JP7539025B2 - Packaging materials and containers - Google Patents

Description

The present invention relates to a packaging material and a packaging container made from the packaging material.

Traditionally, various packaging materials have been developed and proposed for filling and packaging various items such as food and beverages, pharmaceuticals, chemicals, cosmetics, and others. Such packaging materials are required to have various physical properties, depending on the purpose of packaging, the contents to be filled, the storage and distribution of the packaged product, and other factors. For example, one of these physical properties is gas barrier properties that prevent the transmission of oxygen, water vapor, etc.

A variety of gas barrier materials that prevent the permeation of oxygen, water vapor, etc. have been developed and proposed. For example, gas barrier materials such as aluminum foil, nylon film or polyethylene terephthalate film with a coating film of polyvinylidene chloride resin, polyvinyl alcohol film, saponified ethylene-vinyl acetate copolymer film, polyacrylonitrile resin film, etc. have been developed and proposed.

Furthermore, in recent years, transparent barrier films have been proposed that have a vapor-deposited layer of an inorganic oxide, such as silicon oxide or aluminum oxide, on a plastic substrate, or a vapor-deposited layer of a metal, such as aluminum. For example, Patent Document 1 proposes producing a barrier film by forming a vapor-deposited layer of an inorganic oxide on a nylon film.

JP 2007-303000 A

In recent years, with the growing calls for the creation of a recycling-oriented society, there is a desire to move away from fossil fuels in the materials sector, just as there is in the energy sector. For example, there is a desire to reduce the amount of fossil fuels used by using biomass-derived raw materials in the manufacture of packaging materials.

The present invention aims to provide a packaging material that can effectively solve these problems.

The present invention is a packaging material comprising a vapor deposition film and a sealant layer located on the inside of the vapor deposition film, wherein the vapor deposition film comprises a stretched first plastic film, a transparent vapor deposition layer containing aluminum oxide and provided on the first plastic film, and a gas barrier coating film provided on the transparent vapor deposition layer, wherein the first plastic film contains polyester derived from biomass, and the transparent vapor deposition layer comprises a transition region, which is a region between the position of the peak of elemental bond Al 2 _{O 4} H that is transformed into aluminum hydroxide, detected by etching the vapor deposition film from the gas barrier coating film side using time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the interface between the transparent vapor deposition layer and the first plastic film, and the ratio of the thickness of the transition region to the thickness of the transparent vapor deposition layer is 5% or more and 60% or less.

The packaging material according to the present invention may further include an anchor coat layer located between the vapor deposition film and the sealant layer.

The packaging material according to the present invention may further include an adhesive resin layer located between the vapor deposition film and the sealant layer.

The packaging material according to the present invention may further include an adhesive layer located between the vapor deposition film and the sealant layer.

The packaging material according to the present invention may further include a second plastic film located outside the first plastic film.

The packaging material according to the present invention may further comprise a second plastic film located between the first plastic film and the sealant layer.

The present invention is a packaging container made from the packaging material described above.

The present invention provides a packaging material that has gas barrier properties and reduces the environmental impact.

FIG. 2 is a cross-sectional view showing an example of a packaging material according to an embodiment. FIG. 2 is a cross-sectional view showing an example of a packaging material according to an embodiment. FIG. 2 is a cross-sectional view showing an example of a packaging material according to an embodiment. FIG. 2 is a cross-sectional view showing an example of a packaging material according to an embodiment. FIG. 2 is a cross-sectional view showing an example of a packaging material according to an embodiment. FIG. 2 is a cross-sectional view showing an example of a packaging material according to an embodiment. FIG. 13 is a diagram showing an example of the results of analyzing a transparent vapor deposition layer using a time-of-flight secondary ion mass spectrometer. FIG. 2 is a diagram showing an example of a film forming apparatus for forming a transparent deposition layer on a first plastic film. FIG. 2 is a front view showing an example of a packaging container. FIG. 2 is a front view showing an example of a packaging container. FIG. 2 is a front view showing an example of a packaging container. FIG. 2 is a front view showing an example of a packaging container. FIG. 2 is a front view showing an example of a packaging container. FIG. 2 is a front view showing an example of a packaging container. FIG. 2 is a cross-sectional view showing an example of a packaging container. FIG. 2 is a front view showing an example of a packaging container. FIG. 2 is a cross-sectional view showing a sample for measuring the peel strength of a packaging material. FIG. 2 shows how the peel strength of a sample of packaging material is measured. FIG. 13 is a graph showing the change in tensile force relative to the distance between a pair of grippers that pull a portion of a sample to measure peel strength. FIG. 2 is a diagram showing the measurement results of Examples A1 to A3 and Reference Example A1. FIG. 1 is a diagram showing the measurement results of comparative examples A1 to A4. FIG. 2 is a diagram showing the layer structure of the packaging materials of Examples B1 to B10.

<Packaging materials>
The laminate constituting the packaging material according to the present invention comprises a vapor-deposited film and a sealant layer located on the inner side of the vapor-deposited film. The inner side means the side of the packaged product formed from the packaging material that contains the contents to be contained in the packaged product. The outer side means the side away from the contents to be contained in the packaged product.

In the present invention, the biomass degree, as described below, of the entire laminate constituting the packaging material is preferably 3% or more, more preferably 5% to 60%, and even more preferably 10% to 60%. If the biomass degree is within the above range, the amount of fossil fuel used can be reduced, and the environmental burden can be reduced.

Figure 1 is a cross-sectional view showing an example of a packaging material 10 according to an embodiment of the present invention. The packaging material 10 comprises, from outside to inside, a vapor deposition film 11, a printing layer 18, an anchor coat layer 17, and a sealant layer 12, in this order. The vapor deposition film 11 comprises, from outside to inside, a first plastic film 111, a transparent vapor deposition layer 112, and a gas barrier coating film 113, in this order. The first plastic film 111 constitutes the outer surface 10y of the packaging material 10, and the sealant layer 12 constitutes the inner surface 10x of the packaging material 10.

In this application, the outer surface is the surface located on the outermost side of the packaging material 10, and the inner surface is the surface located on the innermost side of the packaging material 10. In addition, in this application, the term "order" in descriptions such as "provided in this order" and "layered in this order" refers to the order from the outside to the inside, unless otherwise specified.

Figure 2 is a cross-sectional view showing an example of a packaging material 10 according to an embodiment of the present invention. The packaging material 10 comprises, in this order, a vapor deposition film 11, a printing layer 18, an anchor coat layer 17, a first adhesive layer 13, and a sealant layer 12. The vapor deposition film 11 comprises, in this order, a first plastic film 111, a transparent vapor deposition layer 112, and a gas barrier coating film 113. The first plastic film 111 constitutes the outer surface 10y of the packaging material 10, and the sealant layer 12 constitutes the inner surface 10x of the packaging material 10.

Figure 3 is a cross-sectional view showing an example of a packaging material 10 according to an embodiment of the present invention. The packaging material 10 comprises, in this order, a vapor deposition film 11, a printing layer 18, a first adhesive layer 13, and a sealant layer 12. The vapor deposition film 11 comprises, in this order, a first plastic film 111, a transparent vapor deposition layer 112, and a gas barrier coating film 113. The first plastic film 111 constitutes the outer surface 10y of the packaging material 10, and the sealant layer 12 constitutes the inner surface 10x of the packaging material 10.

Figure 4 is a cross-sectional view showing an example of a packaging material 10 according to an embodiment of the present invention. The packaging material 10 comprises, in this order, a second plastic film 14, a second adhesive layer 15, a printing layer 18, a vapor deposition film 11, a first adhesive layer 13, and a sealant layer 12. The vapor deposition film 11 comprises, in this order, a gas barrier coating film 113, a transparent vapor deposition layer 112, and a first plastic film 111. The second plastic film 14 constitutes the outer surface 10y of the packaging material 10, and the sealant layer 12 constitutes the inner surface 10x of the packaging material 10.

Figure 5 is a cross-sectional view showing an example of a packaging material 10 according to an embodiment of the present invention. The packaging material 10 comprises, in this order, a second plastic film 14, a printing layer 18, a second adhesive layer 15, a vapor deposition film 11, a first adhesive layer 13, and a sealant layer 12. The vapor deposition film 11 comprises, in this order, a gas barrier coating film 113, a transparent vapor deposition layer 112, and a first plastic film 111. The second plastic film 14 constitutes the outer surface 10y of the packaging material 10, and the sealant layer 12 constitutes the inner surface 10x of the packaging material 10.

