JP2023123494A - Barrier laminate film, and method of manufacturing barrier laminate film, and packaging material having barrier laminate film - Google Patents

Abstract

To provide a barrier laminate film having gas barrier properties and strength.SOLUTION: A barrier laminate film has a base material, and a vapor deposition layer provided on the base material and containing metal or an inorganic compound. The base material has a loop stiffness of 0.0017 N or more in a flow direction and a vertical direction, and contains polyester as the main component. In at least one direction, a tensile elongation of the base material is divided by a tensile strength of it to give a value of 2.0 [MPa/%] or more. The thickness of the base material is 16 μm or more and 25 μm or less.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a barrier laminate film having a substrate and a vapor deposition layer provided on the substrate, and a method for producing the barrier laminate film. The present invention also relates to a packaging material comprising a barrier laminate film and a thermoplastic resin layer laminated on the barrier laminate film.

BACKGROUND ART Conventionally, various packaging materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, chemicals, cosmetics, and the like. Such packaging materials are required to have various physical properties, depending on the purpose of packaging, contents to be filled, storage/distribution of packaged products, and the like. For example, one of their physical properties is a gas barrier property that prevents permeation of oxygen, water vapor, and the like.

Conventionally, various gas barrier materials that block permeation of oxygen, water vapor, etc. have been developed and proposed. For example, gas barrier materials such as aluminum foil, nylon film having polyvinylidene chloride resin coating film, polyethylene terephthalate film, polyvinyl alcohol film, saponified ethylene-vinyl acetate copolymer film, polyacrylonitrile resin film, etc. has been developed and proposed.

Furthermore, in recent years, a transparent barrier film having a structure in which, for example, a vapor deposition layer of an inorganic oxide such as silicon oxide or aluminum oxide is provided on a plastic substrate, or a vapor deposition layer of a metal such as aluminum is provided. A barrier film and the like have also been proposed. For example, Patent Literature 1 proposes making a barrier film by forming a vapor deposition layer of an inorganic oxide on a nylon film.

Japanese Patent Application Laid-Open No. 2007-303000

Packaging materials are required to have so-called stab resistance, which is a characteristic that prevents the bag from tearing even when a sharp member with a sharp tip comes into contact with the bag. The nylon film described in Patent Document 1 is known as a film having high puncture resistance. On the other hand, nylon easily absorbs moisture and has poor heat resistance. Therefore, it is difficult to use nylon film as the film that constitutes the outer surface of the packaging material. For example, in Patent Document 1, a base film containing a polyester-based resin or the like is laminated via an adhesive layer on the outer surface side of a nylon film. Since the packaging material thus includes two plastic films, the nylon film and the base film, the cost of the packaging material is increased.

An object of the present invention is to provide a barrier laminate film that can effectively solve such problems.

The present invention comprises a base material and a deposited layer containing a metal or an inorganic compound provided on the base material, and the base material has a loop stiffness of 0.0017 N or more in the machine direction and the vertical direction. , and contains polyester as a main component, and in at least one direction, the value obtained by dividing the tensile strength of the substrate by the tensile elongation is 2.0 [MPa / %] or more, and the thickness of the substrate is 16 μm It is a barrier laminated film having a thickness of 25 μm or more.

In the barrier laminate film according to the present invention, the base material may have a puncture strength of 9.5 N or more.

The barrier laminate film according to the present invention may further include a gas barrier coating film provided on the vapor deposition layer.

In the barrier laminate film according to the present invention, the vapor deposition layer may be a transparent vapor deposition layer containing an inorganic compound.

In the barrier laminate film according to the present invention, the vapor deposition layer is a transparent vapor deposition layer containing aluminum oxide, the transparent vapor deposition layer includes a transition region, and the transition region extends from the vapor deposition layer side of the vapor deposition layer. The position of the peak of elementally bound Al ₂ O ₄ H detected by etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the relationship between the transparent deposition layer and the first plastic film. A ratio of the thickness of the transition region to the thickness of the transparent deposition layer may be 5% or more and 60% or less.

The present invention comprises a step of preparing a base material and a vapor deposition step of forming a vapor deposition layer on the base material by vapor-depositing a metal or an inorganic compound on the base material. It has a loop stiffness of 0.0017 N or more in the vertical direction, contains polyester as a main component, and has a value obtained by dividing the tensile strength of the substrate by the tensile elongation of 2.0 [MPa / % in at least one direction ] and the thickness of the substrate is 16 μm or more and 25 μm or less.

The method for producing a barrier laminated film according to the present invention further comprises a plasma pretreatment step of subjecting the base material to a plasma treatment to form a plasma-treated surface on the base material, and the vapor deposition step includes applying the plasma to the base material. The deposition layer may be formed on the treated surface.

In the method for producing a barrier laminate film according to the present invention, the vapor deposition step may form the vapor deposition layer on the plasma-treated surface of the substrate by physical vapor deposition.

In the method for producing a barrier laminated film according to the present invention, the plasma pretreatment step includes a step of supplying a mixed gas of oxygen gas and an inert gas as a plasma raw material gas, and The mixing ratio (oxygen gas/inert gas) may be within the range of 6/1 to 1/1.

In the method for producing a barrier laminated film according to the present invention, the vapor-deposited layer is a transparent vapor-deposited layer containing an inorganic compound, and the film-manufacturing method includes applying a coating agent for a gas-barrier coating film onto the vapor-deposited layer, and heating the vapor-deposited layer. A step of forming a gas barrier coating film by drying may be further provided.

In the method for producing a barrier laminate film according to the present invention, the gas barrier coating film may be a layer obtained by applying a mixed solution of a metal alkoxide and a water-soluble polymer, followed by heating and drying.

In the method for producing a barrier laminate film according to the present invention, the gas barrier coating film may be a layer obtained by applying a mixed solution of a metal alkoxide, a silane coupling agent and a water-soluble polymer, followed by heating and drying.

The present invention provides a barrier laminate film having a substrate, a deposited layer containing a metal or an inorganic compound provided on the substrate, and a thermoplastic resin layer laminated on the barrier laminate film. wherein the base material has a loop stiffness of 0.0017 N or more in the machine direction and the vertical direction, and contains polyester as a main component, and the tensile strength of the base material is divided by the tensile elongation in at least one direction. is 2.0 [MPa/%] or more, and the thickness of the substrate is 16 μm or more and 25 μm or less.

The packaging material according to the present invention may be used as a packaging bag for boiling or a packaging bag for retort sterilization.

According to the present invention, a barrier laminate film having gas barrier properties and strength can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the barrier laminated|multilayer film in embodiment of this invention. FIG. 4 is a cross-sectional view showing another example of the barrier laminate film. FIG. 4 is a plan view showing an example of a loop stiffness measuring device; 4 is a cross-sectional view of the loop stiffness measuring device of FIG. 3 along line V-V; FIG. FIG. 4 is a diagram for explaining a process of attaching a test piece to the loop stiffness measuring instrument; It is a figure for demonstrating the process of forming a loop part in a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece. 1 is a cross-sectional view showing an example of a substrate containing PBT; FIG. FIG. 4 is a diagram showing an example of the results of analysis of the vapor deposition layer of the barrier laminated film by a time-of-flight secondary ion mass spectrometer. It is a figure which shows an example of the film-forming apparatus which forms a vapor deposition layer on a base material. 1 is a cross-sectional view showing an example of a packaging material comprising a barrier laminated film; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION A barrier laminate film and a film forming apparatus for depositing a vapor deposition layer of the barrier laminate film according to an embodiment of the present invention will be described below in detail with reference to the drawings. It should be noted that this example is merely an example, and does not limit the present invention in any way.

<Barrier laminated film>
FIG. 1 is a cross-sectional view showing an example of a barrier laminate film 5 according to an embodiment of the invention. The barrier laminate film 5 includes a base material 1 and a deposited layer 2 provided on the base material 1 .

FIG. 2 is a cross-sectional view showing another example of the barrier laminated film 5 according to the embodiment of the invention. The barrier laminate film 5 includes a substrate 1 , a vapor deposition layer 2 provided on the substrate 1 , and a gas barrier coating film 3 provided on the vapor deposition layer 2 .

Although not shown, the barrier laminate film 5 may further include a printed layer provided on the substrate 1, the vapor deposition layer 2, or the gas barrier coating film 3. The printed layer is a layer for showing product information and giving aesthetics to a packaging bag composed of a packaging material 8 that is provided with a barrier laminated film 5 and will be described later. The print layer expresses characters, numbers, symbols, graphics, patterns, and the like. Gravure printing ink and flexographic printing ink can be used as the material forming the printing layer. A specific example of the ink for gravure printing is FINART manufactured by DIC Graphics Corporation.

Each component of the barrier laminated film 5 will be described below.

[Base material]
The substrate 1 used for the barrier laminated film 5 is a polyester film containing polyester as a main component. The base material 1 contains, for example, 51% by mass or more of polyester. The polyester includes at least one aromatic dicarboxylic acid selected from terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, and at least one selected from ethylene glycol, 1,3-propanediol and 1,4-butanediol. A polyester based on an aromatic polyester consisting of one kind of aliphatic alcohol is preferred. Examples of polyester include polyethylene terephthalate (hereinafter also referred to as PET) and polybutylene terephthalate (hereinafter also referred to as PBT). For example, the base material 1 may contain 51% by mass or more of PET as a main component, or may contain 51% by mass or more of PBT as a main component.

In order to prevent the packaging bag made of the packaging material including the barrier laminated film 5 from tearing when a sharp member with a sharp tip comes into contact with the bag, the base of the barrier laminated film 5 is Preferably, the material 1 is resistant, such as puncture resistant. Therefore, in this embodiment, it is proposed to use either a high-stiffness PET film or a PBT film as the substrate 1 . Thereby, for example, the piercing strength of the substrate 1 can be increased. For example, the piercing strength of the substrate 1 can be 9.5 N or more, more preferably 10 N or more. Moreover, the ratio of the tensile strength to the tensile elongation of the substrate 1 can be increased. For example, in at least one direction, the value obtained by dividing the tensile strength of the substrate by the tensile elongation is 2.0 [MPa/%] or more. As a result, the packaging material including the barrier laminated film 5 can be provided with rigidity to prevent the bag from tearing even when a sharp member with a sharp tip comes into contact with the packaging material.

The high-stiffness PET film and PBT film are described in detail below. First, the high stiffness PET film will be explained.

A high-stiffness PET film is an oriented plastic film that has a loop stiffness of 0.0017 N or greater in the machine direction (MD) and vertical direction (TD) and contains 51% or greater by weight of PET. The thickness of the high-stiffness PET film is preferably 5 μm or more, more preferably 7 μm or more. Also, the thickness of the high-stiffness PET film is preferably 25 μm or less, more preferably 20 μm or less.

Loop stiffness is a parameter representing the stiffness of a film. A method of measuring loop stiffness will be described below with reference to FIGS. 3 to 8. FIG.

The measuring method described below can be used not only for single-layer films such as stretched plastic films, but also for multi-layer films such as vapor-deposited films and laminated films. A deposited film is a film that includes a single-layer film and a deposited layer formed on the single-layer film, such as the barrier laminate film 5 described above. A laminated film is a film including a plurality of laminated films, such as the packaging material 8 described below.

