WO2024024952A1

WO2024024952A1 - Biaxially oriented polyester film, laminate, and packaging container

Info

Publication number: WO2024024952A1
Application number: PCT/JP2023/027795
Authority: WO
Inventors: 考道後藤; 信之真鍋
Original assignee: 東洋紡株式会社
Priority date: 2022-07-29
Filing date: 2023-07-28
Publication date: 2024-02-01
Also published as: JP2024018165A

Abstract

This biaxially oriented polyester film contains a chemically recycled polyester. At least one surface of the biaxially oriented polyester film has a surface crystallinity of 1.10-1.31. A laminate may include the biaxially oriented polyester film and a sealant layer. A laminate may also include the biaxially oriented polyester film and an adhesive layer. A packaging container may include the laminate. A packaging container may include the laminate.

Description

Biaxially oriented polyester films, laminates, and packaging containers

The present invention relates to a biaxially oriented polyester film, a laminate, and a packaging container.

Polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), which are thermoplastic resins with excellent heat resistance and mechanical properties, are used in a wide variety of fields such as plastic films, electronics, energy, packaging materials, and automobiles. has been done. Among these, biaxially oriented polyester film has an excellent balance between mechanical strength (that is, mechanical properties), heat resistance, dimensional stability, chemical resistance, optical properties, and cost, so it is used in industrial and packaging fields. It is widely used in

In recent years, with the growing call for building a recycling-oriented society, the use of recycled raw materials has been promoted in the materials field as well. For polyester, used PET bottles are also recycled. It is said that using recycled polyester will lead to a reduction in _CO2 . Under these circumstances, it is desirable to increase the usage ratio of recycled polyester even if only a little.

For example, Patent Document 1 discloses a biaxially oriented polyester film produced using a polyester obtained by mechanically recycling a PET bottle, that is, a mechanically recycled polyester.

However, the degree of contamination of used polyester products such as used PET bottles varies depending on the contents they were filled in and the storage environment, but mechanical recycling can remove contaminants to a high degree. That's difficult.

Chemical recycled polyester, which is obtained by decomposing the polyester contained in used polyester products down to the monomer level and then polymerizing it again, is known as polyester recycled using a method different from mechanical recycling (Patent Document 3 and 4).

For example, Patent Document 2 discloses a printed resin film that includes a polyester film made using chemically recycled polyester and a printed layer.

Patent No. 6036099 Patent No. 6984717 Japanese Patent Application Publication No. 2000-169623 Japanese Patent Application Publication No. 2000-302707

Chemically recycled polyester is often made to have a high molecular weight through solid phase polymerization to make it easier to mold into PET bottles, so the intrinsic viscosity of chemically recycled polyester is similar to that of polyester for general biaxially oriented polyester films. It is often higher than that.

In the process of considering the use of chemically recycled polyester for the production of biaxially oriented polyester films rather than PET bottles, the present inventor found that films using chemically recycled polyesters tend to break during stretching, and therefore the film forming rate was We have found that there is a problem in that there are cases where it is necessary to reduce the amount of water excessively.

The present invention can reduce environmental impact, suppress or reduce film breakage that may occur during stretching, and improve mechanical properties (specifically, tensile strength and puncture strength). The purpose of the present invention is to provide a biaxially oriented polyester film with excellent properties. Another object of the present invention is to provide a laminate including a biaxially oriented polyester film and a packaging container including the laminate.

In order to solve this problem, the present invention includes the following configuration [1].
[1]
Contains chemically recycled polyester
At least one surface has a surface crystallinity of 1.10 or more and 1.31 or less as determined by the attenuated total reflection method using a Fourier transform infrared spectrophotometer,
The melting point is 251°C or higher,
Biaxially oriented polyester film.
Here, "chemically recycled polyester" is a polyester obtained by decomposing polyester contained in used polyester products to the monomer level and then polymerizing it again.
"Surface crystallinity" is the intensity ratio of absorption appearing near 1340 cm ^-1 and absorption appearing near 1410 cm ^-1 . That is, the intensity is 1340 cm -1/1410 ^{cm -1} ^. Note that the absorption that appears around 1340 cm ⁻¹ is due to the bending vibration of CH ₂ (trans structure) of ethylene glycol. This is an absorption characteristic of crystals. On the other hand, the absorption that appears near 1410 cm ^-1 is unrelated to the crystal.

In [1], the biaxially oriented polyester film contains chemically recycled polyester. Here, "the biaxially oriented polyester film contains chemically recycled polyester" means that when the biaxially oriented polyester film includes multiple layers, at least one layer of the multiple layers contains chemically recycled polyester. It means to include.

According to [1], since the biaxially oriented polyester film contains chemically recycled polyester, the environmental load can be reduced.

Moreover, by having a surface crystallinity of 1.31 or less, it is possible to prevent the biaxially oriented polyester film from becoming excessively brittle (in other words, the toughness is excessively deteriorated). Strength and piercing strength can be improved.

Moreover, by having a surface crystallinity of 1.10 or more, the molecular weight of the polyester contained in the biaxially oriented polyester film can be limited to a certain level or less. This will be explained. The crystallization rate becomes faster as the molecular weight of the polyester decreases. Therefore, the higher the surface crystallinity of the biaxially oriented polyester film, the lower the molecular weight of the polyester contained in the biaxially oriented polyester film tends to be. Therefore, by having a surface crystallinity of 1.10 or more, the molecular weight of the polyester contained in the biaxially oriented polyester film can be limited to a certain level or less.

By having a surface crystallinity of 1.10 or more, a certain amount or more of a low molecular weight component that can act like a plasticizer can be present. This will be explained. The lower the molecular weight of the polyester contained in the biaxially oriented polyester film, the more the low molecular weight components in the biaxially oriented polyester film tend to be. This is because low molecular weight components are incorporated into the polyester during the polymerization process. As described above, by having a surface crystallinity of 1.10 or more, the molecular weight of the polyester contained in the biaxially oriented polyester film can be limited to a certain level or less. As a result, a certain amount of low molecular weight components can be present. Therefore, by having a surface crystallinity of 1.10 or more, a certain amount of low molecular weight components that can act like plasticizers can be present.

Therefore, by having a surface crystallinity of 1.10 or more, stress during stretching (that is, stretching stress) in the biaxially oriented polyester film manufacturing process can be prevented from becoming excessively large, which may occur during stretching. Breakage of the film can be suppressed or reduced.

Furthermore, since the melting point is 251°C or higher, it has excellent heat resistance.

It is preferable that the present invention further includes the following configurations [2] and later.

[2]
When the number of moles of all dicarboxylic acid components in the biaxially oriented polyester film is 100 mol%, the number of moles of the isophthalic acid component is 0.1 mol% or more and 3.0 mol% or less, described in [1] biaxially oriented polyester film.

According to [2], when the number of moles of the isophthalic acid component is 0.1 mol% or more,
When a sealant layer is provided on a biaxially oriented polyester film, the peel strength between the biaxially oriented polyester film and the sealant layer can be improved. On the other hand, by setting the number of moles of the isophthalic acid component to 3.0 mol% or less, it is possible to prevent the crystallinity from decreasing excessively, thereby improving heat resistance and mechanical properties (specifically, tensile strength and puncture resistance). strength) can be prevented from decreasing excessively.

[3]
The biaxially oriented polyester film according to [1] or [2], wherein the biaxially oriented polyester film has a puncture strength of 0.50 N/μm or more.

According to [3], a biaxially oriented polyester film can be used to produce a product (for example, a packaging container) with excellent strength. For example, biaxially oriented polyester films can be used to create packaging containers that are resistant to punctures.

[4]
The biaxially oriented polyester film according to any one of [1] to [3], wherein the biaxially oriented polyester film has an intrinsic viscosity of 0.50 dl/g or more and 0.70 dl/g or less.

According to [4], by having an intrinsic viscosity of 0.70 dl/g or less, it is possible to further prevent stress during stretching (that is, stretching stress) in the biaxially oriented polyester film manufacturing process from becoming excessively large. As a result, breakage of the film that may occur during stretching can be further suppressed or reduced. By having an intrinsic viscosity of 0.50 dl/g or more, mechanical properties, specifically tensile strength and puncture strength, can be further improved.

[5]
The biaxially oriented polyester film according to any one of [1] to [4], wherein the content of the chemically recycled polyester is 20% by mass or more.

According to [5], the environmental load can be further reduced.

[6]
The biaxially oriented polyester film according to any one of [1] to [5],
a sealant layer;
laminate.

According to [6], since the laminate includes a sealant layer, a product (for example, a packaging container) including the laminate can be manufactured by heat sealing.

[7]
further comprising a printing layer;
In at least a portion of the laminate, the printing layer, the biaxially oriented polyester film, and the sealant layer are arranged in this order in the thickness direction of the laminate.
The laminate according to [6].
Here, "the printed layer, the biaxially oriented polyester film, and the sealant layer are arranged in this order in the thickness direction of the laminate" means between the printed layer and the biaxially oriented polyester film, or between the printed layer and the biaxially oriented polyester film, This expression allows for the presence of other layers between the polyester film and the sealant layer.

According to [7], since the laminate includes a printing layer, a design (for example, letters, patterns, symbols, etc.) can be applied to the laminate or a product (for example, a packaging container) that includes the laminate.

[8]
further comprising a printing layer;
In at least a portion of the laminate, the biaxially oriented polyester film, the printing layer, and the sealant layer are arranged in this order in the thickness direction of the laminate.
The laminate according to [6].
Here, "the biaxially oriented polyester film, the printed layer, and the sealant layer are arranged in this order in the thickness direction of the laminate" means between the biaxially oriented polyester film and the printed layer, or between the printed layer and the sealant layer. This is an expression that allows the presence of other layers between the sealant layers.

According to [8], since the laminate includes a printing layer, a design (for example, letters, patterns, symbols, etc.) can be applied to the laminate or a product (for example, a packaging container) that includes the laminate.

[9]
The biaxially oriented polyester film according to any one of [1] to [5],
including an adhesive layer;
laminate.

According to [9], since the laminate includes an adhesive layer, a product (for example, a packaging container) including the laminate can be manufactured by pressurization.

[10]
further comprising a printing layer;
In at least a portion of the laminate, the printed layer, the biaxially oriented polyester film, and the adhesive layer are arranged in this order in the thickness direction of the laminate.
The laminate according to [9].
Here, "the printed layer, the biaxially oriented polyester film, and the adhesive layer are arranged in this order in the thickness direction of the laminate" means between the printed layer and the biaxially oriented polyester film, or between the printed layer and the biaxially oriented polyester film, This expression allows for the presence of another layer between the polyester film and the adhesive layer.

According to [10], since the laminate includes a printing layer, a design (for example, letters, patterns, symbols, etc.) can be applied to the laminate or a product (for example, a packaging container) that includes the laminate.

[11]
further comprising a printing layer;
In at least a portion of the laminate, the biaxially oriented polyester film, the printing layer, and the adhesive layer are arranged in this order in the thickness direction of the laminate.
The laminate according to [9].
Here, "the biaxially oriented polyester film, the printed layer, and the adhesive layer are arranged in this order in the thickness direction of the laminate" means between the biaxially oriented polyester film and the printed layer, or between the printed layer and the adhesive layer. This is an expression that allows other layers to exist between the adhesive layers.

According to [11], since the laminate includes a printing layer, a design (for example, letters, patterns, symbols, etc.) can be applied to the laminate or a product (for example, a packaging container) that includes the laminate.

[12]
A packaging container comprising the laminate according to any one of [6] to [11].

According to the present invention, it is possible to reduce environmental load, suppress or reduce film breakage that may occur during stretching, and improve mechanical properties (specifically, tensile strength and puncture strength). It is possible to provide a biaxially oriented polyester film with excellent properties.

It is a schematic sectional view of the biaxially oriented polyester film in this embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment. It is a schematic sectional view of the layered product in one embodiment.

<1. Introduction>
Embodiments of the present invention will be described below.
Note that hereinafter, polyethylene terephthalate may be referred to as PET or PET. In other words, these terms are used as synonyms.
Machine Direction (hereinafter referred to as "MD") is sometimes referred to as the longitudinal direction. That is, MD and longitudinal direction are used as synonyms.
Transverse Direction (hereinafter referred to as "TD") is sometimes referred to as the width direction. That is, TD and width direction are used as synonyms.
In describing embodiments of the present invention, expressions such as "the first layer 81, the second layer 82, and the third layer 83 are arranged in this order in the thickness direction of the biaxially oriented polyester film 8" may be used. . This expression allows other layers to exist between the first layer 81 and the second layer 82 and between the second layer 82 and the third layer 83. The same applies to other expressions (that is, similar expressions) including the description that a plurality of layers are "arranged in this order."

<2. Biaxially oriented polyester film>
As shown in FIG. 1, the biaxially oriented polyester film 8 of this embodiment has a film shape.

The biaxially oriented polyester film 8 contains chemically recycled polyester. Therefore, the environmental load can be reduced.

Chemically recycled polyester is polyester obtained by decomposing the polyester contained in used polyester products down to the monomer level and then polymerizing it again. Chemically recycled polyester is manufactured using polyester contained in used polyester products as raw material, so it can reduce environmental impact. In addition, chemically recycled polyester is superior in terms of hygiene compared to mechanically recycled polyester because foreign substances (such as catalysts, coloring components, dissimilar plastics, and metals) are removed during the recycling process.

Used polyester products can be mentioned as polyester that is decomposed to the monomer level. The used polyester product may be, for example, in the form of a veil, flakes, or pellets. Used PET bottles are preferred as used polyester products.

As a method for decomposing polyester to the monomer level, for example, PET bottle bales are crushed and washed, and then at least ethylene glycol (EG) and a catalyst are added to the flakes, heated, and bis-2-hydroxyethyl A method of decomposing it to terephthalate (BHET) (hereinafter sometimes referred to as "BHET method") can be mentioned (see Patent Document 3, ie, Japanese Patent Application Laid-Open No. 2000-169623). Other methods for decomposing polyester to the monomer level include, for example, the method described in Patent Document 4 (Japanese Unexamined Patent Publication No. 2000-302707). Of course, polyester may be decomposed to the monomer level by methods other than those exemplified here.

Regarding the BHET method, an example of a procedure for decomposing polyethylene terephthalate constituting a used PET bottle to obtain BHET will be described here.
PET bottle bales are put into a crusher and wet crushed. Wet grinding allows for the grinding of plastic bottle bales in wash water (e.g. tap water or ground water with optional detergent added). Note that the washing water may be at room temperature or may be heated.
The wash water is discharged from the crusher along with the PET bottle flakes and subjected to gravity separation to remove foreign matter (eg metal, stone, glass, sand).
The flakes are then rinsed with ion-exchanged water and, if necessary, centrifuged.
After the flakes are melted, a catalyst and excess ethylene glycol are added and heated (in other words, depolymerization occurs). Thereby, the polyethylene terephthalate constituting the flakes can be depolymerized, and as a result, a depolymerization liquid in which BHET is dissolved in ethylene glycol can be obtained. Note that the flakes are preferably melted in a water-containing state (for example, in a water-containing state after centrifugal dehydration).
Remove foreign substances (e.g. foreign plastics, metals, glass) that float or precipitate in the depolymerization solution. Note that, since the melting point of the cyclic oligomer in the depolymerization liquid is higher than that of polyethylene terephthalate, low molecular weight components such as the cyclic oligomer can also be removed by filtration.
The depolymerization solution is passed through activated carbon (i.e., passed) and then passed through an ion exchange resin. By passing the depolymerization liquid through activated carbon, coloring components (for example, pigments, dyes, compounds generated by thermal deterioration of organic substances) can be removed. By passing the depolymerization liquid through an ion exchange resin, catalysts (eg, polymerization catalysts, depolymerization catalysts) and metal ions can be removed.
Next, the depolymerization liquid is cooled, BHET is precipitated, and BHET and ethylene glycol are separated into solid and liquid.
To remove the ethylene glycol remaining in the BHET (ie, to concentrate the BHET), vacuum evaporation is performed.
Molecular distillation is performed on the concentrated BHET.
High purity BHET can be obtained by such a procedure. Note that, although the operation described here involves solid-liquid separation of BHET and ethylene glycol and then vacuum evaporation, ethylene glycol may be distilled from the depolymerization liquid instead of this operation.

Examples of chemically recycled polyester include chemically recycled polyethylene terephthalate (hereinafter sometimes referred to as "chemically recycled PET"), chemically recycled polybutylene terephthalate, and chemically recycled polyethylene-2,6-naphthalate. Of course, these may also contain copolymerized components. Chemically recycled PET is preferred because it is easily available and has excellent mechanical properties and heat resistance. Note that these may be used alone or in combination of two or more.

The chemically recycled polyester may be copolymerized with other components. Examples of the dicarboxylic acid component as a copolymerization component include isophthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid, and ester-forming derivatives thereof. On the other hand, examples of the diol component as a copolymerization component include diethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexanedimethanol. Similarly, mention may also be made of polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol. Note that these may be used alone or in combination of two or more. In addition, considering that PET constituting PET bottles is generally copolymerized with isophthalic acid in order to improve moldability into bottles, chemically recycled PET contains at least an isophthalic acid component as a copolymerized component. It is preferable to include.

When the number of moles of all dicarboxylic acid components in the chemically recycled polyester is 100 mol%, the number of moles of the copolymerized component is preferably 10 mol% or less, more preferably 8 mol% or less, and even more preferably 5 mol% or less. , more preferably 3 mol% or less. The number of moles of the copolymer component is preferably 0.1 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more. In addition, the chemically recycled polyester may contain one kind or two or more kinds satisfying such a suitable number of moles of copolymerization components.

When the chemically recycled polyester is chemically recycled PET, when the number of moles of all dicarboxylic acid components in the chemically recycled PET is 100 mol%, the number of moles of the isophthalic acid component is preferably 10 mol% or less, and 8 mol% or less. is more preferable, 5 mol% or less is even more preferable, and even more preferably 3 mol% or less. The number of moles of the isophthalic acid component is preferably 0.1 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more. In addition, chemically recycled PET may contain one kind or two or more kinds satisfying such a suitable number of moles of isophthalic acid components.

The intrinsic viscosity of the chemically recycled polyester is preferably 0.50 dl/g or more, more preferably 0.55 dl/g or more, and even more preferably 0.57 dl/g or more. When it is 0.50 dl/g or more, the amount of low molecular weight components in the chemically recycled polyester can be limited to a certain level or less, and therefore, the yellow tinge that the biaxially oriented polyester film 8 may exhibit can be reduced. On the other hand, the intrinsic viscosity of the chemically recycled polyester is preferably 0.90 dl/g or less, more preferably 0.85 dl/g or less, further preferably 0.80 dl/g or less, even more preferably 0.75 dl/g, and 0. More preferably, it is .69 dl/g or less. If it is 0.90 dl/g or less, the intrinsic viscosity of the biaxially oriented polyester film 8 can be limited to a certain level or less, so that the stress during stretching (that is, stretching stress) during the manufacturing process of the biaxially oriented polyester film 8 is not excessive. As a result, breakage of the film that may occur during stretching can be further suppressed or reduced. Note that the chemically recycled polyester may contain one or more types that satisfy such a suitable intrinsic viscosity.

In the molecular weight distribution curve obtained by gel permeation chromatography (GPC) of chemically recycled polyester, the area ratio of the region with a molecular weight of 1000 or less may be 3.5% or less of the total peak area, and may be 3.0% or less. The content may be 2.5% or less, 2.2% or less, or 2.0% or less. On the other hand, this area ratio may be 0.8% or more, 1.0% or more, or 1.2% or more.

The melt specific resistance at 285° C. of chemically recycled polyester may be, for example, 30.0×10 ⁸ Ω・cm or less, 25.0×10 ⁸ Ω・cm or less, and 20.0×10 Ω・cm or less. It may be ⁸ Ω·cm or less, or it may be 15.0×10 ⁸ Ω·cm or less. The melt specific resistance at 285° C. of chemically recycled polyester may be, for example, 0.5×10 ⁸ Ω・cm or more, 1.5×10 ⁸ Ω・cm or more, or 3.0×10 Ω・cm or more. It may be ⁸ Ω·cm or more, or it may be 5.0×10 ⁸ Ω·cm or more. Note that the melt specific resistance of the chemically recycled polyester is preferably higher than that of the fossil fuel-derived polyester and mechanically recycled polyester, which will be described later. Note that the chemically recycled polyester may contain one or more types that satisfy such a suitable melt specific resistance.