Figure 6 is a cross-sectional view showing an example of a packaging material 10 according to an embodiment of the present invention. The packaging material 10 comprises, in this order, a vapor deposition film 11, a printing layer 18, a second adhesive layer 15, a second plastic film 14, a first adhesive layer 13, and a sealant layer 12. The vapor deposition film 11 comprises, in this order, a first plastic film 111, a transparent vapor deposition layer 112, and a gas barrier coating film 113. The first plastic film 111 constitutes the outer surface 10y of the packaging material 10, and the sealant layer 12 constitutes the inner surface 10x of the packaging material 10.

The films and layers that make up the packaging material 10 are described below.

[Vapor-deposited film]
The vapor-deposited film 11 has a first plastic film 111, a transparent vapor-deposited layer 112 provided on the first plastic film 111, and a gas barrier coating film 113 provided on the transparent vapor-deposited layer 112. Each layer will be described below.

(First Plastic Film)
The first plastic film 111 is a polyester film stretched in a predetermined direction. The first plastic film 111 may be a uniaxially stretched film stretched in one predetermined direction, or a biaxially stretched film stretched in two predetermined directions. The stretching direction of the first plastic film 111 is not particularly limited. For example, the first plastic film 111 may be stretched in the machine direction (MD) of the film, or may be stretched in a transverse direction (TD) perpendicular to the machine direction.

The first plastic film 111 is a resin composition containing a biomass-derived polyester (hereinafter also referred to as biomass polyester). Biomass polyester is a polyester in which the diol unit is ethylene glycol derived from biomass and the dicarboxylic acid unit is a dicarboxylic acid derived from fossil fuel. An example of the polyester contained in the resin composition of the first plastic film 111 is polyethylene terephthalate. The content of polyethylene terephthalate in the first plastic film 111 may be 80% by mass or more, 90% by mass or more, or 95% by mass or more. The first plastic film 111 contains, for example, 50% by mass or more and 95% by mass or less of biomass polyester, preferably 50% by mass or more and 90% by mass or less of biomass polyester, based on the entire resin composition of the first plastic film 111.

Since biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol, polyester films synthesized using biomass-derived ethylene glycol are comparable in terms of physical properties, such as mechanical properties, to conventional fossil fuel-derived polyester films. Therefore, since the first plastic film 111 and the packaging material 10 comprising it have a layer made of a carbon-neutral material, it is possible to reduce the amount of fossil fuel used and the environmental burden compared to stretched plastic films manufactured from raw materials obtained from conventional fossil fuels and packaging materials comprising it.

Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass such as sugar cane and corn. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide using a conventional method. Commercially available biomass ethylene glycol may also be used; for example, biomass ethylene glycol available from India Glycoal Limited can be suitably used.

The dicarboxylic acid units of the polyester use dicarboxylic acids derived from fossil fuels. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used. As the aromatic dicarboxylic acid, terephthalic acid and isophthalic acid can be mentioned, and as the derivatives of aromatic dicarboxylic acids, lower alkyl esters of aromatic dicarboxylic acids, specifically, methyl esters, ethyl esters, propyl esters, butyl esters, and the like can be mentioned. Among these, terephthalic acid is preferred, and as the derivatives of aromatic dicarboxylic acids, dimethyl terephthalate is preferred.

The resin composition forming the first plastic film 111 may contain one or more of the following in a proportion of 5% by mass or more and 45% by mass or less: polyester derived from fossil fuels; recycled polyester from polyester products derived from fossil fuels; recycled polyester from polyester products derived from biomass.

Carbon dioxide in the atmosphere contains a certain percentage of ^14C (105.5 pMC), and it is known that ^{the 14C} content in plants that grow by absorbing carbon dioxide from the atmosphere, such as corn, is also about 105.5 pMC. It is also known that fossil fuels contain very little ^14C . Therefore, by measuring the percentage of ^14C in the total carbon atoms in polyester, the percentage of carbon derived from biomass can be calculated.

The biomass degree can be used as an index representing the ratio of raw materials derived from biomass. In the present embodiment, the "biomass degree" indicates the weight ratio of biomass-derived components. Taking polyethylene terephthalate as an example, polyethylene terephthalate is a polymer of ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1. Therefore, when only ethylene glycol derived from biomass is used, the weight ratio of biomass-derived components in polyethylene terephthalate is 31.25%, so the biomass degree is 31.25% (molecular weight derived from ethylene glycol derived from biomass/molecular weight of one unit of polyester polymerization=60÷192).
In the polyester derived from fossil fuels, the weight ratio of the biomass-derived component is 0%, so the biomass degree of the polyester derived from fossil fuels is 0%. In the present embodiment, the biomass degree in the first plastic film 111 is preferably 5.0% or more, and more preferably 10.0% or more, in order to exert the effect as a carbon offset material. In addition, the biomass degree in the first plastic film 111 may be 30.0% or less in view of problems in the manufacturing process of the film and physical properties.

The first plastic film 111 can be formed by forming the above-mentioned resin composition into a film, for example, by a T-die method. Specifically, after drying the above-mentioned resin composition, it is supplied to a melt extruder heated to a temperature (Tm) to Tm+70°C above the melting point of the resin composition to melt the resin composition, extruded into a sheet from a die such as a T-die, and the extruded sheet is quenched and solidified by a rotating cooling drum or the like to form a film. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

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

The longitudinally stretched film is then subjected to the sequential processing steps of transverse stretching, heat setting, and heat relaxation to become a biaxially stretched film. Transverse stretching is usually performed at a temperature range of 50°C to 100°C. The transverse stretching ratio is preferably 2.5 times to 5.0 times, depending on the required characteristics of the application. If it is less than 2.5 times, the film thickness becomes uneven and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film production.

After the transverse stretching, a heat setting process is performed. The preferred temperature range for heat setting is Tg+70 to Tm-10°C of PET. The heat setting time is preferably 1 second or more and 60 seconds or less. For applications requiring a reduction in the thermal shrinkage rate, a heat relaxation process may be performed as necessary.

The thickness of the first plastic film 111 obtained as described above is arbitrary depending on the application. The thickness of the first plastic film 111 is, for example, 5 μm or more, and may be 8 μm or more. The thickness of the first plastic film 111 is, for example, 100 μm or less, 50 μm or less, 30 μm or less, or 25 μm or less. The range of the thickness of the first plastic film 111 can be determined by any combination of the above-mentioned lower limit candidate value and upper limit candidate value. The breaking strength of the film is 5 kgf/mm ₂ or more and 40 kgf/mm ² or less in the MD direction, and 5 kgf/mm ² or more and 35 kgf/mm ² or less in the TD direction, and the breaking elongation is 50% or more and 350% or less in the MD direction, and 50% or more and 300% or less in the TD direction. The shrinkage rate when left in a temperature environment of 150° C. for 30 minutes is 0.1% or more and 5% or less.

(Transparent deposition layer)
The transparent deposition layer 112 is a thin film of an inorganic oxide containing aluminum oxide as a main component. The transparent deposition layer 112 may contain an aluminum compound such as aluminum oxide or aluminum nitride, carbide, or hydroxide, either alone or in mixtures thereof. Furthermore, the transparent deposition layer 112 may contain an aluminum compound as a main component and further contain a metal oxide such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, or zirconium oxide, or a metal nitride, carbide, or a mixture thereof.

(Gas barrier coating film)
The gas barrier coating film 113 serves to mechanically and chemically protect the transparent deposition layer 112 and improve the barrier properties of the deposition film 11, and is laminated so as to be in contact with the transparent deposition layer 112. The gas barrier coating film 113 is a cured film formed from a coating agent for gas barrier coating films, which is made of a resin composition containing a metal alkoxide, a hydroxyl group-containing water-soluble resin, and a silane coupling agent added as necessary.

The mass ratio of the hydroxyl-containing water-soluble resin to the metal alkoxide in the resin composition is preferably 5/95 or more and 20/80 or less, and 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 tends to be large.

The thickness of the gas barrier coating film 113 is preferably 100 nm or more and 800 nm or less. If it is thinner than the above range, the barrier effect of the gas barrier coating film 113 is likely to be insufficient, and if it is thicker than the above range, it is likely to become too rigid and brittle.

Metal alkoxides are represented by 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 atomic valence of M. Multiple R _{1 s} and R ₂ s in one molecule may be the same or different) (I).

Specific examples of metal atoms represented by M in metal alkoxides include silicon, zirconium, titanium, aluminum, tin, lead, borane, and others. For example, it is preferable to use an alkoxysilane in which M is Si (silicon).

In the above general formula (I), specific examples of _OR2 include alkoxy groups such as hydroxyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, i-propoxy group, butoxy group, 3-methacryloxy group, 3-acryloxy group, and phenoxy group, and the like.