3 is a plan view showing the test piece 40 and the loop stiffness measuring device 45, and FIG. 4 is a cross-sectional view of the test piece 40 and the loop stiffness measuring device 45 of FIG. 3 along line IV-IV. The test piece 40 is a rectangular film having long sides and short sides. In the present application, the length L1 of the long side of the test piece 40 was set to 150 mm, and the length L2 of the short side was set to 15 mm. As the loop stiffness measuring device 45, for example, No. 1 manufactured by Toyo Seiki Co., Ltd. A 581 Loop Stiffness Tester® LOOP STIFFNESS TESTER Model DA can be used. The length L1 of the long side of the test piece 40 can be adjusted as long as the test piece 40 can be gripped by a pair of chuck portions 46, which will be described later.

The loop stiffness measuring instrument 45 has a pair of chuck portions 46 for gripping a pair of longitudinal ends of the test piece 40 and a support member 47 supporting the chuck portions 46 . The chuck part 46 includes a first chuck 461 and a second chuck 462 . 3 and 4, the test piece 40 is placed on the pair of first chucks 461, and the second chuck 462 still grips the test piece 40 between itself and the first chucks 461. not As will be described later, the test piece 40 is gripped between the first chuck 461 and the second chuck 462 of the chuck portion 46 during measurement. The second chuck 462 may be connected to the first chuck 461 via a hinge mechanism.

If the film to be measured, such as a stretched plastic film, vapor-deposited film, or laminated film, is available in a state before the film is processed into a packaging product, the test piece 40 is prepared by cutting the film to be measured. may Alternatively, the test piece 40 may be made by cutting a packaged product made from a packaging material, such as a bag, and removing the film to be measured.

A method of measuring the loop stiffness of the test piece 40 using the loop stiffness measuring device 45 will be described. First, as shown in FIGS. 3 and 4, the test piece 40 is placed on the first chucks 461 of the pair of chuck portions 46 arranged with an interval L3 therebetween. In the present application, the interval L3 is set so that the length of the loop portion 41 described later (hereinafter also referred to as loop length) is 60 mm. The test piece 40 includes an inner surface 40x positioned on the side of the first chuck 461 and an outer surface 40y positioned on the opposite side of the inner surface 40x. If test strip 40 is made of packaging material, inner surface 40x and outer surface 40y of test strip 40 match the inner and outer surfaces of the packaging material. Subsequently, as shown in FIG. 5 , the second chuck 462 is placed on the test strip 40 so as to grip the longitudinal end of the test strip 40 between itself and the first chuck 461 .

Subsequently, as shown in FIG. 6, at least one of the pair of chuck portions 46 is slid on the support member 47 in the direction in which the distance between the pair of chuck portions 46 is reduced. Thereby, the loop portion 41 can be formed in the test piece 40 . A test piece 40 shown in FIG. 6 has a loop portion 41 , a pair of intermediate portions 42 and a pair of fixing portions 43 . The pair of fixing portions 43 are portions of the test piece 40 that are held by the pair of chuck portions 46 . The pair of intermediate portions 42 are portions of the test piece 40 located between the loop portion 41 and the pair of intermediate portions 42 . As shown in FIG. 6, the chuck portion 46 is slid on the support member 47 until the inner surfaces 40x of the pair of intermediate portions 42 come into contact with each other. Thereby, the loop portion 41 having a loop length of 60 mm can be formed. The loop length of the loop portion 41 is defined by the position P1 where the surface of the second chuck 462 on the loop portion 41 side and the test piece 40 intersect, and the surface of the other second chuck 462 on the loop portion 41 side and the test piece 40 . is the length of the test piece 40 between the crossing position P2. When ignoring the thickness of the test piece 40, the above-mentioned interval L3 is a value obtained by adding 2×t to the length of the loop portion 41. As shown in FIG. t is the thickness of the second chuck 462 of the chuck portion 46 .

After that, as shown in FIG. 7, the posture of the chuck portion 46 is adjusted so that the projection direction Y of the loop portion 41 with respect to the chuck portion 46 is horizontal. For example, the posture of the chuck portion 46 supported by the support member 47 is adjusted by moving the support member 47 so that the normal direction of the support member 47 faces the horizontal direction. In the example shown in FIG. 7, the projecting direction Y of the loop portion 41 coincides with the thickness direction of the chuck portion. Also, the load cell 48 is prepared at a position separated from the second chuck 462 by a distance Z1 in the projecting direction Y of the loop portion 41 . In this application, the distance Z1 is set to 50 mm. Subsequently, the load cell 48 is moved at a speed V toward the loop portion 41 of the test piece 40 by a distance Z2 shown in FIG. The distance Z2 is set so that the load cell 48 contacts the loop portion 41 and then the load cell 48 pushes the loop portion 41 toward the chuck portion 46, as shown in FIGS. In this application, the distance Z2 is set to 40 mm. In this case, the distance Z3 between the load cell 48 and the second chuck 462 of the chuck portion 46 when the load cell 48 pushes the loop portion 41 toward the chuck portion 46 is 10 mm. A speed V for moving the load cell 48 was set to 3.3 mm/sec.

Subsequently, as shown in FIG. 8, the load cell 48 is moved toward the chuck portion 46 by a distance Z2, and in a state where the load cell 48 pushes the loop portion 41 of the test piece 40, the load is applied from the loop portion 41 to the load cell 48. After the load value stabilizes, record the load value. The value of the load thus obtained is adopted as the loop stiffness of the film forming the test piece 40 . In the present application, unless otherwise specified, the environment during the loop stiffness measurement is 23° C. temperature and 50% relative humidity.

Preferred mechanical properties of the high stiffness PET film are further described.
The puncture strength of the high-stiffness PET film is preferably 9.5N or higher, more preferably 10.0N or higher.

The tensile strength of the high stiffness PET film in machine direction is preferably 250 MPa or more, more preferably 280 MPa or more. The tensile strength of the high stiffness PET film in the vertical direction is preferably 250 MPa or higher, more preferably 280 MPa or higher.
The tensile elongation of the high stiffness PET film in the machine direction is preferably 130% or less, more preferably 120% or less. The tensile elongation of the high stiffness PET film in the vertical direction is preferably 120% or less, more preferably 110% or less.
Preferably, as described above, the value obtained by dividing the tensile strength by the tensile elongation of the high-stiffness PET film is 2.0 [MPa/%] or more in at least one direction. For example, the value obtained by dividing the tensile strength of the high-stiffness film in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa/%] or more, more preferably 2.2 [MPa/%] or more. is. The value obtained by dividing the tensile strength of the high-stiffness film in the machine direction (MD) by the tensile elongation is preferably 1.8 [MPa/%] or more, more preferably 2.0 [MPa/%] or more. .
Tensile strength and tensile elongation can be measured according to JIS K7127. As a measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used. As a test piece, a rectangular film having a width of 15 mm and a length of 150 mm cut from a high-stiffness PET film can be used. The distance between the pair of chucks holding the specimen at the start of the measurement is 100 mm, and the pulling speed is 300 mm/min. The environmental temperature during the test is 25° C. and the relative humidity is 50%. The tensile strength and tensile elongation of the barrier laminate film 5 comprising the high-stiffness PET film, the tensile strength and tensile elongation of the PBT film, and the tensile strength and tensile elongation of the barrier laminate film 5 comprising the PBT film also have high stiffness. It is measured in the same way as for PET film.

The heat shrinkage of the high-stiffness PET film in the machine direction is preferably 0.7% or less, more preferably 0.5% or less. The heat shrinkage of the high stiffness PET film in the vertical direction is preferably 0.7% or less, more preferably 0.5% or less. The heating temperature for measuring the thermal shrinkage is 100° C., and the heating time is 40 minutes.
The Young's modulus of the high stiffness PET film in the machine direction is preferably 4.0 GPa or more, more preferably 4.5 MPa or more. The Young's modulus of the high stiffness PET film in the vertical direction is preferably 4.0 GPa or higher, more preferably 4.5 GPa or higher.

In the process of producing a high-stiffness PET film, for example, first, a PET film obtained by melting and molding polyethylene terephthalate is stretched 3-4.5 times at 90-145°C in the machine direction and the vertical direction, respectively. A first stretching step of stretching twice is carried out. Subsequently, the plastic film is stretched 1.1 times to 3.0 times at 100° C. to 145° C. in the machine direction and the vertical direction, respectively. Thereafter, heat setting is performed at a temperature of 190°C to 220°C. Subsequently, a relaxation treatment (a treatment to reduce the width of the film) of about 0.2% to 2.5% is performed at a temperature of 100° C. to 190° C. in the machine direction and the vertical direction. By adjusting the draw ratio, draw temperature, heat setting temperature, and relaxation treatment rate in these steps, a high-stiffness PET film having the mechanical properties described above can be obtained.

Next, preferable mechanical properties of the barrier laminate film 5 having the high stiffness PET film as the base material 1 will be further described.
The loop stiffness in the machine direction (MD) and the vertical direction (TD) of the barrier laminate film 5 is preferably 0.0017 N or more.
The barrier laminate film 5 preferably has a puncture strength of 9.5 N or more, more preferably 10.0 N or more.
The tensile strength of the barrier laminate film 5 in the machine direction is preferably 250 MPa or more, more preferably 280 MPa or more. The tensile strength of the barrier laminate film 5 in the vertical direction is preferably 250 MPa or more, more preferably 280 MPa or more.
The tensile elongation of the barrier laminate film 5 in the machine direction is preferably 130% or less, more preferably 120% or less. The tensile elongation of the barrier laminate film 5 in the vertical direction is preferably 120% or less, more preferably 110% or less.
Preferably, the value obtained by dividing the tensile strength of the barrier laminate film 5 by the tensile elongation in at least one direction is 2.0 [MPa/%] or more. For example, the value obtained by dividing the tensile strength of the barrier laminate film 5 in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa/%] or more, more preferably 2.2 [MPa/%]. ] That is all. The value obtained by dividing the tensile strength of the barrier laminate film 5 in the machine direction (MD) by the tensile elongation is preferably 1.8 [MPa/%] or more, more preferably 2.0 [MPa/%] or more. is.
The thermal shrinkage of the barrier laminate film 5 in the machine direction is preferably 0.7% or less, more preferably 0.5% or less. The heat shrinkage of the barrier laminate film 5 in the vertical direction is preferably 0.7% or less, more preferably 0.5% or less. The heating temperature for measuring the thermal shrinkage is 100° C., and the heating time is 40 minutes.
The Young's modulus of the barrier laminate film 5 in the machine direction is preferably 4.0 GPa or more, more preferably 4.5 MPa or more. The Young's modulus of the barrier laminate film 5 in the vertical direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more.

The PET that constitutes the high-stiffness PET film may include biomass-derived PET. In this case, the high-stiffness PET film may be composed only of biomass-derived PET. Alternatively, the high-stiffness PET film may be composed of biomass-derived PET and fossil fuel-derived PET. By including biomass-derived PET in the high-stiffness PET film, it is possible to reduce the amount of fossil fuel-derived PET compared to conventional methods, thereby reducing carbon dioxide emissions and reducing environmental impact. can. In the biomass-derived PET, biomass-derived ethylene glycol is used as a diol unit, and fossil fuel-derived terephthalic acid is used as a dicarboxylic acid unit. Fossil fuel-derived PET uses fossil fuel-derived ethylene glycol as a diol unit and fossil fuel-derived terephthalic acid as a dicarboxylic acid unit.

