WO2018181405A1 - Laminate, and bag composed of said laminate - Google Patents

Abstract

Provided is a laminate having penetration resistance and sliding properties. A laminate including an outer surface and an inner surface is provided with: a substrate constituting the outer layer of the laminate and having a plastic film that includes 51% by mass or more of polybutylene terephthalate; and a sealant layer constituting the inner surface of the laminate. The layer of the substrate that constitutes the outer surface of the laminate includes polyethylene terephthalate or polybutylene terephthalate.

Description

Laminated body and bag composed of the laminated body

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

A bag made of a flexible packaging material is used as a bag for containing fluid contents such as liquid and powder. A bag has a main-body part in which the contents are accommodated, and a spout part connected to the main-body part and through which liquid passes when the contents are poured out of the bag. The shapes of the main body part and the spout part are defined by a seal part formed by heat-sealing the flexible packaging material.

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

Japanese Patent Laid-Open No. 10-218204

In the bag manufacturing process, the inner surfaces of the laminate are heat sealed so that a part of the outer edge of the bag remains as an opening. Next, the bag is filled with the contents through the opening. Thereafter, the opening is sealed by heat sealing. In this way, a bag containing the contents can be obtained. The manufacturing process of such a bag may include a process in which a frictional force is generated on the outer surface of the bag. For example, there are a step of pulling out a single bag from a plurality of stacked bags, a step of sliding a bag containing the contents on a conveyance path, and the like. In order to carry out these steps efficiently, it is preferable that the friction coefficient of the outer surface of the bag is small.

By the way, nylon is hygroscopic. For this reason, when the outer surface of a laminated body, ie, the outer surface of a bag, is comprised with nylon, the friction coefficient of the outer surface of a bag will increase because nylon absorbs the water | moisture content etc. of ambient atmosphere. As a result, it is considered that the frictional force generated on the outer surface of the bag is increased, causing a problem in part of the bag manufacturing process.

The present invention aims to provide a laminate that can effectively solve such problems.

The present invention is a laminate including an outer surface and an inner surface, the laminate having a plastic film containing 51% by mass or more of polybutylene terephthalate, and constituting the outer surface of the laminate, and the inner surface of the laminate The layer which comprises the said outer surface of the said laminated body among the said base materials is a laminated body containing a polyethylene terephthalate or a polybutylene terephthalate.

In the laminate according to the present invention, two laminates are prepared and measured after being stored for 48 hours in a high-temperature thermostatic chamber at a temperature of 40 ° C. and a humidity of 90%, and the other of the outer surfaces of the laminate is measured on the other side. 0.24 or less may be sufficient as the static friction coefficient with respect to the outer surface of a laminated body, and a dynamic friction coefficient.

In the laminate according to the present invention, two of the laminates are prepared and measured after storage for at least 24 hours in an environment of a temperature of 20 to 30 ° C. and a humidity of 40 to 60%. The static friction coefficient and the dynamic friction coefficient with respect to the outer surface of the other laminate are referred to as a normal temperature static friction coefficient and a normal temperature dynamic friction coefficient, and after measuring the normal temperature static friction coefficient and the normal temperature dynamic friction coefficient, the two laminates are heated at a high temperature of 40 ° C. and a humidity of 90%. When the static friction coefficient and dynamic friction coefficient of the outer surface of one of the laminates measured after storage for 48 hours in a thermostatic bath with respect to the outer surface of the other laminate are referred to as high temperature high humidity static friction coefficients and high temperature high humidity dynamic friction coefficients The value obtained by subtracting the normal temperature static friction coefficient from the high temperature high humidity static friction coefficient is 0.03 or less, and is the high temperature high humidity dynamic friction coefficient? The value obtained by subtracting the normal temperature coefficient of dynamic friction may be 0.03 or less.

In the laminate according to the present invention, the plastic film containing 51% by mass or more of polybutylene terephthalate may have a multilayer structure including 10 layers or more.

In the laminate according to the present invention, the plastic film containing 51% by mass or more of polybutylene terephthalate has a single layer structure, and the polybutylene terephthalate has an IV value of 1.10 dl / g or more and 1.35 dl / g. It may be the following.

In the laminate according to the present invention, the base material may have only one plastic film containing 51% by mass or more of polybutylene terephthalate, and the sealant layer may contain linear low density polyethylene. The piercing strength of the laminate is preferably 12N or more. The laminated body may further include a vapor deposition layer located on the surface of the base material. The laminated body may further include a gas barrier coating film positioned on the vapor deposition layer.

The laminate according to the present invention comprises at least a first base material constituting the outer surface, a second base material, and a sealant layer constituting the inner surface in this order from the outer surface side to the inner surface side.
The first base material includes 51% by mass or more of polyethylene terephthalate or 51% by mass or more of polybutylene terephthalate, and when the first base material includes 51% by mass or more of polyethylene terephthalate, the second base material is It may contain 51% by mass or more of polybutylene terephthalate. The laminated body may further include a vapor deposition layer positioned at least between the first base material and the second base material or between the second base material and the sealant layer. The laminated body may further include a gas barrier coating film positioned on the vapor deposition layer. The laminate may further include a printed layer positioned between the first base material and the second base material. The sealant layer may contain linear low density polyethylene. The piercing strength of the laminate is preferably 13N or more. The first base material may include polybutylene terephthalate, and the second base material may include polyethylene terephthalate. Alternatively, the first base material may include polyethylene terephthalate, and the second base material may include polybutylene terephthalate.

The present invention is a bag having a main body part and a spout part connected to the main body part, the bag comprising the above-mentioned laminated body and a seal part for joining the inner surfaces of the laminated body.

According to the present invention, a laminate having puncture resistance and slipperiness can be provided.

It is a front view which shows the bag in the 1st Embodiment of this invention. It is sectional drawing which shows an example of the laminated constitution of the laminated body in 1st Embodiment. It is sectional drawing which shows the other example of the layer structure of the laminated body in 1st Embodiment. 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 result of having analyzed the transparent vapor deposition layer formed into a film on the base material with a time-of-flight type secondary ion mass spectrometer. It is sectional drawing which shows an example of the laminated constitution of the laminated body in 2nd Embodiment. It is sectional drawing which shows the other example of the layer structure of the laminated body in 2nd Embodiment. It is a figure which shows an example of the measuring method of piercing strength. It is a figure which shows the measurement result of the friction coefficient of Example A1, A2 and Comparative Example A1. It is a figure which shows the layer structure and evaluation result of Example A1, A2 and Comparative Example A1. FIG. 6 is a front view showing a bag produced in Examples B1 to B7. It is a figure which shows the result of the normal temperature drop evaluation of Example B1-B7 and the low temperature drop evaluation at the time of using the bag of the 1st capacity | capacitance. It is a figure which shows the result of normal temperature drop evaluation and low temperature drop evaluation of Examples B1 to B7 when a second capacity bag is used. It is a figure which shows the measurement result of the friction coefficient of Examples D1-D3 and Comparative Example D1. It is a figure which shows the layer structure and evaluation result of Example D1-D3 and Comparative Example D1. It is a figure which shows the result of the normal temperature drop evaluation of Examples E1-E7 and a low temperature drop evaluation at the time of using the bag of 1st capacity | capacitance. It is a figure which shows the result of normal temperature drop evaluation and low temperature drop evaluation of Examples E1 to E7 when a second capacity bag is used.

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.

Bag FIG. 1 is a front view showing a bag 10 according to the present embodiment. The bag 10 is configured to accommodate fluid contents such as liquid and powder refilled into a bottle. In addition, in FIG. 1, the bag 10 of the state (state in which the content is not accommodated) before being filled with the content is shown. Various liquids such as liquid detergents and shampoos can be considered as liquids stored in the bag 10.

In the present embodiment, the bag 10 is a gusset type bag configured to be independent. 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 main body portion 17 in which contents are accommodated, and a spout portion 20 connected to the main body portion 17. The spout portion 20 is a portion through which the liquid passes when the contents are taken out from the bag 10. The width of the spout portion 20 is narrower than the width of the main body portion 17. For this reason, the user can determine the pouring direction of the content poured out from the bag 10 through the pouring port 20 with high accuracy.

Hereinafter, a specific configuration of the bag 10 including the main body portion 17 and the spout portion 20 will be described. 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.

The inner surfaces of the front film 14, the back film 15, and the lower film 16 are joined together by a seal portion. In the 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 extending along the outer edge of the bag 10. The outer edge seal portion includes a lower seal portion 12 a extending in the lower portion 12 and a pair of side seal portions 13 a extending along the pair of side portions 13. The seal portion includes a spout seal portion 20 a that defines the spout portion 20. As shown in FIG. 1, when the spout part 20 is formed in the corner between the upper part 11 and the side part 13 of the bag 10, the spout seal part 20a is connected to the side seal part 13a. In the bag 10 in a state where the contents are not accommodated, 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 part 13a, the spout seal part 20a, and the upper seal part to be described later are seal parts configured by joining the inner surface of the surface film 14 and the inner surface of the back film 15. On the other hand, the lower seal portion 12a is formed by bonding the inner surface of the surface film 14 and the inner surface of the lower film 16, and by bonding the inner surface of the back film 15 and the inner surface of the lower film 16. Including a configured seal.

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

Easy-opening means The surface film 14 and the back film 15 may be provided with easy-opening means 25 for tearing the surface film 14 and the back film 15 to open the spout 20. For example, as shown in FIG. 1, the easy-opening means 25 may include a notch 26 that is formed in the spout seal 20 a of the spout 20 and serves as a starting point for tearing. Moreover, 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 spout 20 is torn.

Although not shown, the easy-opening means 25 may include notches and scars formed in the region where the spout seal portion 20a 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 FIGS. 2 and 3, the laminate 30 includes a first film 40, a sealant film 70, and an adhesive layer 45 that joins the first film 40 and the sealant film 70. The first film 40 is located on the outer surface 30y side, and the sealant film 70 is located on the inner surface 30x side opposite to the outer surface 30y. The inner surface 30x is a surface located on the content side. The first film 40 includes at least a base material 41 constituting the outer surface 30y. The sealant film 70 includes at least a sealant layer 71. As shown in FIG. 2, the first film 40 may further include a printed layer 38 positioned between the base material 41 and the sealant layer 71. It can be said that the laminate 30 shown in FIG. 2 includes a base material / printing layer / adhesive layer / sealant layer in order from the outer surface side to the inner surface side. Note that “/” represents a boundary between layers.

As shown in FIG. 3, the first film 40 may further include a gas barrier layer 35 positioned between the base material 41 and the printing layer 38. It can be said that the laminate 30 shown in FIG. 3 includes a base material / transparent gas barrier layer / printing layer / adhesive layer / sealant layer in order from the outer surface side to the inner surface side.

Hereinafter, each of the first film 40, the adhesive layer 45, and the sealant film 70 will be described in detail.

(First film)
Hereinafter, the substrate 41, the printing layer 38, and the gas barrier layer 35 of the first film 40 will be described.