Although the chemically recycled polyester may contain an alkaline earth metal compound, it is preferably substantially free of it. Since catalysts and metal ions are removed from chemically recycled polyester during the recycling process, alkaline earth metal compounds can be produced by polymerizing with catalysts other than alkaline earth metal compounds (for example, germanium-based catalysts or antimony-based catalysts). may contain little or no

The content of the alkaline earth metal compound in the chemically recycled polyester may be, for example, less than 30 ppm, or 20 ppm or less, on an alkaline earth metal atom basis (i.e., in terms of alkaline earth metal atoms). It may be 10 ppm or less, 5 ppm or less, 3 ppm or less, or 0 ppm.
Here, the content of the alkaline earth metal compound is the mass of the alkaline earth metal compound on the basis of the alkaline earth metal atom with respect to the mass of the chemically recycled polyester (that is, the content of the alkaline earth metal compound on the basis of the alkaline earth metal atom) mass of compound/mass of chemically recycled polyester).
Note that the chemically recycled polyester may contain one or more kinds of alkaline earth metal compounds that satisfy such a suitable content of alkaline earth metal compounds.

The content of the magnesium compound in the chemically recycled polyester is based on magnesium atoms (that is, in terms of magnesium atoms), and may be, for example, less than 30 ppm, 20 ppm or less, 10 ppm or less, or 5 ppm. It may be below, 3 ppm or less, or 0 ppm. In addition, the chemically recycled polyester may contain one kind or two or more kinds satisfying such a suitable magnesium compound content.

The content of the phosphorus compound in the chemically recycled polyester may be 10 ppm or more, 15 ppm or more, 20 ppm or more, 30 ppm or more, on a phosphorus atom basis (i.e., in terms of phosphorus atoms). It may be. On the other hand, the content of the phosphorus compound may be 300 ppm or less, 200 ppm or less, or 100 ppm or less based on phosphorus atoms.
Here, the content of the phosphorus compound is the mass of the phosphorus compound on a phosphorus atom basis with respect to the mass of the chemically recycled polyester (that is, the mass of the phosphorus compound on a phosphorus atom basis/the mass of the chemically recycled polyester).
In addition, the chemically recycled polyester may contain one kind or two or more kinds satisfying such a suitable phosphorus compound content.

The content of the chemically recycled polyester is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the biaxially oriented polyester film 8 is 100% by mass. When the content is 10% by mass or more, the environmental load can be further reduced. On the other hand, the content of the chemically recycled polyester is preferably 95% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, when the biaxially oriented polyester film 8 is 100% by mass.

Preferably, the biaxially oriented polyester film 8 contains fossil fuel-derived polyester, that is, virgin polyester. Fossil fuel-derived polyester is a polyester obtained by condensation polymerization of a fossil fuel-derived diol compound and a fossil fuel-derived dicarboxylic acid compound. Fossil fuel-derived polyesters generally have a wider range of selection than chemically recycled polyesters, but by using fossil fuel-derived polyesters, the range in which the physical properties of the biaxially oriented polyester film 8 can be adjusted can be expanded.

Examples of fossil fuel-derived polyesters include fossil fuel-derived polyethylene terephthalate (hereinafter sometimes referred to as "fossil fuel-derived PET"), fossil fuel-derived polybutylene terephthalate, and fossil fuel-derived polyethylene-2,6-naphthalate. Can be done. Of course, these may also contain copolymerized components. Fossil fuel-derived PET is preferred, and fossil fuel-derived homo-PET is more preferred because it can reduce costs and has excellent mechanical properties and heat resistance. Note that homo-PET may also contain an unavoidable diethylene glycol component. Note that these may be used alone or in combination of two or more.

The intrinsic viscosity of the fossil fuel-derived polyester is preferably 0.50 dl/g or more, more preferably 0.55 dl/g or more, and even more preferably 0.57 dl/g or more. When it is 0.50 dl/g or more, the amount of low molecular weight components in the fossil fuel-derived polyester can be limited to a certain level or less, and therefore, the yellowishness that the biaxially oriented polyester film 8 may exhibit can be reduced. On the other hand, the intrinsic viscosity of the fossil fuel-derived polyester is preferably 0.75 dl/g or less, more preferably 0.70 dl/g or less, even more preferably 0.68 dl/g or less, even more preferably 0.66 dl/g or less, More preferably, it is 0.65 dl/g or less. If it is 0.75 dl/g or less, stress during stretching (that is, stretching stress) in the biaxially oriented polyester film 8 manufacturing process can be further prevented from becoming excessively large, and as a result, breakage of the film that may occur during stretching can be further prevented. , can be further suppressed or reduced. Note that the fossil fuel-derived polyester may contain one or more types that satisfy such a suitable intrinsic viscosity.

In the molecular weight distribution curve obtained by gel permeation chromatography (GPC) of fossil fuel-derived polyester, the area ratio of the region with a molecular weight of 1000 or less may be 3.5% or less of the total peak area, and may be 3.0% or less. It may be 2.8% or less. On the other hand, this area ratio may be 1.0% or more, 1.5% or more, 1.8% or more, or 2.0% or more. .

The melting resistivity at 285°C of fossil fuel-derived polyester may be, for example, 2.0×10 ⁸ Ω·cm or less, 1.5×10 ⁸ Ω·cm or less, or 1.0× It may be 10 ⁸ Ω·cm or less, 0.5×10 ⁸ Ω·cm or less, or 0.4×10 ⁸ Ω·cm or less. The melting specific resistance of the fossil fuel-derived polyester at 285° C. may be, for example, 0.05×10 ⁸ Ω·cm or more, or 0.1×10 ⁸ Ω·cm or more. Note that the fossil fuel-derived polyester may contain one or more types that satisfy such a suitable melting specific resistance.

It is preferable that the fossil fuel-derived polyester contains an alkaline earth metal compound. Note that the alkaline earth metal compound may be added to the fossil fuel-derived polyester, for example, as a polymerization catalyst for producing the fossil fuel-derived polyester, and may be added to lower the specific melting resistance of the biaxially oriented polyester film 8. may have been done.

The content of the alkaline earth metal compound in the fossil fuel-derived polyester is preferably, for example, 30 ppm or more, preferably 35 ppm or more, preferably 40 ppm or more, on an alkaline earth metal atom basis (that is, in terms of alkaline earth metal atoms). 45 ppm or more is preferable.
Here, the content of the alkaline earth metal compound is the mass of the alkaline earth metal compound on the basis of alkaline earth metal atoms (that is, the content of the alkaline earth metal compound on the basis of alkaline earth metal atoms with respect to the mass of the fossil fuel-derived polyester). (mass of metal compound/mass of fossil fuel-derived polyester).
Note that the fossil fuel-derived polyester may contain one or more kinds of alkaline earth metal compounds that satisfy such a suitable alkaline earth metal compound content.

The content of the magnesium compound in the fossil fuel-derived polyester is preferably, for example, 30 ppm or more, preferably 35 ppm or more, preferably 40 ppm or more, and preferably 45 ppm or more, on a magnesium atom basis (that is, in terms of magnesium atoms). In addition, the fossil fuel-derived polyester may contain one or more kinds satisfying such a suitable magnesium compound content.

The content of the phosphorus compound in the fossil fuel-derived polyester may be 10 ppm or more, 15 ppm or more, 20 ppm or more, or 30 ppm on a phosphorus atom basis (i.e., in terms of phosphorus atoms). It may be more than that. On the other hand, the content of the phosphorus compound may be 300 ppm or less, 200 ppm or less, or 100 ppm or less based on phosphorus atoms.
Here, the content of the phosphorus compound is the mass of the phosphorus compound on a phosphorus atom basis with respect to the mass of the fossil fuel-derived polyester (that is, the mass of the phosphorus compound on a phosphorus atom basis/the mass of the fossil fuel-derived polyester).
In addition, the fossil fuel-derived polyester may contain one kind or two or more kinds that satisfy such a suitable phosphorus compound content.

The content of the fossil fuel-derived polyester is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the biaxially oriented polyester film 8 is 100% by mass. When the content is 5% by mass or more, the range in which the physical properties of the biaxially oriented polyester film 8 can be adjusted can be further expanded. On the other hand, the content of the fossil fuel-derived polyester is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, when the biaxially oriented polyester film 8 is 100% by mass.

The biaxially oriented polyester film 8 may or may not contain mechanically recycled polyester. Mechanically recycled polyester is polyester obtained from used polyester products without undergoing an operation that decomposes the polyester contained in the used polyester products down to the monomer level. Mechanically recycled polyester is obtained, for example, by crushing and washing a used polyester product, and regenerating it into flakes or pellets as needed.

In the molecular weight distribution curve obtained by gel permeation chromatography (GPC) of mechanically recycled polyester, the area ratio of the region with a molecular weight of 1000 or less may be 4.5% or less of the total peak area, and may be 4.0% or less. There may be. On the other hand, this area ratio may be 2.5% or more, 3.0% or more, or 3.2% or more.

Preferably, the biaxially oriented polyester film 8 does not substantially contain mechanically recycled polyester. The content of the mechanically recycled polyester is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, when the biaxially oriented polyester film 8 is 100% by mass. Preferably, the biaxially oriented polyester film 8 does not contain any mechanically recycled polyester.

The biaxially oriented polyester film 8 may contain biomass polyester.

When the biaxially oriented polyester film 8 is 100% by mass, the content of polyester (that is, the content of polyester including chemically recycled polyester) is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass. % or more is more preferable, and even more preferably 98% by mass or more.

The biaxially oriented polyester film 8 may contain resin other than polyester (eg, chemically recycled polyester, fossil fuel-derived polyester).

Preferably, the biaxially oriented polyester film 8 further contains particles. Here, "the biaxially oriented polyester film 8 contains particles" means that when the biaxially oriented polyester film 8 contains a plurality of layers, at least one layer among the plurality of layers contains particles. means.

Examples of the particles include inorganic particles and organic particles. Examples of inorganic particles include silica (silicon oxide) particles, alumina (aluminum oxide) particles, titanium dioxide particles, calcium carbonate particles, kaolin particles, crystalline glass fillers, kaolin particles, talc particles, and silica-alumina composite oxide particles. , barium sulfate particles. Among these, silica particles, calcium carbonate particles, and alumina particles are preferred, and silica particles and calcium carbonate particles are more preferred. Silica particles are particularly preferred because they can reduce haze. On the other hand, examples of organic particles include acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles. Among these, acrylic resin particles are preferred. Examples of acrylic resin particles include particles made of polymethacrylate, polymethylacrylate, or derivatives thereof. Note that these may be used alone or in combination of two or more.

The weight average particle diameter of the particles is preferably 0.5 μm or more, more preferably 0.8 μm or more, and even more preferably 1.5 μm or more. If it is 0.5 μm or more, unevenness can be formed on the surface of the biaxially oriented polyester film 8. Therefore, slipperiness can be imparted to the biaxially oriented polyester film 8. In addition to this, air that may be trapped when the biaxially oriented polyester film 8 is wound into a roll shape is easily removed, and appearance defects such as wrinkles and air bubbles can be reduced. On the other hand, the weight average particle diameter of the particles is preferably 4.0 μm or less, more preferably 3.8 μm or less, and even more preferably 3.0 μm or less. When the thickness is 4.0 μm or less, it is possible to prevent coarse protrusions from forming on the biaxially oriented polyester film 8 .

The content of particles in the biaxially oriented polyester film 8 is preferably 100 ppm or more. When it is 100 ppm or more, it is possible to further impart slipperiness to the biaxially oriented polyester film 8 and to further reduce the occurrence of appearance defects. On the other hand, the content of particles in the biaxially oriented polyester film 8 is preferably 1000 ppm or less, more preferably 800 ppm or less. When it is 1000 ppm or less, the arithmetic mean height Sa and maximum protrusion height Sp of the surface of the biaxially oriented polyester film 8 can be prevented from becoming excessively high. In addition, since voids that may occur in the biaxially oriented polyester film 8 can be reduced, deterioration of transparency due to voids can be suppressed.
Here, the particle content is the mass of the particles relative to the mass of the biaxially oriented polyester film 8 (that is, the mass of the particles/the mass of the biaxially oriented polyester film 8).

The biaxially oriented polyester film 8 may further contain additives such as antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, plasticizers, and pigments.

In the molecular weight distribution curve obtained by gel permeation chromatography (GPC) of the biaxially oriented polyester film 8, the area ratio of the region having a molecular weight of 1000 or less is preferably 5.5% or less of the total peak area. By being 5.5% or less, that is, by setting an upper limit on the content of components with a molecular weight of 1,000 or less (i.e., low molecular weight components), the yellowishness that the biaxially oriented polyester film 8 may exhibit is reduced. be able to.
When this area ratio is 5.5% or less, when a sealant layer is formed on the biaxially oriented polyester film 8, the peel strength between the biaxially oriented polyester film 8 and the sealant layer can also be improved. This is considered to be because deterioration in peel strength due to low molecular weight components that can act as plastic components can be suppressed.
This area ratio may be 5.4% or less, 5.3% or less, 5.2% or less, 5.1% or less, 5.4% or less, 5.3% or less, 5.2% or less, 5.1% or less, It may be .0% or less. This area ratio may be 4.9% or less, 4.8% or less, 4.7% or less, 4.6% or less, 4. It may be .5% or less.

In addition, it is preferable that the area ratio of the region having a molecular weight of 1000 or less is 1.9% or more of the total peak area.
By setting the content of the low molecular weight component at 1.9% or more, that is, by setting a lower limit for the content of the low molecular weight component, it is possible to ensure the content of the low molecular weight component that can function like a plasticizer.
By setting the content to 1.9% or more, the molecular weight of the polyester contained in the biaxially oriented polyester film 8 can be limited to a certain level or less. This will be explained. Since low molecular weight components are incorporated into polyester during the polymerization process, there is a tendency that the larger the molecular weight of polyester, the less low molecular weight components, and the smaller the molecular weight of polyester, the more low molecular weight components. According to this embodiment, since the area ratio of the region having a molecular weight of 1000 or less is 1.9% or more, that is, since a certain amount or more of low molecular weight components are present, the molecular weight of the polyester contained in the biaxially oriented polyester film 8 is It can be limited to a certain degree.
Therefore, it is possible to further prevent stress during stretching (that is, stretching stress) during the manufacturing process of biaxially oriented polyester film 8 from becoming excessively large, and as a result, it is possible to further suppress or reduce breakage of the film that may occur during stretching. .
This area ratio may be 2.0% or more, 2.2% or more, 2.4% or more, 2.6% or more, 2.0% or more, 2.2% or more, 2.4% or more, 2.6% or more, It may be .8% or more, or it may be 3.0% or more.

The color b ^* value per 1 μm of thickness of the biaxially oriented polyester film 8 is preferably 0.067 or less, more preferably 0.060 or less, and even more preferably 0.050 or less. If it is 0.067 or less, the yellowishness that the biaxially oriented polyester film 8 may exhibit can be limited. Therefore, for example, when a printed layer is formed on the biaxially oriented polyester film 8, the influence of the color tone of the biaxially oriented polyester film 8 on the appearance (that is, the external appearance) of the printed layer can be reduced. Further, for example, when a packaging container is produced using the biaxially oriented polyester film 8, the influence of the color tone of the biaxially oriented polyester film 8 on the appearance of the contents can be reduced.

The intrinsic viscosity of the biaxially oriented polyester film 8 is preferably 0.50 dl/g or more, more preferably 0.51 dl/g or more. When it is 0.50 dl/g or more, mechanical properties, specifically tensile strength and puncture strength, can be further improved. On the other hand, the intrinsic viscosity of the biaxially oriented polyester film 8 is preferably 0.70 dl/g or less, more preferably 0.65 dl/g or less. If it is 0.70 dl/g or less, stress during stretching (that is, stretching stress) in the biaxially oriented polyester film 8 manufacturing process can be further prevented from becoming excessively large, and as a result, breakage of the film that may occur during stretching can be further prevented. can be further suppressed or reduced.

The surface crystallinity of at least one surface of the biaxially oriented polyester film 8 is 1.10 or more, preferably 1.15 or more, more preferably 1.20 or more, and even more preferably 1.25 or more. Here, "one side" is one of both sides of the biaxially oriented polyester film 8.
By having a surface crystallinity of 1.10 or more, the molecular weight of the polyester contained in the biaxially oriented polyester film 8 can be limited to a certain level or less. This will be explained. The crystallization rate becomes faster as the molecular weight of the polyester decreases. Therefore, the higher the surface crystallinity of the biaxially oriented polyester film 8, the lower the molecular weight of the polyester contained in the biaxially oriented polyester film 8 tends to be. Therefore, by having a surface crystallinity of 1.10 or more, the molecular weight of the polyester contained in the biaxially oriented polyester film 8 can be limited to a certain level or less.
By having a surface crystallinity of 1.10 or more, a certain amount of low molecular weight components that can act as plasticizers can be present. This will be explained. The lower the molecular weight of the polyester contained in the biaxially oriented polyester film 8, the more the low molecular weight components in the biaxially oriented polyester film 8 tend to be. This is because low molecular weight components are incorporated into the polyester during the polymerization process. As described above, by having a surface crystallinity of 1.10 or more, the molecular weight of the polyester contained in the biaxially oriented polyester film 8 can be limited to a certain level or less. As a result, a certain amount of low molecular weight components can be present. Therefore, by having a surface crystallinity of 1.10 or more, a certain amount of low molecular weight components that can act like plasticizers can be present.
Therefore, by having a surface crystallinity of 1.10 or more, stress during stretching (that is, stretching stress) in the biaxially oriented polyester film 8 manufacturing process can be prevented from becoming excessively large, and as a result, the stress generated during stretching can be prevented from becoming excessively large. Breakage of the obtained film can be suppressed or reduced.

Similarly, the surface crystallinity of both surfaces of the biaxially oriented polyester film 8 is preferably 1.10 or more, more preferably 1.15 or more, even more preferably 1.20 or more, and even more preferably 1.25 or more.

The surface crystallinity of at least one side of the biaxially oriented polyester film 8 is 1.31 or less, preferably 1.30 or less, more preferably 1.29 or less, and even more preferably 1.28 or less. By having a surface crystallinity of 1.31 or less, it is possible to prevent the biaxially oriented polyester film 8 from becoming excessively brittle (that is, the toughness is excessively deteriorated), so that the mechanical properties, specifically the tensile strength The sheath piercing strength can be improved.

Similarly, the degree of surface crystallinity on both sides of the biaxially oriented polyester film 8 is preferably 1.31 or less, more preferably 1.30 or less, even more preferably 1.29 or less, and even more preferably 1.28 or less.

Note that the surface crystallinity is determined by ATR-IR. That is, it is determined by obtaining a spectrum by the attenuated total reflection method using a Fourier transform infrared spectrophotometer. The surface crystallinity is the intensity ratio of absorption appearing near 1340 cm ^-1 and absorption appearing near 1410 cm ^-1 , specifically, intensity of 1340 cm ^-1 /intensity of 1410 cm ^-1 . The absorption that appears around 1340 cm ⁻¹ is due to the bending vibration of CH ₂ (trans structure) of ethylene glycol. On the other hand, the absorption that appears near 1410 cm ^-1 is unrelated to crystal or orientation.
ATR-IR measurement is performed under the following conditions.
FT-IR: Bio Rad DIGILAB FTS-60A/896
Single reflection ATR attachment: golden gate MKII (manufactured by SPECAC)
Internal reflective element: Diamond Incident angle: 45°
Resolution: 4cm ^-1
Accumulated number of times: 128 times

The melting point of the biaxially oriented polyester film 8 is 251°C or higher, preferably 252°C or higher. Since the temperature is 251°C or higher, it has excellent heat resistance. On the other hand, the melting point of the biaxially oriented polyester film 8 is preferably 270°C or lower, more preferably 268°C or lower. When the temperature is 270°C or lower, it is possible to prevent the viscosity from becoming excessively high when melt extruding the raw material polyester (for example, chemically recycled polyester) for forming the biaxially oriented polyester film 8, and as a result, high-speed film formation is possible. becomes possible.