Since carbon dioxide in the atmosphere contains a certain amount of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in PET, the ratio of biomass-derived carbon can be calculated. In the present invention, the term "biomass degree" indicates the weight ratio of biomass-derived components. Taking PET as an example, PET is a polymer of ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1. When only biomass-derived ethylene glycol is used for PET, the weight ratio of the biomass-derived component in PET is 31.25%, so the theoretical biomass content of PET is 31.25%. Specifically, the mass of PET is 192, of which the mass derived from biomass-derived ethylene glycol is 60, so 60÷192×100=31.25. Further, the weight ratio of biomass-derived components in fossil fuel-derived PET is 0%, and the biomass degree of fossil fuel-derived PET is 0%. In the present invention, the high-stiffness PET film preferably has a biomass degree of 5.0% or more, more preferably 10.0% or more. Also, the biomass degree of the high-stiffness PET film is preferably 30.0% or less.

Biomass-derived ethylene glycol is produced from biomass-derived ethanol (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method. Raw materials for biomass ethanol include corn, sugar cane, beet, and manioc. Also, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used. India Glycol's biomass ethylene glycol is made from sugar cane molasses as a raw material.

Next, the PBT film will be explained. A PBT film is a stretched plastic film containing 51% by mass or more of PBT. Advantages of the substrate 1 containing PBT will be described below.

PBT is excellent in heat resistance. Therefore, deformation of the base material 1 and reduction in strength of the base material 1 can be suppressed when a packaging bag containing contents such as food is subjected to boiling treatment or retort treatment. Retort treatment is a process in which a packaging bag is filled with contents, sealed, and then heated under pressure using steam or heated hot water. The temperature of the retort treatment is, for example, 120° C. or higher. The boiling process is a process of filling the contents into the bag 10, sealing the bag 10, and then boiling the bag 10 in hot water under atmospheric pressure. The boiling treatment temperature is, for example, 90° C. or higher and 100° C. or lower.

PBT also has high strength. For this reason, the packaging bag can be provided with piercing resistance as in the case where the packaging material 8 constituting the packaging bag contains nylon. The puncture strength of the PBT film is preferably 9.5N or higher, more preferably 10.0N or higher.

The tensile strength of the PBT film in machine direction is preferably 150 MPa or higher, more preferably 180 MPa or higher. The tensile strength of the PBT film in the vertical direction is preferably 250 MPa or higher, more preferably 280 MPa or higher.
The tensile elongation of the PBT film in the machine direction is preferably 220% or less, more preferably 200% or less. The tensile elongation of the PBT film in the vertical direction is preferably 120% or less, more preferably 110% or less.
Preferably, the value obtained by dividing the tensile strength of the PBT film by the tensile elongation is 2.0 [MPa/%] or more in at least one direction. For example, the value obtained by dividing the tensile strength of the PBT film in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa/%] or more, more preferably 2.2 [MPa/%] or more. more preferably 2.5 [MPa/%] or more.

In addition, PBT has the characteristic of being less likely to absorb moisture than nylon. Therefore, even when the base material 1 containing PBT is arranged on the outer surface of the packaging material 8, it is possible to prevent the base material 1 from absorbing moisture and lowering the lamination strength of the packaging material 8. can.

Next, preferable mechanical properties of the barrier laminate film 5 having the above PBT film as the substrate 1 will be further described.
The barrier laminate film 5 preferably has a puncture strength of 9.5 N or more, more preferably 10.0 N or more.
The tensile strength of the barrier laminate film 5 in the machine direction is preferably 150 MPa or more, more preferably 180 MPa or more. The tensile strength of the barrier laminate film 5 in the vertical direction is preferably 250 MPa or more, more preferably 280 MPa or more.
The tensile elongation of the barrier laminate film 5 in the machine direction is preferably 220% or less, more preferably 200% or less. The tensile elongation of the barrier laminate film 5 in the vertical direction is preferably 120% or less, more preferably 110% or less.
Preferably, the value obtained by dividing the tensile strength of the barrier laminate film 5 by the tensile elongation in at least one direction is 2.0 [MPa/%] or more. For example, the value obtained by dividing the tensile strength of the barrier laminate film 5 in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa/%] or more, more preferably 2.2 [MPa/%]. ] or more, more preferably 2.5 [MPa/%] or more.

The configuration of the base material 1 containing PBT will be described in detail below. As the configuration of the substrate 1 containing PBT in the present embodiment, either the following first configuration or second configuration may be adopted.

[First configuration of substrate containing PBT]
The content of PBT in the substrate 1 according to the first configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 75% by mass or more, and most preferably It is 80% by mass or more. By setting the PBT content to 51% by mass or more, the substrate 1 can have excellent impact strength and pinhole resistance.

PBT used as a main component preferably contains 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 100% terephthalic acid as a dicarboxylic acid component. in mol %. 1,4-Butanediol is preferably 90 mol % or more, more preferably 95 mol % or more, still more preferably 97 mol % or more, and most preferably 1,4-butanediol as a glycol component during polymerization. It does not contain anything other than by-products produced by the ether bond of butanediol.

The base material 1 may contain a polyester resin other than PBT. This makes it possible to adjust the film formability and the mechanical properties of the substrate 1 when the film substrate 1 is biaxially stretched, for example.
Polyester resins other than PBT include polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polypropylene terephthalate (PPT), as well as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid. , PBT resins copolymerized with dicarboxylic acids such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, and sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 Examples include PBT resins obtained by copolymerizing diol components such as -pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, and polycarbonate diol.

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

The base material 1 may contain, as an additive, a polyester-based or polyamide-based elastomer obtained by copolymerizing at least one of a flexible polyether component, a polycarbonate component, and a polyester component. This can improve pinhole resistance when bent. The additive amount is, for example, 20% by mass. If the amount of the additive added exceeds 20% by mass, the effect of the additive may be saturated, or the transparency of the substrate 1 may be lowered.

An example of a method for producing the film-like substrate 1 according to the first configuration will be described. Here, a method for producing the film-like substrate 1 by casting will be described. More specifically, a method of casting multiple layers of resin having the same composition at the time of casting will be described.

Since PBT has a high crystallization speed, crystallization proceeds even during casting. At this time, if a single layer is cast without multilayering, there is no barrier that can suppress the growth of crystals, so the crystals grow to a large size, resulting in an unstretched raw roll. yield stress is higher. For this reason, it becomes easy to break when biaxially stretching an unstretched raw fabric. Moreover, the yield stress of the obtained biaxially stretched film becomes high, and the formability of the biaxially stretched film becomes insufficient.
On the other hand, if the same resin is multi-layered during casting, the stretching stress of the unstretched sheet can be reduced. Therefore, stable biaxial stretching becomes possible, and the yield stress of the obtained biaxially stretched film becomes low. This makes it possible to obtain a film that is flexible and has high breaking strength.

FIG. 9 is a cross-sectional view showing an example of the layer structure of the substrate 1. As shown in FIG. When the base material 1 is produced by casting a multilayer resin, as shown in FIG. 9, the base material 1 is composed of a multilayer structure including a plurality of layers 1a. Each of the multiple layers 1a contains PBT as a main component. For example, each of the plurality of layers 1a preferably contains 51% by mass or more of PBT, more preferably 60% by mass or more of PBT. In the plurality of layers 1a, the n+1th layer 1a is directly laminated on the nth layer 1a. That is, no adhesive layer or bonding layer is interposed between the layers 1a.

The reason why the properties of the PBT film are improved by multilayering is presumed as follows. When resins are laminated, even if the resin compositions are the same, interfaces between layers exist, and the interfaces accelerate crystallization. On the other hand, the growth of large crystals beyond the thickness of the layer is suppressed. For this reason, it is considered that the size of the crystals (spherulites) becomes smaller.

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

The substrate 1 is composed of a multilayer structure including at least 10 layers or more, preferably 60 layers or more, more preferably 250 layers or more, still more preferably 1000 layers or more. By increasing the number of layers, the size of the spherulites in the unstretched original PBT can be reduced, and the subsequent biaxial stretching can be stably carried out. In addition, the yield stress of PBT in the state of biaxially stretched film can be reduced. Preferably, the diameter of the spherulites in the unstretched raw PBT is 500 nm or less.

The stretching temperature (hereinafter also referred to as MD stretching temperature) in the longitudinal stretching direction (hereinafter, MD) when biaxially stretching an unstretched raw PBT film to produce a biaxially stretched film is preferably 40 ° C. or higher. and more preferably 45° C. or higher. By setting the MD stretching temperature to 40° C. or higher, it is possible to suppress the occurrence of breakage of the film. Also, the MD stretching temperature is preferably 100° C. or lower, more preferably 95° C. or lower. By setting the MD stretching temperature to 100° C. or lower, it is possible to suppress the phenomenon that the biaxially stretched film is not oriented.

The draw ratio in MD (hereinafter also referred to as MD draw ratio) is preferably 2.5 times or more. This makes it possible to orient the biaxially stretched film and achieve good mechanical properties and a uniform thickness. The MD draw ratio is, for example, 5 times or less.

The stretching temperature (hereinafter also referred to as TD stretching temperature) in the lateral stretching direction (hereinafter also referred to as TD) is preferably 40° C. or higher. By setting the TD stretching temperature to 40° C. or higher, it is possible to suppress the occurrence of breakage of the film. Moreover, the TD stretching temperature is preferably 100° C. or less. By setting the TD stretching temperature to 100° C. or lower, it is possible to suppress the phenomenon that the biaxially stretched film is not oriented.

The draw ratio in TD (hereinafter also referred to as TD draw ratio) is preferably 2.5 times or more. This makes it possible to orient the biaxially stretched film and achieve good mechanical properties and a uniform thickness. The MD draw ratio is, for example, 5 times or less.

The TD relaxation rate is preferably 0.5% or more. Thereby, it is possible to suppress the occurrence of breakage during heat setting of the biaxially stretched film of PBT. Also, the TD relaxation rate is preferably 10% or less. As a result, it is possible to suppress the occurrence of unevenness in thickness due to sagging or the like in the biaxially stretched PBT film.

The thickness of the layer 1a of the substrate 1 shown in FIG. 9 is preferably 3 nm or more, more preferably 10 nm or more. Also, the thickness of the layer 1a is preferably 200 nm or less, more preferably 100 nm or less.
Moreover, the thickness of the substrate 1 is preferably 9 μm or more, more preferably 12 μm or more. Also, the thickness of the substrate 1 is preferably 25 μm or less, more preferably 20 μm or less. By setting the thickness of the base material 1 to 9 μm or more, the base material 1 comes to have sufficient strength. Further, by setting the thickness of the base material 1 to 25 μm or less, the base material 1 exhibits excellent moldability. Therefore, the process of manufacturing the packaging bag by processing the packaging material 8 including the base material 1 can be carried out efficiently.

