example 7)
Example except that PBT constituting the first base material 41 of Example 5 was used as the second base material 51 and PET constituting the second base material 51 of Example 5 was used as the first base material 41 The laminated body 30 was produced like the case of 5. FIG.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 16N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example 5. As a result, coloring was not observed.

(Example 8)
Example except that PBT constituting the first base material 41 of Example 6 was used as the second base material 51 and PET constituting the second base material 51 of Example 6 was used as the first base material 41 The laminated body 30 was produced like the case of 5. FIG.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 1. As a result, the piercing strength was 16N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example 5. As a result, coloring was not observed.

(Comparative Example 3)
The laminated body 30 was produced like the case of Example 5 except having used the base material containing 100 mass% PET as the 1st base material 41 of the 1st film 40. FIG. The thickness of the first base material 41 was 12 μm.

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 5. As a result, the puncture strength was 11N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example 5. As a result, coloring was not observed.

(Comparative Example 4)
The laminated body 30 was produced like the case of the comparative example 3 except having used the 15-micrometer-thick nylon film (Konjin Holdings Co., Ltd. Bonile W) as the 2nd base material 51 of the 2nd film 50. .

  Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example 5. As a result, the piercing strength was 17N. Further, the coloration resistance of the laminate 30 was evaluated in the same manner as in Example 5. As a result, coloring was observed.

  The layer structures and evaluation results of the laminates of Examples 5 to 8 and Comparative Examples 3 and 4 are collectively shown in FIG. In FIG. 11, in the “layer configuration” column, the components of the laminate excluding the adhesive layer are described from the top in order from the outer surface side layer. As can be seen from the comparison between Examples 5 to 8 and Comparative Example 3, when the first base material 41 or the second base material 51 contains PBT, both the first base material 41 and the second base material 51 are made of PET. Compared to the case of inclusion, a high piercing strength could be realized. Moreover, as can be seen from the comparison between Examples 5 to 8 and Comparative Example 4, by using a material other than nylon, specifically, PBT or PET as the second base material 51, the second base material 51 contains nylon. Compared to the case, it was possible to realize better coloring resistance.

DESCRIPTION OF SYMBOLS 10 Bag 11 Upper part 12 Lower part 12a Lower seal part 13 Side part 13a Side part seal part 14 Surface film 15 Back surface film 16 Lower film 17 Storage part 25 Easy-opening means 26 Notch 27 Opening scheduled part 30 Laminate body 40 First film 41 1st base material 41a layer 42 light-shielding print layer 43 picture print layer 45 1st adhesive layer 50 2nd film 51 2nd base material 55 2nd adhesive layer 60 3rd film 61 sealant layer 80 barrier layer 81 transparent vapor deposition layer 82 Gas barrier coating film

Claims (20)

A laminate,
Comprising at least a first substrate, a second substrate and a sealant layer in this order;
The second base material includes 51% by mass or more of polyethylene terephthalate or 51% by mass or more of polybutylene terephthalate,
When the second substrate contains 51% by mass or more of polyethylene terephthalate, the first substrate contains 51% by mass or more of polybutylene terephthalate.   The laminated body of Claim 1 whose piercing strength of the said laminated body is 13 N or more.   The laminated body according to claim 1 or 2, wherein a base material containing 51% by mass or more of polybutylene terephthalate among the first base material and the second base material has a multilayer structure part including 10 layers or more.   Of the first base material and the second base material, a base material containing 51% by mass or more of polybutylene terephthalate has a single layer structure having an IV value of 1.10 dl / g or more and 1.35 dl / g or less. The laminate according to any one of claims 1 to 3. The first base material contains 51% by mass or more of polybutylene terephthalate,
The laminate according to any one of claims 1 to 4, wherein the second base material contains 51% by mass or more of polyethylene terephthalate. The first base material includes 51% by mass or more of polyethylene terephthalate,
The laminate according to any one of claims 1 to 4, wherein the second base material contains 51% by mass or more of polybutylene terephthalate.   The laminate according to any one of claims 1 to 6, wherein the sealant layer includes polypropylene.   The laminate according to any one of claims 1 to 7, wherein the content of propylene in the sealant layer is 90% by mass or more.   The laminate according to any one of claims 1 to 8, wherein the sealant layer contains polyethylene having a melting point of 100 ° C or higher.   The laminated body as described in any one of Claims 1 thru | or 9 further provided with the light-shielding printing layer located between a said 1st base material and a said 2nd base material.   The laminate according to claim 10, wherein the thickness of the light-shielding print layer is 2 μm or more.   The laminate according to claim 10 or 11, wherein the light-shielding print layer contains a chromatic ink.   The laminate according to claim 10 or 11, wherein the light-shielding print layer contains an achromatic ink.   The laminated body as described in any one of Claims 10 thru | or 13 further provided with the pattern printed layer located in the outer surface side of the said laminated body rather than the said light-shielding printed layer.   The laminated body as described in any one of Claims 10 thru | or 14 whose total light transmittance of the said laminated body is 20% or less.   A barrier layer including at least a transparent vapor deposition layer provided between at least one of the first base material and the second base material between the first base material and the second base material; The laminated body as described in any one of Claims 1 thru | or 15. The transparent vapor deposition layer contains aluminum oxide,
A covalent bond between an aluminum atom and a carbon atom is formed at the interface between at least one of the first substrate and the second substrate provided with the transparent deposition layer and the transparent deposition layer. The laminate according to claim 16.   The laminate according to claim 16 or 17, wherein the barrier layer further comprises a gas barrier coating film provided on the surface of the transparent vapor deposition layer. A bag,
A laminate comprising an outer surface and an inner surface;
A seal portion that joins the inner surfaces of the laminate, and
The laminate includes at least a first base material, a second base material, and a sealant layer in this order from the outer surface side to the inner surface side,
The second base material includes 51% by mass or more of polyethylene terephthalate or 51% by mass or more of polybutylene terephthalate,
When the second substrate contains 51% by mass or more of polyethylene terephthalate, the first substrate contains 51% by mass or more of polybutylene terephthalate.   The bag according to claim 19, wherein the laminated body further includes a light-shielding print layer positioned between the first base material and the second base material.