The specific melt resistance at 285°C of the biaxially oriented polyester film 8 is preferably 1.0×10 ⁸ Ω・cm or less, more preferably 0.5×10 ⁸ Ω・cm or less, and 0.25×10 ⁸ Ω・cm. The following are more preferred. If it is 1.0×10 ⁸ Ω・cm or less, when the polyester composition melt-extruded in the manufacturing process of the biaxially oriented polyester film 8 is adhered to the cooling drum by the electrostatic adhesion casting method, the polyester composition Since the surface of the object can be effectively charged with static electricity, the polyester composition can be brought into close contact with the cooling drum. Therefore, the formation of pinner bubbles (ie, streak-like defects caused by air entering between the polyester composition and the cooling drum) can be suppressed without reducing the film forming speed excessively. Note that the film forming speed is the running speed (m/min) of the biaxially oriented polyester film 8 when the biaxially oriented polyester film 8 is wound onto a master roll. The film forming speed can be calculated by multiplying the casting speed by the MD stretching ratio. On the other hand, the melt specific resistance may be, for example, 0.01×10 ⁸ Ω・cm or more, 0.03×10 ⁸ Ω・cm or more, or 0.05×10 ⁸ Ω・cm. It may be more than that. When it is 0.01×10 ⁸ Ω·cm or more, the formation of foreign matter (for example, foreign matter caused by an alkaline earth metal compound that can lower the melting resistivity) can be suppressed or reduced.

The specific melt resistance of the biaxially oriented polyester film 8 can be adjusted by the content of the alkaline earth metal compound and the content of the phosphorus compound in the biaxially oriented polyester film 8. For example, the alkaline earth metal atoms (hereinafter sometimes referred to as "M2") constituting the alkaline earth metal compound have the effect of lowering the melting resistivity, so the content of the alkaline earth metal compound can be increased. The more the melting resistivity can be lowered. On the other hand, although the phosphorus compound itself is not considered to have the effect of lowering the melting resistivity of the biaxially oriented polyester film 8, it contributes to lowering the melting resistivity in the presence of the alkaline earth metal compound. Although the reason for this is not clear, it is thought that the inclusion of a phosphorus compound suppresses the generation of foreign substances and increases the amount of charge carriers.

Examples of alkaline earth metal compounds include alkaline earth metal hydroxides, aliphatic dicarboxylate salts (acetate, butyrate, etc., preferably acetate), aromatic subcarboxylate salts, and compounds having a phenolic hydroxyl group. Examples include salts with (such as salts with phenol). Examples of alkaline earth metals include magnesium, calcium, strontium, and barium. Among them, magnesium is preferred. More specifically, magnesium hydroxide, magnesium acetate, calcium acetate, strontium acetate, barium acetate, etc. can be mentioned. Among them, magnesium acetate is preferred. The alkaline earth metal compounds can be used alone or in combination of two or more. Although there are definitions of alkaline earth metals that do not include magnesium, in this specification, alkaline earth metals are used as a term that includes magnesium. In other words, alkaline earth metals herein refer to elements of group IIa of the periodic table.

In addition, chemically recycled polyester does not contain any or substantially alkaline earth metal compounds because catalysts and metal ions are removed during the recycling process. The content of the alkaline earth metal compound can be adjusted by using a fuel-derived polyester or a masterbatch in which an alkaline earth metal compound is added thereto.

The content of the alkaline earth metal compound in the biaxially oriented polyester film 8 is preferably 20 ppm or more, more preferably 22 ppm or more, and 24 ppm or more on an alkaline earth metal atom basis (that is, in terms of alkaline earth metal atoms). More preferred. On the other hand, the content of the alkaline earth metal compound is preferably 400 ppm or less, more preferably 350 ppm or less, even more preferably 300 ppm or less, based on alkaline earth metal atoms. When the content is 400 ppm or less, it is possible to suppress the generation of foreign substances and coloring caused by the alkaline earth metal compound.
Here, the content of the alkaline earth metal compound is the mass of the alkaline earth metal compound on the basis of the alkaline earth metal atoms (that is, the content of the alkaline earth metal compound on the basis of the alkaline earth metal atoms) with respect to the mass of the biaxially oriented polyester film 8. mass of earth metal compound/mass of biaxially oriented polyester film 8).

The content of the magnesium compound in the biaxially oriented polyester film 8 is preferably 20 ppm or more, more preferably 22 ppm or more, and even more preferably 24 ppm or more on a magnesium atom basis (that is, in terms of magnesium atoms). On the other hand, the content of the magnesium compound is preferably 400 ppm or less, more preferably 350 ppm or less, and even more preferably 300 ppm or less, based on magnesium atoms.

Phosphorus compounds include, for example, phosphoric acids (phosphoric acid, phosphorous acid, hypophosphorous acid, etc.), their esters (alkyl esters, aryl esters, etc.), alkylphosphonic acids, arylphosphonic acids, and their esters (alkyl esters, aryl esters, etc.). Preferred phosphorus compounds include phosphoric acid, aliphatic esters of phosphoric acid (alkyl esters of phosphoric acid, etc.; for example, phosphoric acid mono-C1-6 alkyl esters such as phosphoric acid monomethyl ester, phosphoric acid monoethyl ester, phosphoric acid monobutyl ester) , phosphoric acid di-C1-6 alkyl esters such as phosphoric acid dimethyl ester, phosphoric acid diethyl ester, and phosphoric acid dibutyl ester, phosphoric acid tri-C1-6 alkyl esters such as phosphoric acid trimethyl ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester, etc. ), aromatic esters of phosphoric acid (such as mono-, di-, or tri-C6-9 aryl esters of phosphoric acid, such as triphenyl phosphate, tricresyl phosphate, etc.), aliphatic esters of phosphorous acid (alkyl esters; for example, mono-, di-, or tri-C1-6 alkyl esters of phosphorous acid such as trimethyl phosphite, tributyl phosphite, etc.), alkylphosphonic acids (C1-6 alkyl esters such as methylphosphonic acid, ethylphosphonic acid, etc.); phosphonic acid), alkylphosphonic acid alkyl esters (mono- or di-C1-6 alkyl esters of C1-6 alkylphosphonic acids such as dimethyl methylphosphonate, dimethyl ethylphosphonate, etc.), arylphosphonic acid alkyl esters (dimethyl phenylphosphonate, phenyl mono- or di-C1-6 alkyl esters of C6-9 arylphosphonic acids such as diethyl phosphonate), arylphosphonic acid aryl esters (mono- or di-C6-9 aryl esters of C6-9 arylphosphonic acids such as diphenyl phenylphosphonate); etc.) can be mentioned. Particularly preferred phosphorus compounds include phosphoric acid and trialkyl phosphate (trimethyl phosphate, etc.). These phosphorus compounds can be used alone or in combination of two or more.

The content of the phosphorus compound in the biaxially oriented polyester film 8 is preferably 10 ppm or more, more preferably 11 ppm or more, and even more preferably 12 ppm or more, on a phosphorus atom basis (that is, in terms of phosphorus atoms). When it is 10 ppm or more, melt specific resistance can be effectively lowered. Further, the generation of foreign matter can be suppressed. The content of the phosphorus compound may be 20 ppm or more, 40 ppm or more, or 50 ppm or more in terms of phosphorus atoms. On the other hand, the content of the phosphorus compound is preferably 600 ppm or less, more preferably 550 ppm or less, and even more preferably 500 ppm or less, based on phosphorus atoms. If it is 600 ppm or less, diethylene glycol can reduce the production. The content of the phosphorus compound may be 400 ppm or less, 200 ppm or less, or 100 ppm or less in terms of phosphorus atoms.
Here, the content of the phosphorus compound is the mass of the phosphorus compound on a phosphorus atom basis with respect to the mass of the biaxially oriented polyester film 8 (that is, the mass of the phosphorus compound on a phosphorus atom basis/the mass of the biaxially oriented polyester film 8 ).

In the biaxially oriented polyester film 8, the mass ratio of alkaline earth metal atoms (i.e., M2) to phosphorus atoms (P), that is, the ratio of M2 mass to P mass (M2 mass/P mass) is 1.0 or more. is preferable, 1.1 or more is more preferable, 1.2 or more is even more preferable, 1.3 or more is even more preferable, and 1.4 or more is even more preferable. When it is 1.0 or more, the melt specific resistance of the biaxially oriented polyester film 8 can be effectively reduced. On the other hand, this mass ratio is preferably 5.0 or less, more preferably 4.5 or less, and even more preferably 4.0 or less. When it is 5.0 or less, generation of foreign substances and coloring can be suppressed.

When the number of moles of all the dicarboxylic acid components in the biaxially oriented polyester film 8 is 100 mol%, the number of moles of the isophthalic acid component is preferably 0.1 mol% or more, more preferably 0.15 mol% or more, The content is more preferably 0.2 mol% or more, and even more preferably 0.4 mol% or more. If the content is 0.1 mol % or more, when a sealant layer is provided on the biaxially oriented polyester film 8, the peel strength between the biaxially oriented polyester film 8 and the sealant layer can be improved. On the other hand, the number of moles of the isophthalic acid component is preferably 3.0 mol% or less, more preferably 2.5 mol% or less, even more preferably 2.2 mol% or less, and even more preferably 2.0 mol% or less. If it is 3.0 mol% or less, it is possible to prevent the crystallinity from decreasing excessively, and therefore the heat resistance and mechanical properties (specifically, tensile strength and puncture strength) can be prevented from excessively decreasing. It can be prevented. Moreover, the thickness unevenness of the biaxially oriented polyester film 8 can be reduced, and the heat shrinkage rate of the biaxially oriented polyester film 8 can also be limited.

The tensile strength of the biaxially oriented polyester film 8 in at least one direction is preferably 180 MPa or more, more preferably 185 MPa or more, and even more preferably 190 MPa or more. When it is 180 MPa or more, a product (for example, a packaging container) having excellent strength can be produced using the biaxially oriented polyester film 8.

Similarly, the tensile strength of the biaxially oriented polyester film 8 in the MD (i.e. 0° direction), 45° direction, TD (i.e. 90° direction), and 135° direction is preferably 180 MPa or more, more preferably 185 MPa or more, More preferably, the pressure is 190 MPa or more.

The tensile strength of the biaxially oriented polyester film 8 in at least one direction is preferably 350 MPa or less, more preferably 340 MPa or less, and even more preferably 330 MPa or less. If it is 350 MPa or less, stress during stretching (that is, stretching stress) in the biaxially oriented polyester film 8 manufacturing process can be further prevented from becoming excessively large, and as a result, breakage of the film that may occur during stretching can be further suppressed or reduced. can do. The tensile strength may be 320 MPa or less.

Similarly, the tensile strength of the biaxially oriented polyester film 8 in the MD (i.e. 0° direction), 45° direction, TD (i.e. 90° direction), and 135° direction is preferably 350 MPa or less, more preferably 340 MPa or less, More preferably, it is 330 MPa or less. The tensile strength may be 320 MPa or less.

The puncture strength of the biaxially oriented polyester film 8 is preferably 0.50 N/μm or more, more preferably 0.52 N/μm or more, and even more preferably 0.55 N/μm or more. When it is 0.50 N/μm or more, a product (for example, a packaging container) having excellent strength can be produced using the biaxially oriented polyester film 8. For example, the biaxially oriented polyester film 8 can be used to create a packaging container that is difficult to puncture.

The lamination strength of the biaxially oriented polyester film 8 is preferably 3.0 N/15 mm or more, more preferably 3.5 N/15 mm or more, and even more preferably 4.0 N/15 mm or more. When it is 3.0 N/15 mm or more, when a sealant layer is provided on the biaxially oriented polyester film 8, a product (for example, a packaging container) that is difficult to separate between the sealant layers can be produced.

The heat shrinkage rate of the biaxially oriented polyester film 8 in the longitudinal direction, that is, MD, is preferably 2.0% or less, more preferably 1.8% or less. When the content is 2.0% or less, the frequency of occurrence of deformation and wrinkles due to heat can be reduced when the biaxially oriented polyester film 8 is subjected to secondary processing such as vapor deposition or printing. The heat shrinkage rate of the MD may be, for example, 0.5% or more, or 0.8% or more.

The heat shrinkage rate in the width direction, that is, TD, of the biaxially oriented polyester film 8 is preferably -1.0% or more and 1.0% or less, more preferably -0.8% or more and 0.8% or less. If it is -1.0% or more and 1.0% or less, the frequency of occurrence of deformation and wrinkles due to heat can be reduced when performing secondary processing such as vapor deposition or printing.

The thickness of the biaxially oriented polyester film 8 is preferably 5 μm or more, more preferably 8 μm or more, and even more preferably 9 μm or more. When the thickness is 5 μm or more, the biaxially oriented polyester film 8 has excellent rigidity, so that the frequency of wrinkles occurring when the biaxially oriented polyester film 8 is wound up can be reduced. On the other hand, the thickness of the biaxially oriented polyester film 8 is preferably 200 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 25 μm or less. The thinner the thickness, the lower the cost.

The biaxially oriented polyester film 8 includes a first layer 81 (hereinafter also referred to as "surface layer 81"), a second layer 82 (hereinafter also referred to as "center layer 82"), and a third layer 83 (hereinafter referred to as " (also referred to as "surface layer 83"). The first layer 81, the second layer 82, and the third layer 83 are arranged in this order in the thickness direction of the biaxially oriented polyester film 8. Note that another layer may exist between the first layer 81 and the second layer 82 or between the second layer 82 and the third layer 83.

The first layer 81, that is, the surface layer 81, preferably contains chemically recycled polyester. If the first layer 81 contains chemically recycled polyester, the environmental load can be further reduced.

The explanation of the chemically recycled polyester in the first layer 81 is omitted because it overlaps with the above explanation (that is, the explanation of the chemically recycled polyester of the biaxially oriented polyester film 8). Therefore, the explanation of the chemically recycled polyester in the biaxially oriented polyester film 8 can also be treated as the explanation of the chemically recycled polyester in the first layer 81.

The content of the chemically recycled polyester is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the first layer 81 is 100% by mass. When the content is 10% by mass or more, the environmental load can be further reduced. On the other hand, the content of the chemically recycled polyester is preferably 95% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, when the first layer 81 is 100% by mass.

The first layer 81 preferably contains fossil fuel-derived polyester. The description of the fossil fuel-derived polyester in the first layer 81 is omitted because it overlaps with the above description (that is, the description of the fossil fuel-derived polyester of the biaxially oriented polyester film 8). Therefore, the description of the fossil fuel-derived polyester in the biaxially oriented polyester film 8 can also be treated as the description of the fossil fuel-derived polyester in the first layer 81.

The content of the fossil fuel-derived polyester is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the first layer 81 is 100% by mass. When the content is 5% by mass or more, a certain amount of width in which the physical properties of the first layer 81 can be adjusted can be secured. On the other hand, the content of the fossil fuel-derived polyester can be 100% by mass or less when the first layer 81 is 100% by mass. The content of fossil fuel-derived polyester is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

The first layer 81 may contain other polyesters, such as mechanically recycled polyester or biomass polyester.

When the first layer 81 is 100% by mass, the polyester content is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more.

The first layer 81 may contain resin other than polyester.

Preferably, the first layer 81 further includes particles. When the first layer 81 contains particles, unevenness can be formed on the surface of the biaxially oriented polyester film 8 . Therefore, slipperiness can be imparted to the biaxially oriented polyester film 8. In addition to this, air that may be trapped when the biaxially oriented polyester film 8 is wound into a roll shape is easily removed, and appearance defects such as wrinkles and air bubbles can be reduced.

The explanation of the particles in the first layer 81 is omitted because it overlaps with the above explanation (that is, the explanation of the particles of the biaxially oriented polyester film 8). Therefore, the description of the particles in the biaxially oriented polyester film 8 can also be treated as the description of the particles in the first layer 81.

The content of particles in the first layer 81 is preferably 500 ppm or more, more preferably 600 ppm or more, and even more preferably 700 ppm or more. When it is 500 ppm or more, it is possible to further impart slipperiness to the biaxially oriented polyester film 8 and to further reduce the occurrence of appearance defects. On the other hand, the content of particles in the first layer 81 may be 3000 ppm or less, 2000 ppm or less, or 1500 ppm or less.
Here, the particle content is the mass of the particles relative to the mass of the first layer 81 (that is, the mass of the particles/the mass of the first layer 81).

The thickness of the first layer 81 is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more. The thickness of the first layer 81 is preferably 7 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less.

The description of the third layer 83, that is, the surface layer 83 is omitted because it overlaps with the description of the first layer 81. Therefore, the explanation of the first layer 81 can also be treated as the explanation of the third layer 83. For example, explanations about chemically recycled polyester, fossil fuel-derived polyester, particles, thickness, etc. for the first layer 81 can be treated as explanations for the third layer 83. Of course, the first layer 81 and the third layer 83 can be independent from each other in terms of composition, physical properties (for example, thickness), and the like. Therefore, for example, the compositions of the first layer 81 and the third layer 83 may be the same or different. The thicknesses of both may be the same or different.

The second layer 82, ie, the center layer 82, preferably contains chemically recycled polyester. If the second layer 82 contains chemically recycled polyester, the environmental load can be further reduced.

The explanation of the chemically recycled polyester in the second layer 82 is omitted because it overlaps with the above explanation (that is, the explanation of the chemically recycled polyester of the biaxially oriented polyester film 8). Therefore, the description of the chemically recycled polyester in the biaxially oriented polyester film 8 can also be treated as the description of the chemically recycled polyester in the second layer 82.

The content of the chemically recycled polyester is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the second layer 82 is 100% by mass. When the content is 10% by mass or more, the environmental load can be further reduced. On the other hand, the content of the chemically recycled polyester is preferably 95% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, when the second layer 82 is 100% by mass.

The second layer 82 preferably contains fossil fuel-derived polyester. The description of the fossil fuel-derived polyester in the second layer 82 is omitted because it overlaps with the above description (that is, the description of the fossil fuel-derived polyester of the biaxially oriented polyester film 8). Therefore, the description of the fossil fuel-derived polyester in the biaxially oriented polyester film 8 can also be treated as the description of the fossil fuel-derived polyester in the second layer 82.

The content of the fossil fuel-derived polyester is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the second layer 82 is 100% by mass. When the content is 5% by mass or more, a certain amount of width in which the physical properties of the second layer 82 can be adjusted can be secured. On the other hand, the content of the fossil fuel-derived polyester is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, when the first layer 81 is 100% by mass.

The second layer 82 may include other polyesters, such as mechanically recycled polyester or biomass polyester.

When the second layer 82 is 100% by mass, the polyester content is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more.

The second layer 82 may contain resin other than polyester.

The second layer 82 may or may not contain particles. The explanation of the particles in the second layer 82 is omitted because it overlaps with the above explanation (that is, the explanation of the particles of the biaxially oriented polyester film 8). Therefore, the description of the particles in the biaxially oriented polyester film 8 can also be treated as a description of the particles in the second layer 82. Note that if the second layer 82 does not contain particles, voids that may occur around the particles will not occur, so that odor components can be prevented from passing through the biaxially oriented polyester film 8. In addition to this, it is easy to mix and use recovered raw materials from edge portions generated in the film forming process, recycled raw materials from other film forming processes, etc. in a timely manner, which is advantageous in terms of cost.

The content of particles in the second layer 82 may be 3000 ppm or less, 2000 ppm or less, 1500 ppm or less, 1000 ppm or less, or 500 ppm or less. , 100 ppm or less, 50 ppm or less, or 0 ppm or less.
Here, the content of particles is the mass of particles relative to the mass of second layer 82 (that is, mass of particles/mass of second layer 82).

The thickness of the second layer 82 is preferably larger than the thickness of the first layer 81 and the thickness of the third layer 83. The thickness of the second layer 82 is preferably 5 μm or more, more preferably 8 μm or more, and even more preferably 9 μm or more. When the thickness is 5 μm or more, the biaxially oriented polyester film 8 has excellent rigidity, so that the frequency of wrinkles occurring when the biaxially oriented polyester film 8 is wound up can be reduced. On the other hand, the thickness of the biaxially oriented polyester film 8 is preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. The thinner the thickness, the lower the cost.