[Second Configuration of Substrate Containing PBT]
The substrate 1 according to the second configuration is composed of a single-layer film containing polyester having butylene terephthalate as a main repeating unit. For example, the base material 1 is mainly composed of 1,4-butanediol or its ester-forming derivative as a glycol component and terephthalic acid or its ester-forming derivative as a dibasic acid component, and they are condensed. including homo- or copolymer-type polyesters obtained by The content of PBT in the substrate 1 according to the second configuration is preferably 51% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, further preferably 80% by mass or more, and most preferably. is 90% by mass or more. Moreover, it is preferable that the base material 1 according to the second configuration is composed only of polybutylene terephthalate and an additive.

In order to impart mechanical strength to the base material 1, PBT having a melting point of 200° C. or more and 250° C. or less and an IV value (intrinsic viscosity) of 1.10 dl/g or more and 1.35 dl/g or less is preferred. Furthermore, those having a melting point of 215° C. or more and 225° C. or less and an IV value of 1.15 dl/g or more and 1.30 dl/g or less are particularly preferable. These IV values may be satisfied by the entire material that makes up the substrate 1 . IV values can be calculated based on JIS K 7367-5:2000.

The base material 1 according to the second configuration may contain a polyester resin other than PBT, such as PET, in an amount of 30% by mass or less. By including PET in addition to PBT in the base material 1, crystallization of PBT can be suppressed, and stretchability of the PBT film can be improved. As the PET mixed with the PBT of the base material 1, a polyester having ethylene terephthalate as a main repeating unit can be used. For example, a homotype containing ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component as main components can be preferably used. In order to impart good mechanical strength properties, PET preferably has a melting point of 240° C. or more and 265° C. or less and an IV value of 0.55 dl/g or more and 0.90 dl/g or less. Furthermore, those having a melting point of 245° C. or more and 260° C. or less and an IV value of 0.60 dl/g or more and 0.80 dl/g or less are particularly preferable.
By setting the amount of PET to be 30% by mass or less, it is possible to prevent the stiffness of the unstretched raw fabric and stretched film from becoming too high. As a result, it is possible to prevent the stretched film from becoming brittle and the pressure resistance, impact strength, puncture strength, etc. of the stretched film from deteriorating. In addition, it is possible to suppress the occurrence of stretching failure when stretching an unstretched raw material.

The base material 1 optionally contains a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a coloring agent, a crystallization inhibitor, and a crystallization accelerator. It may contain additives such as In addition, the polyester resin pellet used as the raw material of the base material 1 has a moisture content of 0.05% by weight or less, preferably 0.01% by weight or less, before heating and melting in order to avoid viscosity reduction due to hydrolysis during heating and melting. It is preferable to use it after pre-drying sufficiently so that it becomes

An example of a method for producing the film-like substrate 1 according to the second configuration will be described.

In order to stably produce a film of the substrate 1 having the above structure, it is important to suppress the growth of crystals in the state of the unstretched original sheet. Specifically, when the extruded PBT-based melt is cooled to form a film, the crystallization temperature range of the polymer is cooled at a certain rate or higher, that is, the original fabric cooling rate is an important factor. The raw fabric cooling rate is, for example, 200° C./second or higher, preferably 250° C./second or higher, and particularly preferably 350° C./second or higher. Since the unstretched raw material film-formed at a high cooling rate maintains a low crystallinity, the stability of bubbles during stretching is improved. Furthermore, film formation at high speed becomes possible, so the productivity of the film is also improved. If the cooling rate is less than 200° C./second, it is conceivable that the crystallinity of the obtained unstretched raw material is high and the stretchability is lowered. In extreme cases, the stretching bubble may burst and the stretching may not continue.

The unstretched raw sheet containing PBT as a main component is preferably conveyed to a space for biaxial stretching while maintaining the ambient temperature at 25°C or lower, preferably 20°C or lower. As a result, even when the residence time is long, the crystallinity of the unstretched raw sheet immediately after film formation can be maintained.

A biaxial stretching method for stretching an unstretched raw fabric to obtain a stretched film is not particularly limited. For example, the longitudinal direction and the transverse direction may be stretched simultaneously, or the longitudinal direction and the transverse direction may be successively stretched by a tubular method or a tenter method. Among these methods, the tubular method is particularly preferably employed because it is possible to obtain a stretched film having a good balance of physical properties in the circumferential direction.

In the tubular method, an unstretched raw material introduced into a stretching space is passed between a pair of low-speed nip rolls and then heated by a stretching heater while air is forced into the space. After the stretching is finished, air is blown to the stretched film by a cooling shoulder air ring. The draw ratio is preferably 2.7 times or more and 4.5 times or less in MD and TD, respectively, in consideration of the stretching stability, strength properties, transparency, and thickness uniformity of the stretched film. By setting the stretching ratio to 2.7 times or more, it is possible to sufficiently secure the tensile modulus and impact strength of the stretched film. In addition, by setting the draw ratio to 4.5 times or less, it is possible to suppress the occurrence of excessive strain of the molecular chain due to stretching, and it is possible to suppress the occurrence of breakage and puncture during the stretching process, so the stretched film can be stabilized. can be made.

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

The substrate 1 produced as described above is composed of, for example, a single layer containing polyester having butylene terephthalate as a main repeating unit. According to the production method described above, since the unstretched raw fabric is formed into a film at a high cooling rate, a low crystallinity can be maintained even when the unstretched raw fabric is composed of a single layer. Therefore, the unstretched raw fabric can be stably stretched.

By including PBT in the substrate 1, the heat resistance of the barrier laminate film 5 and the packaging material 8 including the barrier laminate film 5 can be enhanced. For example, the tensile elastic modulus of the barrier laminated film 5 and packaging material 8 can be made sufficiently high. In particular, the tensile elastic modulus (hereinafter also referred to as hot tensile elastic modulus) of the barrier laminated film 5 and the packaging material 8 can be made sufficiently high in a high-temperature atmosphere, for example, an atmosphere of 100°C.

[Vapor deposition layer]
Next, the deposited layer 2 will be described.

The deposited layer 2 is a thin film having gas barrier properties to prevent or block permeation of oxygen gas, water vapor, or the like. The deposited layer 2 may be a metal layer containing a light-shielding metal such as aluminum, or may be a transparent deposited layer made of a transparent inorganic compound. For example, the deposited layer 2 is a transparent deposited layer made of a transparent inorganic oxide.

A case where the deposition layer 2 is a transparent deposition layer will be described below. The inorganic oxide forming the deposition layer 2 contains, as a main component, an aluminum compound containing, for example, at least aluminum oxide or aluminum nitride, carbide, or hydroxide alone or in combination. For example, an inorganic oxide contains aluminum oxide as a main component.
Also, the deposited layer 2 may be a layer containing a silicon compound as a main component. For example, the inorganic oxide layer contains silicon oxide (silicon oxide) as a main component.
Furthermore, the deposited layer 2 contains an aluminum compound such as the aluminum oxide described above as a main component, and further includes silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, and indium oxide. , zinc oxide, zirconium oxide, or the like, or a layer containing these metal nitrides, carbides and mixtures thereof.

The thickness of the deposited layer 2 is preferably 3 nm or more and 50 nm or less, more preferably 9 nm or more and 30 nm or less.

(Gas barrier coating film)
When the vapor deposition layer 2 is a transparent vapor deposition layer, the gas barrier coating film 3 serves to mechanically and chemically protect the vapor deposition layer 2 and to improve the barrier properties of the barrier laminate film 5. It is laminated so as to be in contact with the vapor deposition layer 2 . The gas barrier coating film 3 is a cured film formed from a coating agent for a gas barrier coating film comprising a resin composition containing a metal alkoxide, a hydroxyl group-containing water-soluble resin, and a silane coupling agent added as necessary. be.

The mass ratio of hydroxyl-containing water-soluble resin/metal alkoxide in the resin composition is preferably 5/95 or more and 20/80 or less, more preferably 8/92 or more and 15/85 or less. If it is smaller than the above range, the barrier effect of the barrier coating layer tends to be insufficient, and if it is larger than the above range, the rigidity and brittleness of the barrier coating layer tend to increase.

The thickness of the gas barrier coating film 3 is preferably 100 nm or more and 800 nm or less. When the thickness is less than the above range, the barrier effect of the gas barrier coating film 3 tends to be insufficient, and when the thickness is greater than the above range, rigidity and brittleness tend to increase.

The metal alkoxide has the general formula R ₁ nM (OR ₂ )m (wherein R ₁ and R ₂ represent a hydrogen atom or an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M. Even if each of a plurality of R ₁ and R ₂ in one molecule is the same, It may be different.) ... represented by (I).

Examples of specific metal atoms represented by M in metal alkoxides include silicon, zirconium, titanium, aluminum, tin, lead, borane, and the like. It is preferred to use silanes.

Specific examples of OR ₂ in the general formula (I) are hydroxyl, methoxy, ethoxy, n-propoxy, n-butoxy, i-propoxy, butoxy and 3-methacryloxy. Alkoxy groups such as 3-acryloxy group and phenoxy group, phenoxy groups and the like can be mentioned.

In the above, specific examples of R ₁ include methyl group, ethyl group, n-propyl group, isopropyl group, phenyl group, p-styryl group, 3-chloropropyl group, trifluoromethyl group, vinyl group, γ-glycan sidoxypropyl group, methacryl group, γ-aminopropyl group and the like.

Specific examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, phenylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane silane, isopropyltriethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3- methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltri Examples include various alkoxysilanes such as ethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and phenoxysilane. Condensation products of these alkoxysilanes can also be used in the present embodiment. Specifically, for example, polytetramethoxysilane, polytetraethoxysilane, and the like can be used.

A silane coupling agent is used to adjust the cross-linking density of a cured film of a metal alkoxide and a hydroxyl group-containing water-soluble resin to form a film having barrier properties and hot water treatment properties.

The silane coupling agent has the general formula: R ₃ nSi(OR ₄ )4-n (II)
(In the formula, R ₃ and R ₄ each independently represent an organic functional group, and n is 1 to 3.)
is represented by

In general formula (II) above, R ₃ includes, for example, a hydrocarbon group such as an alkyl group or an alkylene group, an epoxy group, a (meth)acryloxy group, a ureido group, a vinyl group, an amino group, an isocyanurate group, or an isocyanate group. A functional group having Specifically, at least one of two or three R ₃ present is preferably a functional group having an epoxy group, such as a 3-glycidoxypropyl group and a 2-(3,4 epoxycyclohexyl) group. is more preferable. In addition, each R ₃ may be the same or different.

In the above general formula (II), R ₄ is, for example, an organic functional group having 1 to 8 carbon atoms, preferably an optionally branched alkyl group having 1 to 8 carbon atoms or 3 to 3 carbon atoms. 7 alkoxyalkyl group. For example, the alkyl group having 1 to 8 carbon atoms includes methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group and the like. Examples of alkoxyalkyl groups having 3 to 7 carbon atoms include methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, ethyl propyl ether, ethyl isopropyl ether, methyl butyl ether, ethyl butyl ether, methyl sec-butyl ether, and ethyl sec. -Butyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, and other linear or branched ether groups from which one hydrogen atom has been removed. (OR ₄ ) may be the same or different.