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

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, isopropyltriethoxysilane, dimethyldiethoxysilane, and diphenyldimethoxysilane. Examples of the alkoxysilane include various alkoxysilanes and phenoxysilanes such as silane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, and 1,6-bis(trimethoxysilyl)hexane. In the present embodiment, condensation polymers of these alkoxysilanes can also be used, and specifically, for example, polytetramethoxysilane, polytetraethoxysilane, etc. can be used.

Silane coupling agents are used to adjust the crosslink density of the cured film made of metal alkoxide and hydroxyl-containing water-soluble resin, to create a film with barrier properties and resistance to hot water treatment.

The silane coupling agent has the general formula: R ₃ nSi(OR ₄ ) 4-n (II)
(In the formula, _R3 and _R4 each independently represent an organic functional group, and n is 1 to 3.)
It is expressed as:

In the above general formula (II), R ₃ may be, 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 a functional group having an isocyanate group. Specifically, at least one of the two or three R _3s is preferably a functional group having an epoxy group, more preferably a 3-glycidoxypropyl group or a 2-(3,4 epoxycyclohexyl) group. The R _3s 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, and is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 3 to 7 carbon atoms, which may have a branch. For example, examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. Examples of the alkoxyalkyl group having 3 to 7 carbon atoms include a group in which one hydrogen atom has been removed from a straight-chain or branched-chain ether, such as 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, ethyl sec-butyl ether, methyl tert-butyl ether, or ethyl tert-butyl ether. Each of (OR ₄ ) may be the same or different.

Examples of silane coupling agents represented by the above general formula (II) include, for example, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane when n=1. When n=2, examples include 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. When n=3, examples include 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2-(3,4-epoxycyclohexyl)dimethylmethoxysilane, and 2-(3,4-epoxycyclohexyl)dimethylethoxysilane.

In particular, the crosslink density of the cured film of the barrier coating layer using 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane is lower than the crosslink density of a system using trialkoxysilane. Therefore, while the film has excellent gas barrier properties and hot water treatment resistance, it also becomes a flexible cured film and has excellent bending resistance, so that the gas barrier properties of packaging materials using this barrier film are less likely to deteriorate even after the Gelbo flex test.

Silane coupling agents with n=1, 2, or 3 can also be used in combination, and the ratio of the amounts and the amount of silane coupling agent used are determined by the design of the cured film of the barrier coating layer.

The hydroxyl-containing water-soluble resin is capable of dehydration co-condensation with the metal alkoxide, and the degree of saponification is preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, and even more preferably 99% or more and 100% or less. If the degree of saponification is smaller than the above range, the hardness of the barrier coating layer is likely to decrease.

Specific examples of hydroxyl-containing water-soluble resins include polyvinyl alcohol resins, ethylene-vinyl alcohol copolymers, and polymers of bifunctional phenolic compounds and bifunctional epoxy compounds. Each of these may be used alone, or two or more of them may be mixed or copolymerized. Among these, polyvinyl alcohol is particularly preferred because of its excellent flexibility and affinity, and polyvinyl alcohol resins are preferred.

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

(Preferable structure of vapor-deposited film)
Next, a preferred configuration of the vapor-deposited film 11 in the thickness direction will be described with reference to Fig. 7. Fig. 7 is a diagram showing the results of measuring ions derived from the transparent vapor-deposited layer 112 and ions derived from the first plastic film 111 using time-of-flight secondary ion mass spectrometry (TOF-SIMS) while repeatedly performing soft etching at a constant rate on the surface of the vapor-deposited film 11 on the side of the gas barrier coating film 113 with a Cs (cesium) ion gun. The transparent vapor-deposited layer 112 of the vapor-deposited film 11 includes a transition region identified by the graph analysis diagram shown in Fig. 7.

The transition region is a region between the peak position _T2 of the element bond _Al2O4H that transforms into aluminum _hydroxide , detected by etching the vapor-deposited film 11 from the gas barrier coating film 113 side using TOF-SIMS, and the interface _T1 between the transparent vapor-deposited layer 112 and the first plastic film 111. The interface T1 between the transparent vapor-deposited layer 112 and the first plastic film 111 is identified as the position where the intensity of the graph of element _C6 is half the intensity of element _C6 in the first plastic film 111. In _Figure 7, the symbol _W1 represents the thickness of the transition region.

The ratio of the thickness W ₁ of the transition region to the thickness of the transparent vapor deposition layer 112 (hereinafter also referred to as the transformation rate of the transition region) is preferably 5% or more and 60% or less. By setting the transformation rate to 5% or more and 60% or less, it is possible to suppress the degradation of the barrier property of the vapor deposition film 11 against water vapor when a sterilization treatment such as boiling treatment or retort treatment is performed on a packaging material containing the vapor deposition film 11. The retort treatment is a treatment in which the contents are filled into a packaging container, the packaging container is sealed, and then the packaging container is heated under pressure. The temperature of the retort treatment is, for example, 120°C or more. The boiling treatment is a treatment in which the contents are filled into a packaging container, the packaging container is sealed, and then the packaging container is heated in a hot water bath under atmospheric pressure. The temperature of the boiling treatment is, for example, 90°C or more and 100°C or less. A packaging material including a vapor-deposited film 11 having a transformation rate in the transition region of 5% or more and 60% or less can effectively maintain barrier properties against gases such as oxygen and water vapor even when used in a packaging container for which no sterilization treatment such as boiling or retort treatment is performed. The transformation rate may be 30% or less, 25% or less, or 20% or less. The transformation rate may be 10% or more, or 15% or more. The range of the transformation rate may be determined by any combination of the above-mentioned lower limit candidate value and upper limit candidate value.

The interface between the first plastic film 111 and the transparent vapor deposition layer 112 is subjected to mechanical and chemical stress due to heat. Therefore, in order to prevent a decrease in adhesion and barrier properties, it is important to firmly coat the first plastic film 111 with the transparent vapor deposition layer 112 at the interface between the first plastic film 111 and the transparent vapor deposition layer 112.

Aluminum hydroxide has good adhesion to plastic films due to its chemical structure, and because it forms a dense network of its own, it has high water vapor barrier properties. However, the bond structure based on hydrogen bonds between the aluminum hydroxide and the plastic film is easily broken down microscopically by heat stress. In addition, water molecules easily penetrate into the film due to the affinity between the grain boundaries of aluminum hydroxide and the aluminum hydroxide network.

In this embodiment, in order to narrow as much as possible the transition region formed by aluminum hydroxide in the aluminum oxide vapor _{-deposited film at the interface with the plastic film, attention is focused on the elemental bond Al2O4H, and by controlling its abundance, aluminum hydroxide generated from the elemental bond Al2O4H due to thermal} stress is suppressed, and the ratio of the aluminum oxide film containing relatively less aluminum hydroxide is increased, thereby suppressing microscopic destruction of the vapor-deposited film and destruction of the interface with the plastic film caused by water molecules due to thermal stress. As a result, it is possible to provide a vapor-deposited film 11 with unprecedented adhesion and barrier properties.

The aluminum oxide vapor deposition film can be formed by depositing a vapor deposition film on the surface of a plastic film that has been pretreated with oxygen plasma. As a vapor deposition method for depositing the vapor deposition film, various vapor deposition methods can be applied from among physical vapor deposition and chemical vapor deposition. As a physical vapor deposition method, a method can be selected from the group consisting of vapor deposition, sputtering, ion plating, ion beam assisted deposition, and cluster ion beam deposition, and as a chemical vapor deposition method, a method can be selected from the group consisting of plasma CVD, plasma polymerization, thermal CVD, and catalytic reaction CVD. In this embodiment, the vapor deposition method of physical vapor deposition is preferred.

A specific example of a method for obtaining the graph in Figure 7 will be described. First, etching is performed from the outermost surface of the gas barrier coating film 113 using Cs, and analysis is performed on the elemental bonds at the interfaces between the gas barrier coating film 113 and films such as the transparent deposition layer 112 and the first plastic film 111, as well as the elemental bonds of the deposition film. This makes it possible to obtain the graph shown in Figure 7.

Next, a specific example of a method for analyzing the graph in FIG. 7 will be described. Here, a case where the gas barrier coating film 113 contains silicon oxide will be described.

First, in the graph, the position where the strength of SiO ₂ (mass number 59.96), a constituent element of the gas barrier coating film 113, is half of the strength in the gas barrier coating film 113 is identified as the interface between the gas barrier coating film 113 and the transparent vapor deposition layer 112. Next, the position where the strength of C ₆ (mass number 72.00), a constituent material of the first plastic film 111, is half of the strength in the first plastic film 111 is identified as the interface between the first plastic film 111 and the transparent vapor deposition layer 112. The distance in the thickness direction between the two interfaces is used as the thickness of the transparent vapor deposition layer 112.