〔Base material〕
The base material 41 has only one base material that forms the outer surface 30 y of the laminate 30. That is, the plastic film constituting the base material 41 is only one. As long as there is one plastic film constituting the base material 41 in the laminate 30, the plastic film constituting the base material 41 may be constituted by a single layer or by a plurality of layers. May be. When the plastic film which comprises the base material 41 contains several layers, the plastic film which comprises the base material 41 is a co-extrusion film produced by co-extrusion, for example.

The plastic film which is a layer constituting the outer surface 30y in the base material 41 includes polybutylene terephthalate (hereinafter also referred to as PBT) as a main component. For example, the plastic film constituting the base material 41 includes 51% by mass or more of PBT. Hereinafter, the advantage that the plastic film which comprises the base material 41 contains PBT is demonstrated.

PBT has excellent dimensional stability and therefore excellent printability. For this reason, as in the case of polyethylene terephthalate (hereinafter also referred to as PET), the printing layer 38 can be provided on the substrate 41 containing PBT.

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

Also, PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, it can suppress that the base material 41 absorbs a water | moisture content and the laminate strength of the laminated body 30 falls, and that the friction coefficient of the outer surface 30y of the 1st film 40 increases.

Hereinafter, the configuration of the base material 41 including PBT will be described in detail. As the configuration of the base material 41 including PBT in the present embodiment, any of the following first configuration or second configuration may be adopted.

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

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

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

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

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

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

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 structure of the first film. When the base material 41 is produced by casting the resin in multiple layers, as shown in FIG. 4, the base material 41 of the first film 40 is composed of a multilayer structure including a plurality of layers 41a. Each of the plurality of layers 41a may include 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 properties of the PBT film are improved by multilayering is estimated as follows. When the resins are laminated, even if the resin composition is the same, a layer interface exists, and crystallization is accelerated by the interface. On the other hand, the growth of large crystals beyond the layer thickness is suppressed. For this reason, it is considered that the size of the crystal (spherulite) becomes small.

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

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

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

TD 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 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, more preferably 100 nm or less, and further preferably 75 nm or less.
The thickness of the base material 41 is preferably 9 μm or more, and more preferably 12 μm or more. Moreover, the thickness of the base material 41 is preferably 25 μm or less, more preferably 20 μm or less. By setting the thickness of the base material 41 to 9 μm or more, the base material 41 has sufficient strength. Moreover, the base material 41 comes to show the moldability which was excellent by making the thickness of the base material 41 into 25 micrometers or less. For this reason, the process which processes the laminated body 30 containing the base material 41 and manufactures the bag 10 can be implemented efficiently.

As described above, when the base material 41 includes a multilayer structure including a plurality of layers 41a, a part of the plurality of layers 41a may include a polyester resin other than PBT as a main component. For example, the base material 41 may be configured by a plurality of layers 41a including PBT as a main component and a layer 41a including, for example, PET as a main component, which is positioned between two PBT layers 41a. That is, the base material 41 may be configured by alternately laminating layers 41a containing PBT as a main component and layers 41a containing PET as a main component, for example.

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

In order to impart mechanical strength to the 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 whole material constituting the base material 41. The IV value can be calculated based on JIS K 7367-5: 2000.

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

The base material 41 is a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a colorant, a crystallization inhibitor, a crystallization accelerator, if necessary. Etc. may be contained. The polyester resin pellets used as the raw material of the base material 41 have a moisture content of 0.05% by weight or less, preferably 0.01% by weight or less before heating and melting in order to avoid a decrease in viscosity due to hydrolysis during heating and melting. It is preferable to use after sufficiently pre-drying so that

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

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

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

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

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

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

(Print layer)
The printed layer 38 is a layer printed on the base material 41 in order to show product information or impart aesthetics to the bag 10. The print layer 38 expresses characters, numbers, symbols, figures, patterns, and the like. As a material constituting the printing layer 38, 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.

[Gas barrier layer]
The gas barrier layer 35 is formed on the surface on the inner surface 30x side of the base material 41 and includes at least a vapor deposition layer 36 made of an inorganic material. The gas barrier layer 35 may further include a gas barrier coating film 37 located on the surface on the inner surface 30 x side of the vapor deposition layer 36.

The vapor deposition layer 36 functions as a layer having a gas barrier function that prevents permeation of oxygen gas, water vapor, and the like. Two or more vapor deposition layers 36 may be provided. When two or more vapor deposition layers 36 are provided, each may have the same composition or a different composition. Examples of the method for forming the vapor deposition layer 36 include physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum vapor deposition, sputtering, and ion plating, or plasma chemical vapor deposition, thermal Examples thereof include chemical vapor deposition and chemical vapor deposition (chemical vapor deposition, CVD) such as photochemical vapor deposition.

In the present embodiment, the vapor deposition layer 36 is preferably formed of a transparent inorganic material such as aluminum oxide (aluminum oxide) or silicon oxide. Since the vapor deposition layer 36 has transparency, the user can visually recognize the printing layer 38 located on the inner surface 30x side from the vapor deposition layer 36 from the outer surface 30y side. As the vapor deposition layer 36, it is preferable to use an amorphous thin film of aluminum oxide. Specifically, the vapor deposition layer 36 is an amorphous thin film of aluminum oxide represented by the formula AlO _X (where X represents a number in the range of 0.5 to 1.5). As the vapor deposition layer 36, an amorphous thin film of aluminum oxide in which the value of X decreases in the depth direction from the film surface toward the inner surface can be used. The amorphous thin film of aluminum oxide is represented by the formula AlO _X (wherein X represents a number in the range of 0.5 to 1.5), and in the depth direction from the thin film surface toward the inner surface. It is preferable that the value of X is increasing. In addition, as a value of X in the above formula, a value of X = 0.5 or more can be basically used. However, when X is less than 1.0, coloring is intense and transparent. Since it is inferior in property, it is preferable to use the thing of X = 1.0 or more. Moreover, since the thing of X = 1.5 is a thing in which Al and oxygen were completely oxidized, the thing to X = 1.5 can be used as an upper limit. In addition, when the value of X in said formula is 0, it is a perfect inorganic simple substance (pure substance), and is not transparent.

In addition, the decreasing rate of the value of X is determined by using a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy: XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy: SIMS). This can be confirmed by performing an elemental analysis of the vapor deposition layer 36 using a method of analyzing by ion etching or the like.

<First Preferred Form of Transparent Deposition Layer>
Hereinafter, the 1st preferable form of the vapor deposition layer 36 is demonstrated. The vapor deposition layer 36 may be a layer made of a mixture of inorganic compounds containing a covalent bond between an aluminum atom and a carbon atom. In this case, the vapor deposition layer 36 is a covalent bond between an aluminum atom and a carbon atom at a peak measured by ion etching in the depth direction using an X-ray photoelectron spectrometer (measurement conditions: X-ray source AlKα, X-ray output 120 W). In addition, it may have a gas barrier property that is transparent and that 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 vapor deposition layer 36 and the substrate 41. For example, when the vapor deposition layer 36 contains aluminum oxide, a covalent bond between an aluminum atom and a carbon atom can be formed at the interface between the base material 41 and the vapor deposition layer 36. The covalent bond can be detected by measurement by X-ray photoelectron spectroscopy (hereinafter referred to as “XPS measurement” for short).

Moreover, in the vapor deposition layer 36, the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is the total bond including carbon atoms observed when the interface between the vapor deposition layer 36 and the substrate 41 is measured by XPS measurement. It is preferable that it is within the range of 0.3% or more and 30% or less. Thereby, the adhesiveness of the vapor deposition layer 36 and the base material 41 is strengthened, transparency is excellent, and the thing of the performance with a good balance as a gas barrier property vapor deposition film is obtained.

If the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is less than 0.3%, the adhesion of the vapor deposition layer 36 is not sufficiently improved, and it is difficult to stably maintain the barrier property.

Furthermore, the AL (aluminum) / O (oxygen) ratio of the vapor deposition layer 36 containing aluminum oxide as a main component is such that the vapor deposition layer 36 on the opposite side of the base material 41 from the interface between the base material 41 and the vapor deposition layer 36. In the range up to 3 nm toward the surface, it is preferably 1.0 or less.
If the AL / O ratio exceeds 1.0 within the range from the interface between the vapor deposition layer 36 and the base material 41 toward the surface of the vapor deposition layer 36 on the side opposite to the base material 41, the base material 41 and the vapor deposition layer Adhesiveness with 36 becomes insufficient, the proportion of aluminum increases, and the transparency of the vapor deposition layer 36 decreases.

The thickness of the vapor deposition layer 36 is, for example, 20 mm or more and 200 mm, preferably 30 mm or more and 150 mm. If it is less than 30 mm, the gas barrier property may be insufficient even when the gas barrier coating film 37 is used together. On the other hand, if it exceeds 150 mm, the gas barrier performance of the laminate 30 may not be maintained. The reason for this is not clear, but if the thickness of the vapor deposition layer 36 exceeds 150 mm, the flexibility of the laminated body 30 decreases, and when the laminated body 30 is used for the bag 10, a part of the vapor deposition layer 36 is cracked or pinholed. It is considered that gas barrier properties are reduced due to the occurrence of gas. The thickness of the vapor deposition layer 36 is preferably 40 mm or more and 130 mm or less, more preferably 50 mm or more and 120 mm or less. In addition, the thickness of the vapor deposition layer 36 can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (trade name: RIX2000 type, manufactured by Rigaku Corporation). As a means for changing the thickness of the vapor deposition layer 36, a method for changing the deposition rate of the vapor deposition layer 36, a method for changing the vapor deposition rate, or the like can be used.

When forming the vapor deposition layer 36 on the surface on the inner surface 30x side of the base material 41, the surface on the inner surface 30x side of the base material 41 may be subjected in advance to corona discharge treatment, flame treatment, plasma treatment, or the like. In particular, when a covalent bond of a metal atom and a carbon atom is formed at the interface between the vapor deposition layer 36 and the base material 41, a pretreatment is performed on the surface of the base material 41 on which the vapor deposition layer 36 is to be formed. Is preferred. When the pretreatment is plasma treatment, plasma is supplied to the surface with the base material 41 in a reduced pressure environment of 0.1 Pa or more and 100 Pa or less by the pretreatment apparatus. Plasma uses an inert gas such as argon alone or a mixed gas of oxygen, nitrogen, carbon dioxide and one or more of them as a plasma source gas, and the plasma source gas is excited by a potential difference due to a high-frequency voltage or the like. By doing so, it can be generated.

The plasma can be confined in the vicinity of the surface of the base material 41 by the pretreatment. Thereby, the shape of the surface of the base material 41, a chemical bonding state, and a functional group can be changed, and the chemical properties of the surface of the base material 41 can be changed. As a result, the adhesion between the base material 41 and the vapor deposition layer 36 can be improved.

<Second Preferred Form of Transparent Deposition Layer>
Next, the 2nd preferable form of the vapor deposition layer 36 is demonstrated. In addition, in this application, the vapor deposition layer 36 may satisfy | fill both the above-mentioned 1st preferable form and the 2nd preferable form demonstrated below, and may satisfy | fill only any one form. Moreover, the case where the vapor deposition layer 36 of this application does not satisfy | fill both of the above-mentioned 1st preferable form and the 2nd preferable form demonstrated below can also be considered.