Examples of the silane coupling agent represented by the general formula (II) include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane when n=1. When n=2, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and the like are included, and when n=3, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, sidoxypropyldimethylethoxysilane, 2-(3,4-epoxycyclohexyl)dimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)dimethylethoxysilane and the like.

In particular, the crosslink density of cured films of barrier coating layers using 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane is lower than that of systems using trialkoxysilane. Become. Therefore, it becomes a flexible cured film while being excellent as a film with gas barrier properties and hot water treatment, and has excellent flex resistance. Hard to deteriorate.

The silane coupling agent can be used by mixing n = 1, 2, 3, and the amount ratio and the amount of silane coupling agent used are determined by the design of the cured film of the barrier coating layer. .

The hydroxyl group-containing water-soluble resin is capable of undergoing dehydration co-condensation with a metal alkoxide. % or less is more preferable. If the degree of saponification is smaller than the above range. The hardness of the barrier coating layer tends to decrease.

Specific examples of hydroxyl group-containing water-soluble resins include, for example, polyvinyl alcohol-based resins, ethylene-vinyl alcohol copolymers, polymers of bifunctional phenol compounds and bifunctional epoxy compounds, and the like. They may be used, two or more of them may be mixed and used, or they may be copolymerized and used. Among these, polyvinyl alcohol is preferred, and polyvinyl alcohol-based resins are particularly preferred, because they are excellent in flexibility and affinity.

Specifically, for example, a polyvinyl alcohol-based resin obtained by saponifying polyvinyl acetate or an ethylene-vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate is used. can do.
Examples of such polyvinyl alcohol resins include PVA-124 (degree of saponification = 99%, degree of polymerization = 2,400) manufactured by Kuraray Co., Ltd., and Gohsenol NM-14 (degree of saponification) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. = 99%, degree of polymerization = 1,400).

(Preferred configuration of barrier laminate film)
Next, a preferred configuration of the barrier laminate film 5 in the thickness direction when the vapor deposition layer 2 is a transparent vapor deposition layer containing aluminum oxide will be described with reference to FIG. FIG. 10 shows time-of-flight secondary ion mass spectrometry (TOF- SIMS) is a diagram showing the results of measuring ions originating from a deposited layer 2 containing aluminum oxide and ions originating from a substrate 1. FIG. The vapor-deposited layer 2 of the barrier laminate film 5 includes a transition region specified by the graphical analysis diagram shown in FIG.

The transition region is the position of the peak of elemental bonding Al ₂ O ₄ H that transforms into aluminum hydroxide detected by etching the barrier laminate film 5 from the gas barrier coating film 3 side using TOF-SIMS. It is the region between T ₂ and the interface T ₁ between the deposited layer 2 and the substrate 1 . The interface T ₁ between the deposited layer 2 and the substrate 1 is specified as the position where the intensity of the element C ₆ graph is half the intensity of the element C ₆ in the substrate 1 . In FIG. 10, _W1 represents the thickness of the transition region.

The ratio of the thickness W ₁ of the transition region to the thickness of the deposited layer 2 (hereinafter also referred to as the transformation ratio of the transition region) is desirably 5% or more and 60% or less. By setting the transformation rate to 5% or more and 60% or less, the barrier property of the barrier laminated film 5 against water vapor is improved when the packaging material containing the barrier laminated film 5 is subjected to sterilization treatment such as boiling treatment or retort treatment. It is possible to suppress the decrease. The retort treatment is a process in which a packaging bag made of a packaging material including the barrier laminated film 5 is filled with contents, sealed, and then heated under pressure. The temperature of the retort treatment is, for example, 120° C. or higher. The boiling process is a process in which the contents are filled into a packaging bag, the packaging bag is sealed, and then the packaging bag is boiled in hot water under atmospheric pressure. The boiling treatment temperature is, for example, 90° C. or higher and 100° C. or lower. It should be noted that the packaging material containing the barrier laminated film 5 having a transformation rate of the transition region of 5% or more and 60% or less is used in a packaging bag that is not subjected to sterilization treatment such as boiling treatment or retort treatment. can also function effectively in maintaining barrier properties against gases such as oxygen and water vapor.

The interface between the substrate 1 and the deposition layer 2 is subjected to mechanical and chemical stress due to heat. Therefore, it is important to firmly cover the base material 1 with the vapor deposition layer 2 at the interface between the base material 1 and the vapor deposition layer 2 in order to suppress deterioration of adhesion and barrier properties.

Due to its chemical structure, aluminum hydroxide has good adhesion to plastic films such as polyester films, and since it itself forms a dense network, it has high water vapor barrier properties. However, the bonding structure based on hydrogen bonding between aluminum hydroxide and plastic film tends to collapse microscopically due to thermal stress. Also, the aluminum hydroxide network easily permeates into the film due to the affinity between the water molecules and the grain boundaries of the aluminum hydroxide.

In the present embodiment, in order to narrow the transition region at the interface with the substrate 1 formed by aluminum hydroxide in the vapor deposition layer 2 containing aluminum oxide, attention is paid to the elemental bond Al ₂ O ₄ H, and its existence control the amount. As a result, aluminum hydroxide generated from elemental bonds Al ₂ O ₄ H due to thermal stress is suppressed, and by increasing the ratio of the aluminum oxide layer containing relatively less aluminum hydroxide, microscopic It is intended to suppress the destruction of the deposition layer 2 and the destruction of the interface with the plastic film. As a result, it is possible to provide a barrier laminate film 5 having unprecedented adhesion and barrier properties.

The vapor deposition layer 2 containing aluminum oxide can be formed by forming the vapor deposition layer 2 on the surface of the substrate 1 pretreated with oxygen plasma. As a vapor deposition method for forming the vapor deposition layer 2, various vapor deposition methods out of physical vapor deposition and chemical vapor deposition can be applied. The physical vapor deposition method can be selected from the group consisting of vapor deposition method, sputtering method, ion plating method, ion beam assist method, and cluster ion beam method, and the chemical vapor deposition method includes plasma CVD method, plasma polymerization method, thermal It can be selected from the group consisting of CVD method and catalytic CVD method. In this embodiment, a vapor deposition method of physical vapor deposition is suitable.

A specific example of a method for obtaining the graph of FIG. 10 will now be described. First, using Cs, etching is performed from the outermost surface of the gas barrier coating film 3, and elemental bonding at the interface between the gas barrier coating film 3, the deposition layer 2, and the film such as the base material 1, and the element bonding of the deposition layer 2 Conduct analysis. Thereby, the graph shown in FIG. 10 can be obtained.

Next, a specific example of a method of analyzing the graph of FIG. 10 will be described. Here, the case where the gas barrier coating film 3 contains silicon oxide will be described.

First, in the graph, the position where the strength of SiO ₂ (mass number: 59.96), which is a constituent element of the gas barrier coating film 3, is half the strength of the gas barrier coating film 3 is 2 interface. Next, the position where the strength of C ₆ (mass number: 72.00), which is the constituent material of the base material 1, is half the strength of the base material 1 is specified as the interface between the base material 1 and the deposition layer 2 . Also, the distance in the thickness direction between the two interfaces is adopted as the thickness of the deposited layer 2 .

Next, the peak of the measured elemental bond Al ₂ O ₄ H (mass number: 118.93) is determined, and the transition region from the peak to the interface is defined. However, when the component of the gas barrier coating film 3 is composed of a material having the same mass number as Al ₂ O ₄ H (mass number 118.93), it is necessary to separate the waveform of 118.93.

When reactants AlSiO ₄ and hydroxide Al ₂ O ₄ H are generated at the interface between the gas barrier coating film 3 and the vapor deposition layer 2 , the Al present at the interface between them and the substrate 1 and the vapor deposition layer 2 ₂ O ₄ H can be separated. In this manner, the separation of the waveforms can be appropriately handled according to the material of the gas barrier coating film 3 .

In waveform separation, for example, a profile with a mass number of 118.93 obtained by TOF-SIMS is subjected to nonlinear curve fitting using a Gaussian function, and overlapping peaks are separated using a least squares method Levenberg Marquardt algorithm. It can be carried out.

The above analysis assumes that the barrier laminate film 5 includes the substrate 1, the vapor deposition layer 2, and the gas barrier coating film 3, but the similar analysis assumes that the barrier laminate film 5 is the substrate 1. and a vapor-deposited layer 2 is included but the gas barrier coating film 3 is not included. Even if the barrier laminate film 5 does not contain the gas barrier coating film 3, the transformation rate of the transition region of the vapor deposition layer 2 is set within a predetermined range so that the packaging material including the barrier laminate film 5 can be boiled. It is possible to suppress deterioration of the barrier property of the barrier laminate film 5 against water vapor when sterilization treatment such as treatment or retort treatment is performed. When the barrier laminated film 5 includes the base material 1 and the vapor deposition layer 2 and etching is performed from the vapor deposition layer 2 side using time-of-flight secondary ion mass spectrometry (TOF-SIMS), the transition region of the vapor deposition layer 2 It is preferable that the transformation ratio is 45% or less.

<Method for producing barrier laminate film>
Next, an example of a method for producing the barrier laminated film 5 will be described.

First, the base material 1 is prepared. Subsequently, a deposition layer 2 containing aluminum oxide is formed on the surface of the substrate 1 . FIG. 11 is a diagram showing an example of the film forming apparatus 60. As shown in FIG. A film forming apparatus 60 and a film forming method using the film forming apparatus 60 will be described below.

As shown in FIG. 11, in the film forming apparatus 60, partition walls 85a to 85c are formed in the decompression chamber 62. As shown in FIG. The partition walls 85a to 85c form a substrate transfer chamber 62A, a plasma pretreatment chamber 62B, and a film formation chamber 62C. 62C are formed, and each chamber is further formed with an exhaust chamber inside as required.

The plasma pretreatment chamber 62B and the plasma pretreatment process in the plasma pretreatment chamber 62B will be described. In the plasma pretreatment chamber 62B, a part of a plasma pretreatment roller 70 that conveys the substrate 1 to be pretreated and enables plasma treatment is provided so as to be exposed to the substrate transfer chamber 62A. there is The substrate 1 moves to the plasma pretreatment chamber 62B while being wound up.

The plasma pretreatment chamber 62B and the film formation chamber 62C are provided in contact with the substrate transfer chamber 62A, and can be moved without exposing the substrate 1 to the atmosphere. A rectangular hole connects the pretreatment chamber 62B and the base material transfer chamber 62A, and a part of the plasma pretreatment roller 70 protrudes toward the base material transfer chamber 62A through the rectangular hole. A gap is formed between the wall of the transfer chamber and the pretreatment roller 70, and the substrate 1 can be moved from the substrate transfer chamber 62A to the film formation chamber 62C through the gap. A similar structure is provided between the substrate transfer chamber 62A and the film forming chamber 62C, and the substrate 1 can be moved without exposing it to the atmosphere.

The base material transfer chamber 62A serves as a winding means to roll up the base material 1 having the deposition layer 2 formed on one side thereof, which has been moved to the base material transfer chamber 12A again by the film forming roller 75. A take-up roller is provided so that the substrate 1 on which the deposition layer 2 is formed can be taken up.