Next, a peak representing the measured element bond _Al2O4H (mass number _118.93 ) is obtained, and the region from the peak to the interface is defined as the transition region. However, if the gas barrier coating film 113 is composed of a material with the same mass number as _Al2O4H (mass number _118.93 ), it is necessary to separate the waveform of 118.93.

When the reactants _AlSiO4 and _{hydroxide Al2O4H are} generated at the interface between the gas barrier coating film 113 and the transparent vapor deposition layer 112, they can be separated from the _Al2O4H present at the interface between the first plastic film ₁₁₁ and the transparent vapor deposition layer 112. In this way, the separation of the corrugations can be dealt with appropriately depending on the material of the gas barrier coating film 113.

In waveform separation, for example, the profile of mass number 118.93 obtained by TOF-SIMS can be nonlinearly curve-fitted using a Gaussian function, and overlapping peaks can be separated using the least squares Levenberg Marquardt algorithm.

[Sealant layer]
The sealant layer 12 is a layer containing a thermoplastic resin that constitutes the inner surface 10x of the packaging material 10. The sealant layer 12 may be formed by extruding a thermoplastic resin onto another film, or by laminating a film of a thermoplastic resin to another film. For example, in the example shown in FIG. 1, the sealant layer 12 is a layer formed by extruding a thermoplastic resin onto a film including the vapor-deposited film 11. In addition, in the examples shown in FIGS. 2 to 6, the sealant layer 12 is a layer formed by laminating a film including a thermoplastic resin to a film including the vapor-deposited film 11 or a film including the second plastic film 14.

The sealant layer 12 may or may not contain a biomass-derived component. When the sealant layer 12 is formed from a material containing a biomass-derived component, the sealant layer 12 can be formed from the biomass polyolefin described below. When the sealant layer 12 is formed from a material not containing a biomass-derived component, the sealant layer 12 can be formed from a conventionally known thermoplastic resin derived from fossil fuels.

Biomass polyolefins are polymers of monomers containing olefins such as ethylene derived from biomass. Since biomass-derived olefins are used as the raw material monomers, the polyolefins obtained by polymerization are derived from biomass. Note that the raw material monomers for polyolefins do not have to contain 100% by mass of biomass-derived olefins.

For example, biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use biomass-derived fermented ethanol obtained from plant raw materials. There are no particular limitations on the plant raw material, and any conventionally known plant can be used. Examples include corn, sugarcane, beet, and manioc.

Fermented ethanol derived from biomass refers to ethanol produced by contacting a culture solution containing a carbon source obtained from plant raw materials with an ethanol-producing microorganism or a product derived from its crushed material, and then purifying the ethanol. Conventional methods such as distillation, membrane separation, and extraction can be used to purify ethanol from the culture solution. For example, methods include adding benzene, cyclohexane, etc., and performing azeotropic distillation, or removing water by membrane separation, etc.

The monomers that are the raw materials for biomass polyolefins may further contain fossil fuel-derived ethylene monomers and/or fossil fuel-derived α-olefin monomers, or may further contain biomass-derived α-olefin monomers.

The above α-olefins are not particularly limited in the number of carbon atoms, but those with 3 to 20 carbon atoms can usually be used, and butylene, hexene, or octene are preferable. This is because butylene, hexene, or octene can be produced by polymerizing ethylene, a raw material derived from biomass. In addition, by including such α-olefins, the polyolefin obtained by polymerization has alkyl groups as a branched structure, making it more flexible than simple linear ones.

As the biomass polyolefin, polyethylene or a copolymer of ethylene and α-olefin may be used alone or in combination of two or more. In particular, it is preferable that the biomass polyolefin is polyethylene. This is because, by using ethylene, which is a raw material derived from biomass, it is theoretically possible to produce it from 100% biomass-derived components.

The biomass polyolefin may contain two or more types of biomass polyolefins with different biomass degrees, and the biomass degree of the entire polyolefin resin layer may be within the range described below.

The biomass polyolefin preferably has a density of 0.91 g/cm ³ or more and 0.93 g/cm ³ or less, more preferably 0.912 g/cm ³ or more and 0.928 g/cm ³ or less, and even more preferably 0.915 g/cm ³ or more and 0.925 g/cm ³ or less. The density of the biomass polyolefin is a value measured according to the method specified in the A method of JIS K7112-1980 after performing annealing described in JIS K6760-1995. If the density of the biomass polyolefin is 0.91 g/cm ³ or more, the rigidity of the polyolefin resin layer containing the biomass polyolefin can be increased, and it can be suitably used as an inner layer of a packaging product. In addition, if the density of the biomass polyolefin is 0.93 g/cm ³ or less, the transparency and mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be increased, and it can be suitably used as an inner layer of a packaging product.

The biomass polyolefin has a melt flow rate (MFR) of 0.1 g/10 min to 10 g/10 min, preferably 0.2 g/10 min to 9 g/10 min, more preferably 1 g/10 min to 8.5 g/10 min. The melt flow rate is a value measured by method A under conditions of a temperature of 190°C and a load of 21.18 N in the method specified in JIS K7210-1995. If the MFR of the biomass polyolefin is 0.1 g/10 min or more, the extrusion load during molding can be reduced. Also, if the MFR of the biomass polyolefin is 10 g/10 min or less, the mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be increased.

Suitable biomass polyolefins include biomass-derived low-density polyethylene manufactured by Braskem (product name: SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree 95%), biomass-derived low-density polyethylene manufactured by Braskem (product name: SPB681, density: 0.922 g/cm ³ , MFR: 3.8 g/10 min, biomass degree 95%), and biomass-derived linear low-density polyethylene manufactured by Braskem (product name: SLL118, density: 0.916 g/cm ³ , MFR: 1.0 g/10 min, biomass degree 87%).

Examples of the above-mentioned fossil fuel-derived thermoplastic resins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, and ionomers.

The sealant layer 12 preferably has a biomass ratio of 5% or more, more preferably 5% to 60%, and even more preferably 10% to 60%. If the biomass ratio is within the above range, the amount of fossil fuel used can be reduced, and the environmental burden can be reduced.

The sealant layer 12 may be a single layer or a multilayer. When the sealant layer uses a biomass polyolefin as described above, the sealant layer may have three layers: an inner layer, an intermediate layer, and an outer layer. In that case, it is preferable that the intermediate layer is a layer made of biomass polyolefin or a layer made of a mixture of biomass polyolefin and a conventionally known polyolefin derived from fossil fuels, and the inner layer and the outer layer are conventionally known polyolefins derived from fossil fuels.

The sealant layer 12 preferably has a thickness of 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and even more preferably 30 μm or more and 150 μm or less.

[Second plastic film]
Various plastics such as polyethylene, polypropylene, polyamide, polyvinyl chloride, polystyrene, polyester, etc. can be used as the material of the second plastic film 14. The second plastic film 14 may or may not contain a biomass-derived component.

When the second plastic film 14 contains a biomass-derived component, the second plastic film 14 may contain the biomass polyester described in the first plastic film 111, or may contain the biomass polyolefin described in the sealant layer 12.

When the second plastic film 14 contains a biomass-derived component, the biomass content in the second plastic film 14 is 5% or more, preferably 10% or more and 30% or less, and more preferably 15% or more and 25% or less.

When the second plastic film 14 includes a stretched polyester film such as a stretched polyethylene terephthalate film or a stretched polybutylene terephthalate film, the thickness of the second plastic film 14 is, for example, 9 μm or more and 25 μm or less. When the second plastic film 14 includes a stretched polyamide film such as a stretched nylon film, the thickness of the second plastic film 14 is, for example, 15 μm or more and 25 μm or less. When the second plastic film 14 includes a stretched polypropylene film, the thickness of the second plastic film 14 is, for example, 20 μm or more and 100 μm or less. When the second plastic film 14 includes a polyethylene film, the thickness of the second plastic film 14 is, for example, 20 μm or more and 150 μm or less.

[Adhesive layer]
The first adhesive layer 13 is a layer that bonds the film including the sealant layer 12 to another film. In the examples shown in Figs. 2 to 5, the first adhesive layer 13 bonds the film including the sealant layer 12 to the film including the vapor-deposited film 11. In the example shown in Fig. 6, the first adhesive layer 13 bonds the film including the sealant layer 12 to the film including the second plastic film 14. When the sealant layer 12 is formed by extrusion molding on the film including the vapor-deposited film 11 or on the film including the second plastic film 14, the packaging material 10 does not need to include the first adhesive layer 13. For example, in the example shown in Fig. 1, the sealant layer 12 is formed by extrusion molding on the anchor coat layer 17 provided on the vapor-deposited film 11, so that the packaging material 10 does not include the first adhesive layer 13.