In the vapor deposition layer 36, a transition region defining the adhesion strength between the base material 41 and the vapor deposition layer 36 such as an aluminum oxide vapor deposition film may be formed in the vapor deposition layer 36. When the vapor deposition layer 36 is an aluminum oxide vapor deposition film, the transition region is an aluminum hydroxide detected by etching the aluminum oxide vapor deposition film using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Includes a transforming bond structure (Al2O4H). The transition region transformation rate defined by the ratio of the transition region transformed using TOF-SIMS to the aluminum oxide vapor deposition membrane prescribed by etching using TOF-SIMS is preferably 45% or less. Such a form is based on the knowledge that by specifying the metamorphic rate of the transition region, the adhesion strength between the base material 41 and the aluminum oxide vapor-deposited film can be improved, and the laminate 30 having barrier properties can be specified. Is based.

The transition region metamorphic rate will be explained in detail. First, etching is performed from the outermost surface of the aluminum oxide vapor deposition film by Cs using a time-of-flight secondary ion mass spectrometer, and the element bond of the interface between the aluminum oxide vapor deposition film and the plastic substrate and the element bond of the vapor deposition film are performed. taking measurement. Subsequently, as shown in FIG. 5, respective measured graphs are obtained for the measured elements and element bonds.

To narrow the transition region of the interface of the plastic substrate and the vapor deposition film of aluminum hydroxide formed in the aluminum oxide deposited film as much as possible, paying attention to AL2O4H, 1) intensity H ₀ of the graph element C6 is halved position ( The position where the intensity (Intensity) becomes H ₁ in FIG. 5) is specified as the interface between the plastic substrate and the aluminum oxide deposition film (the position where the horizontal axis (Cycle) is T ₁ in FIG. 5). Further, the surface from the interface to the surface of the aluminum oxide vapor deposition film (the position where the horizontal axis (Cycle) is T ₀ in FIG. 5) is specified as the aluminum oxide vapor deposition film. Subsequently, 2) peak in the graph representing the element binding AL2O4H (horizontal axis shows 5 (Cycle) is asked to T ₂ of the position) is specified from the position of the peak to the position of the interface as a transition region. Subsequently, 3) (transition region from the peak of the element bond AL2O4H to the interface / aluminum oxide vapor deposition film) × 100 (%) is obtained to determine the conversion rate of the transition region into aluminum hydroxide. In the example shown in FIG. 5, the metamorphic rate is (W2 / W1) × 100 (%).

In forming the aluminum oxide vapor deposition film, it is preferable to perform plasma pretreatment on the surface of the plastic substrate 41 before the aluminum oxide vapor deposition step in order to obtain a preferable value for the transformation rate of the transition region of the aluminum oxide vapor deposition film. . In the plasma pretreatment, the mixing ratio of oxygen gas supplied as plasma gas and argon or helium is 5 to 1, preferably 2 to 1. By setting the mixing ratio to 5: 1, the film formation energy of vapor-deposited aluminum on the plastic substrate is increased, and by further setting 2: 1, the formation of aluminum hydroxide is formed in the vicinity of the interface of the substrate. That is, the transformation rate of the transition region is lowered.

As a vapor deposition method for forming a vapor deposition film, various vapor deposition methods can be applied among physical vapor deposition and chemical vapor deposition. The physical vapor deposition method can be selected from the group consisting of vapor deposition method, sputtering method, ion plating method, ion beam assist method, and cluster ion beam method. Chemical vapor deposition methods include plasma CVD method, plasma polymerization method, thermal method. It can be selected from the group consisting of CVD method and catalytic reaction type CVD method. In this embodiment, a physical vapor deposition method is preferred.

The thickness of the aluminum oxide vapor deposition film formed as described above is preferably 3 nm or more and 50 nm or less, and preferably 8 nm or more and 30 nm or less. If it is this range, it will be easy to hold | maintain barrier property.

[Gas barrier coating film]
The gas barrier coating film 37 is a layer that functions as a layer that suppresses permeation of oxygen gas, water vapor, and the like. The gas barrier coating film 37 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.) and a polyvinyl alcohol as described above And a transparent gas barrier composition that is polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. It is done.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one kind of a partial hydrolyzate of alkoxide and a condensate of hydrolysis of alkoxide can be used. Moreover, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which 1 or more was hydrolyzed, and its mixture may be sufficient. As the condensate of hydrolysis of alkoxide, a dimer or more of partially hydrolyzed alkoxide, specifically, a dimer to hexamer is used.

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , as the metal atom represented by M, silicon, zirconium, titanium, aluminum, and the like can be used. Examples of preferable metals include silicon and titanium. In the present invention, alkoxides may be used alone or in combination of two or more different metal atom alkoxides in the same solution.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others. In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group, and the like. These alkyl groups in the same molecule may be the same or different.

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

(Adhesive layer)
The adhesive layer 45 includes an adhesive for bonding the first film 40 and the sealant film 70. Examples of adhesives include ether-based two-component reactive adhesives and ester-based two-component reactive adhesives.

Examples of ether-based two-component reactive adhesives 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. Isocyanate compounds include aromatic isocyanate compounds such as tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and the like. Aliphatic isocyanate compounds, or adducts or multimers of the above-mentioned various isocyanate compounds can be used. Preferably, an aromatic isocyanate compound is used as the curing agent. Thereby, the lamination strength between the 1st film 40 and the sealant film 70 can be raised more compared with the case where an aliphatic isocyanate compound is 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.

For example, the adhesive layer 45 is applied to the first film 40 or the sealant film 70 after the adhesive composition is applied, and then the adhesive composition is dried, and the main agent and the solvent in the adhesive composition are reacted. The adhesive composition is formed by curing. The thickness of the adhesive layer 45 is preferably 1 μm or more, more preferably 2 μm or more.

(Sealant film)
The sealant film 70 includes at least a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30. As a material constituting the sealant layer 71, a resin such as polyethylene can be used.

For example, polyethylene is classified into low density polyethylene, medium density polyethylene, and high density polyethylene based on density. The low-density polyethylene, density of 0.910 g / cm ³ or more and 0.925 g / cm ³ or less of polyethylene. Medium density polyethylene is polyethylene having a density of 0.926 g / cm ³ or more and 0.940 g / cm ³ or less. The high density polyethylene is polyethylene having a density of 0.941 g / cm ³ or more and 0.965 g / cm ³ or less. Low density polyethylene is obtained, for example, by polymerizing ethylene at a high pressure of 1000 atm or more and less than 2000 atm. The medium density polyethylene and the high density polyethylene are obtained, for example, by polymerizing ethylene at a medium pressure or low pressure of 1 atm or more and less than 1000 atm. The medium density polyethylene and the high density polyethylene may partially contain a copolymer of ethylene and α-olefin.

Even when ethylene is polymerized at an intermediate pressure or a low pressure, when a copolymer of ethylene and α-olefin is contained, an intermediate density or low density polyethylene can be produced. Such polyethylene is referred to as linear low density polyethylene. The linear low density polyethylene is obtained by introducing a short chain branch by copolymerizing an α-olefin with a linear polymer obtained by polymerizing ethylene at a medium pressure or a low pressure. Examples of α-olefins include 1-butene (C ₄ ), 1-hexene (C ₆ ), 4-methylpentene (C ₆ ), 1-octene (C ₈ ) and the like. The density of the linear low density polyethylene is, for example, 0.915 g / cm ³ or more and 0.945 g / cm ³ or less.

As the polyethylene constituting the sealant layer 71, low density polyethylene, linear low density polyethylene, or the like can be used. Preferably, the sealant layer 71 includes linear low density polyethylene. Thereby, seal strength can be improved and the impact resistance of the bag 10 such as drop strength can be increased. The sealant layer 71 may further include a low density polyethylene in addition to the linear low density polyethylene. Thereby, the tearability of the laminated body 30 can be improved. When the sealant layer 71 includes both linear low density polyethylene and low density polyethylene, the content (% by weight) of the linear low density polyethylene is preferably larger than the content (% by weight) of the low density polyethylene. . The sealant layer 71 may be a single layer or a multilayer.

The thickness of the sealant layer 71 is preferably 80 μm or more, and more preferably 120 μm or more. The thickness of the sealant layer 71 is preferably 170 μm or less, and more preferably 150 μm or less.

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

The layer structure of the lower film 16 is arbitrary as long as it has an inner surface that can be joined to the inner surface of the front film 14 and the inner surface of the back film 15. For example, similar to the front film 14 and the back film 15, the above-described laminate 30 may be used as the lower film 16. Alternatively, a film having an inner surface constituted by a sealant layer and a configuration different from that of the laminate 30 may be used as the lower film 16. For example, since the tearing property is not required for the lower film 16, the content (% by weight) of the low density polyethylene in the sealant layer of the lower film 16 is the same as that of the low density polyethylene in the sealant layer 71 of the front film 14 and the back film 15. It may be smaller than the content (% by weight). Alternatively, the sealant layer of the lower film 16 may not include low density polyethylene. The thickness of the sealant layer of the lower film 16 is, for example, 60 μm or more, preferably 80 μm or more, more preferably 100 μm or more, and further preferably 110 μm or more.

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. Subsequently, the film-like base material 41 is produced by extruding a resin material by a melt extrusion method such as a cast method or a tubular method. Subsequently, an inorganic material such as aluminum oxide may be deposited on the film-like substrate 41 to form the deposited layer 36. Subsequently, a gas barrier coating film 37 may be formed by applying a transparent gas barrier composition on the vapor deposition layer 36. Thereafter, the printing layer 38 is formed on the base material 41 or the gas barrier coating film 37. Thus, the 1st film 40 provided with the base material 41 and the printing layer 38, or the base material 41, the gas barrier layer 35 containing the vapor deposition layer 36 and the gas barrier coating film 37, and the printing layer 38 are provided. The first film 40 can be obtained.

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

First, a sealant film 70 including the first film 40 and the sealant layer 71 described above is prepared. Subsequently, the first film 40 and the sealant film 70 are laminated via the adhesive layer 45 by a dry laminating method. Thereby, the laminated body 30 provided with the 1st film 40 and the sealant film 70 can be obtained.

In the dry laminating method, first, an adhesive composition is applied to one of two laminated films. Subsequently, the applied adhesive composition is dried to volatilize the solvent. Then, two films are laminated | stacked through the adhesive composition after drying. Subsequently, aging is performed for 24 hours or more in an environment of 20 ° C. or higher, for example, in a state where the two laminated films are wound up.

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 each film are heat-sealed to form seal portions such as a lower seal portion 12a, a side seal portion 13a, and a spout seal portion 20a. 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 plurality of stacked bags 10 are put into a filling device. In the filling apparatus, the bags 10 are pulled out one by one, and the bags 10 are transported to a place for filling the contents. Next, the contents are filled into the bag 10 through the opening 11 b of the upper portion 11. Thereafter, the upper part 11 is heat-sealed to form an upper seal part. Subsequently, the bag 10 in a state where the contents are accommodated is slid on a conveyance path having a metal surface, and the bag 10 is discharged from the filling device. 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 surface film 15 of the bag 10 contains the base material 41 which has PBT as a main component, there can exist the following effect.
First, PBT is excellent in printability. For this reason, as in the case of polyethylene terephthalate (hereinafter also referred to as PET), the printing layer 38 can be provided on the substrate 41 containing PBT.
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 12N or more, more preferably 15N or more, and still more preferably 16N or more. The method for measuring the piercing strength will be described in Example A1 described later.