When manufacturing the barrier laminated film 5 having the deposited layer 2 containing aluminum oxide, the plasma pretreatment chamber 62B separates the space where the plasma is generated from other regions so that the opposite space can be efficiently evacuated. With this configuration, control of the plasma gas concentration is facilitated, and productivity is improved. The pretreatment pressure formed by reducing the pressure can be set and maintained at about 0.1 Pa to 100 Pa, and in particular, oxygen plasma pretreatment is performed in order to obtain a preferable transformation rate of the transition region of the vapor deposition layer 2 containing aluminum oxide. A treatment pressure of 1 to 20 Pa is preferable.

The transport speed of the substrate 1 is not particularly limited, but from the viewpoint of production efficiency, it can be at least 200 to 1000 m / min. The conveying speed for plasma pretreatment is preferably 300 to 800 m/min.

The plasma pretreatment roller 70 constituting the plasma pretreatment device prevents the substrate 1 from shrinking or breaking due to heat during plasma treatment by the plasma pretreatment means, and applies the oxygen plasma P to the substrate 1 uniformly and over a wide range. It is intended to be applied to It is preferable that the pretreatment roller 70 can be adjusted to a constant temperature between -20° C. and 100° C. by adjusting the temperature of the temperature adjusting medium circulating in the pretreatment roller.

The plasma pretreatment means includes plasma supply means and magnetic forming means. The plasma pretreatment means cooperates with the plasma pretreatment roller 70 to confine the oxygen plasma P near the substrate 1 surface.

The plasma pretreatment means is provided so as to partially cover the pretreatment roller 70 . Specifically, along the surface of the pretreatment roller 70 in the vicinity of the outer circumference, the plasma supply means 72 and the magnetism formation means 73 constituting the plasma pretreatment means are arranged. The plasma supply means 72 includes a plasma supply nozzle that supplies plasma material gas. The magnetism forming means 73 has a magnet or the like in order to promote the generation of the plasma P. As shown in FIG. The plasma pretreatment means also has an electrode 71 to which a voltage is applied between the pretreatment roller 70 . Although FIG. 11 shows an example in which the electrode 71 and the plasma supply means 72 are separate members, the present invention is not limited to this. Although not shown, the electrode 71 and the plasma supply means 72 may be configured as an integral member.

Plasma P is generated in the space sandwiched between the pretreatment roller 70 and the magnetism forming means 73, and a region with high plasma density is formed in the vicinity of the surface of the pretreatment roller 70 and the substrate 1, so that the substrate 1 can be subjected to an oxygen plasma pretreatment to form a plasma treated surface.

The plasma supply means 72 of the plasma pretreatment means includes a raw material gas volatilization supply device 68 connected to a plasma supply nozzle provided outside the decompression chamber 62, and a raw material gas supply line for supplying the raw material gas from the device. The supplied plasma material gas is oxygen alone or a mixed gas of an oxygen gas and an inert gas, which is supplied from the gas reservoir via a flow rate controller while measuring the flow rate of the gas. Examples of inert gases include one or a mixture of two or more gases selected from the group consisting of argon, helium, and nitrogen.

These gases to be supplied are mixed at a predetermined ratio as required to form a plasma raw material gas alone or a mixed gas for plasma formation, which is supplied to the plasma supply means. The single or mixed gas is supplied to the plasma supply nozzle of the plasma supply means, and is supplied to the vicinity of the outer periphery of the pretreatment roller 70 where the supply port of the plasma supply nozzle opens. The nozzle openings are directed toward the substrate 1 on the pretreatment roller 70 , and are arranged and configured so that the oxygen plasma P can be uniformly diffused and supplied to the entire surface of the substrate 1 . Thereby, a uniform plasma pretreatment can be applied to a large-area portion of the substrate 1 .

In order to set the transformation rate of the transition region of the vapor deposition layer 2 containing aluminum oxide to 5% or more and 60% or less as described above, as the oxygen plasma pretreatment, the mixing ratio of the oxygen gas and the inert gas (oxygen gas/ inert gas) is preferably 6/1 to 1/1, more preferably 5/2 to 3/2. By setting the mixing ratio to 6/1 to 1/1, the film formation energy of the vapor deposition layer 2 on the substrate 1 is increased, and by setting the mixing ratio to 5/2 to 3/2, aluminum hydroxide is formed. is formed near the interface of the substrate 1, ie the metamorphic rate of the transition region is reduced.

The electrode 71 functions as a counter electrode for the pretreatment roller 70 . The plasma raw material gas supplied between the pretreatment roller 70 and the pretreatment roller 70 is excited by the potential difference due to the high frequency voltage, low frequency voltage, etc., and the plasma P is generated and supplied.

Specifically, the electrode 71 is provided with a plasma pretreatment roller as a plasma power source, and an AC voltage with a frequency of 10 Hz to 2.5 GHz is applied between the electrode 71 and the counter electrode to perform input power control or impedance control. , and the plasma pretreatment roller 70 can be in a state in which any voltage is applied. The film forming apparatus 60 is equipped with a power source 82 capable of applying a bias voltage to make the oxygen plasma P capable of physically or chemically modifying the surface properties of the base material 1 have a positive potential.

The plasma intensity per unit area is preferably 50-8000 W·sec/m ² . At 50 W·sec/m ² or less, the effect of the plasma pretreatment is not observed, and at 8000 W·sec/m ² or more, deterioration of the base material 1 due to plasma such as consumption, breakage, coloring, and burning of the base material 1 occurs. There is a tendency. In particular, the plasma intensity per unit area is preferably 100 to 1000 W·sec/m ² . By applying a bias voltage perpendicular to the base material 1 and applying the above-mentioned plasma intensity, it is possible to stably improve the adhesiveness and the like with the deposition layer 2 containing aluminum oxide.

As the magnetism forming means 73, a magnet having an insulating spacer and a base plate provided in a magnet case and a magnet provided to the base plate can be used. An insulating shield plate is provided in the magnet case, and the electrodes can be attached to this insulating shield plate. The magnet case and the electrodes are electrically insulated, and even if the magnet case is installed and fixed in the decompression chamber 62, the electrodes can be electrically floating. By providing the magnet, the reactivity in the vicinity of the surface of the substrate 1 is increased, and it becomes possible to form a favorable plasma pretreated surface at high speed.

Preferably, the magnet is configured such that the magnetic flux density at the surface of the substrate 1 is between 10 Gauss and 10000 Gauss. If the magnetic flux density on the surface of the base material 1 is 10 gauss or more, the reactivity in the vicinity of the surface of the base material 1 can be sufficiently increased, and a good pretreated surface can be formed at high speed.

Next, the film forming chamber 62C and the film forming process in the film forming chamber 62C will be described. The film forming apparatus 60 has a film forming roller 75 arranged in a depressurized film forming chamber 62</b>C and a target of a vapor deposition film forming means 74 arranged to face the film forming roller 75 . The film-forming roller 75 wraps around the base material 1 and transports the base material 1 with the treated surface of the base material 1 pretreated by the plasma pretreatment device facing outward. In the film forming step, the target of the vapor deposition film forming means 74 is evaporated to form an aluminum oxide film on the surface of the substrate 1 .

The vapor deposition film forming means 74 is, for example, a resistance heating method, uses aluminum as an evaporation source, uses an aluminum metal wire, supplies oxygen to oxidize aluminum vapor, and includes aluminum oxide on the surface of the base material 1. A deposition layer 2 is deposited.

The thickness of the deposited layer 2 containing aluminum oxide formed as described above is preferably 3 to 50 nm, more preferably 9 to 30 nm. Within this range, barrier properties can be maintained. However, if the deposited layer 2 containing aluminum oxide is very thin, it becomes difficult to calculate the transformation ratio of the transition region by TOF-SIMS measurement.

Next, a method for forming the gas barrier coating film 3 on the deposited layer 2 will be described. First, the metal alkoxide, silane coupling agent, hydroxyl group-containing water-soluble resin, reaction accelerator (sol-gel process catalyst, acid, etc.), and organic solvent such as water, methyl alcohol, ethyl alcohol, isopropanol, etc. By mixing, a coating agent for a gas barrier coating film comprising the resin composition is prepared.

When the gas barrier coating film 3 contains a silane coupling agent, the coating agent for the gas barrier coating film may be prepared as follows. First, a metal alkoxide such as alkoxysilane and a silane coupling agent are mixed. The metal alkoxide and the silane coupling agent are preferably mixed at 10°C or less. As a result, the film structure of the gas barrier coating film 3 to be formed tends to be dense. Subsequently, a mixture of a metal alkoxide and a silane coupling agent is mixed with a hydroxyl group-containing water-soluble resin such as a polyvinyl alcohol-based resin.

After preparing the coating agent for the gas barrier coating film, the vapor deposition layer 2 is coated with the coating agent for the gas barrier coating film by a conventional method and dried. This drying step further promotes the condensation or co-condensation reaction to form a coating film. A plurality of coating films consisting of two or more layers may be formed on the first coating film by repeating the coating operation described above.

Further, heat treatment is performed at a temperature in the range of 20 to 200° C., preferably 50 to 180° C., and at a temperature not higher than the softening point of the resin constituting the base material 1, for 3 seconds to 10 minutes. As a result, the gas barrier coating film 3 made of the gas barrier coating film coating agent can be formed on the deposited layer 2 . In this manner, the barrier laminated film 5 having the base material 1, the deposition layer 2 and the gas barrier coating film 3 can be produced.

<Packaging material>
Next, the packaging material 8 for constructing the packaging bag will be described. The packaging material 8 includes the barrier laminated film 5 and the thermoplastic resin layer 7 laminated on the barrier laminated film 5 . In the example shown in FIG. 12 , a thermoplastic resin layer 7 is laminated on the vapor-deposited layer 2 side of the barrier laminated film 5 with an adhesive layer 6 interposed therebetween. The thermoplastic resin layer 7 constitutes the inner surface of the packaging material 8 (the inner surface of the packaging bag made of the packaging material 8). Although not shown, a printed layer may be provided between the barrier laminate film 5 and the adhesive layer 6 .

(Thermoplastic resin layer)
The thermoplastic resin layer 7 may be a resin layer or film that can be melted and bonded to each other by heat. Examples include low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene. , polypropylene, polymethylpentene, polystyrene, ethylene-vinyl acetate copolymer, α-olefin copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer It is preferable to use a resin made of one or more of resins such as polymers, ethylene-propylene copolymers, elastomers, etc., or a film of these. It is more preferable to use a resin or a film made of one or more olefin resins such as polyethylene and polypropylene, which are excellent in heat resistance, chemical resistance and aroma retention.
The thickness is preferably 3 μm or more and 100 μm or less, more preferably 15 μm or more and 70 μm or less.
The thermoplastic resin layer 7 preferably consists of an unstretched film. The term "unstretched" is a concept including not only films that are not stretched at all but also films that are slightly stretched due to the tension applied during film formation.

A packaging bag made of the packaging material 8 is sometimes subjected to sterilization treatment such as boiling treatment or retort treatment at a high temperature. Preferably, as the thermoplastic resin layer 7, one having heat resistance to withstand these high-temperature treatments is used.

(Other aspects)
Another aspect of the present invention comprises a base material, and a deposited layer containing a metal or an inorganic compound provided on the base material, the base material containing polyester as a main component, and in at least one direction and a barrier laminate film, wherein the value obtained by dividing the tensile strength of the base material by the tensile elongation is 2.0 [MPa/%] or more.