The second adhesive layer 15 is a layer that bonds the film including the second plastic film 14 to the film including the vapor-deposited film 11, as shown in Figures 4 to 6.

The adhesive layers such as the first adhesive layer 13 and the second adhesive layer 15 are adhesive layers or adhesive resin layers. For example, in the example shown in FIG. 2, the first adhesive layer 13 is an adhesive resin layer. Also, in the example shown in FIG. 3, the first adhesive layer 13 is an adhesive layer. In the examples shown in FIGS. 4 to 6, the first adhesive layer 13 and the second adhesive layer 15 may be adhesive layers or adhesive resin layers. The adhesive layer and adhesive resin layer will be described below.

The adhesive layer can be formed by a conventional method, such as the dry lamination method. When two layers are bonded by the dry lamination method, the adhesive layer is formed by applying an adhesive to the surface of the layer to be laminated and drying it. The adhesive to be applied can be, for example, a one-component or two-component cured or non-cured vinyl, (meth)acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, or other solvent, water-based, or emulsion adhesive. A two-component cured adhesive can be a cured product of a polyol and an isocyanate compound. The above-mentioned lamination adhesive can be applied by, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fountain method, a transfer roll coating method, or other methods. The adhesive layer after drying has a thickness of, for example, 1 μm to 10 μm, preferably 2 μm to 5 μm.

The adhesive layer may contain a biomass-derived component. For example, when the adhesive layer contains a cured product of a polyol and an isocyanate compound, at least one of the polyol and the isocyanate compound may contain a biomass-derived component. This can further improve the biomass content of the packaging material 10.

The adhesive resin layer includes a thermoplastic resin. The adhesive resin layer can be formed by a conventional method such as a melt extrusion lamination method or a sand lamination method. Thermoplastic resins that can be used for the adhesive resin layer include polyethylene resins, polypropylene resins, or cyclic polyolefin resins, or copolymer resins, modified resins, or mixtures (including alloys) that contain these resins as the main components. Examples of polyolefin resins include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), ethylene-α-olefin copolymers polymerized using a metallocene catalyst, random or block copolymers of ethylene and polypropylene, ethylene-vinyl acetate copolymers (EVA), ethylene-acrylic acid copolymers (EAA), ethylene-ethyl acrylate copolymers (EEA), ethylene-methacrylic acid copolymers (EMAA), ethylene-methyl methacrylate copolymers (EMMA), ethylene-maleic acid copolymers, ionomer resins, and acid-modified polyolefin resins obtained by modifying the above-mentioned polyolefin resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid in order to improve adhesion between layers. In addition, resins obtained by graft-polymerizing or copolymerizing unsaturated carboxylic acids, unsaturated carboxylic anhydrides, and ester monomers with polyolefin resins can be used. These materials can be used alone or in combination of two or more. Examples of cyclic polyolefin resins that can be used include cyclic polyolefins such as ethylene-propylene copolymers, polymethylpentene, polybutene, and polynorbornene. These resins can be used alone or in combination of two or more. The adhesive resin layer has a thickness of, for example, 5 μm to 50 μm, preferably 10 μm to 30 μm.

The polyethylene resin may be one that uses biomass-derived ethylene as a monomer unit, as described for the sealant layer 12. This can further improve the biomass content of the packaging material 10.

[Anchor coat layer]
The anchor coat layer 17 is a layer formed by applying an anchor coat agent onto a predetermined layer or film and drying it. The anchor coat layer can increase the adhesion between the predetermined layer or film on which the anchor coat layer is provided and a layer formed by extrusion on the predetermined layer or film. The anchor coat layer after drying has a thickness of, for example, 0.1 μm to 1 μm, preferably 0.3 μm to 0.5 μm.

When the first adhesive layer 13 is an adhesive resin layer, for example, as shown in Fig. 2, an anchor coat layer 17 can be provided on the deposited film 11 or on a printed layer 18 provided on the deposited film 11. This can increase the adhesion of the first adhesive layer 13 to the deposited film 11 or the printed layer 18.
When the sealant layer 12 is formed by extrusion molding, for example, as shown in Fig. 1, an anchor coat layer 17 can be provided on the deposited film 11 or on a printed layer 18 provided on the deposited film 11. This can enhance the adhesion of the sealant layer 12 to the deposited film 11 or the printed layer 18.

The anchor coating agent may be any resin with a heat resistance of 135°C or higher, such as vinyl modified resin, epoxy resin, urethane resin, polyester resin, polyethyleneimine, etc., but it is particularly preferable to use an anchor coating agent that is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups in the structure and an isocyanate compound as a curing agent. A silane coupling agent may also be used as an additive, and nitrocellulose may also be used in combination to increase heat resistance.

The anchor coat layer may contain a biomass-derived component. For example, when the anchor coat layer contains a cured product of a polyol and an isocyanate compound, at least one of the polyol and the isocyanate compound may contain a biomass-derived component. This can further improve the biomass content of the packaging material 10.

[Printed layer]
The printing layer 18 is a layer on which any desired printed pattern such as letters, numbers, pictures, figures, symbols, patterns, etc. is formed for decoration, display of contents, display of expiration date, display of manufacturer, seller, etc., and for imparting aesthetics. The printing layer 18 can be provided as necessary, for example, on a film including the deposition film 11 or a film including the second plastic film 14. The printing layer 18 may be provided on the entire surface of the film, or on a part of it. The printing layer 18 can be formed using a conventionally known pigment or dye, and the method of forming the printing layer is not particularly limited.

The printing layer 18 preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and even more preferably 1 μm or more and 3 μm or less.

The printed layer 18 may contain a biomass-derived component. For example, when the printed layer 18 contains a cured product of a polyol and an isocyanate compound, at least one of the polyol and the isocyanate compound may contain a biomass-derived component.

<Method of manufacturing packaging material>
Next, an example of a method for producing the packaging material 10 will be described. First, an example of a method for producing the vapor-deposited film 11 will be described.

(Production process of vapor-deposited film)
First, a first plastic film 111 is prepared. Then, a transparent deposition layer 112 containing aluminum oxide is formed on the surface of the first plastic film 111. Fig. 7 is a diagram showing an example of a film forming apparatus 60. The film forming apparatus 60 and a film forming method using the film forming apparatus 60 will be described below.

As shown in FIG. 7, in the film forming apparatus 60, partition walls 85a to 85c are formed in the decompression chamber 62. The partition walls 85a to 85c form the substrate transport chamber 62A, the plasma pretreatment chamber 62B, and the film forming chamber 62C. In particular, the plasma pretreatment chamber 62B and the film forming chamber 62C are formed as spaces surrounded by the partition walls and the partition walls 85a to 85c, and each chamber further has an exhaust chamber formed inside as necessary.

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 plasma pretreatment roller 70 that transports the first plastic film 111 to be pretreated and enables plasma treatment is provided so that a portion of the roller 70 is exposed to the substrate transport chamber 62A. The first plastic film 111 moves to the plasma pretreatment chamber 62B while being wound up.

The plasma pretreatment chamber 62B and the deposition chamber 62C are provided adjacent to the substrate transport chamber 62A, and the first plastic film 111 can be moved without being exposed to the atmosphere. The pretreatment chamber 62B and the substrate transport chamber 62A are connected by a rectangular hole, through which a part of the plasma pretreatment roller 70 protrudes to the substrate transport chamber 62A side, and a gap is opened between the wall of the transport chamber and the pretreatment roller 70, and the first plastic film 111 can be moved from the substrate transport chamber 62A to the deposition chamber 62C through the gap. The same structure is also formed between the substrate transport chamber 62A and the deposition chamber 62C, and the first plastic film 111 can be moved without being exposed to the atmosphere.

The substrate transport chamber 62A is provided with a winding roller as a winding means for winding up the first plastic film 111, which has a vapor deposition film formed on one side and has been moved again to the substrate transport chamber 12A by the deposition roller 75, into a roll, so that the first plastic film 111, which has a vapor deposition film formed on it, can be wound up.

When manufacturing a deposition film 11 having an aluminum oxide deposition film, the plasma pretreatment chamber 62B is configured to separate the space where the plasma is generated from other areas and to efficiently evacuate the opposing space, which makes it easier to control the plasma gas concentration and improves productivity. The pretreatment pressure formed by reducing the pressure can be set and maintained at approximately 0.1 Pa to 100 Pa. In particular, the treatment pressure of the oxygen plasma pretreatment to achieve a preferred transformation rate in the transition region of the aluminum oxide deposition film is preferably 1 Pa to 20 Pa, or less, and may be 10 Pa or less, or 5 Pa or less. The range of the pretreatment pressure can be determined by any combination of the lower limit candidate value and the upper limit candidate value described above.