Some composition patterns of the first layer 81, second layer 82, and third layer 83 will be supplementarily explained.
As a first composition pattern (hereinafter also referred to as "composition pattern A"), the first layer 81 contains chemically recycled polyester, the second layer 82 contains chemically recycled polyester, and the third layer 83 contains chemically recycled polyester. One example is a pattern that includes. According to composition pattern A, chemically recycled polyester with few impurities constitutes both surface layers of the biaxially oriented polyester film 8, so defects in the biaxially oriented polyester film 8 can be reduced. The description of the first layer 81, second layer 82, and third layer 83 in composition pattern A is omitted because it overlaps with the above description (i.e., the description of the first layer 81, second layer 82, and third layer 83). . Therefore, the above description can also be treated as a description of the first layer 81, second layer 82, and third layer 83 in composition pattern A. Therefore, the first layer 81 may contain polyester other than chemically recycled polyester, the second layer 82 may contain polyester other than chemically recycled polyester, and the third layer 83 may contain polyester other than chemically recycled polyester. It may also contain polyester.
The second composition pattern (hereinafter also referred to as "composition pattern B") is a pattern in which the first layer 81 contains chemically recycled polyester, and neither the second layer 82 nor the third layer 83 contains chemically recycled polyester. can be mentioned. According to composition pattern B, the surface layer of the biaxially oriented polyester film 8 is made of chemically recycled polyester containing few impurities, so that defects in the biaxially oriented polyester film 8 can be reduced. The explanation of the first layer 81, second layer 82, and third layer 83 in composition pattern B is omitted because it overlaps with the above explanation (i.e., the explanation of the first layer 81, second layer 82, and third layer 83). . Therefore, the above description can also be treated as a description of the first layer 81, second layer 82, and third layer 83 in composition pattern B. Therefore, the first layer 81 may contain polyester other than chemically recycled polyester.
In addition, in composition pattern B, it is preferable that the second layer 82 and/or the third layer 83 contain mechanically recycled polyester. According to this, the recycled raw material ratio can be further increased. In other words, the environmental load can be further reduced.
A third composition pattern (hereinafter also referred to as "composition pattern C") is a pattern in which the second layer 82 contains chemically recycled polyester, and neither the first layer 81 nor the third layer 83 contains chemically recycled polyester. can be mentioned. The description of the first layer 81, second layer 82, and third layer 83 in composition pattern C is omitted because it overlaps with the above description (i.e., the description of the first layer 81, second layer 82, and third layer 83). . Therefore, the above explanation can also be treated as explanation of the first layer 81, second layer 82, and third layer 83 in composition pattern C. Therefore, the second layer 82 may contain polyester other than chemically recycled polyester.
In addition, in composition pattern C, it is preferable that the first layer 81 and/or the third layer 83 contain mechanically recycled polyester. According to this, the recycled raw material ratio can be further increased. In other words, the environmental load can be further reduced.
As a fourth composition pattern (hereinafter also referred to as "composition pattern D"), the first layer 81 contains chemically recycled polyester, the second layer 82 contains chemically recycled polyester, and the third layer 83 contains chemically recycled polyester. One example is a pattern that does not include . According to composition pattern D, the surface layer of the biaxially oriented polyester film 8 is made of chemically recycled polyester containing few impurities, so that defects in the biaxially oriented polyester film 8 can be reduced. The description of the first layer 81, second layer 82, and third layer 83 in composition pattern D is omitted because it overlaps with the above description (i.e., the description of the first layer 81, second layer 82, and third layer 83). . Therefore, the above description can also be treated as a description of the first layer 81, second layer 82, and third layer 83 in composition pattern D. Therefore, the first layer 81 may contain polyester other than chemically recycled polyester, and the second layer 82 may contain polyester other than chemically recycled polyester.
In addition, in composition pattern D, it is preferable that the third layer 83 contains mechanically recycled polyester. According to this, the recycled raw material ratio can be further increased. In other words, the environmental load can be further reduced.
As a fifth composition pattern (hereinafter also referred to as "composition pattern E"), the first layer 81 contains chemically recycled polyester, the second layer 82 does not contain chemically recycled polyester, and the third layer 83 contains chemically recycled polyester. One example is a pattern that includes. According to composition pattern E, chemically recycled polyester with few impurities constitutes both surface layers of the biaxially oriented polyester film 8, so defects in the biaxially oriented polyester film 8 can be reduced. The description of the first layer 81, second layer 82, and third layer 83 in composition pattern E is omitted because it overlaps with the above description (i.e., the description of the first layer 81, second layer 82, and third layer 83). . Therefore, the above description can also be treated as a description of the first layer 81, second layer 82, and third layer 83 in composition pattern E. Therefore, the first layer 81 may contain polyester other than chemically recycled polyester, and the third layer 83 may contain polyester other than chemically recycled polyester.
Note that in composition pattern E, the second layer 82 preferably contains mechanically recycled polyester. According to this, the recycled raw material ratio can be further increased. In other words, the environmental load can be further reduced.

The raw material for forming the first layer 81 is supplied to the first extruder, the raw material for forming the second layer 82 is supplied to the second extruder, and the raw material for forming the third layer 83 is supplied to the second extruder. They are fed to a third extruder, then melted, guided from the first, second and third extruders to a T-die, laminated within the T-die, and then melted from the T-die. The biaxially oriented polyester film 8 can be produced by extruding, solidifying with a cooling drum, and biaxially stretching. Of course, these raw materials may be led from the first, second, and third extruders to the feed block, stacked in the feed block, and then extruded from the T-die. Note that a method other than the T-die method, such as a tubular method, may be employed.

Examples of raw materials for forming the first layer 81 include chemically recycled polyester, fossil fuel-derived polyester, particle-containing masterbatch, and alkaline earth metal compound/phosphorus compound-containing masterbatch (hereinafter referred to as "MP masterbatch"). ) can be mentioned. It is preferable to use at least these as raw materials for forming the first layer 81.

The particle-containing masterbatch can include polyester and particles (eg, silica). The particle-containing masterbatch may include particles (eg, silica) at the highest concentration of the individual ingredients used to form the first layer 81 .

The polyester of the particle-containing masterbatch may be chemically recycled polyester, fossil fuel-derived polyester, mechanically recycled polyester, or biomass polyester. Among these, chemically recycled polyester and fossil fuel-derived polyester are preferred, and fossil fuel-derived polyester is more preferred.

The content of particles in the particle-containing masterbatch is preferably 5,000 ppm or more, more preferably 10,000 ppm or more, and even more preferably 20,000 ppm or more. On the other hand, the content of particles in the particle-containing masterbatch may be 1,000,000 ppm or less, 200,000 ppm or less, or 100,000 ppm or less.
Here, the content of particles is the mass of particles relative to the mass of masterbatch containing particles (that is, mass of particles/mass of masterbatch containing particles).

On the other hand, the MP masterbatch (that is, the alkaline earth metal compound/phosphorus compound-containing masterbatch) can contain polyester, an alkaline earth metal compound, and a phosphorus compound. Among the individual raw materials for forming the first layer 81, the MP masterbatch contains the alkaline earth metal compound at the highest concentration and also contains the phosphorus compound at the highest concentration.

The polyester of the MP masterbatch may be chemically recycled polyester, fossil fuel-derived polyester, mechanically recycled polyester, or biomass polyester. Among these, chemically recycled polyester and fossil fuel-derived polyester are preferred, and fossil fuel-derived polyester is more preferred. Note that the MP masterbatch can be produced, for example, by adding a large amount of an alkaline earth metal compound and a phosphorus compound when polymerizing polyester.

The content of the alkaline earth metal compound in the MP masterbatch is preferably 200 ppm or more, preferably 400 ppm or more, preferably 600 ppm or more, and 700 ppm on an alkaline earth metal atom basis (that is, in terms of alkaline earth metal atoms). The above is preferable. The content of the alkaline earth metal compound may be, for example, 3000 ppm or less, 2000 ppm or less, or 1500 ppm or less, based on alkaline earth metal atoms.
Here, the content of the alkaline earth metal compound is the mass of the alkaline earth metal compound on the basis of alkaline earth metal atoms (in other words, the content of the alkaline earth metal compound on the basis of alkaline earth metal atoms) with respect to the mass of the MP masterbatch. mass of compound/mass of MP masterbatch).

The content of the magnesium compound in the MP masterbatch is, for example, preferably 200 ppm or more, preferably 400 ppm or more, preferably 600 ppm or more, and preferably 700 ppm or more, on a magnesium compound atom basis (that is, in terms of magnesium compound atoms). The content of the alkaline earth metal compound may be, for example, 3000 ppm or less, 2000 ppm or less, or 1500 ppm or less, based on magnesium compound atoms.

The content of the phosphorus compound in the MP masterbatch is preferably, for example, 150 ppm or more, more preferably 300 ppm or more, even more preferably 350 ppm or more, and even more preferably 400 ppm or more, on a phosphorus atom basis (that is, in terms of phosphorus atoms). On the other hand, the content of the phosphorus compound may be 1000 ppm or less, 800 ppm or less, or 700 ppm or less based on phosphorus atoms.
Here, the content of the phosphorus compound is the mass of the phosphorus compound on a phosphorus atom basis with respect to the mass of the MP masterbatch (that is, the mass of the phosphorus compound on a phosphorus atom basis/the mass of the MP masterbatch).

Note that instead of the MP masterbatch, an alkaline earth metal compound-containing masterbatch and a phosphorus compound-containing masterbatch may be used. The alkaline earth metal compound-containing masterbatch can include a polyester and an alkaline earth metal compound. This masterbatch contains the alkaline earth metal compound at the highest concentration among the individual raw materials for forming the first layer 81. The phosphorus compound-containing masterbatch can include a polyester and a phosphorus compound. This masterbatch contains the highest concentration of phosphorus compounds among the individual raw materials for forming the first layer 81.

Examples of raw materials for forming the second layer 82 include chemically recycled polyester, fossil fuel-derived polyester, and a masterbatch containing an alkaline earth metal compound and a phosphorus compound (that is, MP masterbatch). It is preferable to use at least these as raw materials for forming the second layer 82.

The description of the MP masterbatch in the second layer 82 is omitted because it overlaps with the above description (that is, the description of the MP masterbatch in the first layer 81). Therefore, the explanation of the MP masterbatch in the first layer 81 can also be treated as the explanation of the MP masterbatch in the second layer 82.

The description of the raw materials for forming the third layer 83 is omitted because it overlaps with the description of the raw materials for forming the first layer 81. Therefore, the description of the raw materials for forming the first layer 81 can also be treated as the description of the raw materials for forming the third layer 83. Of course, the raw material for forming the first layer 81 and the raw material for forming the third layer 83 can be independent from each other. Therefore, for example, these raw materials may be the same or different.

These raw materials (specifically, the raw materials for forming the first layer 81, second layer 82, and third layer 83) are preferably dried before being supplied to the extruder. For drying, for example, a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer can be used.

The raw material for forming the first layer 81 is sent to the first extruder, the raw material for forming the second layer 82 is sent to the second extruder, and the raw material for forming the third layer 83 is sent to the third extruder. After being fed to an extruder and melted, they can be led from the first, second and third extruders to a T-die or feedblock where they can be laminated. It is preferable that these raw materials melt at a temperature not lower than the melting point of the polyester in the raw materials and not lower than 200°C and not higher than 300°C.

A film-like polyester composition can be extruded from a T-die and cast onto a cooling drum. Thereby, the polyester composition can be rapidly solidified, and as a result, a substantially unoriented unstretched film can be obtained. Note that the surface temperature of the cooling drum is preferably 40° C. or lower.

Next, the unstretched film can be biaxially stretched. Biaxial stretching can enhance mechanical properties such as tensile strength. The biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. Among these, sequential biaxial stretching is preferred. In the sequential biaxial stretching, it is preferable that the unstretched film is stretched in the longitudinal direction, that is, MD, and the sheet after MD stretching is stretched in the width direction, that is, TD. According to this, the biaxially oriented polyester film 8 having excellent thickness uniformity can be manufactured at a relatively high film forming speed.

The temperature at which the unstretched film is stretched in the longitudinal direction, that is, the MD stretching temperature, is preferably 80°C or higher and 130°C or lower. The stretching ratio at this time, that is, the MD stretching ratio is preferably 3.3 times or more and 4.7 times or less. When the temperature is 80°C or more and 4.7 times or less, shrinkage stress in the longitudinal direction can be reduced, the bowing phenomenon can be reduced, and variations in molecular orientation and heat shrinkage rate in the width direction of the biaxially oriented polyester film 8 can be reduced. and distortion can be reduced.

Note that the method for stretching the unstretched film in the longitudinal direction may be, for example, a method of stretching in multiple stages between a plurality of rolls, or a method of stretching by heating with an infrared heater or the like. The latter is preferred because it is easy to raise the temperature, local heating is easy, and scratches and defects caused by the roll can be reduced.

At least one surface of the longitudinally stretched film may be subjected to surface treatment such as corona treatment or plasma treatment, if necessary. If necessary, a resin dispersion or a resin solution may be applied to at least one surface of the film stretched in the longitudinal direction. As a result, functions such as easy slipping, easy adhesion, and antistatic properties can be imparted. Note that both surface treatment such as corona treatment or plasma treatment and application of a resin dispersion or resin solution may be performed.

The film stretched in the longitudinal direction is guided into a tenter device, both ends of the film are gripped with clips, the film is heated to a predetermined temperature with hot air, and the distance between the clips is widened while being conveyed in the longitudinal direction. can be stretched in the width direction.

The preheating temperature when stretching the film in the width direction is preferably 100°C or more and 130°C or less. When the temperature is 100°C or higher, the shrinkage stress generated when stretching in the longitudinal direction can be reduced, the bowing phenomenon can be reduced, and variations in molecular orientation and heat shrinkage rate in the width direction of the biaxially oriented polyester film 8 can be reduced. and distortion can be reduced.

The temperature at which the film is stretched in the width direction, that is, the TD stretching temperature, is preferably 105°C or more and 135°C or less. When the temperature is 105° C. or higher, stretching stress in the longitudinal direction caused by TD stretching can be reduced, and an increase in the bowing phenomenon can be suppressed. When the temperature is 135° C. or lower, even when polyester (for example, chemically recycled polyester) whose heating crystallization temperature is about 130° C. is used, breakage of the film that may occur during stretching can be suppressed or reduced.

The stretching ratio when stretching the film in the width direction, that is, the TD stretching ratio, is preferably 3.5 times or more and 5.0 times or less. When it is 3.5 times or more, it is easy to obtain a high yield in terms of material balance, and it is also possible to suppress a decrease in mechanical strength, and also to suppress an increase in thickness unevenness in the width direction. If it is 5.0 times or less, breakage of the film that may occur during stretching can be suppressed or reduced.

The biaxially stretched film can be heated for heat setting. The heat setting temperature is preferably 220°C or more and 250°C or less. When the temperature is 220° C. or higher, it is possible to prevent the thermal shrinkage rate from becoming excessively high in both the longitudinal direction and the width direction. Therefore, thermal dimensional stability during secondary processing can be improved. When the temperature is 250° C. or lower, an increase in the bowing phenomenon can be suppressed, and variations and distortions in the molecular orientation and thermal shrinkage rate in the width direction of the biaxially oriented polyester film 8 can be reduced.

A heat relaxation treatment can be performed in conjunction with the heat setting treatment or separately from the heat setting treatment. The relaxation rate in the width direction in the thermal relaxation treatment is preferably 4% or more and 8% or less. When it is 4% or more, it is possible to prevent the heat shrinkage rate in the width direction from becoming excessively high. Therefore, thermal dimensional stability during secondary processing can be improved. When it is 8% or less, it is possible to prevent the stretching stress in the longitudinal direction at the center portion in the width direction of the film from becoming excessively large, and it is possible to suppress an increase in the bowing phenomenon.

During thermal relaxation treatment, until the biaxially stretched film shrinks due to thermal relaxation, the binding force in the width direction decreases and the film loosens due to its own weight, and hot air blows out from nozzles installed above and below the film. Air currents may cause the film to swell. As described above, since the film is likely to fluctuate up and down, the amount of change in the orientation angle of the biaxially oriented polyester film 8 tends to fluctuate greatly. For example, the speed of the hot air blown from the nozzle can be adjusted so that the film can remain parallel.

Corona discharge treatment, glow discharge treatment, flame treatment, and surface roughening treatment may be performed. Furthermore, anchor coating treatment or the like may be performed.

The wide biaxially oriented polyester film 8 stretched and formed by such a procedure may be wound up using a winder device to form a roll. In other words, a master roll may be produced.

The width of the master roll is preferably 5000 mm or more and 10000 mm or less. When it is 5000 mm or more, the cost per film area can be suppressed in subsequent secondary processing such as slitting process, vapor deposition process, and printing process.

The winding length of the master roll is preferably 10,000 m or more and 100,000 m or less. When the length is 10,000 m or more, the cost per film area can be suppressed in subsequent secondary processing such as slitting process, vapor deposition process, and printing process.

It is also possible to slit the master roll and wind it up to form a roll. In other words, a film roll may be produced.

The winding width of the film roll is preferably 400 mm or more and 3000 mm or less. If it is 400 mm or more, the frequency of replacing the film roll in the printing process can be reduced, and costs can be reduced. When it is 3000 mm or less, the roll width is not excessively large and the roll weight can be prevented from becoming excessively heavy. In other words, the handling property is good.

The winding length of the film roll is preferably 2000 m or more and 65000 m or less. When the length is 2000 m or more, the frequency of replacing the film roll in the printing process can be reduced, and costs can be reduced. When it is 65,000 m or less, the roll diameter is not excessively large and the roll weight can be prevented from becoming excessively heavy. In other words, the handling property is good.

The core used for the film roll is not particularly limited, and may be made of plastic or metal with a diameter of 3 inches (37.6 mm), 6 inches (152.2 mm), 8 inches (203.2 mm), etc. A cylindrical winding core made of aluminum or paper can be used.

The biaxially oriented polyester film 8 can be used for various purposes. For example, it can be suitably used as a packaging container, a label (for example, a label for wrapping around a PET bottle), and an exterior film for electronic components such as the exterior for lithium ion batteries. Among these, it can be suitably used for packaging containers. In particular, it can be suitably used for food packaging containers.

<3. Laminated body＞
As shown in FIG. 2, in one embodiment, the laminate 9 includes a biaxially oriented polyester film 8 and a sealant layer 21. Since the laminate 9 includes the sealant layer 21, a product (for example, a packaging container) including the laminate 9 can be manufactured by heat sealing.

The sealant layer 21 is a layer that can be softened at a lower temperature than the biaxially oriented polyester film 8. That is, the sealant layer 21 can be melted at a lower temperature than the biaxially oriented polyester film 8. The sealant layer 21 may be formed of, for example, a hot melt adhesive, a film, or a material other than these. Thermoplastic resin can be used as a material constituting the sealant layer 21. Examples of materials constituting the sealant layer 21 include polyethylene resins such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE), polypropylene resins, ethylene-vinyl acetate copolymers, and ethylene. -α-olefin random copolymers and ionomer resins can be mentioned. In addition, the sealant layer 21 may contain one kind of these, and may contain two or more kinds.

Note that biomass polyethylene is preferable as the polyethylene from the viewpoint of further reducing environmental load. Biomass polyethylene is polyethylene manufactured using biomass ethanol as a raw material. In particular, biomass polyethylene produced using fermented ethanol derived from biomass obtained from plant materials as a raw material is preferred. As plant materials, mention may be made, for example, of corn, sugar cane, beets and manioc.

The sealant layer 21 can contain additives. As additives, for example, oxygen absorbers, plasticizers, UV stabilizers, antioxidants, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, friction reducers, slip agents. , a mold release agent, an antioxidant, an ion exchange agent, an anti-blocking agent, and a coloring agent.

The thickness of the sealant layer 21 may be, for example, 5 μm or more, or 7 μm or more. The thickness of the sealant layer 21 may be, for example, 50 μm or less or 30 μm or less. Note that the sealant layer 21 may have a single layer structure or may have a two or more layer structure.

As shown in FIG. 3, the laminate 9 can further include a printed layer 11. The laminate 9 can include a printed layer 11 , a biaxially oriented polyester film 8 , and a sealant layer 21 . In at least a portion of the laminate 9, the printed layer 11, the biaxially oriented polyester film 8, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9.

The printing layer 11, that is, the ink layer 11 can impart a design to the laminate 9. The design may be, for example, a design such as a pattern, a picture, a photograph, or a figure, or a symbol such as a letter, code, or mark, or it may be a combination of two or more of these. Any combination may be used. The design may be plain.

The shape of the printed layer 11 when the laminate 9 is viewed in the perpendicular direction can be set as appropriate. When the laminate 9 is viewed in the perpendicular direction, the size of the printed layer 11 may be the same as the size of the biaxially oriented polyester film 8 or may be smaller than the biaxially oriented polyester film 8.