In the barrier laminate film according to another aspect of the present invention, the substrate may have a puncture strength of 9.5 N or more.

In the barrier laminate film according to another aspect of the present invention, the substrate may have a loop stiffness of 0.0017 N or more in the machine direction and the vertical direction, and may contain polyester as a main component.

In the barrier laminate film according to another aspect of the present invention, the substrate may contain polybutylene terephthalate as a main component.

The barrier laminate film according to another aspect of the present invention may further include a gas barrier coating film provided on the vapor deposition layer.

In the barrier laminate film according to another aspect of the present invention, the vapor deposition layer may be a transparent vapor deposition layer containing an inorganic compound.

In the barrier laminated film according to another aspect of the present invention, the vapor deposition layer is a transparent vapor deposition layer containing aluminum oxide, the transparent vapor deposition layer includes a transition region, and the transition region divides the vapor deposition film into the transparent vapor deposition layer. The position of the peak of the elemental bond Al ₂ O ₄ H detected by etching from the vapor deposition layer side using time-of-flight secondary ion mass spectrometry (TOF-SIMS), the transparent vapor deposition layer and the first A ratio of the thickness of the transition region to the thickness of the transparent deposition layer may be 5% or more and 60% or less.

Another aspect of the present invention comprises a step of preparing a base material, and a vapor deposition step of forming a vapor deposition layer on the base material by vapor-depositing a metal or an inorganic compound on the base material, wherein the base material is A method for producing a barrier laminated film, wherein the value obtained by dividing the tensile strength of the substrate by the tensile elongation in at least one direction is 2.0 [MPa/%] or more. .

A method for producing a barrier laminated film according to another aspect of the present invention further comprises a plasma pretreatment step of plasma-treating the base material to form a plasma-treated surface on the base material, and the vapor deposition step includes: The deposited layer may be formed on the plasma-treated surface of the material.

In the method for producing a barrier laminate film according to another aspect of the present invention, the vapor deposition step may form the vapor deposition layer on the plasma-treated surface of the substrate by physical vapor deposition.

In the method for producing a barrier laminated film according to another aspect of the present invention, the plasma pretreatment step includes a step of supplying a mixed gas of oxygen gas and an inert gas as a plasma raw material gas, and The mixing ratio (oxygen gas/inert gas) with the active gas may be in the range of 6/1 to 1/1.

In the method for producing a barrier laminate film according to another aspect of the present invention, the vapor deposition layer is a transparent vapor deposition layer containing an inorganic compound, and the film manufacturing method comprises applying a coating agent for a gas barrier coating film on the vapor deposition layer. A step of forming a gas barrier coating film by coating and drying by heating may be further included.

In the method for producing a barrier laminate film according to another aspect of the present invention, the gas barrier coating film may be a layer obtained by applying a mixed solution of a metal alkoxide and a water-soluble polymer, followed by heating and drying.

In the method for producing a barrier laminate film according to another aspect of the present invention, the gas barrier coating film is a layer formed by applying a mixed solution of a metal alkoxide, a silane coupling agent, and a water-soluble polymer, followed by heating and drying. may

Another aspect of the present invention is a barrier laminate film having a base material and a deposited layer containing a metal or an inorganic compound provided on the base material, and a thermoplastic resin laminated on the barrier laminate film. and a layer, wherein the substrate contains polyester as a main component, and the value obtained by dividing the tensile strength of the substrate by the tensile elongation in at least one direction is 2.0 [MPa / %] or more. , packaging materials.

A packaging material according to another aspect of the present invention may be used for a packaging bag for boiling or a packaging bag for retort sterilization.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the description of the Examples below as long as it does not exceed the gist thereof.

[Example A1]
As a substrate 1, a high-stiffness PET film made of petroleum-derived PET and having a loop stiffness of 0.0017 N or more was prepared. Specifically, XP-55 manufactured by Toray Industries, Inc. was used as the high-stiffness PET film. The thickness of the high stiffness PET film was 16 µm. Also, the measured loop stiffness of the high stiffness PET film was 0.0021 N in both machine and vertical directions. The Young's modulus of the high-stiffness PET film in the machine direction was 4.8 GPa, and the Young's modulus of the high-stiffness polyester film in the vertical direction was 4.7 GPa.
Also, the tensile strength of the high stiffness PET film in the machine direction was 292 MPa, and the tensile strength of the high stiffness polyester film in the vertical direction was 257 MPa. The high-stiffness PET film had a tensile elongation of 107% in the machine direction, and the high-stiffness polyester film had a tensile elongation of 102% in the vertical direction. In this case, the value obtained by dividing the tensile strength of the high-stiffness PET film in the machine direction by the tensile elongation is 2.73 [MPa/%], and the value obtained by dividing the tensile strength of the high-stiffness PET film in the vertical direction by the tensile elongation The value is 2.52 [MPa/%].
In addition, the thermal shrinkage of the high stiffness PET film in both the machine direction and the vertical direction was 0.4%.

Subsequently, the puncture strength of the high-stiffness PET film was measured according to JIS Z1707 7.4. As a measuring instrument, a Tensilon universal material testing machine RTC-1310 manufactured by A&D was used. Specifically, a semicircular needle with a diameter of 1.0 mm and a tip shape radius of 0.5 mm was applied to a test piece of a high-stiffness PET film in a fixed state from the outer surface 30y side at 50 mm / min (1 The needle was pierced at a speed of 50 mm per minute), and the maximum stress until the needle penetrated the high-stiffness PET film was measured. The maximum value of stress was measured for 5 or more test pieces, and the average value was taken as the puncture strength of the high-stiffness PET film. The environment during the measurement was a temperature of 23° C. and a relative humidity of 50%. As a result, the puncture strength was 10.2N.

[Example A2]
As the base material 1, a PBT film including a plurality of layers and produced by a casting method, which was described in the above-described first configuration, was prepared. The content of PBT in each layer was 80%, the number of layers was 1024, and the thickness of the PBT film was 15 μm. Also, the tensile strength of the PBT film in the machine direction was 191 MPa, and the tensile strength of the PBT film in the vertical direction was 289 MPa. Also, the tensile elongation of the PBT film in the machine direction was 195%, and the tensile elongation of the PBT film in the vertical direction was 100%. In this case, the value obtained by dividing the tensile strength of the PBT film in the machine direction by the tensile elongation is 0.98 [MPa/%], and the value obtained by dividing the tensile strength by the tensile elongation of the PBT film in the vertical direction is 2.00 [MPa/%]. It is 89 [MPa/%].
Moreover, the heat shrinkage of the PBT film in both the machine direction and the vertical direction was 0.4%.

[Example B1]
An example in which a vapor deposition layer 2 is formed on a substrate 1 and a gas barrier coating film 3 is formed on the vapor deposition layer 2 to produce a barrier laminate film 5 will be described.

First, as the substrate 1, a roll was prepared by winding a high-stiffness PET film having a thickness of 16 μm, which was used in Example A1 described above. Subsequently, using the film forming apparatus 60 described above shown in FIG. 11, the base material 1 was subjected to oxygen plasma treatment, and then a deposited layer 2 containing aluminum oxide and having a thickness of 12 nm was formed on the oxygen plasma treated surface. . The oxygen plasma treatment and film formation treatment will be described in detail below.

In the oxygen plasma treatment, plasma is introduced from the plasma supply nozzle 72 under the following conditions in the plasma pretreatment chamber 62B to the surface of the substrate 1 on which the vapor deposition layer 2 is provided, and the substrate is transported at a transport speed of 400 m/min. Material 1 was subjected to plasma pretreatment. As a result, an oxygen plasma-treated surface was formed on the surface of the substrate 1 on which the deposited layer 2 was provided.
[Oxygen plasma pretreatment conditions]
・Plasma intensity: 200 W·sec/m ²
- Plasma forming gas ratio: oxygen/argon = 2/1
・Applied voltage between pretreatment drum and plasma supply nozzle: 340V
・Vacuum degree of pretreatment section: 3.8 Pa

In the film forming process, in the film forming chamber 62C into which the substrate 1 continuously transported from the plasma pretreatment chamber 62B is loaded, aluminum is used as a target to deposit a thickness on the oxygen plasma-treated surface of the substrate 1. A deposited layer 2 containing aluminum oxide with a thickness of 12 nm was formed on the substrate 1 by a vacuum deposition method. A reactive resistance heating system was adopted as a heating means for the vacuum deposition method. The film formation conditions are as follows.
[Aluminum oxide film formation conditions]
・Degree of vacuum: 8.1×10 ⁻² Pa
・Conveyance speed: 400m/min
・Oxygen gas supply amount: 20000sccm

Subsequently, a gas barrier coating film 3 was formed on the deposited layer 2 . Specifically, first, 385 g of water, 67 g of isopropyl alcohol, and 9.1 g of 0.5 N hydrochloric acid were mixed and adjusted to pH 2.2. A solution A was prepared by mixing 9.2 g of oxypropyltrimethoxysilane while cooling to 10°C.
As a water-soluble polymer, a solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of polymerization of 2400 and a degree of saponification of 99% or more, 324 g of water, and 17 g of isopropyl alcohol.
Subsequently, A liquid and B liquid were mixed so that the weight ratio was 6.5:3.5. The solution thus obtained was used as a coating agent for a gas barrier coating film.

The vapor-deposited layer 2 was coated with the gas-barrier coating film coating agent prepared above by spin coating. Thereafter, heat treatment was performed in an oven at 180° C. for 60 seconds to form a gas barrier coating film 3 having a thickness of about 400 nm on the deposited layer 2 . Thus, a barrier laminate film 5 having the base material 1, the deposition layer 2 and the gas barrier coating film 3 was obtained.

The barrier laminate film 5 of Example B1 was subjected to measurement of transformation rate, oxygen permeability, water vapor permeability, and loop stiffness.

(Metamorphic rate)
In an evacuated environment, the surface of the gas barrier coating film 3 of the barrier laminated film 5 was repeatedly subjected to soft etching with a Cs (cesium) ion gun at a constant rate, while time-of-flight secondary ion mass spectrometry (TOF) was performed. -SIMS), ions derived from the gas barrier coating film 3, ions derived from the deposited layer 2, and ions derived from the substrate 1 were measured. For example, C ₆ (mass number: 72.00) derived from the resin film of the substrate 1 and Al ₂ O ₄ H (mass number: 118.93) ions derived from the deposited aluminum oxide film of the deposition layer 2 were analyzed by mass spectrometry.

As a time-of-flight secondary ion mass spectrometer used for TOF-SIMS, TOF. Using SIMS5, measurement was performed under the following measurement conditions. As a result, a graph as shown in FIG. 10 was obtained.
(TOFSIMS measurement conditions)
・Primary ion type: Bi ₃ ++ (0.2 pA, 100 μs)
・Measurement area: 150×150 μm ²
・Type of etching gun: Cs (1 keV, 60 nA)
・Etching area: 600×600 μm ²
・Etching Et rate: 3 sec/cycle
Evacuation time: 15 hours or more at 1×10 ⁻⁶ mbar or less Measurement using a time-of-flight secondary ion mass spectrometer was performed within 30 hours after the start of evacuation.