The transport speed of the first plastic film 111 is not particularly limited, but from the viewpoint of production efficiency, it can be at least 200 to 1000 m/min. In particular, the transport speed for oxygen plasma pretreatment is preferably 300 to 800 m/min in order to obtain the transformation rate in the transition region of the aluminum oxide vapor deposition film.

The plasma pretreatment roller 70 constituting the plasma pretreatment device is intended to prevent shrinkage or damage of the first plastic film 111 due to heat during plasma treatment by the plasma pretreatment means, and to apply oxygen plasma P uniformly and widely to the first plastic film 111. 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 control medium circulating inside the pretreatment roller.

The plasma pretreatment means includes a plasma supply means and a magnetic forming means. The plasma pretreatment means cooperates with the plasma pretreatment roller 70 to confine the oxygen plasma P near the surface of the first plastic film 111.

The plasma pretreatment means is provided so as to cover a portion of the pretreatment roller 70. Specifically, the plasma supply means 72 and the magnetic field forming means 73 constituting the plasma pretreatment means are arranged along the surface near the outer periphery of the pretreatment roller 70. The plasma supply means 72 includes a plasma supply nozzle that supplies plasma raw material gas. The magnetic field forming means 73 has a magnet or the like to promote the generation of plasma P. The plasma pretreatment means also has an electrode 71 to which a voltage is applied between the pretreatment roller 70. Note that, in FIG. 7, an example is shown in which the electrode 71 and the plasma supply means 72 are separate members, but this is not limiting. Although not shown, the electrode 71 and the plasma supply means 72 may be configured as an integrated member.

By generating plasma P in the space between the pretreatment roller 70 and the magnetic forming means 73 and forming an area of high plasma density near the surface of the pretreatment roller 70 and the first plastic film 111, oxygen plasma pretreatment can be performed on the inner surface of the first plastic film 111 to form a plasma-treated surface.

The plasma supply means 72 of the plasma pretreatment means includes a raw material volatilization supply device 68 connected to a plasma supply nozzle provided outside the decompression chamber 62, and a raw material gas supply line that supplies raw material gas from the device. The plasma raw material gas to be supplied is oxygen alone or a mixed gas of oxygen gas and an inert gas, which is supplied from a gas storage section through a flow controller while the gas flow rate is measured. The inert gas may be one or a mixed gas of two or more types selected from the group consisting of argon, helium, and nitrogen.

These supplied gases are mixed in a predetermined ratio as necessary to form a plasma raw material gas alone or a mixed gas for plasma formation, which is then supplied to the plasma supply means. The single or mixed gas is supplied to the plasma supply nozzle of the plasma supply means, and supplied near the outer periphery of the pretreatment roller 70 where the supply port of the plasma supply nozzle opens. The nozzle opening is directed toward the first plastic film 111 on the pretreatment roller 70, and is arranged and configured so that oxygen plasma P can be diffused and supplied uniformly over the entire surface of the first plastic film 111. This allows uniform plasma pretreatment to be performed on a large area of the first plastic film 111.

In order to set the transformation rate of the transition region of the aluminum oxide vapor deposition film to 5% or more and 60% or less as described above, the mixture ratio of oxygen gas and the inert gas (oxygen gas/inert gas) in the oxygen plasma pretreatment is preferably 1/1 or more, may be 3/2.5 or more, or may be 3/2 or more. The mixture ratio of oxygen gas and the inert gas (oxygen gas/inert gas) is preferably 6/1 or less, may be 3/1 or less, or may be 5/2 or less. By setting the mixture ratio to 1/1 or more and 6/1 or less, the film formation energy of the vapor deposition aluminum on the plastic film substrate increases, and by setting it to 3/2 or more and 5/2 or less, aluminum hydroxide is formed near the interface of the substrate, that is, the transformation rate of the transition region decreases. The range of the mixture ratio of oxygen gas and the inert gas (oxygen gas/inert gas) can be determined by any combination of the above-mentioned lower limit candidate value and upper limit candidate value.

The electrode 71 functions as an opposing electrode for the pretreatment roller 70. The plasma raw material gas supplied is excited by the potential difference caused by the high-frequency voltage, low-frequency voltage, etc. supplied between the electrode 71 and the pretreatment roller 70, and plasma P is generated and supplied.

Specifically, the electrode 71 is a plasma pretreatment roller that is installed as a plasma power source, and an AC voltage with a frequency of 10 Hz to 2.5 GHz is applied between the opposing electrode, and input power control or impedance control, etc., can be performed to apply any voltage between the plasma pretreatment roller 70. The film forming device 60 is equipped with a power source 82 that can apply a bias voltage that makes the oxygen plasma P, which can be processed to physically or chemically modify the surface properties of the first plastic film 111, a positive potential.

The plasma intensity per unit area is preferably 50 W·sec/m ² or more and 8000 W·sec/m ² or less. If it is 50 W·sec/m ² or less, the effect of the plasma pretreatment is not observed, and if it is 8000 W·sec/m ² or more, the first plastic film 111 tends to deteriorate due to the plasma, such as wear, damage, coloring, and baking of the first plastic film 111. In particular, the plasma intensity per unit area is preferably 100 W·sec/m ² or more. The plasma intensity per unit area is preferably 1000 W·sec/m ² or less, more preferably 500 W·sec/m ² or less, and may be 300 W·sec/m ² or less. By applying the above-mentioned plasma intensity with a bias voltage perpendicular to the first plastic film 111, the adhesion with the aluminum oxide vapor deposition film can be stably improved. The range of plasma intensity per unit area may be defined by any combination of the lower limit candidate values and upper limit candidate values described above.

The magnetic forming means 73 may be one in which an insulating spacer and a base plate are provided inside a magnet case, and a magnet is provided on this base plate. An insulating shield plate may be provided on the magnet case, and an electrode may be attached to this insulating shield plate. The magnet case and the electrode are electrically insulated, and even if the magnet case is installed and fixed inside the reduced pressure chamber 62, the electrode can be at an electrically floating level. By providing a magnet, reactivity near the surface of the first plastic film 111 is increased, making it possible to form a good plasma pre-treated surface at high speed.

Preferably, the magnet is configured so that the magnetic flux density at the surface of the first plastic film 111 is between 10 Gauss and 10,000 Gauss. If the magnetic flux density at the surface of the first plastic film 111 is 10 Gauss or more, it is possible to sufficiently increase the reactivity near the surface of the first plastic film 111, and a good pre-treated surface can be formed at high speed.

Next, the film formation chamber 62C and the film formation process in the film formation chamber 62C will be described. The film formation device 60 has a film formation roller 75 arranged in the reduced pressure film formation chamber 62C, and a target of the vapor deposition film formation means 74 arranged opposite the film formation roller 75. The film formation roller 75 wraps and transports the first plastic film 111 with the treatment surface of the first plastic film 111, which has been pretreated in the plasma pretreatment device, facing outward. In the film formation process, the target of the vapor deposition film formation means 74 is evaporated to form an aluminum oxide film on the surface of the first plastic film 111.

The deposition film forming means 74 is, for example, a resistance heating type, and uses an aluminum metal wire as an evaporation source for aluminum, and supplies oxygen to oxidize the aluminum vapor, forming an aluminum oxide deposition film on the surface of the first plastic film 111.

The thickness of the transparent deposition layer 112 including the deposition film of aluminum oxide formed as described above is preferably 3 nm or more, and may be 8 nm or more, or 10 nm or more. The thickness of the transparent deposition layer 112 is preferably 50 nm or less, and may be 30 nm or less, 20 nm or less, 15 nm or less, or 14 nm or less. The range of the thickness of the transparent deposition layer 112 can be determined by any combination of the lower limit candidate value and the upper limit candidate value described above. Within this range, the barrier properties can be maintained. However, if the deposition film of aluminum oxide is very thin, it becomes difficult to calculate the transformation rate of the transition region by TOF-SIMS measurement.

Next, a method for forming the gas barrier coating film 113 on the transparent deposition layer 112 will be described. First, the above-mentioned metal alkoxide, silane coupling agent, hydroxyl group-containing water-soluble resin, reaction accelerator (sol-gel catalyst, acid, etc.), and organic solvent such as water as a solvent, methyl alcohol, ethyl alcohol, isopropanol, etc., are mixed to prepare a coating agent for the gas barrier coating film made of a resin composition.