The printing layer 11 can contain resin. Examples of the resin include acrylic resin, urethane resin, polyester resin, vinyl chloride resin, vinyl acetate copolymer resin, and mixtures of two or more of these resins. Print layer 11 can contain a colorant. Examples of colorants include pigments and dyes. The printed layer 11 can contain additives. Examples of additives include antistatic agents, light blocking agents, ultraviolet absorbers, plasticizers, lubricants, fillers, stabilizers, lubricants, antifoaming agents, crosslinking agents, antiblocking agents, antioxidants, etc. can.

The printed layer 11 can be formed using ink. In addition to the above-mentioned components, the ink can include, for example, a solvent. Note that the ink may be an ink using raw materials derived from biomass.

The printed layer 11 can be formed by printing ink and drying it. Examples of printing methods include offset printing, gravure printing, and screen printing. Examples of drying methods after printing include hot air drying, hot roll drying, and infrared drying.

The laminate 9 may further include a paper layer. For example, the laminate 9 may include a paper layer between the biaxially oriented polyester film 8 and the printed layer 11, or may include a paper layer between the printed layer 11 and the sealant layer 21. Among these, it is preferable to include a paper layer between the biaxially oriented polyester film 8 and the printing layer 11. In this case, in at least a portion of the laminate 9, the biaxially oriented polyester film 8, the paper layer, the printing layer 11, and the sealant layer 21 may be arranged in this order in the thickness direction of the laminate 9 (not shown). do not have).

As the paper layer, for example, high quality paper, art paper, coated paper, resin coated paper, cast coated paper, paperboard, synthetic paper, impregnated paper, etc. can be used. The thickness of the paper layer is preferably, for example, 30 g/m ² or more and 400 g/m ² or less.

The paper layer can be laminated to the biaxially oriented polyester film 8 via other layers (for example, an adhesive layer, an adhesive resin layer, an anchor coat layer).

The adhesive layer can be formed with an adhesive, ie, a laminating adhesive. For example, it can be formed by applying a laminating adhesive to the biaxially oriented polyester film 8 and/or the paper layer and drying. The laminating adhesive may be a one-component curing type or a two-component curing type. The laminating adhesive may be solvent-based, water-based, or emulsion-based. Examples of laminating adhesives include vinyl adhesives, (meth)acrylic adhesives, polyamide adhesives, polyester adhesives, polyether adhesives, polyurethane adhesives, epoxy adhesives, and rubber adhesives. can be mentioned. Note that these may be used alone or in combination of two or more.

The thickness of the adhesive layer may be, for example, 0.1 μm or more, or 1 μm or more. The thickness of the adhesive layer may be, for example, 10 μm or less, or 5 μm or less.

The adhesive resin layer contains a thermoplastic resin. Examples of thermoplastic resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methacrylic acid copolymer. , ethylene-methyl methacrylate copolymer, ethylene-maleic acid copolymer, and ionomer resin. In addition, resins in which at least one of an unsaturated carboxylic acid, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, and an ester monomer is graft-polymerized and/or copolymerized with a polyolefin resin can also be mentioned. A resin obtained by graft-modifying maleic anhydride onto a polyolefin resin can also be mentioned. Note that these may be used alone or in combination of two or more.

The thickness of the adhesive resin layer may be, for example, 0.1 μm or more, 1 μm or more, 5 μm or more, or 10 μm or more. The thickness of the adhesive resin layer may be, for example, 100 μm or less, 50 μm or less, 10 μm or less, or 5 μm or less.

The anchor coat layer can be formed from a composition containing a resin and a curing agent. Examples of the resin include urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based, and polybutadiene-based resins. Among these, urethane-based, polyester-based, and acrylic-based resins are preferred. From the viewpoint of adhesion, urethane resin is preferred. On the other hand, acrylic resin is preferred from the viewpoint of water resistance. Note that these may be used alone or in combination of two or more. Examples of the curing agent include epoxy, isocyanate, and melamine curing agents. Note that these may be used alone or in combination of two or more.

The composition for forming the anchor coat layer preferably contains a silane coupling agent. It is preferable that the silane coupling agent has one or more organic functional groups in the molecule. When the silane coupling agent has a plurality of organic functional groups (that is, one or more) in the molecule, the plurality of organic functional groups may be the same or different. In other words, each of the plurality of organic functional groups can be independent. Examples of organic functional groups include alkoxy groups, amino groups, epoxy groups, and isocyanate groups.

The composition for forming the anchor coat layer may contain a solvent. Examples of solvents include aromatic solvents such as benzene and toluene, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, and polyhydric alcohols such as ethylene glycol monomethyl ether. Derivatives can be mentioned.

The anchor coat layer can be formed by applying a composition for forming the anchor coat layer to the biaxially oriented polyester film 8 and drying it.

The thickness of the anchor coat layer may be, for example, 0.1 μm or more, or 0.2 μm or more. The thickness of the anchor coat layer may be, for example, 2 μm or less, or 1 μm or less.

As shown in FIG. 4A, the laminate 9 may further include an inorganic thin film layer 31, that is, a vapor deposition layer 31. For example, the laminate 9 may include a printed layer 11 , a biaxially oriented polyester film 8 , an inorganic thin film layer 31 , and a sealant layer 21 . In at least a portion of the laminate 9, the printed layer 11, the biaxially oriented polyester film 8, the inorganic thin film layer 31, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9. Since the laminate 9 includes the inorganic thin film layer 31, gas barrier properties can be improved.

The inorganic thin film layer 31 can contain an inorganic oxide. Examples of inorganic oxides include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), lead (Pb), zirconium (Zr), and yttrium (Y) oxides. Preferable materials for forming the inorganic thin film layer 31 include silicon oxide (ie, silica), aluminum oxide (ie, alumina), and a mixture of silicon oxide and aluminum oxide. Among these, a composite oxide of silicon oxide and aluminum oxide is more preferable because it can achieve both flexibility and denseness of the inorganic thin film layer 31. In this composite oxide, the mixing ratio of silicon oxide and aluminum oxide is a mass ratio in terms of metal atoms, that is, a mass ratio in terms of metal atoms, and Al is preferably 20% by mass or more and 70% by mass or less. When the content is 20% by mass or more, gas barrier properties are excellent. When the content is 70% by mass or less, the inorganic thin film layer 31 can be prevented from becoming excessively hard. Note that silicon oxide herein refers to various silicon oxides such as SiO and SiO ₂ or mixtures thereof, and aluminum oxide refers to various aluminum oxides such as AlO and Al ₂ O ₃ or mixtures thereof. .

The inorganic thin film layer 31 may be a metal vapor deposition layer. Examples of the metal of the metal vapor deposition layer include magnesium, aluminum, titanium, chromium, iron, nickel, copper, zinc, silver, tin, platinum, and gold. Among them, aluminum is preferred. That is, it is preferable that the inorganic thin film layer 31 is an aluminum vapor deposited layer.

The thickness of the inorganic thin film layer 31 may be, for example, 1 nm or more, 5 nm or more, 10 nm or more, or 20 nm or more. The thickness of the inorganic thin film layer 31 may be, for example, 200 nm or less, 100 nm or less, or 50 nm or less.

The inorganic thin film layer 31 may have a single layer structure, or may have a two or more layer structure. When the inorganic thin film layer 31 has two or more layers, these layers can be independent from each other in terms of composition, physical properties (for example, thickness), and the like.

The inorganic thin film layer 31 can be formed by, for example, a physical vapor deposition method (PVD method) such as a vacuum evaporation method, a sputtering method, or an ion plating method, a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. It can be formed by a chemical vapor deposition method (CVD method) such as. In addition, when forming a silicon oxide/aluminum oxide thin film by a vacuum evaporation method, a mixture of SiO ₂ and Al ₂ O ₃ or a mixture of SiO ₂ and Al can be used as the evaporation raw material, for example. These vapor deposition raw materials are preferably in the form of particles. The size of the particles is preferably such that the pressure during vapor deposition does not change. For example, the particle size is preferably 1 mm to 5 mm. For heating, methods such as resistance heating, high frequency induction heating, electron beam heating, laser heating, etc. can be adopted. It is also possible to introduce oxygen, nitrogen, hydrogen, argon, carbon dioxide, water vapor, etc. as a reactive gas, or to adopt reactive vapor deposition using means such as ozone addition or ion assist. Furthermore, the film forming conditions can also be changed arbitrarily, such as by applying a bias to the object to be deposited (the laminated film to be subjected to vapor deposition), heating or cooling the object to be deposited. The evaporation material, reaction gas, bias of the evaporation target, heating/cooling, etc. can be changed in the same way when sputtering or CVD is employed.

Note that, as shown in FIG. 4B, the laminate 9 may include the biaxially oriented polyester film 8, the inorganic thin film layer 31, and the sealant layer 21. In at least a portion of the laminate 9, the biaxially oriented polyester film 8, the inorganic thin film layer 31, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9.

As shown in FIG. 5A, the laminate 9 may further include an anchor coat layer 32, that is, a covering layer 32. For example, the laminate 9 may include a printed layer 11 , a biaxially oriented polyester film 8 , an anchor coat layer 32 , an inorganic thin film layer 31 , and a sealant layer 21 . In at least a portion of the laminate 9, the printed layer 11, the biaxially oriented polyester film 8, the anchor coat layer 32, the inorganic thin film layer 31, and the sealant layer 21 may be arranged in this order in the thickness direction of the laminate 9. . The anchor coat layer 32 can connect the biaxially oriented polyester film 8 and the inorganic thin film layer 31.

Although the term "anchor coat layer" that includes the anchor coat layer 32 has already been explained, an explanation will be added because there are suitable examples specific to the anchor coat layer 32.

The anchor coat layer 32 can be formed from a composition containing a resin and a curing agent. Examples of the resin include urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based, and polybutadiene-based resins. Among these, urethane-based, polyester-based, and acrylic-based resins are preferred. From the viewpoint of adhesion, urethane resin is preferred. On the other hand, acrylic resin is preferred from the viewpoint of water resistance. Note that these may be used alone or in combination of two or more. Examples of the curing agent include epoxy, isocyanate, and melamine curing agents. Note that these may be used alone or in combination of two or more.

The composition for forming the anchor coat layer 32 preferably contains a silane coupling agent. It is preferable that the silane coupling agent has one or more organic functional groups in the molecule. When the silane coupling agent has a plurality of organic functional groups (that is, one or more) in the molecule, the plurality of organic functional groups may be the same or different. In other words, each of the plurality of organic functional groups can be independent. Examples of organic functional groups include alkoxy groups, amino groups, epoxy groups, and isocyanate groups.

The composition for forming the anchor coat layer 32 preferably contains a resin containing an oxazoline group, that is, a polymer containing an oxazoline group. The oxazoline group has a high affinity with the inorganic thin film layer 31 and can react with the oxygen-deficient parts of the inorganic oxide and metal hydroxide that may be generated during the formation of the inorganic thin film layer 31. Can be firmly attached. In addition, the unreacted oxazoline groups present in the anchor coat layer 32 are free from carboxylic acid terminals that may occur in the biaxially oriented polyester film 8 and the anchor coat layer 32 (for example, carboxylic acid terminals that may occur due to hydrolysis). Because they can react, crosslinks can be formed.

The composition for forming the anchor coat layer 32 may contain a solvent. Examples of solvents include aromatic solvents such as benzene and toluene, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, and polyhydric alcohols such as ethylene glycol monomethyl ether. Derivatives can be mentioned.

The anchor coat layer 32 can be formed by applying a composition for forming the anchor coat layer 32 to the biaxially oriented polyester film 8 and drying it.

Note that, as shown in FIG. 5B, the laminate 9 may include the biaxially oriented polyester film 8, the anchor coat layer 32, the inorganic thin film layer 31, and the sealant layer 21. In at least a portion of the laminate 9, the biaxially oriented polyester film 8, the anchor coat layer 32, the inorganic thin film layer 31, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9.

As shown in FIG. 6A, the laminate 9 may further include a protective layer 33 on the inorganic thin film layer 31. That is, the laminate 9 may further include a protective layer 33 adjacent to the inorganic thin film layer 31. For example, the laminate 9 may include a printed layer 11 , a biaxially oriented polyester film 8 , an anchor coat layer 32 , an inorganic thin film layer 31 , a protective layer 33 , and a sealant layer 21 . In at least a portion of the laminate 9, the printed layer 11, the biaxially oriented polyester film 8, the anchor coat layer 32, the inorganic thin film layer 31, the protective layer 33, and the sealant layer 21 are arranged in this order in the thickness direction of the laminate 9. I can be there. By including the protective layer 33, the laminate 9 can suppress or reduce gas permeation. The protective layer 33 plays a role in improving the gas barrier properties of the laminate 9.

By forming the protective layer 33 with a composition containing a resin and a curing agent, the gas barrier properties of the laminate 9 can be improved. This will be explained. Generally, the inorganic thin film layer 31 is dotted with minute defects. By coating such a composition on the inorganic thin film layer 31 to form the protective layer 33, the composition can be penetrated into the defective parts of the inorganic thin film layer 31, and as a result, the laminate 9 is Gas barrier properties can be improved.

Examples of the resin include urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based, and polybutadiene-based resins. Note that these may be used alone or in combination of two or more. Examples of the curing agent include epoxy, isocyanate, and melamine curing agents. Note that these may be used alone or in combination of two or more.

Among these, urethane-based resins, that is, urethane resins are preferred. In the urethane resin, the polar group of the urethane bond interacts with the inorganic thin film layer 31, and the amorphous portion in the urethane resin exhibits flexibility, so damage to the inorganic thin film layer 31 is suppressed when bending load is applied. be able to.

The acid value of the urethane resin is preferably within the range of 10 mgKOH/g or more and 60 mgKOH/g or less. More preferably, it is within the range of 15 mgKOH/g or more and 55 mgKOH/g or less, and even more preferably within the range of 20 mgKOH/g or more and 50 mgKOH/g or less. When the acid value of the urethane resin is within the above range, the liquid stability is improved when it is made into an aqueous dispersion, and the protective layer 33 can be uniformly deposited on the highly polar inorganic thin film, so that the coat appearance is improved. becomes good.

The glass transition temperature (Tg) of the urethane resin is preferably 80°C or higher, more preferably 90°C or higher. By setting Tg to 80° C. or higher, it is possible to reduce swelling of the protective layer 33 due to molecular movement during the moist heat treatment process (temperature increase, temperature retention, and temperature decrease).

From the viewpoint of improving gas barrier properties, the urethane resin preferably contains an aromatic or araliphatic diisocyanate component as a main component. Among these, it is particularly preferable to contain a metaxylylene diisocyanate component. By using such a urethane resin, the cohesive force of urethane bonds can be further increased due to the stacking effect of aromatic rings, and as a result, good gas barrier properties can be obtained.

The proportion of aromatic or araliphatic diisocyanate in the urethane resin is preferably in the range of 50 mol% or more (that is, 50 mol% or more and 100 mol% or less) based on 100 mol% of the polyisocyanate component. The proportion of the total amount of aromatic or araliphatic diisocyanates is preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, and still more preferably 80 mol% or more and 100 mol% or less. . As such a resin, the "Takelac (registered trademark) WPB" series commercially available from Mitsui Chemicals, Inc. can be suitably used. When the total amount of aromatic or araliphatic diisocyanate is 50 mol% or more, good gas barrier properties can be obtained.

It is preferable that the urethane resin has a carboxylic acid group (carboxyl group) from the viewpoint of improving affinity with the inorganic thin film layer 31. In order to introduce a carboxylic acid (salt) group into the urethane resin, for example, a polyol compound having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid may be introduced as a copolymerization component as a polyol component. Moreover, if a carboxylic acid group-containing urethane resin is synthesized and then neutralized with a salt forming agent, an aqueous dispersion of the urethane resin can be obtained. As a salt forming agent, for example, ammonia, trialkylamines such as trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, N-alkyl such as N-methylmorpholine, N-ethylmorpholine, etc. Examples include morpholines, N-dialkylalkanolamines such as N-dimethylethanolamine, and N-diethylethanolamine. These may be used alone or in combination of two or more.

The composition for forming the protective layer 33 may contain a solvent. Examples of solvents include aromatic solvents such as benzene and toluene, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, and polyhydric alcohols such as ethylene glycol monomethyl ether. Derivatives can be mentioned.

On the other hand, the protective layer 33 may be formed of a composition that is polycondensed by a sol-gel method. According to this, since the protective layer 33 with high gas barrier properties can be formed, the gas barrier properties of the laminate 9 can be improved. Such a composition can contain the alkoxide represented by Formula 1 and at least one of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer.
Formula 1 R ¹ _n M(OR ² ) _m
R ¹ represents an organic group having 1 to 8 carbon atoms. R ² represents 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. n+m represents the valence of M.
Note that in Formula 1, when there is a plurality of R ^{1 s} , each of the plural R ^1s can be independent. In Formula 1, when there is a plurality of R ² s, each of the plural R ^2s can be independent.

As the alkoxide represented by Formula 1, at least one of a partial hydrolyzate of an alkoxide and a condensate of hydrolysis of an alkoxide can be used. In the alkoxide partial hydrolyzate, not all of the alkoxy groups need to be hydrolyzed. As the condensate of alkoxide hydrolysis, a dimer or more of partially hydrolyzed alkoxide, specifically a dimer to hexamer, can be used.

Examples of the metal atom represented by M include silicon, zirconium, titanium, and aluminum. Among these, silicon and titanium are preferred. Note that alkoxides of two or more different metal atoms may be used alone or in combination.

Examples of the organic group having 1 to 8 carbon atoms represented by R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t Examples include alkyl groups such as -butyl group, n-hexyl group, and n-octyl group.

Examples of the organic group represented by R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n- Examples include alkyl groups such as hexyl and n-octyl groups.

This composition may contain a silane coupling agent. Examples of the silane coupling agent include organoalkoxysilane containing an organic reactive group. Particularly preferred are organoalkoxysilanes having epoxy groups. Examples of the organoalkoxysilane having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. can. Note that these may be used alone or in combination of two or more.

Note that this composition can further contain, for example, a sol-gel method catalyst, an acid, water, and an organic solvent.

Note that, as shown in FIG. 6B, the laminate 9 may include the biaxially oriented polyester film 8, the anchor coat layer 32, the inorganic thin film layer 31, the protective layer 33, and the sealant layer 21. In at least a portion of the laminate 9, the biaxially oriented polyester film 8, the anchor coat layer 32, the inorganic thin film layer 31, the protective layer 33, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9. .

As shown in FIG. 7, the laminate 9 may further include a sealant layer 22. For example, the laminate 9 may include a sealant layer 22, a biaxially oriented polyester film 8, and a sealant layer 21. In at least a portion of the laminate 9, the sealant layer 22, the biaxially oriented polyester film 8, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9. Of course, the laminate 9 having the laminate configuration shown in FIGS. 3 to 6B may further include the sealant layer 22. It is preferable that one surface of both surfaces of the laminate 9 be constituted by the sealant layer 21 and the other surface be constituted by the sealant layer 22. That is, it is preferable that one of the pair of outermost layers of the laminate 9 is the sealant layer 21 and the other outermost layer is the sealant layer 22. The description of the sealant layer 22 is omitted because it overlaps with the description of the sealant layer 21. Therefore, the description of the sealant layer 21 can also be treated as the description of the sealant layer 22.

3, FIG. 4A, FIG. 5A, and FIG. 6A, the configuration in which the printing layer 11, the biaxially oriented polyester film 8, and the sealant layer 21 are arranged in this order in the thickness direction of the laminate 9 is explained, but of course , these do not need to be arranged in that order.

For example, as shown in FIG. 8, in at least a portion of the laminate 9, the biaxially oriented polyester film 8, the printed layer 11, and the sealant layer 21 may be arranged in this order in the thickness direction of the laminate 9. The laminate 9 can include a biaxially oriented polyester film 8 , a printed layer 11 , and a sealant layer 21 .

As shown in FIG. 9, in at least a portion of the laminate 9, the biaxially oriented polyester film 8, the printed layer 11, the inorganic thin film layer 31, and the sealant layer 21 are arranged in this order in the thickness direction of the laminate 9. good. The laminate 9 can include a biaxially oriented polyester film 8 , a printed layer 11 , an inorganic thin film layer 31 , and a sealant layer 21 .

As shown in FIG. 10, in at least a portion of the laminate 9, the biaxially oriented polyester film 8, the printed layer 11, the anchor coat layer 32, the inorganic thin film layer 31, and the sealant layer 21 are arranged in the thickness direction of the laminate 9. They may be arranged in order. The laminate 9 can include a biaxially oriented polyester film 8 , a printing layer 11 , an anchor coat layer 32 , an inorganic thin film layer 31 , and a sealant layer 21 .