In the graph, the position where the strength of SiO ₂ (mass number: 59.96), which is a constituent element of the gas-barrier coating film 3, is half the strength of the gas-barrier coating film 3 is the position between the gas-barrier coating film 3 and the deposited layer 2. identified as an interface. In addition, the position where the strength of C ₆ (mass number: 72.00), which is the constituent material of the base material 1, is half the strength of the base material 1 was specified as the interface between the base material 1 and the deposited layer 2 . Also, the distance in the thickness direction between the two interfaces was adopted as the thickness of the deposited layer 2 .

Next, a peak representing the measured elemental bond Al ₂ O ₄ H (mass number: 118.93) was determined, and the transition region from the peak to the interface was defined. However, when the component of the gas barrier coating film 3 is composed of a material having the same mass number as Al ₂ O ₄ H (mass number 118.93), it is necessary to separate the waveform of 118.93.

When reactants AlSiO ₄ and hydroxide Al ₂ O ₄ H are generated at the interface between the gas barrier coating film 3 and the vapor deposition layer 2 , the Al present at the interface between them and the substrate 1 and the vapor deposition layer 2 ₂ O ₄ H can be separated. In this manner, the separation of the waveforms can be appropriately handled according to the material of the gas barrier coating film 3 .

In waveform separation, for example, a profile with a mass number of 118.93 obtained by TOF-SIMS is subjected to nonlinear curve fitting using a Gaussian function, and overlapping peaks are separated using a least squares method Levenberg Marquardt algorithm. you can go

Two samples were prepared from the barrier laminated film 5 of Example B1, and the transformation rate of the vapor deposition layer 2 for each of the two samples was calculated as (thickness W ₁ of transition region/thickness of vapor deposition layer 2) × 100 (% ). As a result, the alteration rate in the first sample was 36.2%, and the alteration rate in the second sample was 28.8%.

(loop stiffness)
Further, from the barrier laminate film 5 of Example B1, the above rectangular test piece 40 was produced, and the loop stiffness in the machine direction and the vertical direction was measured. As a measuring instrument, Toyo Seiki Co., Ltd. No. A 581 Loop Stiffness Tester (registered trademark) LOOP STIFFNESS TESTER DA type was used. The environment during the measurement was a temperature of 23° C. and a relative humidity of 50%. As a result, the loop stiffness in the machine direction of the barrier laminate film 5 was 0.0021N, and the loop stiffness in the vertical direction was 0.0.0021N.

(oxygen permeability)
The barrier laminate film 5 prepared as described above and a non-stretched polypropylene film (CPP film) having a thickness of 60 μm are laminated by a dry lamination method via a two-liquid curable polyurethane adhesive to form a packaging material 8 . was made. As the CPP film, an unstretched polypropylene film ZK207 manufactured by Toray Advanced Film Co., Ltd. was used.

Subsequently, the packaging material 8 was subjected to aging treatment for 48 hours, and a sample for evaluating the oxygen permeability before the retort treatment was produced from the packaging material 8 .

Also, using packaging material 8, a B5 size four-sided seal pouch was produced. Subsequently, 100 mL of water was poured into the interior of the four-side-sealed pouch from the opening at the top of the four-side-sealed pouch, and then a seal was formed at the top to seal the four-side-sealed pouch. Subsequently, the four-sided seal pouch was subjected to retort treatment at 121° C. for 40 minutes.
Subsequently, the packaging material 8 constituting one side of the four-sided seal pouch after the retort treatment was cut out to prepare a sample for evaluating the oxygen permeability after the retort treatment.

Subsequently, the sample before retort treatment and the sample after retort treatment were set so that the base material 1 was on the oxygen supply side, and measured under the conditions of 23 ° C. and 100% RH atmosphere according to JIS K 7126 B method. Oxygen permeability was measured according to As a measuring device, an oxygen permeability measuring device (manufactured by MOCON [model name: OX-TRAN 2/21]) was used. As a result, the oxygen permeability of the sample before retorting was 0.24 cc/m ² /24 hr/atm. In addition, the oxygen permeability of the sample after retort treatment was 0.20 cc/m ² /24 hr/atm. Thus, the oxygen permeability was able to be less than 0.50 cc/m ² /24 hr/atm both before and after retort treatment.

(water vapor permeability)
Water vapor permeability measurements were performed using the same samples as for the oxygen permeability measurements. Specifically, each sample is set so that the base material 1 is on the sensor side, and the water vapor permeability is measured in accordance with JIS K 7126 B method under the measurement conditions of 37.8 ° C. and 100% RH atmosphere. was measured. As a measuring device, a water vapor permeability measuring device (measuring device manufactured by MOCON [model name, PERMATRAN 3/33]) was used. As a result, the water vapor transmission rate of the sample before retorting was 0.61 g/m ² /24hr. The water vapor transmission rate of the sample after retorting was 1.05 g/m ² /24hr. Thus, the water vapor transmission rate could be less than 1.5 g/m ² /24 hr both before and after retort treatment.

[Example B2]
A barrier comprising a base material 1 and a vapor deposition layer 2 provided on the base material 1 in the same manner as in Example B1 except that the gas barrier coating film 3 was not formed on the vapor deposition layer 2. A flexible laminated film 5 was produced. Subsequently, in the same manner as in Example B1, two samples were prepared from the barrier laminate film 5 of Example B2, and for each of the two samples, the transformation rate of the deposited layer 2 was calculated as (thickness of the transition region It was calculated as W ₁ /thickness of deposition layer 2)×100 (%). As a result, the alteration rate in the second sample was 37.8%, and the alteration rate in the second sample was 42.2%.

A rectangular test piece 40 was prepared from the barrier laminate film 5 of Example B2, and the loop stiffness in the machine direction and the vertical direction was measured in the same manner as in Example B1. As a result, the loop stiffness in the machine direction of the barrier laminate film 5 was 0.0021N, and the loop stiffness in the vertical direction was 0.0021N.

[Comparative Example B1]
As in Example B1, except that as the substrate 1, a biaxially oriented PET film made of petroleum-derived PET having a loop stiffness of less than 0.0017 N in both the machine and vertical directions was used. Thus, a barrier laminate film 5 comprising a base material 1, a vapor deposition layer 2 provided on the base material 1, and a gas barrier coating film 3 provided on the vapor deposition layer 2 was produced. Subsequently, a rectangular test piece 40 was prepared from the barrier laminate film 5 of Comparative Example B1 in the same manner as in Example B1, and the loop stiffness in the machine direction and vertical direction was measured. As a result, the loop stiffness in the machine direction of the barrier laminate film 5 was 0.0014N, and the loop stiffness in the vertical direction was 0.0016N.

1 Substrate 2 Vapor deposition layer 3 Gas barrier coating film 5 Barrier laminated film 6 Adhesive layer 7 Thermoplastic resin layer 8 Packaging material 60 Film formation device 62 Decompression chamber 62A Substrate transfer chamber 62B Plasma pretreatment chamber 62C Film formation chamber 63 Winding Feeding roller 64 Guide roller 65 Winding roller 68 Source gas volatilization supply device 69 Source gas supply nozzle 70 Plasma pretreatment roller 71 Electrode 72 Plasma supply nozzle 75 Film formation roller 76 Film formation means 80 Vacuum pump 81 Power supply wiring 82 Power source 85a~ 85c bulkhead

Claims (14)

a substrate;
A deposited layer provided on the base material and containing a metal or an inorganic compound,
The base material has a loop stiffness of 0.0017 N or more in the machine direction and the vertical direction and contains polyester as a main component,
In at least one direction, the value obtained by dividing the tensile strength of the base material by the tensile elongation is 2.0 [MPa / %] or more,
The barrier laminate film, wherein the substrate has a thickness of 16 μm or more and 25 μm or less. 2. The barrier laminate film according to claim 1, wherein the substrate has a puncture strength of 9.5 N or more. 3. The barrier laminate film according to claim 1, further comprising a gas barrier coating film provided on said vapor deposition layer. The barrier laminate film according to any one of claims 1 to 3, wherein the vapor deposition layer is a transparent vapor deposition layer containing an inorganic compound. The vapor deposition layer is a transparent vapor deposition layer containing aluminum oxide,
The transparent deposition layer includes a transition region,
The transition region is an elemental bond of Al ₂ O ₄ H detected by etching the barrier laminated film from the transparent deposition layer side using time-of-flight secondary ion mass spectrometry (TOF-SIMS). A region between the position of the peak and the interface between the transparent deposited layer and the substrate,
4. The barrier laminate film according to any one of claims 1 to 3, wherein the ratio of the thickness of the transition region to the thickness of the transparent deposition layer is 5% or more and 60% or less. preparing a substrate;
a vapor deposition step of forming a vapor deposition layer on the base material by vapor-depositing a metal or an inorganic compound on the base material;
The base material has a loop stiffness of 0.0017 N or more in the machine direction and the vertical direction and contains polyester as a main component,
In at least one direction, the value obtained by dividing the tensile strength of the base material by the tensile elongation is 2.0 [MPa / %] or more,
The method for producing a barrier laminate film, wherein the substrate has a thickness of 16 μm or more and 25 μm or less. further comprising a plasma pretreatment step of plasma-treating the base material to form a plasma-treated surface on the base material;
7. The method for producing a barrier laminate film according to claim 6, wherein said vapor deposition step forms said vapor deposition layer on said plasma-treated surface of said substrate. 8. The method for producing a barrier laminate film according to claim 7, wherein the vapor deposition step forms the vapor deposition layer on the plasma-treated surface of the substrate by physical vapor deposition. The plasma pretreatment step includes a step of supplying a mixed gas of oxygen gas and an inert gas as a plasma raw material gas,
9. The method for producing a barrier laminate film according to claim 7, wherein the mixing ratio of the oxygen gas and the inert gas (oxygen gas/inert gas) is within the range of 6/1 to 1/1. . The vapor deposition layer is a transparent vapor deposition layer containing an inorganic compound,
10. The method for producing the barrier laminated film further comprising the step of forming a gas barrier coating film by applying a coating agent for a gas barrier coating film onto the deposited layer and drying by heating. The method for producing the barrier laminate film according to any one of the items. 11. The method for producing a barrier laminate film according to claim 10, wherein the gas barrier coating film is a layer obtained by applying a mixed solution of a metal alkoxide and a water-soluble polymer and drying the applied layer by heating. 11. The method for producing a barrier laminated film according to claim 10, wherein the gas barrier coating film is a layer formed by applying a mixed solution of a metal alkoxide, a silane coupling agent and a water-soluble polymer, followed by heating and drying. a barrier laminate film comprising a base material and a deposited layer containing a metal or an inorganic compound provided on the base material;
a thermoplastic resin layer laminated on the barrier laminated film,
The base material has a loop stiffness of 0.0017 N or more in the machine direction and the vertical direction and contains polyester as a main component,
In at least one direction, the value obtained by dividing the tensile strength of the base material by the tensile elongation is 2.0 [MPa / %] or more,
The packaging material, wherein the base material has a thickness of 16 μm or more and 25 μm or less. 14. The packaging material according to claim 13, which is used for packaging bags for boiling or packaging bags for retort sterilization.