Next, the above-mentioned gas barrier coating agent is applied onto the transparent vapor deposition layer 112 by a conventional method and dried. This drying step causes the condensation or co-condensation reaction to proceed further, forming a coating film. The above-mentioned coating operation may be further repeated on the first coating film to form multiple coating films consisting of two or more layers.

Furthermore, the film is heat-treated for 3 seconds to 10 minutes at a temperature in the range of 20 to 200°C, preferably 50 to 180°C, and at a temperature below the softening point of the resin constituting the base layer. This allows a gas barrier coating film 113 made of the coating agent for gas barrier coating film to be formed on the transparent deposition layer 112. In this way, a deposition film 11 having a first plastic film 111, a transparent deposition layer 112, and a gas barrier coating film 113 can be produced.

(Lamination process of other films or layers)
Next, a method for producing the above-mentioned packaging material 10 by laminating other films or layers onto the vapor-deposited film 11 will be described.

An example of a method for producing the packaging material 10 shown in Figure 1 will be described. First, a vapor-deposited film 11 is prepared, and a printed layer 18 is formed on the gas barrier coating film 113 of the vapor-deposited film 11, for example, by gravure printing. Next, an anchor coat layer 17 is provided on the printed layer 18. After that, a sealant layer 12 is formed on the anchor coat layer 17 by melt extrusion lamination. In this case, the sealant layer 12 contains, for example, low-density polyethylene. In this manner, the packaging material 10 shown in Figure 1 can be obtained.

Next, an example of a method for producing the packaging material 10 shown in FIG. 2 will be described. First, a vapor-deposited film 11 is prepared, and a printed layer 18 is formed on the gas barrier coating film 113 of the vapor-deposited film 11, for example, by gravure printing. Next, an anchor coat layer 17 is provided on the printed layer 18. In addition, a film constituting the sealant layer 12 is prepared. After that, a film including the vapor-deposited film 11 and a film constituting the sealant layer 12 are bonded together via a first adhesive layer 13 made of an adhesive resin layer by sand lamination. In this manner, the packaging material 10 shown in FIG. 2 can be obtained.

Next, an example of a method for producing the packaging material 10 shown in FIG. 3 will be described. First, a vapor-deposited film 11 is prepared, and a printing layer 18 is formed on the gas barrier coating film 113 of the vapor-deposited film 11, for example, by gravure printing. A film constituting the sealant layer 12 is also prepared. Then, a film including the vapor-deposited film 11 and a film constituting the sealant layer 12 are bonded together via a first adhesive layer 13 made of an adhesive layer by a dry lamination method. In this manner, the packaging material 10 shown in FIG. 3 can be obtained.

Next, an example of a method for producing the packaging material 10 shown in FIG. 4 will be described. First, a vapor-deposited film 11 is prepared, and a printed layer 18 is formed on the gas barrier coating film 113 of the vapor-deposited film 11, for example, by gravure printing. A second plastic film 14 is also prepared. Then, a film including the vapor-deposited film 11 and the second plastic film 14 are bonded to each other via a second adhesive layer 15 made of an adhesive layer by a dry lamination method. A film constituting the sealant layer 12 is also prepared. Then, a laminate including the vapor-deposited film 11 and the second plastic film 14 and a film constituting the sealant layer 12 are bonded to each other via a first adhesive layer 13 made of an adhesive layer by a dry lamination method. In this manner, the packaging material 10 shown in FIG. 4 can be obtained.
Alternatively, after bonding the deposited film 11 and the film constituting the sealant layer 12, the laminate including the deposited film 11 and the sealant layer 12 may be bonded to the second plastic film 14.

Next, an example of a method for producing the packaging material 10 shown in FIG. 5 will be described. First, the second plastic film 14 is prepared, and the printing layer 18 is formed on the second plastic film 14, for example, by gravure printing. Also, the vapor-deposited film 11 is prepared. Then, by dry lamination, a film including the second plastic film 14 and the vapor-deposited film 11 are bonded via the second adhesive layer 15 consisting of an adhesive layer. Also, a film constituting the sealant layer 12 is prepared. Then, by dry lamination, a laminate including the second plastic film 14 and the vapor-deposited film 11 and a film constituting the sealant layer 12 are bonded via the first adhesive layer 13 consisting of an adhesive layer. In this way, the packaging material 10 shown in FIG. 5 can be obtained.
Alternatively, after the deposition film 11 and the film constituting the sealant layer 12 are bonded together, the laminate including the deposition film 11 and the sealant layer 12 may be bonded to the second plastic film 14 .

Next, an example of a method for producing the packaging material 10 shown in FIG. 6 will be described. First, a vapor-deposited film 11 is prepared, and a printing layer 18 is formed on the gas barrier coating film 113 of the vapor-deposited film 11, for example, by gravure printing. A second plastic film 14 is also prepared. Then, a film including the vapor-deposited film 11 and the second plastic film 14 are bonded to each other via a second adhesive layer 15 made of an adhesive layer by a dry lamination method. A film constituting the sealant layer 12 is also prepared. Then, a laminate including the vapor-deposited film 11 and the second plastic film 14 and a film constituting the sealant layer 12 are bonded to each other via a first adhesive layer 13 made of an adhesive layer by a dry lamination method. In this manner, the packaging material 10 shown in FIG. 6 can be obtained.
Alternatively, after the second plastic film 14 and the film that constitutes the sealant layer 12 are bonded together, a laminate including the second plastic film 14 and the sealant layer 12 and the vapor-deposited film 11 may be bonded together.

<Packaging container>
Examples of packaging products formed using the packaging material 10 include packaging bags, laminated tubes, lid materials, and sheet molded products.

A packaged product comprising the packaging material 10 can be suitably used for packaging various foods and beverages, such as food and beverages, fruit juice, juice, drinking water, alcohol, cooked foods, fish paste products, frozen foods, meat products, stews, mochi, liquid soups such as soup for hot pots, seasonings, liquid detergents, cosmetics such as shampoos, rinses, and conditioners, hygiene products, daily necessities, and chemical products. Specific examples of foods and beverages include coffee, coffee beans, coffee powder, ice cream, gummies, side dishes, pasta sauce, curry, jelly, bacon, chocolate, and chocolate paste. Specific examples of daily necessities include absorbent cotton, masks, bath salts, and powdered milk. In addition, as exemplified in the examples described below, a packaged product comprising the packaging material 10 configured to have heat resistance can be used in applications that contain contents that are to be subjected to heat sterilization treatments such as retort treatment and boiling treatment. Note that retort treatment is a process in which the packaged product is filled with the contents and sealed, and then the packaged product is heated under pressure using steam or heated hot water. The temperature of the retort process is, for example, 120°C or higher. The boiling process is a process in which the contents are filled into a packaged product, the packaged product is sealed, and then the packaged product is heated in a water bath under atmospheric pressure. The temperature of the boiling process is, for example, 90°C or higher and 100°C or lower.

The packaging bag for the packaged product can be produced by folding the packaging material 10 in half, or by preparing two sheets of packaging material 10, overlapping the sealant layer 12 of the front packaging material 10 with the sealant layer 12 of the back packaging material 10 facing each other, and then heat sealing the peripheral edge of the material 10 in various forms, such as a side seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope seal type, hem seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, etc. It is also possible to produce a gusset-type packaging bag by inserting the folded packaging material 10 between the front packaging material 10 and the back packaging material 10 and heat sealing the material 10. It is not necessary that all of the packaging materials 10 constituting the packaging bag are the packaging materials 10 according to the present invention. That is, at least a portion of the packaging material 10 constituting the packaging bag may be a packaging material 10 having a vapor deposition film 11 having a first plastic film 111 containing a biomass-derived component, and the other portion of the packaging material 10 constituting the packaging bag may be a packaging material 10 having a vapor deposition film derived from a fossil fuel.

Heat sealing can be performed by known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, ultrasonic sealing, etc.

Figure 9 is a diagram showing an example in which a packaging container 30 containing packaging material 10 is a packaging bag. The packaging container 30 shown in Figure 9 includes a surface film 34A constituting the surface, a back film 34B constituting the back surface, and a lower film 36 constituting the lower portion 32. The lower film 36 is folded back at fold-back portion 36f and is disposed between the surface film 34A and the back film 34B. In this way, the packaging container 30 shown in Figure 9 is a self-supporting standing pouch with the lower portion configured as a gusset portion.

The inner surfaces of the surface film 34A, the back film 34B, and the lower film 36 are joined together by a seal portion. In the front view of the packaging container 30 such as FIG. 9, the seal portion is hatched. As shown in FIG. 9, the seal portion has an outer edge seal portion that extends along the outer edge of the packaging container 30. The outer edge seal portion includes a lower seal portion 32a that extends to the lower portion 32, and a pair of side seal portions 33a that extend along a pair of side portions 33. In the packaging container 30 before the contents are filled (a state in which the contents are not filled), as shown in FIG. 9, the upper portion 31 of the packaging container 30 is an opening 31b. After the contents are placed in the packaging container 30, the inner surface of the surface film 34A and the inner surface of the back film 34B are joined at the upper portion 31 to form an upper seal portion and seal the packaging container 30.