As shown in FIG. 11, in at least a portion of the laminate 9, the biaxially oriented polyester film 8, the printed layer 11, the anchor coat layer 32, the inorganic thin film layer 31, the protective layer 33, and the sealant layer 21 are included in the laminate 9. They may be arranged in this order in the thickness direction. The laminate 9 can include a biaxially oriented polyester film 8 , a printing layer 11 , an anchor coat layer 32 , an inorganic thin film layer 31 , a protective layer 33 , and a sealant layer 21 .

As shown in FIG. 12, the laminate 9 may further include a sealant layer 22. For example, the laminate 9 may include a sealant layer 22, a biaxially oriented polyester film 8, a printed layer 11, and a sealant layer 21. In at least a portion of the laminate 9, the sealant layer 22, the biaxially oriented polyester film 8, the printed layer 11, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9. Of course, the laminate 9 having the laminate configuration shown in FIGS. 9 to 11 may further include the sealant layer 22. It is preferable that one surface of both surfaces of the laminate 9 be constituted by the sealant layer 21 and the other surface be constituted by the sealant layer 22. That is, it is preferable that one of the pair of outermost layers of the laminate 9 is the sealant layer 21 and the other outermost layer is the sealant layer 22.

In the laminate 9, the role played by the biaxially oriented polyester film 8 is not particularly limited. For example, the biaxially oriented polyester film 8 may play the role of holding the above-mentioned layers (eg, the sealant layer 21, the printing layer 11, the inorganic thin film layer 31), that is, the role of a base material. On the other hand, the biaxially oriented polyester film 8 may be used not as a base material but for the purpose of improving some physical properties of the laminate 9, such as strength. In other words, the biaxially oriented polyester film 8 used for that purpose plays the role of a support. That is, the biaxially oriented polyester film 8 may serve as a support.
In addition, when the biaxially oriented polyester film 8 plays a role as a support body, another layer (for example, a resin film, a paper layer) can play a role as a base material.

Note that when the biaxially oriented polyester film 8 serves as a base material, the laminate 9 may further include a layer that serves as a support (hereinafter referred to as a "support layer"). good. On the other hand, when the biaxially oriented polyester film 8 plays a role as a support (that is, when it is a support layer), the laminate 9 is a layer that plays a role as a base material (hereinafter referred to as a "base material layer"). ) may also be included.

In FIGS. 2 to 12, the laminate 9 has been explained by focusing on the biaxially oriented polyester film 8, but from here on, we will focus on the base material layer and support layer rather than the biaxially oriented polyester film 8. Next, the laminate 9 will be explained. That is, the laminate 9 will be explained from a different perspective. Therefore, the explanation from here may have some overlap with the previous explanation.

As shown in FIG. 13, the laminate 9 includes a base layer 51 and a sealant layer 21. Since the laminate 9 includes the sealant layer 21, a product (for example, a packaging container) including the laminate 9 can be manufactured by heat sealing.

A biaxially oriented polyester film 8 is used as the base layer 51. That is, the base material layer 51 is the biaxially oriented polyester film 8. On the other hand, the base material layer 51 may have a single layer structure or may have a two or more layer structure. It may also have a laminated structure with a stretched nylon film).

As shown in FIG. 14, the laminate 9 can further include a printed layer 11. The laminate 9 can include a printed layer 11 , a base layer 51 , and a sealant layer 21 . In at least a portion of the laminate 9, the printed layer 11, the base material layer 51, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9.

As shown in FIG. 15A, the laminate 9 can further include an intermediate layer 61. For example, the laminate 9 can include a printed layer 11 , a base layer 51 , an intermediate layer 61 , and a sealant layer 21 . In at least a portion of the laminate 9, the printed layer 11, the base layer 51, the intermediate layer 61, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9.

The intermediate layer 61 may include a support layer, a gas barrier layer, a metal foil, or two or more of these. Of course, layers other than these, such as an adhesive layer, an adhesive resin layer, and an anchor coat layer, may also be included. Intermediate layer 61 may include printed layer 11 . By including the support in the intermediate layer 61, some physical properties of the laminate 9, such as strength, can be improved. When the intermediate layer 61 includes a gas barrier layer or metal foil, the gas barrier properties of the laminate 9 can be improved.

Examples of the support layer include a resin film and a paper layer. Examples of resin films include polyester, (meth)acrylic resin, polyolefin (e.g. polyethylene, polypropylene, polymethylpentene), vinyl resin, cellulose resin, ionomer resin, polyamide (nylon 6, nylon 6,6, polymethaxylylene adipate). Examples include films containing one or more resin materials such as Mido (MXD6). Among them, polyester is preferred. That is, it is preferable that the resin film contains polyester. The resin film may be a stretched resin film or an unstretched resin film. The stretched resin film may be a uniaxially stretched resin film or a biaxially stretched resin film. Among these, biaxially stretched resin films are preferred because they have excellent dimensional stability.

The support layer can contain additives. Examples of additives include oxygen absorbers, plasticizers, ultraviolet stabilizers, antioxidants, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, friction reducers, and slip agents. agent, mold release agent, antioxidant, ion exchange agent, antiblocking agent, and coloring agent.

A biaxially oriented polyester film 8 may be used as the support layer. That is, the support layer may be a biaxially oriented polyester film 8.

When the biaxially oriented polyester film 8 is used as the support layer, the biaxially oriented polyester film 8, a resin film, or a paper layer may be used as the base layer 51. In this way, when the biaxially oriented polyester film 8 is used as the support layer, it is not necessary to use the biaxially oriented polyester film 8 as the base layer 51.

When the biaxially oriented polyester film 8 is used as the support layer, examples of the base layer 51 include the biaxially oriented polyester film 8, a resin film other than the biaxially oriented polyester film 8, and a paper layer. Examples of resin films include polyester, (meth)acrylic resin, polyolefin (e.g. polyethylene, polypropylene, polymethylpentene), vinyl resin, cellulose resin, ionomer resin, polyamide (nylon 6, nylon 6,6, polymethaxylylene adipate). Examples include films containing one or more resin materials such as Mido (MXD6). Among them, polyester is preferred. That is, it is preferable that the resin film contains polyester. The resin film may be a stretched resin film or an unstretched resin film. The stretched resin film may be a uniaxially stretched resin film or a biaxially stretched resin film. Among these, biaxially stretched resin films are preferred because they have excellent dimensional stability.

Note that the intermediate layer 61 may include the anchor coat layer 32 on at least one surface of the support layer, or may include the inorganic thin film layer 31. Intermediate layer 61 may include protective layer 33 (not shown).

The gas barrier layer contains a gas barrier resin. Examples of gas barrier resins include ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, polyamide (for example, nylon 6, nylon 6,6, polymethaxylylene adipamide (MXD6)), polyester, polyurethane, (Meth)acrylic resin can be mentioned. The gas barrier layer may contain two or more kinds of gas barrier resins. The gas barrier layer may further contain other resins or additives.

The thickness of the gas barrier layer may be, for example, 3 μm or more, 5 μm or more, or 7 μm or more. The thickness of the gas barrier layer may be, for example, 30 μm or less, or 20 μm or less.

Examples of the metal foil include aluminum foil and magnesium foil. Among these, aluminum foil is preferred. Among these, aluminum foil containing iron is preferred from the viewpoint of pinhole resistance and spreadability. The content of iron is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in 100% by mass of the aluminum foil. On the other hand, the iron content is preferably 9.0% by mass or less, more preferably 2.0% by mass or more.

The metal foil may be pretreated. Examples of pretreatment include degreasing, acid cleaning, alkali cleaning, and the like.

The thickness of the metal foil may be, for example, 3 μm or more, or 6 μm or more. The thickness of the metal foil may be, for example, 100 μm or less, or 25 μm or less.

Here, in at least a portion of the laminate 9, the printed layer 11, the base material layer 51, the intermediate layer 61, and the sealant layer 21 are arranged in this order in the thickness direction of the laminate 9. The printed layer 11, the intermediate layer 61, the base material layer 51, and the sealant layer 21 may be arranged in this order in the thickness direction of the laminate 9 (not shown).

Note that, as shown in FIG. 15B, the laminate 9 may include a base layer 51, an intermediate layer 61, and a sealant layer 21. In at least a portion of the laminate 9, the base layer 51, the intermediate layer 61, and the sealant layer 21 can be arranged in this order in the thickness direction of the laminate 9.

In FIGS. 14 and 15A, a configuration in which the printing layer 11, the base material layer 51, and the sealant layer 21 are arranged in this order in the thickness direction of the laminate 9 has been explained, but of course, these are not arranged in that order. You don't have to.

For example, as shown in FIG. 16, in at least a portion of the laminate 9, the base layer 51, the print layer 11, and the sealant layer 21 may be arranged in this order in the thickness direction of the laminate 9. The laminate 9 can include a base layer 51 , a printed layer 11 , and a sealant layer 21 .

As shown in FIG. 17A, in at least a portion of the laminate 9, the base layer 51, the printed layer 11, the intermediate layer 61, and the sealant layer 21 may be arranged in this order in the thickness direction of the laminate 9. The laminate 9 can include a base layer 51 , a printed layer 11 , an intermediate layer 61 , and a sealant layer 21 .

As shown in FIG. 17B, in at least a portion of the laminate 9, the base layer 51, the intermediate layer 61, and the sealant layer 21 may be arranged in this order in the thickness direction of the laminate 9. The laminate 9 can include a base layer 51 , an intermediate layer 61 , and a sealant layer 21 .

The laminate 9 having the laminate configuration shown in FIGS. 13 to 17B may further include a sealant layer 22 (not shown). It is preferable that one surface of both surfaces of the laminate 9 be constituted by the sealant layer 21 and the other surface be constituted by the sealant layer 22. That is, it is preferable that one of the pair of outermost layers of the laminate 9 is the sealant layer 21 and the other outermost layer is the sealant layer 22.

Although the configuration has been described so far in which the laminate 9 includes the sealant layer 21 and, if necessary, the sealant layer 22, it is of course not limited to this. The laminate 9 may include an adhesive layer in place of at least one of the sealant layer 21 and the sealant layer 22. The adhesive layer can be formed using an adhesive. Examples of the adhesive include synthetic rubbers such as styrene-butadiene rubber, acrylonitrile-butadiene rubber, and polyisobutylene rubber, natural rubber, acrylic resins, silicone resins, and polypropylene. Note that these may be used alone or in combination of two or more.

In this way, the laminate 9 is
Including a base material layer 51 and a sealant layer 21 or an adhesive layer,
The base material layer 51 may include the biaxially oriented polyester film 8 .

On the other hand, the laminate 9 is
Including a base material layer 51, an intermediate layer 61, a sealant layer 21 or an adhesive layer,
A configuration in which the intermediate layer 61 includes the biaxially oriented polyester film 8 is also possible.

The laminate 9 has been described above with reference to FIGS. 2 to 17B. Here's a more specific example.
Prior to that, the meanings of the abbreviations are shown below.
CRF biaxially oriented polyester film 8
PET Polyethylene terephthalate ONY Stretched nylon OPP Stretched polypropylene CPP Unstretched polypropylene PVC Polyvinyl chloride PE Polyethylene PEF Polyethylene film Al Aluminum MO Metal oxide MOR Metal alkoxide

Here are some specific examples. In the example given here, the base material layer 51 is a biaxially oriented polyester film 8.
(1) Base material layer (CRF)/adhesive layer/heat seal layer (PEF)
(2) Base material layer (CRF)/heat seal layer (PE)
(3) Base material layer (CRF)/anchor coat layer/heat seal layer (PE)
(4) Base material layer (CRF)/anchor coat layer/adhesive resin layer (PE)/heat seal layer (PEF)
(5) Base material layer (CRF)/Adhesive layer (6) Base material layer (CRF)/Inorganic thin film layer (MO)/Protective layer (MOR)/Adhesive layer/Heat seal layer (PEF)
(7) Base material layer (CRF)/Inorganic thin film layer (MO)/Protective layer (MOR)/Heat seal layer (PE)
(8) Base material layer (CRF)/Inorganic thin film layer (MO)/Protective layer (MOR)/Anchor coat layer/Heat seal layer (PE)
(9) Base material layer (CRF) / Inorganic thin film layer (MO) / Protective layer (MOR) / Anchor coat layer / Adhesive resin layer (PE) / Heat seal layer (PEF)
(10) Base material layer (CRF)/Inorganic thin film layer (Al)/Adhesive layer (11) Base material layer (CRF)/Inorganic thin film layer (Al)/Heat seal layer (PE)
(12) Base material layer (CRF)/Inorganic thin film layer (Al)/Anchor coat layer/Heat seal layer (PE)

Here are some more specific examples. In the example given here as well, the base layer 51 is the biaxially oriented polyester film 8.
(1) Base material layer (CRF)/printing layer/adhesive layer/heat sealing layer (PEF)
(2) Base material layer (CRF)/printing layer/heat sealing layer (PE)
(3) Base material layer (CRF)/printing layer/anchor coat layer/heat sealing layer (PE)
(4) Base material layer (CRF)/Print layer/Anchor coat layer/Adhesive resin layer (PE)/Heat seal layer (PEF)
(5) Base layer (CRF)/Print layer/Adhesive layer (6) Print layer/Base layer (CRF)/Inorganic thin film layer (Al)/Adhesive layer (7) Print layer/Base layer (CRF)/ Inorganic thin film layer (Al)/heat seal layer (PE)
(8) Printing layer/base material layer (CRF)/inorganic thin film layer (Al)/anchor coat layer/heat seal layer (PE)

Here are some more specific examples. In the example given here as well, the base layer 51 is the biaxially oriented polyester film 8.
(1) Base material layer (CRF)/adhesive layer/metal foil (Al)/adhesive layer/support layer (ONY)/adhesive layer/heat seal layer (PEF)
(2) Base material layer (CRF)/adhesive layer/metal foil (Al)/adhesive layer/heat seal layer (CPP)
(3) Base material layer (CRF)/adhesive layer/inorganic thin film layer (Al)/support layer (PET)/adhesive layer/heat seal layer (PEF)
(4) Base material layer (CRF)/adhesive layer/support layer (ONY)/adhesive layer/heat seal layer (PEF)
(5) Base material layer (CRF) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / support layer (PET) / adhesive layer / heat seal layer (CPP)
(6) Base material layer (CRF)/adhesive layer/inorganic thin film layer (Al)/support layer (PET)/adhesive layer/heat seal layer (CPP)
(7) Base material layer (CRF)/adhesive layer/support layer (ONY)/adhesive layer/metal foil (Al)/adhesive layer/heat seal layer (CPP)
(8) Base material layer (CRF)/anchor coat layer/adhesive resin layer (PE)/metal foil (Al)/heat seal layer (PE)
(9) Base material layer (CRF)/anchor coat layer/adhesive resin layer (PE)/metal foil (Al)/anchor coat layer/heat seal layer (PE)
(10) Base material layer (CRF)/anchor coat layer/adhesive resin layer (PE)/inorganic thin film layer (Al)/support layer (PET)/anchor coat layer/adhesive resin layer (PE)/heat seal layer ( PEF)
(11) Base material layer (CRF)/anchor coat layer/adhesive resin layer (PE)/metal foil (Al)/anchor coat layer/adhesive resin layer (PE)/heat seal layer (PEF)
(12) Base material layer (CRF)/adhesive layer/support layer (PET)/adhesive layer/heat seal layer (PEF)/hot melt layer (hot melt adhesive)
(13) Base material layer (CRF)/Inorganic thin film layer (MO)/Protective layer (MOR)/Adhesive layer/Support layer (ONY)/Adhesive layer/Heat seal layer (CPP)
(14) Base material layer (CRF)/Inorganic thin film layer (MO)/Protective layer (MOR)/Adhesive layer/Support layer (ONY)/Adhesive layer/Heat seal layer (PEF)
(15) Base material layer (CRF) / Inorganic thin film layer (MO) / Protective layer (MOR) / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (PET) / Adhesive layer /Heat seal layer (CPP)
(16) Base material layer (CRF) / Inorganic thin film layer (MO) / Protective layer (MOR) / Adhesive layer / Inorganic thin film layer (Al) / Support layer (PET) / Adhesive layer / Heat seal layer (CPP )
(17) Base material layer (CRF)/Inorganic thin film layer (MO)/Protective layer (MOR)/Adhesive layer/Support layer (ONY)/Adhesive layer/Metal foil (Al)/Adhesive layer/Heat seal layer (CPP)
(18) Base material layer (CRF) / Inorganic thin film layer (MO) / Protective layer (MOR) / Adhesive layer / Support layer (PET) / Adhesive layer / Heat seal layer (PEF) / Hot melt layer (Hot melt adhesive)
(19) Heat seal layer (PEF) / adhesive layer / base material layer (CRF) / adhesive layer / metal foil (Al) / adhesive layer / heat seal layer (PEF)
(20) Heat seal layer (PEF) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / base material layer (CRF) / adhesive layer / heat seal layer (PEF)
(21) Heat seal layer (PE)/base material layer (CRF)/adhesive layer/support layer (PEF)/adhesive layer/metal foil (Al)/adhesive layer/heat seal layer (PEF)
(22) Heat seal layer (PEF) / adhesive layer / base material layer (CRF) / adhesive layer / support layer (PEF) / adhesive layer / support layer (PET) / inorganic thin film layer (MO) / Protective layer (MOR)/Adhesive layer/Heat seal layer (PEF)
(23) Heat seal layer (PEF) / adhesive layer / base material layer (CRF) / adhesive layer / support layer (PEF) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / support Body layer (PET)/adhesive layer/heat seal layer (PEF)

Here are some more specific examples. In the example given here as well, the base layer 51 is the biaxially oriented polyester film 8.
(1) Base layer (CRF)/Print layer/Adhesive layer/Metal foil (Al)/Adhesive layer/Support layer (ONY)/Adhesive layer/Heat seal layer (PEF)
(2) Base material layer (CRF)/Print layer/Adhesive layer/Metal foil (Al)/Adhesive layer/Heat seal layer (CPP)
(3) Base layer (CRF)/Print layer/Adhesive layer/Inorganic thin film layer (Al)/Support layer (PET)/Adhesive layer/Heat seal layer (PEF)
(4) Base layer (CRF)/Print layer/Adhesive layer/Support layer (ONY)/Adhesive layer/Heat seal layer (PEF)
(5) Base material layer (CRF) / Printing layer / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (PET) / Adhesive layer / Heat seal layer (CPP)
(6) Base material layer (CRF)/Printing layer/Adhesive layer/Inorganic thin film layer (Al)/Support layer (PET)/Adhesive layer/Heat seal layer (CPP)
(7) Base material layer (CRF)/Print layer/Adhesive layer/Support layer (ONY)/Adhesive layer/Metal foil (Al)/Adhesive layer/Heat seal layer (CPP)
(8) Base material layer (CRF)/Print layer/Anchor coat layer/Adhesive resin layer (PE)/Metal foil (Al)/Heat seal layer (PE)
(9) Base material layer (CRF)/Print layer/Anchor coat layer/Adhesive resin layer (PE)/Metal foil (Al)/Anchor coat layer/Heat seal layer (PE)
(10) Base material layer (CRF) / Printing layer / Anchor coat layer / Adhesive resin layer (PE) / Inorganic thin film layer (Al) / Support layer (PET) / Anchor coat layer / Adhesive resin layer (PE) / Heat Seal layer (PEF)
(11) Base material layer (CRF) / Printing layer / Anchor coat layer / Adhesive resin layer (PE) / Metal foil (Al) / Anchor coat layer / Adhesive resin layer (PE) / Heat seal layer (PEF)
(12) Base material layer (CRF)/Print layer/Adhesive layer/Support layer (PET)/Adhesive layer/Heat seal layer (PEF)/Hot melt layer (Hot melt adhesive)
(13) Heat seal layer (PEF) / adhesive layer / base material layer (CRF) / printing layer / adhesive layer / metal foil (Al) / adhesive layer / heat seal layer (PEF)
(14) Heat seal layer (PEF) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / base material layer (CRF) / printing layer / adhesive layer / heat seal layer (PEF)
(15) Heat seal layer (PE) / Base material layer (CRF) / Printing layer / Adhesive layer / Support layer (PEF) / Adhesive layer / Metal foil (Al) / Adhesive layer / Heat seal layer (PEF) )
(16) Heat seal layer (PEF) / adhesive layer / base material layer (CRF) / printing layer / adhesive layer / support layer (PEF) / adhesive layer / support layer (PET) / inorganic thin film layer ( MO) / Protective layer (MOR) / Adhesive layer / Heat seal layer (PEF)
(17) Heat seal layer (PEF) / adhesive layer / base material layer (CRF) / printing layer / adhesive layer / support layer (PEF) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO )/Support layer (PET)/Adhesive layer/Heat seal layer (PEF)