Also, PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 41 containing PBT is arrange | positioned on the outer surface 30y of the laminated body 30, it suppresses that the base material 41 absorbs a water | moisture content and the friction coefficient of the outer surface of the bag 10 will increase. be able to. For example, there is a large difference between the coefficient of friction between the outer surfaces of the bag 10 when placed in a room temperature environment and the coefficient of friction between the outer surfaces of the bag 10 after placed in a high temperature and high humidity environment. It can be suppressed. Thereby, the above-mentioned extraction process and conveyance process of the bag 10 in a filling apparatus can be implemented efficiently. The coefficient of friction between the outer surfaces of the bag 10 when placed in an environment with a temperature of 20-30 ° C. and a humidity of 40-60% and after being stored for 48 hours in a high-temperature thermostatic chamber at a temperature of 40 ° C. and a humidity of 90% The difference from the coefficient of friction between the outer surfaces of the bag 10 is preferably 0.03 or less.

Further, in the present embodiment, when the laminate 30 includes the gas barrier layer 35, the first film 40 can be provided with a gas barrier property.

Moreover, according to this Embodiment, the sealant layer 71 of the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains polyethylene resins, such as a linear low density polyethylene. Thereby, seal strength can be improved and the impact resistance of the bag 10 such as drop strength can be increased.

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)
2 and 3 described above, an example in which the printing layer 38 is provided on the base material 41 is shown, but the present invention is not limited to this, and the printing layer 38 may not be provided on the base material 41. For example, the first film 40 may be made of the base material 41. Further, the first film 40 may be composed of a base material 41 and a gas barrier layer 35 provided on the base material 41.

Examples of the arrangement of each layer are listed below.
Arrangement Example 1: Substrate / Adhesive Layer / Sealant Layer Arrangement Example 2: Substrate / Printing Layer / Adhesive Layer / Sealant Layer Arrangement Example 3: Substrate / Transparent Gas Barrier Layer / Printing Layer / Adhesive Layer / Sealant Layer Arrangement Example 4: Substrate / transparent gas barrier layer / adhesive layer / sealant layer

Second Embodiment With reference to FIGS. 6 and 7, a second embodiment of the present invention will be described. In the above-described first embodiment, an example in which there is only one plastic film constituting the base material of the laminated body has been shown. In the present embodiment, an example in which two plastic films constituting the base material of the laminate are present will be described. In the present embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Moreover, when it is clear that the effect obtained in the first embodiment can be obtained in the present embodiment, the description thereof may be omitted.

FIG. 6 is a cross-sectional view illustrating an example of the layer configuration of the stacked body 30 in the second embodiment. Moreover, FIG. 7 is sectional drawing which shows the other example of the layer structure of the laminated body 30 in 2nd Embodiment. As shown in FIG.6 and FIG.7, the laminated body 30 contains the 1st film 50, the 2nd film 60, and the sealant film 70 at least in this order. The first film 50 is located on the outer surface 30y side, and the sealant film 70 is located on the inner surface 30x side opposite to the outer surface 30y.

The first film 50 includes at least a first base material 51. Moreover, the 1st film 50 may further contain the printing layer 38 located between the 1st base material 51 and the 2nd base material 61, as shown in FIG.6 and FIG.7. For example, the first film 50 may further include a printing layer 38 provided on the first base material 51. The second film 60 includes at least a second base material 61. Moreover, the 2nd film 60 may further be provided with the vapor deposition layer 36 provided in the 2nd base material 61, as shown in FIG.6 and FIG.7. In the example shown in FIG. 6, the vapor deposition layer 36 is provided on the outer surface 30 y side of the second base material 61. In the example shown in FIG. 7, the vapor deposition layer 36 is provided on the inner surface 30 x side of the second base material 61. The sealant film 70 includes at least a sealant layer 71.

The first film 50 and the second film 60 are joined by a first adhesive layer 55, and the second film 60 and the sealant film 70 are joined by a second adhesive layer 65. Therefore, the laminate 30 shown in FIG. 6 is sequentially from the outer surface side to the inner surface side.
First substrate / printing layer / first adhesive layer / deposition layer / second substrate / second adhesive layer / sealant layer,
It can be said that it has. Moreover, the laminated body 30 shown in FIG. 7 in order from the outer surface side to the inner surface side,
First substrate / printing layer / first adhesive layer / second substrate / deposition layer / second adhesive layer / sealant layer,
It can be said that it has. Thus, the vapor deposition layer 36 may be located between the 1st base material 51 and the 2nd base material 61, and may be located between the 2nd base material 61 and the sealant layer 71. . Note that “/” represents a boundary between layers.

Hereinafter, each of the first film 50, the first adhesive layer 55, the second film 60, the second adhesive layer 65, and the sealant film 70 will be described in detail.

(First film)
In the example shown in FIGS. 6 and 7, the first film 50 includes a first base 51 that constitutes the outer surface 30 y of the laminate 30, a printed layer 38 provided on the inner surface 30 x side of the first base 51, including. The 1st base material 51 contains polybutylene terephthalate as a main ingredient like base material 41 in the above-mentioned 1st embodiment. For example, the 1st base material 51 contains 51 mass% or more PBT. As the configuration of the first base material 51 including PBT, any of the first configuration and the second configuration described with respect to the base material 41 in the first embodiment described above may be adopted.

(First adhesive layer)
The first adhesive layer 55 includes a first adhesive for bonding the first film 50 and the second film 60. Examples of the first adhesive include an ether-based two-component reactive adhesive, an ester-based two-component reactive adhesive, and the like, as in the case of the adhesive layer 45 in the first embodiment described above. be able to.

(Second film)
The second film 60 includes a second substrate 61 and a vapor deposition layer 36 provided on the second substrate 61.

[Second base material]
The 2nd base material 61 contains PET as a main component. For example, the 2nd base material 61 contains 51 mass% or more of PET. When the second base material 61 contains PET, the hygroscopicity of the second base material 61 becomes lower than when the second base material 61 contains nylon. Thereby, it can suppress that the 2nd base material 61 expand | swells due to the water | moisture content contained in the content, or the characteristic of the 2nd base material 61 falls. When the main component of the 2nd base material 61 is PET, 95 mass% or more of content of PET in the 2nd base material 61 may be sufficient.

The thickness of the second substrate 61 is preferably 9 μm or more, more preferably 12 μm or more. Moreover, the thickness of the 2nd base material 61 becomes like this. Preferably it is 25 micrometers or less, More preferably, it is 20 micrometers or less. By setting the thickness of the second substrate 61 to 9 μm or more, the second substrate 61 has sufficient strength. Moreover, the 2nd base material 61 comes to show the outstanding moldability by the thickness of the 2nd base material 61 being 25 micrometers or less. For this reason, the process which processes the laminated body 30 and manufactures the bag 10 can be implemented efficiently.

[Deposition layer]
The vapor deposition layer 36 is a layer provided on the stacked body 30 in order to improve the gas barrier property of the stacked body 30. The vapor deposition layer 36 may be formed of an inorganic material having transparency, such as aluminum oxide (aluminum oxide) and silicon oxide, as in the case of the first embodiment. In this case, a gas barrier coating film may be provided on the vapor deposition layer 36 as in the case of the first embodiment. 6 and 7, when the vapor deposition layer 36 is located on the inner surface 30x side of the printing layer 38, the vapor deposition layer 36 may be formed of an inorganic material that does not have transparency. For example, a metal such as aluminum may be used as a material constituting the vapor deposition layer 36.

(Second adhesive layer)
The second adhesive layer 65 includes a second adhesive for bonding the second film 60 and the sealant film 70. Examples of the second adhesive include ether-based two-component reaction type adhesives. Examples of the ether-based two-component reaction type adhesive include polyurethane as in the case of the first adhesive layer 55. 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 the curing agent, it is preferable to use an aromatic isocyanate compound as in the case of the first adhesive layer 55.

The second adhesive layer 65 is formed by, for example, applying the adhesive composition to the second film 60 or the sealant film 70, and then drying the adhesive composition. Also, the main agent and the solvent in the adhesive composition are removed. It is formed by reacting and curing the adhesive composition. The thickness of the second adhesive layer 65 is preferably 1 μm or more, more preferably 2 μm or more.

(Sealant film)
The sealant film 70 includes at least a sealant layer 71 that constitutes the inner surface 30 x of the laminate 30. As a material constituting the sealant layer 71, a resin such as polyethylene can be used as in the case of the first embodiment described above.

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

First, the first film 50 and the second film 60 described above are prepared. Subsequently, the first film 50 and the second film 60 are laminated via the first adhesive layer 55 by a dry laminating method. Thereafter, the laminate including the first film 50 and the second film 60 and the sealant film 70 are laminated via the second adhesive layer 65 by a dry laminating method. Thereby, the laminated body 30 provided with the 1st film 50, the 2nd film 60, and the sealant film 70 can be obtained.

Alternatively, first, the second film 60 and the sealant film 70 are laminated by the dry laminating method through the second adhesive layer 65, and then the first film 50, and the laminate including the second film 60 and the sealant film 70, The laminated body 30 may be manufactured by laminating the layers by the dry laminating method through the first adhesive layer 55.

In the dry laminating method, first, an adhesive composition is applied to one of two laminated films. Subsequently, the applied adhesive composition is dried to volatilize the solvent. Then, two films are laminated | stacked through the adhesive composition after drying. Subsequently, aging is performed for 24 hours or more in an environment of 20 ° C. or higher, for example, in a state where the two laminated films are wound up.

Hereinafter, effects produced by the laminate 30 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 51 which has PBT as a main component, there can exist the following effect.
First, PBT is excellent in printability. For this reason, the printing layer 38 can be provided on the 1st base material 51 containing PBT similarly to the case of a polyethylene terephthalate (henceforth PET).
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.

Also, PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the 1st substrate 51 containing PBT is arranged on outer surface 30y of layered product 30, the 1st substrate 51 will absorb moisture and the coefficient of friction of the outer surface of bag 10 will increase. This can be suppressed. For example, there is a large difference between the coefficient of friction between the outer surfaces of the bag 10 when placed in a room temperature environment and the coefficient of friction between the outer surfaces of the bag 10 after placed in a high temperature and high humidity environment. It can be suppressed. Thereby, the above-mentioned extraction process and conveyance process of the bag 10 in a filling apparatus can be implemented efficiently. The coefficient of friction between the outer surfaces of the bag 10 when placed in an environment with a temperature of 20-30 ° C. and a humidity of 40-60% and after being stored for 48 hours in a high-temperature thermostatic chamber at a temperature of 40 ° C. and a humidity of 90% The difference from the coefficient of friction between the outer surfaces of the bag 10 is preferably 0.03 or less.