Here are some more specific examples. In the example given here, the support layer is a biaxially oriented polyester film 8.
(1) Base material layer (paper)/adhesive layer/metal foil (Al)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (PVC)
(2) Base material layer (ONY)/adhesive layer/support layer (CRF)/adhesive layer/metal foil (Al)/adhesive layer/heat seal layer (PEF)
(3) Base material layer (PET) / Inorganic thin film layer (MO) / Protective layer (MOR) / Adhesive layer / Support layer (CRF) / Adhesive layer / Heat seal layer (PEF)
(4) Base material layer (paper)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (CPP)
(5) Base material layer (OPP)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (CPP)
(6) Base material layer (ONY)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (CPP)
(7) Base material layer (PET)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (PEF)/hot melt layer (hot melt adhesive)
(8) Base material layer (OPP)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (PEF)
(9) Base material layer (PET) / Inorganic thin film layer (MO) / Protective layer (MOR) / Adhesive layer / Support layer (CRF) / Adhesive layer / Heat seal layer (CPP)
(10) Heat seal layer (PE) / Base material layer (paper) / Adhesive resin layer (PE) / Anchor coat layer / Metal foil (Al) / Adhesive layer / Support layer (CRF) / Anchor coat layer / Adhesion Resin layer (PE)/heat seal layer (PEF)
(11) Base material layer (paper)/adhesive resin layer (PE)/support layer (CRF)/heat seal layer (PE)
(12) Base material layer (paper)/adhesive resin layer (PE)/support layer (CRF)/anchor coat layer/heat seal layer (PE)
(13) Base material layer (OPP)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (OPP)
(14) Base material layer (PET)/adhesive layer/inorganic thin film layer (Al)/support layer (CRF)/adhesive layer/heat seal layer (PEF)
(15) Base material layer (ONY) / Anchor coat layer / Adhesive resin layer (PE) / Inorganic thin film layer (Al) / Support layer (CRF) / Anchor coat layer / Adhesive resin layer (PE) / Heat seal layer ( PEF)
(16) Base material layer (paper) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / support layer (CRF) / adhesive layer / heat seal layer (CPP)
(17) Base material layer (OPP) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / support layer (CRF) / adhesive layer / heat seal layer (CPP)
(18) Base layer (PET) / Inorganic thin film layer (MO) / Protective layer (MOR) / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Adhesive layer /Heat seal layer (PEF)
(19) Base layer (ONY)/Adhesive layer/Protective layer (MOR)/Inorganic thin film layer (MO)/Support layer (CRF)/Adhesive layer/Heat seal layer (CPP)
(20) Base material layer (PET) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / support layer (CRF) / adhesive layer / heat seal layer (PEF) / hot melt layer (hot melt adhesive)
(21) Base material layer (OPP)/adhesive layer/protective layer (MOR)/inorganic thin film layer (MO)/support layer (CRF)/adhesive layer/heat seal layer (PEF)
(22) Base material layer (PET) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / support layer (CRF) / adhesive layer / heat seal layer (CPP)
(23) Base material layer (paper) / Adhesive resin layer (PE) / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Anchor coat layer / Heat seal layer (PE)
(24) Base material layer (OPP) / adhesive layer / protective layer (MOR) / inorganic thin film layer (MO) / support layer (CRF) / adhesive layer / heat seal layer (OPP)
(25) Base material layer (PET)/adhesive layer/support layer (CRF)/heat seal layer (PE)
(26) Base material layer (PET)/adhesive layer/support layer (CRF)/anchor coat layer/heat seal layer (PE)
(27) Heat sealing layer (PE)/base material layer (paper)/adhesive resin layer (PE)/support layer (CRF)/adhesive layer/heat sealing layer (PEF)
(28) Heat seal layer (PE)/base material layer (paper)/adhesive resin layer (PE)/support layer (CRF)/heat seal layer (PE)
(29) Heat seal layer (PE)/base material layer (paper)/adhesive resin layer (PE)/support layer (CRF)/anchor coat layer/heat seal layer (PE)

Here are some more specific examples. In the example given here as well, the support layer is a biaxially oriented polyester film 8.
(1) Printing layer/base material layer (paper)/adhesive layer/metal foil (Al)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (PVC)
(2) Base layer (ONY)/Print layer/Adhesive layer/Support layer (CRF)/Adhesive layer/Metal foil (Al)/Adhesive layer/Heat seal layer (PEF)
(3) Printing layer/base material layer (paper)/adhesive layer/support layer (CRF)/adhesive layer/heat seal layer (CPP)
(4) Base layer (OPP)/Print layer/Adhesive layer/Support layer (CRF)/Adhesive layer/Heat seal layer (CPP)
(5) Base layer (ONY)/Print layer/Adhesive layer/Support layer (CRF)/Adhesive layer/Heat seal layer (CPP)
(6) Base material layer (PET)/Printing layer/Adhesive layer/Support layer (CRF)/Adhesive layer/Heat seal layer (PEF)/Hot melt layer (Hot melt adhesive)
(7) Base layer (OPP)/Print layer/Adhesive layer/Support layer (CRF)/Adhesive layer/Heat seal layer (PEF)
(8) Heat seal layer (PE) / Printing layer / Base material layer (paper) / Adhesive resin layer (PE) / Anchor coat layer / Metal foil (Al) / Adhesive layer / Support layer (CRF) / Anchor coat Layer/Adhesive resin layer (PE)/Heat seal layer (PEF)
(9) Printing layer/base layer (paper)/adhesive resin layer (PE)/support layer (CRF)/heat seal layer (PE)
(10) Printing layer/base layer (paper)/adhesive resin layer (PE)/support layer (CRF)/anchor coat layer/heat seal layer (PE)
(11) Base material layer (OPP)/adhesive layer/support layer (CRF)/printing layer/adhesive layer/heat seal layer (OPP)
(12) Base layer (PET)/Print layer/Adhesive layer/Inorganic thin film layer (Al)/Support layer (CRF)/Adhesive layer/Heat seal layer (PEF)
(13) Base material layer (ONY) / Printing layer / Anchor coat layer / Adhesive resin layer (PE) / Inorganic thin film layer (Al) / Support layer (CRF) / Anchor coat layer / Adhesive resin layer (PE) / Heat Seal layer (PEF)
(14) Printing layer / Base material layer (paper) / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Adhesive layer / Heat seal layer (CPP)
(15) Base material layer (OPP) / Printing layer / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Adhesive layer / Heat seal layer (CPP)
(16) Base material layer (ONY) / Printing layer / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Adhesive layer / Heat seal layer (CPP)
(17) Base material layer (PET) / Printing layer / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Adhesive layer / Heat seal layer (PEF) / Hot melt layer (hot melt adhesive)
(18) Base material layer (OPP) / Printing layer / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Adhesive layer / Heat seal layer (PEF)
(19) Base material layer (PET) / Printing layer / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Adhesive layer / Heat seal layer (CPP)
(20) Printing layer / Base material layer (paper) / Adhesive resin layer (PE) / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Heat seal layer (PE)
(21) Printing layer / Base material layer (paper) / Adhesive resin layer (PE) / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Anchor coat layer / Heat seal layer (PE)
(22) Base material layer (OPP) / Printing layer / Adhesive layer / Protective layer (MOR) / Inorganic thin film layer (MO) / Support layer (CRF) / Adhesive layer / Heat seal layer (OPP)
(23) Base material layer (PET)/adhesive layer/printing layer/support layer (CRF)/heat seal layer (PE)
(24) Base layer (PET)/Print layer/Adhesive layer/Support layer (CRF)/Heat seal layer (PE)
(25) Base material layer (PET)/adhesive layer/printing layer/support layer (CRF)/anchor coat layer/heat seal layer (PE)
(26) Base layer (PET)/Print layer/Adhesive layer/Support layer (CRF)/Anchor coat layer/Heat seal layer (PE)
(27) Heat-sealing layer (PE)/printing layer/base material layer (paper)/adhesive resin layer (PE)/support layer (CRF)/adhesive layer/heat-sealing layer (PEF)
(28) Heat-sealing layer (PE)/printing layer/base layer (paper)/adhesive resin layer (PE)/support layer (CRF)/heat-sealing layer (PE)
(29) Heat-sealing layer (PE)/printing layer/base material layer (paper)/adhesive resin layer (PE)/support layer (CRF)/anchor coat layer/heat-sealing layer (PE)

In the specific examples described above, there are several laminates 9 in which the base material layer 51 and the inorganic thin film layer 31 are adjacent to each other. In these laminates 9, an anchor coat layer 32 may be provided between the base material layer 51 and the inorganic thin film layer 31.

In the specific examples described above, there are several laminates 9 in which the support layer and the inorganic thin film layer 31 are adjacent to each other. In these laminates 9, an anchor coat layer 32 may be provided between the support layer and the inorganic thin film layer 31.

In the specific examples mentioned above, there are several laminates 9 that include a protective layer 33 made of MOR, that is, a composition containing a metal alkoxide. In those laminates 9, the protective layer 33 may be formed of a composition containing a resin and a curing agent.

Among the specific examples described above, there are some laminates 9 that include both the base material layer 51 and the support layer. In those examples, both the base layer 51 and the support layer may be biaxially oriented polyester films 8.

The laminate 9 can be used for various purposes. For example, it can be suitably used as a packaging container, a label (for example, a label for wrapping around a PET bottle), and an exterior film for electronic components such as the exterior for lithium ion batteries. Among these, it can be suitably used for packaging containers. In particular, it can be suitably used for food packaging containers.

<4. Packaging container>
The packaging container of this embodiment includes a laminate 9. That is, the packaging container of this embodiment can be produced using the laminate 9. Here, "the packaging container includes the laminate 9" means that when the packaging container is composed of a plurality of members, at least one member includes the laminate 9. Examples of packaging containers include packaging bags (ie, pouches), lids, laminate tubes, paper containers, and paper cups (see, for example, Japanese Patent No. 6984717). The packaging container may be a food packaging container or a non-food packaging container. In other words, the contents may be food or non-food. Among these, the packaging container is preferably a food packaging container.

Examples of packaging bags include standing pouches, pillow bags (i.e. gassho sticker bags), two-side seal bags, three-side seal bags, four-side seal bags, side seal bags, envelope sticker bags, and pleated sticker bags. Examples include molded bags, flat-bottom sealed bags, square-bottom sealed bags, and gusseted bags.

<5. Various changes can be made to the above embodiment>
Various modifications can be made to the embodiments described above. For example, the above-described embodiment can be modified by selecting one or more of the following modifications.

In the embodiment described above, the biaxially oriented polyester film 8 has a three-layer structure composed of the first layer 81, the second layer 82, and the third layer 83. However, the embodiments described above are not limited to this configuration. The biaxially oriented polyester film 8 may have a single-layer structure, or may have a two-layer structure composed of a first layer 81 and a second layer 82. Of course, the biaxially oriented polyester film 8 may have a structure of four or more layers.

The present invention will be explained in more detail with reference to Examples and Comparative Examples below. Hereinafter, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass." Note that polyesters A to G, which will be described later, may be collectively referred to as raw material polyester.

<Measurement method of each physical property>
(intrinsic viscosity)
0.2 g of the sample (specifically, raw material polyester and biaxially oriented polyester film) was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane (60/40 (mass ratio)). Then, the intrinsic viscosity (IV) was measured at 30°C using an Ostwald viscometer. Note that the unit of intrinsic viscosity is dl/g.

(Content of terephthalic acid component and isophthalic acid component)
A sample (specifically, raw polyester and biaxially oriented polyester film) was dissolved in a solvent in which chloroform D (manufactured by Eurysop) and trifluoroacetic acid-D1 (manufactured by Eurysop) were mixed at a ratio of 10:1 (volume ratio). Ta. Regarding this sample solution, proton NMR was measured using a nuclear magnetic resonance (NMR) spectrometer ("GEMINI-200" manufactured by Varian) under the conditions of a temperature of 23° C. and a cumulative number of measurements of 64 times. In this NMR measurement, the peak intensity of a predetermined proton was calculated, and then the content (mol %) of the terephthalic acid component and the isophthalic acid component in 100 mol % of the acid component was calculated.

(Quantitative analysis of magnesium)
A sample (specifically, a raw material polyester and a biaxially oriented polyester film) was incinerated and decomposed in a platinum crucible, and then 6 mol/L hydrochloric acid was added and evaporated to dryness. After dissolving this in 1.2 mol/L hydrochloric acid, magnesium was quantified using an inductively coupled plasma (ICP) emission spectrometer ("ICPS-2000" manufactured by Shimadzu Corporation).

(Quantitative analysis of phosphorus)
Samples (specifically, raw polyester and biaxially oriented polyester films) are decomposed by dry ashing in the coexistence of sodium carbonate, or using either sulfuric acid/nitric acid/perchloric acid systems or sulfuric acid/hydrogen peroxide aqueous systems. Phosphorus was converted to orthophosphoric acid by a wet decomposition method. Next, molybdate was reacted in a 1 mol/L sulfuric acid solution to form phosphomolybdic acid, and this was reduced with hydrazine sulfate. 150-02'') (that is, colorimetric determination was performed).

(Melting specific resistance)
A sample (specifically, a raw material polyester and a biaxially oriented polyester film) was melted at 285° C., a pair of electrode plates was inserted into the sample, and a voltage of 120 V was applied. The current at that time was measured, and melt specific resistance Si (Ω·cm) was calculated based on the following formula.
Si=(A/I)×(V/io)
Here, A is the area of the electrode (cm ² ), I is the distance between the electrodes (cm), V is the voltage (V), and io is the current (A).

(Area ratio of area with molecular weight 1000 or less)
10 g of the sample (specifically, raw material polyester and biaxially oriented polyester film) was placed in a 30 mL vial and weighed. A mixed solution of chloroform/HFIP=98/2 (volume ratio) was added to the vial, and the sample was dissolved by standing for 12 hours. Next, this was diluted with chloroform/hexafluoroisopropanol (HFIP) = 98/2 (volume ratio) to prepare a 0.1% solution. The 0.1% solution was filtered with a 0.45 μm filter (GL Chromato Disc non-aqueous N type 13N manufactured by GL Science). Gel permeation chromatography (GPC) measurements were performed on the filtrate under the following conditions.
Column used: Tosoh Corporation, TSKgel SuperHM-H×2, and TSKgel SuperH2000
Column temperature: 40℃
Mobile phase: Chloroform/HFIP=98/2 (volume ratio)
Flow rate: 0.6mL/min
Injection volume: 20μL
Detection: 254nm (UV-visible detector)
Molecular weight calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation)
Equipment: HLC-8300GPC manufactured by Tosoh Corporation
In the molecular weight distribution curve obtained by GPC measurement, the area ratio of the region having a molecular weight of 1000 or less was determined.
In general, in GPC analysis, areas outside the range of the calibration curve are generally excluded from the calculation range of GPC analysis, but in this analysis, in order to more accurately determine the area ratio of the area with a molecular weight of 1000 or less. Next, the GPC chromatogram area (ie, total peak area) was calculated, including not only the area within the calibration curve but also the area outside the calibration curve.

(thickness)
The thickness of the biaxially oriented polyester film was measured using a dial gauge in accordance with JIS K7130-1999 A method.

(melting point)
Using a differential scanning calorimeter ("DSC60" manufactured by Shimadzu Corporation), 5 mg of a sample (specifically, a biaxially oriented polyester film) was heated from 25 °C to 320 °C at a rate of 10 °C/min, and as it melted, The main peak top temperature of the endothermic curve was determined as the melting point.

(Tensile strength)
A test piece with a width of 15 mm and a length of 100 mm was cut from a biaxially oriented polyester film. In accordance with JIS K 7127, this test piece was pulled using a tensile tester ("Autograph AG-I" manufactured by Shimadzu Corporation) at a distance between gauge lines of 50 mm and a tension speed of 200 mm/min. The tensile strength of the test piece, that is, the tensile strength at break, was calculated from the stress/strain curve thus obtained. Using this procedure, the tensile strengths in the MD (ie, 0° direction), 45° direction, TD (ie, 90° direction), and 135° direction were determined.

(Heat shrinkage rate)
A test piece with a width of 10 mm and a length of 250 mm was cut from a biaxially oriented polyester film. A pair of marks (that is, a pair of marked lines) was placed along the length of this test piece at intervals of 200 mm, and the distance between the marked lines was measured under a tension of 5 gf. This test piece was heat-treated at 150° C. for 30 minutes under no load, and then the distance between the gauge lines was measured. From these measurement results, the thermal shrinkage rate was determined using the following formula.
Heat shrinkage rate (%) = {(AB)/A} x 100
Here, A is the distance between gauge lines before heat treatment, and B is the distance between gauge lines before heat treatment.
Through this procedure, the heat shrinkage rates of MD and TD were determined.

(color b ^* value)
A stack of 10 biaxially oriented polyester films was set in a colorimeter (ZE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the color b ^* value was determined using a reflection method. The color b ^* value per 1 μm thickness was calculated using the following formula.
Color b ^* value per 1 μm thickness = (color b ^* value of 10 stacked biaxially oriented polyester films) / (10 x thickness of biaxially oriented polyester film)

(Surface crystallinity)
FT-IR ATR measurements were performed on both the corona-treated and untreated surfaces of the biaxially oriented polyester film under the following conditions. That is, a spectrum was obtained by the attenuated total reflection method using a Fourier transform infrared spectrophotometer.
FT-IR: Bio Rad DIGILAB FTS-60A/896
Single reflection ATR attachment: golden gate MKII (manufactured by SPECAC)
Internal reflective element: Diamond Incident angle: 45°
Resolution: 4cm ^-1
Number of integrations: 128 times The surface crystallinity was calculated from the intensity ratio of the absorption appearing near 1340 cm ^-1 and the absorption appearing near 1410 cm ^-1 (intensity at 1340 cm ^-1 / intensity at 1410 cm ^-1 ). The absorption that appears around 1340 cm ⁻¹ is due to the bending vibration of CH ₂ (trans structure) of ethylene glycol. On the other hand, the absorption that appears near 1410 cm ^-1 is unrelated to crystal or orientation.

(Piercing strength)
The puncture strength of a 5 cm square test piece cut from a biaxially oriented polyester film was measured using a digital force gauge (“ZTS-500N” manufactured by Imada Co., Ltd.), an electric measuring stand (“MX2-500N” manufactured by Imada Co., Ltd.), Then, measurements were made in accordance with JIS Z1707 using a film puncture test jig ("TKS-250N" manufactured by Imada Co., Ltd.). Based on the puncture strength determined by this measurement (that is, the puncture strength of the biaxially oriented polyester film), the puncture strength per 1 μm of thickness was also calculated.

(laminate strength)
On the corona-treated side of the biaxially oriented polyester film, a urethane two-component curing adhesive (specifically, "Takelac (registered trademark) A525S" manufactured by Mitsui Chemicals, Inc. and "Takenate (registered trademark)" manufactured by Mitsui Chemicals, Inc. A 70 μm thick unstretched polypropylene film (P1147 manufactured by Toyobo Co., Ltd.) was used as a polyolefin sealant layer by dry laminating using an adhesive containing 13.5:1 (mass ratio) of A50 (Trademark). A laminate was produced by bonding them together and then aging them at 40° C. for 4 days. The peel strength (N/15 mm) of the bonded surface between the corona-treated surface of the biaxially oriented polyester film and the polyolefin resin layer was measured for a test piece having a width of 15 mm and a length of 200 mm cut out from this laminate. The peel strength was measured at a temperature of 23°C and a relative humidity of 65% using a Tensilon UMT-II-500 manufactured by Toyo Baldwin Co., Ltd. at a tensile rate of 20 cm/min and a peel angle of 180 degrees. .

(maximum cast speed)
The presence or absence of pinner bubbles was visually determined using a polarizing plate (manufactured by Nishida Kogyo Co., Ltd.) for unstretched films produced while changing the rotational speed of the cooling drum in stages. As a result, the maximum casting speed was determined from the maximum rotational speed at which pinner bubbles did not occur.