In the present embodiment, the second film 60 can be provided with a gas barrier property by providing the second substrate 61 with the vapor deposition layer 36.

Moreover, according to this Embodiment, the sealant layer 71 of the laminated body 30 which comprises the surface film 14 and the back film 15 of the bag 10 contains polyethylene resins, such as a linear low density polyethylene. Thereby, seal strength can be improved and the impact resistance of the bag 10 such as drop strength can be increased.

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 51 contains 51 mass% or more of PBT, and the second base material 61 contains 51 mass% or more of PET, whereby the stab resistance and slipping property of the laminate 30. The example which raises is shown. However, the present invention is not limited to this, and the first substrate 51 includes 51% by mass or more of PET, and the second substrate 61 includes 51% by mass or more of PBT. May be. As PBT of the 2nd base material 61, PBT which concerns on the 1st structure demonstrated by the base material 41 in the above-mentioned 1st Embodiment, or PBT which concerns on a 2nd structure can be used.

The fact that the second base material 61 contains 51% by mass or more of PBT and the first base material 51 contains 51% by mass or more of PET contributes to the improvement of the dimensional stability, printability and slipperiness of the laminate 30. To do. For example, in the present modification, since the first base material 51 that is a layer constituting the outer surface 30y of the multilayer body 30 includes PET, the first base material 51 includes the PBT as in the case where the first base material 51 includes PBT. Slidability can be ensured.

Moreover, both the 1st base material 51 and the 2nd base material 61 may contain 51 mass% or more of PBT. As the PBT in this case, the PBT according to the first configuration or the PBT according to the second configuration described in the base member 41 in the above-described first embodiment can be used.

Table 1 summarizes examples of combinations of materials constituting the first base member 51 and the second base member 61. In Table 1, the notation “PBT” means that 51 mass% or more of PBT is contained in the resin constituting the film of the first base material 51 or the second base material 61. In Table 1, the expression “PET” means that 51% by mass or more of PET is contained in the resin constituting the film of the first base material 51 or the second base material 61.

Further, in the above-described embodiment, the example in which the printing layer 38 is provided on the inner surface 30x side of the first base material 51 is shown, but the present invention is not limited to this, and the outer surface 30y side of the second base material 61 is provided. Alternatively, the printing layer 38 may be provided on the inner surface 30x side.

In the above-described embodiment, the example in which the vapor deposition layer 36 is provided on the second base material 61 has been described. However, the present invention is not limited to this, and vapor deposition is performed on the inner surface 30x side of the first base material 51. A layer 36 may be provided. Further, the stacked body 30 may not include the vapor deposition layer 36.

Examples of the arrangement of each layer are listed below.
Arrangement example 1: first base material / first adhesive layer / deposition layer / second base material / second adhesive layer / sealant layer Arrangement example 2: first base material / printing layer / first adhesive layer / deposition Layer / second substrate / second adhesive layer / sealant layer Arrangement Example 3: First substrate / first adhesive layer / printing layer / deposition layer / second substrate / second adhesive layer / sealant layer Example 4: First substrate / first adhesive layer / deposition layer / second substrate / printing layer / second adhesive layer / sealant layer Arrangement Example 5: first substrate / first adhesive layer / second Base material / deposition layer / second adhesive layer / sealant layer arrangement example 6: first base material / printing layer / first adhesive layer / second base material / deposition layer / second adhesive layer / sealant layer arrangement example 7: First base material / first adhesive layer / printing layer / second base material / evaporation layer / second adhesive layer / sealant layer Arrangement Example 8: first base material / first adhesive layer / second group Material / deposition layer / printing layer / second adhesive layer / system -Land Layer Arrangement Example 9: First Substrate / Deposition Layer / First Adhesive Layer / Second Substrate / Second Adhesive Layer / Sealant Layer Arrangement Example 10: First Substrate / Deposition Layer / Printing Layer / First Adhesive layer / second base material / second adhesive layer / sealant layer Arrangement Example 11: first base material / deposition layer / first adhesive layer / printing layer / second base material / second adhesive layer / sealant Layer Arrangement Example 12: First Substrate / Vapor Deposition Layer / First Adhesive Layer / Second Substrate / Printing Layer / Second Adhesive Layer / Sealant Layer Arrangement Example 13: First Substrate / Vapor Deposition Layer / Gas Barrier Application Film / printing layer / first adhesive layer / second base material / second adhesive layer / sealant layer When the vapor deposition layer is arranged on the outer surface side of the print layer, the vapor deposition layer has transparency. It is a vapor deposition layer. The transparent vapor-deposited layer may satisfy both the first preferred form and the second preferred form described in the first embodiment, or may satisfy only one form, both. It is not necessary to satisfy the form. Further, a laminate in which the vapor deposition layer is deleted from each of the above arrangement examples 1 to 13 is also included in the example of the laminate 30 of the present embodiment.

(Bag variant)
In the first embodiment and the second embodiment described above, 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. Further, the bag 10 may not include the spout portion 20. For example, the bag 10 may be a gusseted bag that does not include the spout portion 20 and is configured to be self-supporting.

(Variation of bag application)
In the first embodiment and the second embodiment described above, an example is shown in which the bag 10 is a refill bag that contains a fluid content such as liquid or powder refilled into a bottle. However, the use of the bag 10 is not limited to the refill bag. For example, the user may use the contents stored in the bag 10 as they are without refilling them into bottles.

(Modified example of use of laminate)
In the first embodiment and the second embodiment described above, the example in which the laminate 30 is used as a packaging material that forms the front film 14 and the back film 15 of the bag 10 has been shown. However, the use of the laminated body 30 is not limited to the packaging material for constituting the bag. For example, the laminate 30 may be used as a label or sheet material that is not a sealed container such as a bag.

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.

Examples A1 to A2, B1 to B7, C1, and Comparative Example A1 described below are examples related to the case where there is only one plastic film constituting the base material of the laminate described in the first embodiment. It is. Examples D1 to D3, E1 to E7, F1, and Comparative Example D1 are examples related to the case where there are two plastic films constituting the base material of the laminated body described in the second embodiment. First, Examples A1 to A2, B1 to B7, C1, and Comparative Example A1 will be described.

Example A1
A film-like base material 41 including a plurality of layers 41a described in the first configuration and manufactured by a casting method was prepared. The content of PBT in each layer 41a was 80%, the number of layers 41a was 1024, and the thickness of the base material 41 was 15 μm. Subsequently, the print layer 38 was formed on the film-like base material 41 using a finart manufactured by DIC Graphics Corporation. The thickness of the printing layer 38 was 1 μm. Thus, the 1st film 40 containing the base material 41 and the printing layer 38 was produced.

In addition, a film-like sealant film 70 including the sealant layer 71 was prepared. As a material constituting the sealant layer 71, a mixture of the following three types of resins at the following weight% was used.
・ Linear low-density polyethylene (density: 0.918 g / cm ³ , MFR: 3.8) 63.5% by weight
・ Low-density polyethylene (density: 0.919 g / cm ³ , MFR: 2.0) 35.0% by weight
・ Slip agent masterbatch based on low density polyethylene (density: 0.921 g / cm ³ , MFR: 5.4) 1.5% by weight
MFR means melt flow rate. The thickness of the sealant layer 71 was 120 μm.

Next, the first film 40 and the sealant film 70 were laminated by the dry laminating method through the adhesive layer 45 to obtain the laminated body 30. As the adhesive layer 45, a material containing Takelac (registered trademark) A-310 manufactured by Mitsui Chemicals, Inc. as the main agent and Takenate (registered trademark) A-3 manufactured by Mitsui Chemicals, Inc. as the curing agent was used. A-310 contains a polyol. A-3 contains an aromatic isocyanate compound. The thickness of the adhesive layer 45 was 3 μm.

(Evaluation of piercing strength)
Subsequently, the piercing strength of the laminate 30 was measured in accordance with JIS Z1707 7.4. As a measuring instrument, Tensilon universal material testing machine RTC-1310 manufactured by A & D was used. Specifically, as shown in FIG. 8, a semicircular needle 80 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 pierced at a speed of 50 mm / min (50 mm per minute), and the maximum value of stress until the needle 80 penetrated the laminate 30 was measured. About five or more test pieces, the maximum value of stress was measured, and the average value was defined as the piercing strength of the laminate 30. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. As a result, the piercing strength was 15N.

(Evaluation of slipperiness)
Subsequently, the slipperiness of the outer surface 30y of the laminate 30 was evaluated. Here, the friction coefficient of the outer surface 30y of the laminate 30 was measured. Specifically, the static friction coefficient and the dynamic friction coefficient between the outer surface 30y of the laminate 30 and the metal surface, and the static friction coefficient and the dynamic friction coefficient between the outer surfaces 30y of the laminate 30 were measured. The measurement was performed according to JIS K-7125 using a friction measuring instrument TR-2 manufactured by Toyo Seiki Seisakusho. Aluminum was used as the metal constituting the metal surface.

Hereinafter, a specific measurement method will be described. In this example, the following first to fourth measurements were performed.

[First measurement of friction coefficient]
First, the laminate 30 was cut to prepare a test piece having a width of 70 mm and a length of 152 mm. Subsequently, after the test piece is stored in a room at a temperature of 20 to 30 ° C. and a humidity of 40 to 60% for at least 24 hours, the test piece is placed on the metal surface so that the outer surface of the test piece is in contact with the metal surface. did. Subsequently, a thread including a member having a width of 63 mm and a length of 63 mm and having a mass of 200 g was placed on the test piece. Subsequently, the test piece was slid on the metal surface at a speed of 100 mm / min. The static friction coefficient and the dynamic friction coefficient of the outer surface of the test piece were calculated based on the force applied to the test piece when sliding started and the force applied to the test piece during the activity. As a result, the static friction coefficient and the dynamic friction coefficient were 0.11 and 0.11. The environment at the time of measurement was a standard state specified in JIS K7100, and the temperature was 23 ° C. and the humidity was 50%.
[Second measurement of friction coefficient]
The outer surface of the test piece was the same as in the case of the first measurement except that the test piece was stored for 48 hours in a high-temperature thermostatic chamber at a temperature of 40 ° C. and a humidity of 90%, and then placed on the metal surface. The coefficient of static friction and the coefficient of dynamic friction were measured. The measurement was carried out within 5 minutes after removing the test piece from the high-temperature thermostatic chamber. As a result, the static friction coefficient and the dynamic friction coefficient were 0.14 and 0.13.
[Third measurement of friction coefficient]
Two laminates 30 are prepared, and the test piece of one laminate 30 is placed on the other laminate 30 such that the outer surface of the test piece obtained from one laminate 30 is in contact with the outer surface 30y of the other laminate 30. The static friction coefficient and the dynamic friction coefficient of the outer surface of the test piece were measured in the same manner as in the first measurement except that the sample was placed. As a result, the static friction coefficient (room temperature static friction coefficient) and the dynamic friction coefficient (room temperature dynamic friction coefficient) were 0.21 and 0.22.
[Fourth measurement of friction coefficient]
After preparing two laminated bodies 30 and storing the two laminated bodies 30 in a high-temperature thermostatic chamber at a temperature of 40 ° C. and a humidity of 90% for 48 hours, the outer surface of the test piece of one laminated body 30 is used as the other laminated body 30. The static friction coefficient and the dynamic friction coefficient of the outer surface of the test piece were measured in the same manner as in the first measurement except that the test piece was placed on the outer surface 30y. As a result, the static friction coefficient (high temperature and high humidity static friction coefficient) and the dynamic friction coefficient (high temperature and high humidity dynamic friction coefficient) were 0.24 and 0.24.

Example A2
As the base material 41 of the first film 40, the PBT containing 51% by mass described in the second configuration described above is included, the melting point of the PBT is 224 ° C., and the IV value is 1.26 dl / g. A laminate 30 was produced in the same manner as in Example A1, except that the produced single-layer film was used. The base material 41 was a single layer film composed only of PBT and an additive, and the thickness of the base material 41 was 15 μm.

Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 16N. Further, the coefficient of friction of the laminate 30 was measured in the same manner as in Example A1. The results were as follows.
First measurement Static coefficient of friction: 0.12 Dynamic coefficient of friction: 0.10
Second measurement Coefficient of static friction: 0.14 Coefficient of dynamic friction: 0.13
Third measurement Static friction coefficient: 0.20 Dynamic friction coefficient: 0.22
-Fourth measurement Coefficient of static friction: 0.22 Coefficient of dynamic friction: 0.22

Comparative Example A1
A laminate 30 was produced in the same manner as in Example A1 except that a nylon film having a thickness of 15 μm (bonile W manufactured by Kojin Holdings Co., Ltd.) was used as the base material 41 of the first film 40.

Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 16N. Further, the coefficient of friction of the laminate 30 was measured in the same manner as in Example A1. The results were as follows.
First measurement Static friction coefficient: 0.13 Dynamic friction coefficient: 0.13
Second measurement Coefficient of static friction: 0.16 Coefficient of dynamic friction: 0.15
Third measurement Static coefficient of friction: 0.20 Dynamic coefficient of friction: 0.19
-Fourth measurement Coefficient of static friction: 0.27 Coefficient of dynamic friction: 0.25

The measurement results of Example A1, the static friction coefficient of the laminate of the A2 and Comparative Example A1 mu _S and the dynamic friction coefficient mu _D, are summarized in Figure 9. Moreover, the layer structure and evaluation result of the laminated body of Example A1, A2 and Comparative Example A1 are collectively shown in FIG. In FIG. 10, in the “layer configuration” column, the components of the laminate excluding the adhesive layer are listed from the top in order from the outer surface side layer.

As shown in FIG. 9, when the outer surface 30y of the laminate 30 is made of nylon, and the laminate 30 is exposed to a high humidity environment, the static friction coefficient (high temperature high humidity static friction coefficient) with respect to the metal surface The dynamic friction coefficient (high temperature and high humidity dynamic friction coefficient) was 0.15 or more, and the static friction coefficient and dynamic friction coefficient for the laminate 30 were 0.25 or more. Further, regarding the friction coefficient between the outer surfaces of the two laminates, the value obtained by subtracting the normal temperature static friction coefficient from the high temperature high humidity static friction coefficient is 0.07, and the value obtained by subtracting the normal temperature dynamic friction coefficient from the high temperature high humidity dynamic friction coefficient is 0.06.
On the other hand, when the outer surface 30y of the laminated body 30 is made of PBT or PET, the static friction coefficient and the dynamic friction coefficient with respect to the metal surface are 0 even when the laminated body 30 is exposed to a high humidity environment. The static friction coefficient (high temperature and high humidity static friction coefficient) and the dynamic friction coefficient (high temperature and high humidity dynamic friction coefficient) for the laminate 30 were 0.24 or less. Further, regarding the friction coefficient between the outer surfaces of the two laminates, the value obtained by subtracting the normal temperature static friction coefficient from the high temperature high humidity static friction coefficient is 0.03 or less, and the value obtained by subtracting the normal temperature dynamic friction coefficient from the high temperature high humidity dynamic friction coefficient Was 0.03 or less, more specifically 0.02 or less. In particular, when the outer surface 30y of the laminate 30 is made of PET, the static friction coefficient and the dynamic friction coefficient on the metal surface are 0.10 or less even when the laminate 30 is exposed to a high humidity environment. The static friction coefficient and the dynamic friction coefficient for the laminate 30 were 0.18 or less.

As can be seen from the comparison between Examples A1 and A2 and Comparative Example A1 in FIG. 10, when the base material 41 includes PBT, a piercing strength equivalent to that when the base material 41 includes nylon can be realized.

Example B1
As a packaging material (hereinafter also referred to as a body material) constituting the front film 14 and the back film 15, a laminate having the following layer structure was prepared.
Base material / deposition layer / adhesive layer / sealant layer As the base material 41, a PBT film including a plurality of layers 41a described in the above first configuration, produced by a casting method, and deposited with aluminum is used. Using. The content of PBT in each layer 41a was 80%, the number of layers 41a was 1024, and the thickness of the base material 41 was 12 μm. As the sealant layer, a 100 μm thick polyethylene film containing linear low density polyethylene was used.

Moreover, the laminated body which has the following layer structure as a packaging material (henceforth a bottom material) which comprises the lower film 16 was prepared.
Base material / deposition layer / adhesive layer / sealant layer As the base material, a PBT film having a thickness of 12 μm on which aluminum was vapor-deposited was used as in the case of the above-mentioned body. As the sealant layer, a polyethylene film having a thickness of 100 μm containing linear low density polyethylene was used.

Then, the bag 10 was produced using the above-mentioned body material and bottom material. Thereafter, water was filled into the bag 10 as the contents, and the upper portion 11 was heat sealed. Thereby, as shown in FIG. 11, the bottom gusset type bag 10 in which the upper part 11 was sealed was obtained. At this time, the bag 10 (hereinafter also referred to as the first capacity bag 10) containing 200 ml of water and the bag 10 (hereinafter referred to as second capacity bag) containing 250 ml of stored water. 2 types) were also prepared. In any type of bag 10, the height S1 of the bag 10 was 180 mm and the width S2 was 130 mm. Further, the height S3 of the folded lower film 16, that is, the height from the lower end portion of the bag 10 to the folded portion 16f was 35 mm.

(Normal temperature drop evaluation)
Subsequently, for each of the first capacity bag 10 and the second capacity bag 10, the bag 10 is dropped in a normal temperature (about 20 ° C.) environment, and it is inspected whether the bag 10 breaks or not. Evaluation was performed. Specifically, a test (hereinafter also referred to as a horizontal drop test) of dropping the bag 10 held so that the front film 14 and the back film 15 are horizontal from a height of 1.5 m was repeated 10 times. As a result, no bag breakage occurred in either the first capacity bag 10 or the second capacity bag 10. Further, after the horizontal drop test, a test (hereinafter also referred to as a vertical drop test) in which the bag 10 held so that the lower portion 12 is positioned below is dropped from a height of 1.5 m (hereinafter also referred to as a vertical drop test) was repeatedly performed 10 times. As a result, no bag breakage occurred in either the first capacity bag 10 or the second capacity bag 10.

(Low temperature drop evaluation)
Moreover, the low temperature drop evaluation was implemented using the sample different from what was used by the normal temperature drop evaluation. In the low temperature drop evaluation, first, each of the first capacity bag 10 and the second capacity bag 10 was cooled to 3 ° C. Subsequently, for each of the first-capacity bag 10 and the second-capacity bag 10 cooled to 3 ° C., is the bag 10 dropped in an environment of room temperature (about 20 ° C.) and the bag 10 breaks? Inspected for no. Specifically, the horizontal drop test and the vertical drop test described above were performed on each of the first capacity bag 10 and the second capacity bag 10 as in the case of the room temperature drop evaluation. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Example B2
A laminated body constituting the body was prepared in the same manner as in Example B1 except that the thickness of the sealant layer was 90 μm. Moreover, the bottom material similar to the case of Example B1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Example B3
A laminated body constituting the body was prepared in the same manner as in Example B1 except that the thickness of the sealant layer was 80 μm. Moreover, the bottom material similar to the case of Example B1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage did not occur in the horizontal drop test, but bag breakage occurred in the vertical drop test. When the drop height was set to 1.0 m instead of 1.5 m, no bag breakage occurred in the vertical drop test. Also in Examples B4 to B7 to be described later, when the drop height was 1.0 m, no bag breakage occurred in the horizontal drop test and the vertical drop test at a low temperature.

Example B4
A laminated body constituting the body was prepared in the same manner as in Example B1, except that the thickness of the sealant layer was 70 μm. Moreover, the bottom material similar to the case of Example B1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage did not occur in the horizontal drop test, but bag breakage occurred in the vertical drop test. When the drop height was set to 1.0 m instead of 1.5 m, no bag breakage occurred in the vertical drop test. Also in Examples B5 to B7 to be described later, when the drop height was 1.0 m, no bag breakage occurred in the horizontal drop test and the vertical drop test at room temperature.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in the first capacity bag 10, no bag breakage occurred in the horizontal drop test, but a bag breakage occurred in the vertical drop test. In the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Example B5
A laminated body constituting the body was prepared in the same manner as in Example B1, except that the thickness of the sealant layer was 60 μm. Moreover, the bottom material similar to the case of Example B1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, in the first capacity bag 10, no bag breakage occurred in the horizontal drop test, but a bag breakage occurred in the vertical drop test. In the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in the first capacity bag 10, no bag breakage occurred in the horizontal drop test, but a bag breakage occurred in the vertical drop test. In the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Example B6
A laminated body constituting the body was prepared in the same manner as in Example B1, except that the thickness of the sealant layer was 50 μm. Moreover, the bottom material similar to the case of Example B1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Example B7
A laminated body constituting the body was prepared in the same manner as in Example B1 except that the thickness of the sealant layer was 30 μm. Moreover, the bottom material similar to the case of Example B1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

The results of room temperature drop evaluation and low temperature drop evaluation of Examples B1 to B7 when the first capacity bag 10 is used are collectively shown in FIG. Further, the results of the normal temperature drop evaluation and the low temperature drop evaluation of Examples B1 to B7 when the second capacity bag 10 is used are collectively shown in FIG. In FIGS. 12 and 13, “OK” means that no bag breakage occurred in the bag 10 after repeated dropping 10 times. “NG” means that the bag 10 was broken during or after the fall was repeated 10 times.

When 200 ml of water is stored in the bag 10, as shown in FIG. 12, the bag 10 is produced using a body material including a sealant layer having a thickness of 60 μm or more, so that a horizontal drop for normal temperature drop evaluation is performed. It was possible to suppress the occurrence of bag breakage in the test. Moreover, by producing the bag 10 using the body including the sealant layer having a thickness of 80 μm or more, it was possible to suppress the occurrence of bag breakage in the vertical drop test of room temperature drop evaluation. Moreover, by producing the bag 10 using the body including the sealant layer having a thickness of 60 μm or more, it was possible to suppress the occurrence of bag breakage in the horizontal drop test of the low temperature drop evaluation. Moreover, by producing the bag 10 using the body including the sealant layer having a thickness of 90 μm or more, it was possible to suppress the occurrence of bag breakage in the vertical drop test of the low temperature drop evaluation.