(Film forming property)
The film formability of the biaxially oriented polyester film was evaluated based on the following criteria.
○: No breakage occurred for 60 minutes or more. That is, continuous film formation for 60 minutes or more was possible.
Δ: Broken at least once during 30 minutes or more and less than 60 minutes.
×: Broken at least once in less than 30 minutes.

<Raw material polyester>
(Polyester B)
The separated and recovered PET bottle bales were pulverized while being circulated in a wet pulverizer together with a cleaning solution (specifically, a cleaning solution prepared by adding 500 g of liquid kitchen detergent to 1000 liters of water). A gravity separator connected to the wet crusher precipitates foreign substances with high specific gravity, such as metals, sand, and glass, and extracts flakes from the upper layer. The flakes were rinsed with pure water and dehydrated by centrifugation. Recovered flakes were obtained by such a procedure.
30 kg of undried molten recovered flakes were mixed with a preheated mixed solution, specifically, a mixed solution of 150 kg of ethylene glycol and 150 g of zinc acetate dihydrate in a stirring autoclave. Then, fractions with boiling points lower than ethylene glycol, such as water and acetic acid, were removed. Then, the mixture was reacted for 4 hours at a temperature of 195°C to 200°C using a reflux condenser.
After the reaction was completed, the temperature of the reactor contents was lowered to 97° C. to 98° C., and then filtered while hot to remove suspended matter and precipitates.
After further cooling the filtrate and ensuring that the crude BHET was completely dissolved, the filtrate was passed through an activated carbon bed and then an anion/cation exchange mixed bed at 50° C. to 51° C. for 30 minutes. In other words, pre-purification treatment was performed.
The pre-purification treatment liquid was charged into a stirring autoclave, heated and excess ethylene glycol was distilled off at normal pressure to obtain a concentrated BHET molten liquid.
After the melt of concentrated BHET was allowed to cool down naturally while being stirred under a nitrogen gas atmosphere, it was taken out from the stirring autoclave to obtain a block of concentrated BHET strips.
After heating and melting the strip block to 130° C., it was supplied to a thin film vacuum evaporator using a metering pump, evaporated, and cooled and condensed to obtain purified BHET.
2,650 kg of this purified BHET was supplied at once to a dissolution tank purged with nitrogen, and after replacing the tank with nitrogen again, the temperature of the dissolution tank was set at 150° C. for dissolution. After the dissolution was completed, the temperature of the dissolution tank was raised to 230° C. for 30 minutes while using a stirrer. 2,650 kg of the obtained BHET solution was transferred to a polycondensation reaction tank, and 300 ppm of antimony trioxide, 170 ppm of cobalt acetate, and phosphoric acid were added to the BHET solution, based on the amount of PET obtained (approximately 2,000 kg of PET can be obtained from 2,650 kg of BHET). 55 ppm and 0.3% by weight of titanium dioxide were added, and while stirring at 10 to 40 rpm, the temperature of the polycondensation reactor was gradually raised from 230° C. to 290° C., and the pressure was lowered to 40 Pa. After that, when a predetermined stirring torque was reached, the polycondensation reaction tank was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, and the mixture was discharged in the form of a strand, cooled, and immediately cut to obtain polyester chips.
Through these procedures, a chemically recycled polyester having an intrinsic viscosity of 0.59 dl/g, ie, polyester B, was obtained.

(Polyester A)
Polyester B (ie, a chemically recycled polyester with an intrinsic viscosity of 0.59 dl/g) was continuously fed to a crystallizer, crystallized at 150°C, and then fed to a dryer and dried at 130°C for 10 hours. The dried polyester B was sent to a preheater, heated to 180°C, and then supplied to a solid phase polymerization machine. A solid phase polymerization reaction was carried out at 190° C. for 24 hours under nitrogen gas to obtain a chemically recycled polyester, ie, polyester A, having an intrinsic viscosity of 0.79 dl/g.

(Polyester C)
A chemically recycled polyester having an intrinsic viscosity of 0.83 dl/g, that is, polyester C, was obtained in the same manner as polyester A, except that the time for the solid phase polymerization reaction was changed from 24 hours to 50 hours.

(Polyester D)
After washing away foreign substances such as remaining beverage from the PET beverage bottle, flakes were obtained by crushing the PET beverage bottle. The flakes were washed by mixing them with a 3.5% by mass sodium hydroxide solution and stirring at a flake concentration of 10% by mass at 85° C. for 30 minutes (that is, alkaline washing was performed). The flakes taken out after alkaline washing were washed with distilled water by stirring at a flake concentration of 10% by weight at 25° C. for 20 minutes. This water washing was repeated two more times, replacing the distilled water each time. The flakes washed with water were dried and melted in an extruder, and then passed through a filter to remove foreign substances. The filters were installed in the extruder up to the third filter so that the opening size of the filters gradually decreased. The opening size of the third stage filter was 50 μm. Through these procedures, mechanically recycled polyester, ie, polyester D, having an intrinsic viscosity of 0.69 dl/g was obtained.

(Polyester E-1)
As the polyester E-1, that is, as the fossil fuel-derived polyester, a polyester (manufactured by Toyobo Co., Ltd.) with an intrinsic viscosity of 0.62 dl/g and a terephthalic acid/ethylene glycol ratio of 100 mol%/100 mol% was used. That is, homopolyethylene terephthalate (ie, homoPET) with an intrinsic viscosity of 0.62 dl/g was used. It should be noted that both terephthalic acid and ethylene glycol were not derived from used polyester products, but from fossil fuels.

(Polyester E-2)
As the polyester E-2, that is, as the fossil fuel-derived polyester, a polyester (manufactured by Toyobo Co., Ltd.) with an intrinsic viscosity of 0.75 dl/g and a terephthalic acid/ethylene glycol ratio of 100 mol%/100 mol% was used. That is, homopolyethylene terephthalate (ie, homoPET) with an intrinsic viscosity of 0.75 dl/g was used. It should be noted that both terephthalic acid and ethylene glycol were not derived from used polyester products, but from fossil fuels.

(Polyester E-3)
As polyester E-3, that is, as a fossil fuel-derived polyester, a polyester with an intrinsic viscosity of 0.63 dl/g and terephthalic acid/ethylene glycol/isophthalic acid = 92.1 mol%/98 mol%/7.9 mol% (Toyobo (manufactured by) was used. That is, isophthalic acid copolymerized polyethylene terephthalate (ie, IPA copolymerized PET) having an intrinsic viscosity of 0.63 dl/g was used. It should be noted that terephthalic acid, ethylene glycol, and isophthalic acid were not derived from used polyester products, but from fossil fuels.

(Polyester F)
When the temperature of the esterification reactor was raised to 200°C, a slurry consisting of 86.4 parts by mass of terephthalic acid and 64.4 parts by mass of ethylene glycol was charged, and while stirring, 0.017 parts of antimony trioxide was added as a catalyst. parts by weight and 0.16 parts by weight of triethylamine were added. Next, heating was carried out to raise the temperature, and a pressurized esterification reaction was carried out at a gauge pressure of 0.34 MPa and a temperature of 240°C.
Thereafter, the inside of the esterification reactor was returned to normal pressure, and 0.071 parts by mass of magnesium acetate tetrahydrate and then 0.014 parts by mass of trimethyl phosphate were added. After raising the temperature to 260° C. over 15 minutes, 0.012 parts by mass of trimethyl phosphate and then 0.0036 parts by mass of sodium acetate were added. Fifteen minutes after these were added, 3.0 parts by mass of ethylene glycol slurry of amorphous silica particles having an average particle diameter of 2.7 μm was added based on the particle content. The obtained esterification reaction product was transferred to a polycondensation reactor, and a polycondensation reaction was carried out at 280° C. under reduced pressure to obtain polyester F having an intrinsic viscosity of 0.61 dl/g.
Here, the above-mentioned ethylene glycol slurry of amorphous silica particles is prepared by mixing amorphous silica particles with ethylene glycol, performing a dispersion process using a high-pressure disperser, and then centrifuging to cut off 35% of the coarse particle portion. The slurry was then filtered through a metal filter with an opening of 5 μm.
It should be noted that both terephthalic acid and ethylene glycol were not derived from used polyester products, but from fossil fuels.

(Polyester G)
When the temperature of the esterification reactor was raised to 200°C, a slurry consisting of 86.4 parts by mass of terephthalic acid and 64.4 parts by mass of ethylene glycol was charged, and while stirring, 0.025 parts of antimony trioxide was added as a catalyst. parts by weight and 0.16 parts by weight of triethylamine were added. Next, heating was carried out to raise the temperature, and a pressurized esterification reaction was carried out at a gauge pressure of 0.34 MPa and a temperature of 240°C.
Thereafter, the inside of the esterification reactor was returned to normal pressure, and 0.34 parts by mass of magnesium acetate tetrahydrate and then 0.042 parts by mass of trimethyl phosphate were added. After raising the temperature to 260° C. over 15 minutes, 0.036 parts by mass of trimethyl phosphate and then 0.0036 parts by mass of sodium acetate were added. The obtained esterification reaction product was transferred to a polycondensation reactor, and the temperature was gradually raised from 260°C to 280°C under reduced pressure, followed by a polycondensation reaction at 285°C. After the polycondensation reaction was completed, filtration was performed using a stainless steel sintered filter with a pore size of 5 μm (initial filtration efficiency of 95%) to obtain polyester G with an intrinsic viscosity of 0.62 dl/g. It should be noted that both terephthalic acid and ethylene glycol were not derived from used polyester products, but from fossil fuels.

A supplementary explanation will be given regarding Table 1. TPA is an abbreviation for terephthalic acid. EG is an abbreviation for ethylene glycol. IPA is an abbreviation for isophthalic acid.
In the TPA, EG, and IPA columns, "-" means not measured.
Mg indicates the content of a magnesium compound on the basis of magnesium atoms. This content is the mass of the magnesium compound on a magnesium atom basis with respect to the mass of the polyester (that is, the mass of the magnesium compound on a magnesium atom basis/the mass of the polyester). In addition, only the content of the magnesium compound among the alkaline earth metal compounds is shown here. This is because the raw material polyester did not contain any alkaline earth metal compounds other than the magnesium compound (it could be said that it was below the detection limit).
P indicates the content of phosphorus compounds on the basis of phosphorus atoms. This content is the mass of the phosphorus compound on a phosphorus atom basis with respect to the mass of the polyester (that is, the mass of the phosphorus compound on a phosphorus atom basis/the mass of the polyester).

As shown in Table 1, among polyesters A, B, and C, polyester C had the highest intrinsic viscosity and the lowest amount of low molecular weight components. Polyester B had the lowest intrinsic viscosity and the highest amount of low molecular weight components. In other words, the higher the intrinsic viscosity, the lower the content of low molecular weight components.

Although polyester B (i.e., chemically recycled polyester) had a lower intrinsic viscosity than polyester E-1 (i.e., fossil fuel-derived polyester), the content of low molecular weight components was comparable to that of polyester E-1.

On the other hand, although polyester D (i.e., mechanically recycled polyester) had a higher intrinsic viscosity than polyester E-1 (i.e., fossil fuel-derived polyester), it had a higher content of low molecular weight components than polyester E-1.

<Example 1>
A biaxially oriented polyester film having a three-layer structure was formed using three extruders. To form the base layer of the biaxially oriented polyester film, that is, layer B, 50.0% by mass of polyester A, 42.0% by mass of polyester E-1, and 8.0% by mass of polyester G were used. On the other hand, to form a pair of surface layers of the biaxially oriented polyester film, that is, a pair of A layers, 50.0% by mass of polyester A, 39.0% by mass of polyester E-1, and 3.0% by mass of polyester F were used. 0% by mass, and 8.0% by mass of polyester G was used. The film forming procedure will be explained below.
After drying the raw material polyester for forming layer A, it is supplied to the first and third extruders and melted at 285°C, and after drying the raw material polyester for forming layer B, , fed to a second extruder and melted at 285°C. The molten polyester is led from each extruder to the T-die, and the layers are laminated in the T-die to form layer A/layer B/layer A (thickness 1μm/10μm/1μm), and then extruded from the T-die at a surface temperature of 25°C. It was cooled and solidified in a casting drum, that is, a cooling drum. At that time, the film extruded from the T-die and before contact with the cooling drum was charged with a wire-shaped electrode having a diameter of 0.15 mm. Casting speed was 70 m/min. An unstretched film was produced by such a procedure.
The unstretched film was heated to 120° C. with an infrared heater and stretched once in the longitudinal direction (ie, MD) at a stretching ratio of 4.0 times.
Subsequently, it was stretched in the width direction (i.e. TD) using a tenter type horizontal stretching machine at a preheating temperature of 120°C, a stretching temperature of 130°C, and a stretching ratio of 4.2 times, heat setting at 245°C, and 5% heat treatment in the width direction. Relaxation treatment was performed. The length of the widthwise stretching zone was 12.2 m, and the widthwise stretching speed (ie, TD stretching ratio) was 122.66%/sec. Next, of the pair of A layers, the A layer in contact with the cooling drum was subjected to corona treatment at 40 W min/m ² and then wound into a roll using a winder.
A master roll (winding length: 60,000 m, width: 8,000 mm) of a biaxially oriented polyester film having a thickness of 12 μm was obtained by such a procedure.
A biaxially oriented polyester film is unwound from a master roll, and while being slit to a width of 800 mm, while applying surface pressure with a contact roll and tension with a biaxial turret winder, the slit biaxially oriented polyester film is slit into a diameter of 6 mm. It was wound into a roll around an inch (152.2 mm) core.
A biaxially oriented polyester film was obtained by such a procedure.

<Examples 2 to 5 and Comparative Examples 1 to 4 and 6>
A biaxially oriented polyester film was produced in the same manner as in Example 1, except that the mixing ratio of raw polyesters and film forming conditions were changed according to the recipe in Table 2. Note that the casting speed was 70 m/min in all these examples. In all these examples, the length of the widthwise stretching zone was 12.2 m, and the widthwise stretching speed (i.e., TD stretching ratio) was 122.66%/sec.

<Comparative example 5>
A biaxially oriented polyester film was produced in the same manner as in Example 1, except that the mixing ratio of raw polyesters and film forming conditions were changed according to the recipe in Table 2. Note that the casting speed was 65 m/min. The length of the widthwise stretching zone was 12.2 m, and the widthwise stretching speed (ie, TD stretching ratio) was 113.7%/sec.

<Example 6>
An unstretched film was obtained in the same manner as in Example 1, except that the mixing ratio of the raw material polyester was changed according to the recipe in Table 2. Note that the casting speed was 70 m/min.
The ends of the unstretched film were gripped with the clips of a tenter-type simultaneous biaxial stretching machine, and after running through a 120°C preheating zone, the film was stretched at 130°C, 4.0 times in the longitudinal direction (i.e., MD), and 4.0 times in the width direction (i.e., TD). ) Simultaneous biaxial stretching was carried out at 4.2 times. Next, the film was heat-treated at a temperature of 245° C. with a relaxation rate in the width direction of 5%, and then cooled to room temperature and wound up to obtain a biaxially oriented polyester film with a thickness of 12 μm.

A supplementary explanation will be given regarding Table 2. The "mixing ratio" listed in Table 2 is expressed as a value when the total mass of the raw material polyester used to form the target layer is 100% by mass. For example, for layer B in Example 1, it is shown that polyester A was 50% by mass out of 100% by mass of the total mass of polyesters A, E-1, and G used to form layer B.
The silica content is the mass of silica relative to the mass of the target layer (that is, the mass of silica/the mass of the target layer). The mass of the target layer means the total mass of raw materials (eg, polyester and particles) for forming the target layer. "CRPET" is a generic term for polyesters A, B and C.
Mg indicates the content of the magnesium compound on the basis of magnesium atoms. This content is the mass of the magnesium compound on the basis of magnesium atoms relative to the mass of the biaxially oriented polyester film.
P indicates the content of phosphorus compounds on the basis of phosphorus atoms. This content is the mass of the phosphorus compound on a phosphorus atom basis with respect to the mass of the biaxially oriented polyester film.

By replacing 80% by mass of polyester E-1 (i.e., fossil fuel-derived homo-PET with an intrinsic viscosity of 0.62 dl/g) with polyester C (i.e., a chemically recycled polyester with an intrinsic viscosity of 0.83 dl/g), the surface crystallinity was excessively reduced, the intrinsic viscosity was excessively high, and the film was broken during stretching (see Comparative Examples 1 and 3). Even in Comparative Example 5, which had an excessively low surface crystallinity and an excessively high intrinsic viscosity, the film broke during stretching.

By replacing 91% by mass of polyester E-1 (i.e., fossil fuel-derived homo-PET with an intrinsic viscosity of 0.62 dl/g) with polyester B (i.e., a chemically recycled polyester with an intrinsic viscosity of 0.59 dl/g), the surface crystallinity was excessively high, the intrinsic viscosity was excessively low, and the tensile strength and puncture strength were decreased (see Comparative Examples 1 and 4). In addition to this, the color b ^* values were excessively high.

The biaxially oriented polyester film of Comparative Example 6, which had an excessively high content of isophthalic acid components, had an excessively low melting point and surface crystallization, and was inferior in tensile strength and puncture strength.

On the other hand, by replacing some of the polyester E-1 (specifically 50%, 20%, 80% by mass) with polyester A (i.e., a chemically recycled polyester with an intrinsic viscosity of 0.79 dl/g), the tensile strength and A biaxially oriented polyester film with excellent puncture strength and heat resistance could be produced without breakage (see Comparative Example 1 and Examples 1 to 3). Even with simultaneous biaxial stretching, a biaxially oriented polyester film could be produced without breakage (see Example 6).

By replacing some of the polyester E-1 (specifically 50% by mass, 80% by mass) with polyester B (i.e., chemically recycled polyester with an intrinsic viscosity of 0.59 dl/g), the tensile strength and puncture strength can be improved. , a biaxially oriented polyester film with excellent heat resistance could be produced without breakage (see Comparative Example 1 and Examples 4 and 5).

Since the present invention relates to a biaxially oriented polyester film, the present invention has industrial applicability.

8... Biaxially oriented polyester film, 81... First layer, 82... Second layer, 83... Third layer, 9... Laminate, 11... Printing layer, 21... Sealant layer, 22... Sealant layer, 31... Inorganic thin film Layer, 32... Anchor coat layer, 33... Protective layer, 51... Base material layer, 61... Intermediate layer

Claims

Contains chemically recycled polyester
At least one surface has a surface crystallinity of 1.10 or more and 1.31 or less as determined by the attenuated total reflection method using a Fourier transform infrared spectrophotometer,
The melting point is 251°C or higher,
Biaxially oriented polyester film.
When the number of moles of all dicarboxylic acid components in the biaxially oriented polyester film is 100 mol%, the number of moles of the isophthalic acid component is 0.1 mol% or more and 3.0 mol% or less, according to claim 1. biaxially oriented polyester film.
The biaxially oriented polyester film according to claim 1, wherein the biaxially oriented polyester film has a puncture strength of 0.50 N/μm or more.
The biaxially oriented polyester film according to claim 1, wherein the biaxially oriented polyester film has an intrinsic viscosity of 0.50 dl/g or more and 0.70 dl/g or less.
The biaxially oriented polyester film according to claim 1, wherein the content of the chemically recycled polyester is 20% by mass or more.
The biaxially oriented polyester film according to claim 1,
a sealant layer;
laminate.
further comprising a printing layer;
In at least a portion of the laminate, the printing layer, the biaxially oriented polyester film, and the sealant layer are arranged in this order in the thickness direction of the laminate.
The laminate according to claim 6.
further comprising a printing layer;
In at least a portion of the laminate, the biaxially oriented polyester film, the printing layer, and the sealant layer are arranged in this order in the thickness direction of the laminate.
The laminate according to claim 6.
The biaxially oriented polyester film according to claim 1,
including an adhesive layer;
laminate.
further comprising a printing layer;
In at least a portion of the laminate, the printed layer, the biaxially oriented polyester film, and the adhesive layer are arranged in this order in the thickness direction of the laminate.
The laminate according to claim 9.
further comprising a printing layer;
In at least a portion of the laminate, the biaxially oriented polyester film, the printing layer, and the adhesive layer are arranged in this order in the thickness direction of the laminate.
The laminate according to claim 9.
A packaging container comprising the laminate according to any one of claims 6 to 11.