When 250 ml of water is stored in the bag 10, as shown in FIG. 13, the bag 10 is produced using a body material including a sealant layer having a thickness of 70 μm or more, so that the horizontal drop of the normal temperature drop evaluation is performed. It was possible to suppress the occurrence of bag breakage in the test. Moreover, by producing the bag 10 using the body including the sealant layer having a thickness of 80 μm or more, it was possible to suppress the occurrence of bag breakage in the vertical drop test of room temperature drop evaluation. Moreover, by producing the bag 10 using the trunk including the sealant layer having a thickness of 80 μm or more, it was possible to suppress the occurrence of bag breakage in the horizontal drop test of the low temperature drop evaluation. Moreover, by producing the bag 10 using the body including the sealant layer having a thickness of 90 μm or more, it was possible to suppress the occurrence of bag breakage in the vertical drop test of the low temperature drop evaluation.

Example C1
A film-like base material 41 including a plurality of layers 41a described in the first configuration and manufactured by a casting method was prepared. The content of PBT in each layer 41a was 80%, the number of layers 41a was 1024, and the thickness of the base material 41 was 12 μm. Subsequently, plasma pretreatment for introducing plasma from a plasma supply nozzle was performed on the surface of the base material 41 while the base material 41 was wound around the pretreatment drum and transported at a transport speed of 400 m / min. The conditions for the plasma pretreatment are as follows.
・ Plasma intensity: 150 W · sec / m ²
Plasma forming gas: Argon 1200 (sccm), oxygen 3000 (sccm)
・ Applied voltage between pretreatment drum and plasma supply nozzle: 340V
・ Vacuum degree around the pretreatment drum: 3.8 Pa

Subsequently, in a film formation chamber adjacent to the pretreatment chamber where the pretreatment drum is located, an aluminum oxide vapor deposition film having a thickness of 12 nm was formed on the surface of the base material 41 subjected to the plasma pretreatment by a vacuum vapor deposition method. The film forming conditions are as follows.
・ Degree of vacuum: 8.1 × 10 ⁻² Pa
・ Conveying speed: 400m / min
The transmittance of light with a wavelength of 366 nm in the obtained aluminum oxide deposited film was 92%.

Subsequently, a barrier coating agent was coated on the aluminum oxide deposited film by a spin coating method. Then, it heat-processed in 180 degreeC for 60 second (s), and formed the transparent gas barrier coating film about 400 nm thick on the aluminum oxide vapor deposition film. Thus, the 1st film 40 which has the base material 41 with which the transparent vapor deposition layer and the gas barrier coating film were provided was obtained.

The procedure for creating the barrier coating agent is as follows. First, 385 g of water, 67 g of isopropyl alcohol and 9.1 g of 0.5N hydrochloric acid were mixed, and 175 g of tetraethoxysilane and 9.2 g of glycidoxypropyltrimethoxysilane were cooled to 10 ° C. in a solution adjusted to pH 2.2. Solution A was prepared by mixing. Further, a solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of polymerization of 99% or more and a polymerization degree of 2400, 324 g of water, and 17 g of isopropyl alcohol. A solution obtained by mixing A liquid and B liquid in a weight ratio of 6.5: 3.5 was used as a barrier coating agent.

Subsequently, in the same manner as in Example A1, the first film 40 and the sealant film 70 were laminated by a dry laminating method to obtain a laminate 30. Since the laminated body 30 has a transparent vapor deposition layer and a gas barrier coating film, the gas barrier property of the laminated body 30 could be improved.

Next, Examples D1 to D3, E1 to E7, and Comparative Example D1 relating to the case where there are two plastic films constituting the base material of the laminate described in the second embodiment will be described.

Example D1
Similar to the case of Example A1 described above, a film-like first base material 51 including a plurality of layers and manufactured by a casting method, which was described in the first configuration, was prepared. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the first base material 51 was 15 μm. Subsequently, the print layer 38 was formed on the film-like first base material 51 using a final manufactured by DIC Graphics Corporation. The thickness of the printing layer 38 was 1 μm. Thus, the 1st film 50 containing the 1st base material 51 and the printing layer 38 was produced.

Moreover, the 2nd base material 61 containing 100 mass% PET was prepared. The thickness of the second substrate 61 was 12 μm. Subsequently, aluminum was vapor-deposited on the surface on the outer surface 30 y side of the second base material 61 to form a vapor deposition layer 36. Thus, the 2nd film 60 containing the 2nd base material 61 and the vapor deposition layer 36 was produced.

In addition, a film-like sealant film 70 including the sealant layer 71 was prepared. As a material constituting the sealant layer 71, a mixture of the following three types of resins at the following weight% was used.
・ Linear low-density polyethylene (density: 0.918 g / cm ³ , MFR: 3.8) 63.5% by weight
・ Low-density polyethylene (density: 0.919 g / cm ³ , MFR: 2.0) 35.0% by weight
・ Slip agent masterbatch based on low density polyethylene (density: 0.921 g / cm ³ , MFR: 5.4) 1.5% by weight
MFR means melt flow rate. The thickness of the sealant layer 71 was 120 μm.

Next, the first film 50 and the second film 60 were laminated by the dry laminating method through the first adhesive layer 55. The adhesive of the first adhesive layer 55 includes Takelac (registered trademark) A-310 made by Mitsui Chemicals as the main agent, and Takenate (registered trademark) A-3 made by Mitsui Chemicals as the curing agent. A thing was used. A-310 contains a polyol. A-3 contains an aromatic isocyanate compound. The thickness of the first adhesive layer 55 was 3 μm.

Next, the laminate of the first film 50 and the second film 60 and the sealant film 70 were laminated by the dry laminating method through the second adhesive layer 65 to obtain the laminate 30. As with the first adhesive layer 55, the second adhesive layer 65 includes Takelac (registered trademark) A-310 manufactured by Mitsui Chemicals, Inc. as the main agent, and Takenate (registered by Mitsui Chemicals, Inc.) as the curing agent. (Trademark) A material containing A-3 was used. The thickness of the second adhesive layer 65 was 3 μm. In the laminate 30 thus obtained, the first base material, the printing layer, the first adhesive layer, the vapor deposition layer, the second base material, the second adhesive layer, and the sealant layer are sequentially laminated from the outer surface side. It is a thing.

Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the coefficient of friction of the laminate 30 was measured in the same manner as in Example A1. The results were as follows.
First measurement Static friction coefficient: 0.11 Dynamic friction coefficient: 0.11
Second measurement Coefficient of static friction: 0.14 Coefficient of dynamic friction: 0.13
Third measurement Static friction coefficient: 0.21 Dynamic friction coefficient: 0.22
-Fourth measurement Coefficient of static friction: 0.24 Coefficient of dynamic friction: 0.24

Example D2
As the first substrate 51 of the first film 50, the PBT containing 51% 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 D1, except that the single-layer film produced by the method was used. The first base 51 was a single layer film composed only of PBT and additives, and the thickness of the first base 51 was 15 μm.

Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the coefficient of friction of the laminate 30 was measured in the same manner as in Example A1. The results were as follows.
First measurement Static coefficient of friction: 0.12 Dynamic coefficient of friction: 0.10
Second measurement Coefficient of static friction: 0.14 Coefficient of dynamic friction: 0.13
Third measurement Static friction coefficient: 0.20 Dynamic friction coefficient: 0.22
-Fourth measurement Coefficient of static friction: 0.22 Coefficient of dynamic friction: 0.22

Example D3
Example except that PBT constituting the first substrate 51 of Example D1 was used as the second substrate 61 and PET constituting the second substrate 61 of Example D1 was used as the first substrate 51 The laminated body 30 was produced like the case of D1.

Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the coefficient of friction of the laminate 30 was measured in the same manner as in Example A1. The results were as follows.
First measurement Static friction coefficient: 0.11 Dynamic friction coefficient: 0.09
Second measurement Static friction coefficient: 0.10 Dynamic friction coefficient: 0.10
Third measurement Static coefficient of friction: 0.18 Dynamic coefficient of friction: 0.18
-Fourth measurement Coefficient of static friction: 0.18 Coefficient of dynamic friction: 0.17

Comparative Example D1
A laminated body 30 was produced in the same manner as in Example D1, except that a nylon film having a thickness of 15 μm (bonile W manufactured by Kojin Holdings Co., Ltd.) was used as the first substrate 51 of the first film 50. .

Subsequently, the puncture strength of the laminate 30 was measured in the same manner as in Example A1. As a result, the piercing strength was 17N. Further, the coefficient of friction of the laminate 30 was measured in the same manner as in Example A1. The results were as follows.
First measurement Static friction coefficient: 0.13 Dynamic friction coefficient: 0.13
Second measurement Coefficient of static friction: 0.16 Coefficient of dynamic friction: 0.15
Third measurement Static coefficient of friction: 0.20 Dynamic coefficient of friction: 0.19
-Fourth measurement Coefficient of static friction: 0.27 Coefficient of dynamic friction: 0.25

The measurement results of the static friction coefficient μ _S and the dynamic friction coefficient μ _D of the laminates of Examples D1 to D3 and Comparative Example D1 are collectively shown in FIG. Further, the layer configurations and evaluation results of the laminates of Examples D1 to D3 and Comparative Example D1 are collectively shown in FIG. In FIG. 15, 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 shown in FIG. 14, when the outer surface 30y of the laminate 30 is made of nylon and the laminate 30 is exposed to a high humidity environment, the static friction coefficient and the dynamic friction coefficient with respect to the metal surface are 0.15. The static friction coefficient (high temperature high humidity static friction coefficient) and the dynamic friction coefficient (high temperature high humidity dynamic friction coefficient) with respect to the laminate 30 were 0.25 or more. Further, regarding the friction coefficient between the outer surfaces of the two laminates, the value obtained by subtracting the normal temperature static friction coefficient from the high temperature high humidity static friction coefficient is 0.07, and the value obtained by subtracting the normal temperature dynamic friction coefficient from the high temperature high humidity dynamic friction coefficient is 0.06.
On the other hand, when the outer surface 30y of the laminated body 30 is made of PBT or PET, the static friction coefficient and the dynamic friction coefficient with respect to the metal surface are 0 even when the laminated body 30 is exposed to a high humidity environment. The static friction coefficient (high temperature and high humidity static friction coefficient) and the dynamic friction coefficient (high temperature and high humidity dynamic friction coefficient) for the laminate 30 were 0.24 or less. Further, regarding the friction coefficient between the outer surfaces of the two laminates, the value obtained by subtracting the normal temperature static friction coefficient from the high temperature high humidity static friction coefficient is 0.03 or less, and the value obtained by subtracting the normal temperature dynamic friction coefficient from the high temperature high humidity dynamic friction coefficient Was 0.03 or less, more specifically 0.02 or less. In particular, when the outer surface 30y of the laminate 30 is made of PET, the static friction coefficient and the dynamic friction coefficient on the metal surface are 0.10 or less even when the laminate 30 is exposed to a high humidity environment. The static friction coefficient and the dynamic friction coefficient for the laminate 30 were 0.18 or less.

As can be seen from the comparison between Examples D1 to D3 and Comparative Example D1 in FIG. 15, when the first base material 51 or the second base material 61 contains PBT, the first base material 51 or the second base material 61 becomes nylon. The piercing strength equivalent to that including

Example E1
As a packaging material (hereinafter also referred to as a body material) constituting the front film 14 and the back film 15, a laminate having the following layer structure was prepared.
First base material / first adhesive layer / evaporation layer / second base material / second adhesive layer / sealant layer As the first base material, as in Example A1, the first configuration has been described. A PBT film including a plurality of layers and produced by a casting method was used. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the first substrate was 12 μm. As the deposition layer and the second substrate, a PET film having a thickness of 12 μm on which aluminum was deposited was used. As the sealant layer, a 100 μm thick polyethylene film containing linear low density polyethylene was used.

Moreover, the laminated body which has the following layer structure as a packaging material (henceforth a bottom material) which comprises the lower film 16 was prepared.
First base material / first adhesive layer / evaporation layer / second base material / second adhesive layer / sealant layer As the first base material, a PBT film having a thickness of 12 μm is the same as in the case of the above-mentioned body. Was used. As the vapor deposition layer and the second substrate, a PET film having a thickness of 12 μm on which aluminum was vapor-deposited was used as in the case of the above-mentioned body. Further, as the sealant layer, a polyethylene film having a thickness of 100 μm including linear low density polyethylene was used.

Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Example E2
A laminated body constituting the body was prepared in the same manner as in Example E1 except that the thickness of the sealant layer was 90 μm. Moreover, the bottom material similar to the case of Example E1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Example E3
A laminated body constituting the body was prepared in the same manner as in Example E1 except that the thickness of the sealant layer was 80 μm. Moreover, the bottom material similar to the case of Example E1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, no bag breakage occurred in the horizontal drop test and the vertical drop test in both the first capacity bag 10 and the second capacity bag 10.

Example E4
A laminated body constituting the body was prepared in the same manner as in Example E1 except that the thickness of the sealant layer was 70 μm. Moreover, the bottom material similar to the case of Example E1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, in the first capacity bag 10, no bag breakage occurred in the horizontal drop test and the vertical drop test. On the other hand, in the second capacity bag 10, no bag breakage occurred in the horizontal drop test, but a bag breakage occurred in the vertical drop test.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage did not occur in the horizontal drop test, but bag breakage occurred in the vertical drop test.

Example E5
A laminated body constituting the body was prepared in the same manner as in Example E1 except that the thickness of the sealant layer was 60 μm. Moreover, the bottom material similar to the case of Example E1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage did not occur in the horizontal drop test, but bag breakage occurred in the vertical drop test.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in the first capacity bag 10, no bag breakage occurred in the horizontal drop test, but a bag breakage occurred in the vertical drop test. In the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Example E6
A laminated body constituting the body was prepared in the same manner as in Example E1 except that the thickness of the sealant layer was 50 μm. Moreover, the bottom material similar to the case of Example E1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage did not occur in the horizontal drop test, but bag breakage occurred in the vertical drop test.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Example E7
A laminated body constituting the body was prepared in the same manner as in Example E1 except that the thickness of the sealant layer was 30 μm. Moreover, the bottom material similar to the case of Example E1 was prepared. Subsequently, in the same manner as in Example B1, a bag 10 is produced using the trunk and the bottom material, water is filled into the bag 10 as the contents, and the upper portion 11 is heat-sealed. A capacity bag 10 and a second capacity bag 10 were prepared.

Subsequently, a room temperature drop evaluation including a horizontal drop test and a vertical drop test was performed in the same manner as in Example B1. As a result, in the first capacity bag 10, no bag breakage occurred in the horizontal drop test, but a bag breakage occurred in the vertical drop test. In the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

Further, in the same manner as in Example B1, a low temperature drop evaluation including a horizontal drop test and a vertical drop test was performed. As a result, in both the first capacity bag 10 and the second capacity bag 10, bag breakage occurred in the horizontal drop test and the vertical drop test.

FIG. 16 shows the results of room temperature drop evaluation and low temperature drop evaluation of Examples E1 to E7 when the first capacity bag 10 is used. In addition, FIG. 17 collectively shows the results of room temperature drop evaluation and low temperature drop evaluation of Examples E1 to E7 when the second capacity bag 10 is used. 16 and 17, “OK” means that no bag breakage occurred in the bag 10 after the dropping was repeated 10 times. “NG” means that the bag 10 was broken during or after the fall was repeated 10 times.

When 200 ml of water is stored in the bag 10, as shown in FIG. 16, the bag 10 is produced using a body material including a sealant layer having a thickness of 30 μm or more, so that a horizontal drop for normal temperature drop evaluation is performed. It was possible to suppress the occurrence of bag breakage in the test. Moreover, by producing the bag 10 using the body material including the sealant layer having a thickness of 70 μm or more, it was possible to suppress the occurrence of bag breakage in the vertical drop test of room temperature drop evaluation. Moreover, by producing the bag 10 using the body material including the sealant layer having a thickness of 50 μm or more, it was possible to suppress the occurrence of bag breakage in the horizontal drop test of the low temperature drop evaluation. Moreover, by producing the bag 10 using the body including the sealant layer having a thickness of 80 μm or more, it was possible to suppress the occurrence of bag breakage in the vertical drop test of the low temperature drop evaluation.

When 250 ml of water is stored in the bag 10, as shown in FIG. 17, the bag 10 is produced using a body material including a sealant layer having a thickness of 60 μm or more, so that a horizontal drop for normal temperature drop evaluation is performed. It was possible to suppress the occurrence of bag breakage in the test. Moreover, by producing the bag 10 using the body including the sealant layer having a thickness of 80 μm or more, it was possible to suppress the occurrence of bag breakage in the vertical drop test of room temperature drop evaluation. Moreover, by producing the bag 10 using the body material including the sealant layer having a thickness of 70 μm or more, it was possible to suppress the occurrence of bag breakage in the horizontal drop test of the low temperature drop evaluation. Moreover, by producing the bag 10 using the body including the sealant layer having a thickness of 80 μm or more, it was possible to suppress the occurrence of bag breakage in the vertical drop test of the low temperature drop evaluation.

Example F1
The 1st film 50 was produced using the base material 41 with which the aluminum oxide vapor deposition film and gas barrier coating film which were demonstrated in the above-mentioned Example C1 were provided as the 1st base material 51. FIG. Subsequently, in the same manner as in Example D1, the first film 50, the second film 60, and the sealant film 70 were laminated by a dry laminating method to obtain a laminate 30. Since the laminated body 30 has a transparent vapor deposition layer and a gas barrier coating film, the gas barrier property of the laminated body 30 could be improved.

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 Main body part 20 Outlet part 20a Outlet seal part 25 Easy-opening means 26 Notch 30 Laminate 35 Gas barrier layer 36 Vapor deposition layer 37 Gas barrier coating film 38 Print layer 40 First film 41 Base material 41a Layer 45 Adhesive layer 50 First film 51 First base material 60 Second film 61 Second base material 65 Second adhesive layer 70 Sealant film 71 Sealant layer

Claims (18)

A laminate comprising an outer surface and an inner surface,
Having a plastic film containing 51% by mass or more of polybutylene terephthalate, and constituting the outer surface of the laminate,
A sealant layer constituting the inner surface of the laminate,
The layer which comprises the said outer surface of the said laminated body among the said base materials is a laminated body containing a polyethylene terephthalate or a polybutylene terephthalate. Coefficient of static friction of the outer surface of one of the laminates and the outer surface of the other laminate as measured after preparing two of the laminates and storing them for 48 hours in a high-temperature thermostatic chamber at a temperature of 40 ° C. and a humidity of 90% And the laminated body of Claim 1 whose coefficient of dynamic friction is 0.24 or less. Two of the laminates are prepared and measured after storage for at least 24 hours in an environment of a temperature of 20 to 30 ° C. and a humidity of 40 to 60%, the outer surface of one of the laminates and the outer surface of the other laminate The static friction coefficient and the dynamic friction coefficient with respect to are referred to as normal temperature static friction coefficient and normal temperature dynamic friction coefficient,
After measuring the room temperature static friction coefficient and the room temperature dynamic friction coefficient, the two laminates are measured after being stored for 48 hours in a high-temperature thermostatic chamber at a temperature of 40 ° C. and a humidity of 90%. When the static friction coefficient and the dynamic friction coefficient for the outer surface of the laminate are referred to as a high temperature high humidity static friction coefficient and a high temperature high humidity dynamic friction coefficient,
The value obtained by subtracting the normal temperature static friction coefficient from the high temperature high humidity static friction coefficient is 0.03 or less, and the value obtained by subtracting the normal temperature dynamic friction coefficient from the high temperature high humidity dynamic friction coefficient is 0.03 or less. The laminate according to 1 or 2. The laminate according to any one of claims 1 to 3, wherein the plastic film containing 51% by mass or more of polybutylene terephthalate has a multilayer structure part including 10 layers or more. The plastic film containing 51% by mass or more of polybutylene terephthalate has a single-layer structure, and the polybutylene terephthalate has an IV value of 1.10 dl / g or more and 1.35 dl / g or less. The laminated body as described in any one of thru | or 3. The substrate has only one plastic film containing 51% by mass or more of polybutylene terephthalate,
The said sealant layer is a laminated body as described in any one of Claims 1 thru | or 5 containing a linear low density polyethylene. The laminate according to claim 6, wherein the puncture strength of the laminate is 12 N or more. The laminate according to claim 6 or 7, further comprising a vapor deposition layer located on the surface of the substrate. The laminate according to claim 8, further comprising a gas barrier coating film located on the vapor deposition layer. The laminate includes, from the outer surface side to the inner surface side, at least a first base material that forms the outer surface, a second base material, and a sealant layer that forms the inner surface, in this order,
The first base material includes 51% by mass or more of polyethylene terephthalate or 51% by mass or more of polybutylene terephthalate,
The laminate according to any one of claims 1 to 5, wherein when the first base material contains 51% by mass or more of polyethylene terephthalate, the second base material contains 51% by mass or more of polybutylene terephthalate. . The laminate according to claim 10, further comprising a vapor deposition layer located at least either between the first base material and the second base material or between the second base material and the sealant layer. The laminate according to claim 11, further comprising a gas barrier coating film positioned on the vapor deposition layer. The laminate according to any one of claims 10 to 12, further comprising a printing layer positioned between the first base material and the second base material. The laminate according to any one of claims 10 to 13, wherein the sealant layer contains linear low-density polyethylene. The laminate according to any one of claims 10 to 14, wherein the puncture strength of the laminate is 13 N or more. The first substrate comprises polybutylene terephthalate;
The laminate according to any one of claims 10 to 15, wherein the second base material contains polyethylene terephthalate. The first substrate comprises polyethylene terephthalate;
The laminate according to any one of claims 10 to 15, wherein the second base material contains polybutylene terephthalate. A bag having a main body part and a spout part connected to the main body part,
The laminate according to any one of claims 1 to 17,
A bag comprising: a seal portion that joins the inner surfaces of the laminate.

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