The terms "surface film", "back film" and "lower film" mentioned above merely divide each film according to its positional relationship, and the method of providing the packaging material 10 when manufacturing the packaging container 30 is not limited by the terms mentioned above. For example, the packaging container 30 may be manufactured using one sheet of packaging material 10 in which the surface film 34A, the back film 34B and the lower film 36 are connected together, or may be manufactured using a total of two packaging materials 10, one sheet of packaging material 10 in which the surface film 34A and the lower film 36 are connected together and one back film 34B, or may be manufactured using a total of three packaging materials 10, one sheet of surface film 34A, one sheet of back film 34B and one sheet of lower film 36.

At least one of the front film 34A, back film 34B and lower film 36 is composed of a packaging material 10 including a vapor deposition film 11 having a first plastic film 111 containing a biomass-derived component. This allows the amount of fossil fuel used to be reduced compared to conventional methods, and reduces the environmental impact. Furthermore, in the vapor deposition film 11 of the packaging material 10, the adhesion between the first plastic film 111 and the transparent vapor deposition layer 112 is improved compared to conventional methods. This allows the barrier properties of the packaging container 30 to be improved compared to conventional methods.

Figure 10 is a diagram showing another example of a packaging container 30 including a packaging material 10. The packaging container 30 shown in Figure 12 differs only in that it further includes a steam release mechanism 40, and other configurations are substantially the same as the packaging container 30 shown in Figure 9. In the packaging container 30 shown in Figure 10, the same parts as those in the packaging container 30 shown in Figure 9 are given the same reference numerals and detailed descriptions are omitted.

As shown in FIG. 10, the packaging container 30 is provided with a steam vent mechanism 40 for releasing steam generated when the contents contained in the storage section 39 are heated to the outside. The steam vent mechanism 40 is configured to communicate between the inside and outside of the packaging container 30 to release steam when the steam pressure reaches or exceeds a predetermined value, and to prevent steam from escaping from any location other than the steam vent mechanism 40.

In the example shown in FIG. 10, the steam release mechanism 40 has a steam release seal portion 41 that protrudes from the side seal portion 33a toward the inside of the packaging container 30, and an unsealed portion 42 that is isolated from the storage portion 39 by the steam release seal portion 41. The unsealed portion 42 is connected to the outside of the packaging container 30. When the pressure in the storage portion 39 increases due to heating in a microwave oven or the like, the steam release seal portion 41 peels off. Steam in the storage portion 39 can escape to the outside of the packaging container 30 through the peeled portion of the steam release seal portion 41 and the unsealed portion 42.

The configuration of the steam release mechanism 40 is not limited to the configuration shown in FIG. 10. The configuration of the steam release mechanism 40 is arbitrary as long as it can connect the storage section 39 to the outside of the packaging container 30 when the steam pressure reaches or exceeds a predetermined value.

In the packaging container 30 shown in FIG. 10, at least one of the front film 34A, back film 34B, and bottom film 36 is composed of a packaging material 10 having an adhesive layer containing a biomass-derived component. This makes it possible to reduce the amount of fossil fuel used compared to conventional methods, thereby reducing the environmental burden. Furthermore, in the vapor deposition film 11 of the packaging material 10, the adhesion between the first plastic film 111 and the transparent vapor deposition layer 112 is improved compared to conventional methods. This makes it possible to improve the barrier properties of the packaging container 30 compared to conventional methods.

Figure 11 is a diagram showing another example of a packaging container 30 including a packaging material 10. The packaging container 30 shown in Figure 11 is substantially the same as the packaging container 30 shown in Figure 9 except that it further includes a spout portion 43. In the packaging container 30 shown in Figure 11, the same parts as those in the packaging container 30 shown in Figure 9 are designated by the same reference numerals and detailed description will be omitted.

As shown in FIG. 11, the spout 43 of the packaging container 30 is a portion through which the contents stored in the storage section 39 pass when the contents are removed. In this case, the contents are a liquid having flowability. The width of the spout 43 is narrower than the width of the storage section 39. This allows the user to accurately determine the pouring direction of the contents poured from the packaging container 30 through the spout 43.

In the example shown in FIG. 11, the spout section 43 is formed by a portion of the front film 34A and the back film 34B. For example, the spout section 43 includes a spout seal section 44 that joins the front film 34A and the back film 34B to define the spout section 43 having a width narrower than the storage section 39. A packaging container 30 having such a spout section 43 is suitable for use as a refill pouch that contains contents such as detergent, shampoo, and conditioner that can be refilled into a bottle.

As long as the contents can be appropriately poured, the configuration of the pouring outlet 43 is not limited to the configuration shown in FIG. 11. For example, the pouring outlet 43 may be a member, such as a spout, separate from the front film 34A and the back film 34B.

In the packaging container 30 shown in FIG. 11, at least one of the front film 34A, back film 34B, and bottom film 36 is composed of a packaging material 10 having an adhesive layer containing a biomass-derived component. This makes it possible to reduce the amount of fossil fuel used compared to conventional methods, thereby reducing the environmental burden. Furthermore, in the vapor deposition film 11 of the packaging material 10, the adhesion between the first plastic film 111 and the transparent vapor deposition layer 112 is improved compared to conventional methods. This makes it possible to improve the barrier properties of the packaging container 30 compared to conventional methods.

Figure 12 is a diagram showing another example of a packaging container 30 including a packaging material 10. The packaging container 30 shown in Figure 12 is a three-sided sealed pouch formed by joining a front film 34A and a back film 34B on three sides along the outer edge. Note that an upper seal portion is formed in the upper portion 31 after the contents are placed in the packaging container 30 through the opening 31b, as in the case of the examples shown in Figures 9 to 11.

In the packaging container 30 shown in FIG. 12, at least one of the front film 34A and the back film 34B is composed of a packaging material 10 having an adhesive layer containing a biomass-derived component. This makes it possible to reduce the amount of fossil fuel used compared to conventional methods, thereby reducing the environmental burden. Furthermore, in the vapor deposition film 11 of the packaging material 10, the adhesion between the first plastic film 111 and the transparent vapor deposition layer 112 is improved compared to conventional methods. This makes it possible to improve the barrier properties of the packaging container 30 compared to conventional methods.

Although not shown, the packaging container 30 may be a four-sided sealed pouch formed by joining the front film 34A and the back film 34B at four sides along the outer edge. As shown in FIG. 13, the packaging container 30 may be a pillow pouch joined at the upper portion 31, the lower portion 32, and the seam portion 38. As shown in FIG. 14, the packaging container 30 may be a side gusset pouch having a joined seam portion 38 and having the side portion 33 folded back at the fold portion 33f.

Figure 15 is a diagram showing an example in which a packaging container 30 containing a packaging material 10 is a container with a lid. The container with a lid includes a container body 45 produced by sheet forming such as drawing, and a lid portion 46 joined to the container body 45.

In the example shown in FIG. 15, for example, the container body 45 is produced by drawing a packaging material 10 including a vapor deposition film 11 having a first plastic film 111 containing a biomass-derived component. This allows the amount of fossil fuel used to be reduced compared to conventional methods, and reduces the environmental impact. Also, in the vapor deposition film 11 of the packaging material 10, the adhesion between the first plastic film 111 and the transparent vapor deposition layer 112 is improved compared to conventional methods. This allows the barrier properties of the container body 45 to be improved compared to conventional methods.

In the example shown in FIG. 15, the lid portion 46 may be formed from a packaging material 10 including a vapor deposition film 11 having a first plastic film 111 containing a biomass-derived component. This allows the amount of fossil fuel used to be reduced compared to conventional methods, and reduces the environmental impact. In addition, in the vapor deposition film 11 of the packaging material 10, the adhesion between the first plastic film 111 and the transparent vapor deposition layer 112 is improved compared to conventional methods. This allows the barrier properties of the lid portion 46 to be improved compared to conventional methods.

Figure 16 is a diagram showing an example in which the packaging container 30 containing the packaging material 10 is a tube. The tube includes a tube body 47 containing the packaging material 10 and a cap 48 attached to the tube body 47.

In the example shown in FIG. 16, the tube body 47 is produced by processing the packaging material 10, which includes a vapor deposition film 11 having a first plastic film 111 containing biomass-derived components, into a cylindrical shape. This allows the amount of fossil fuel used to be reduced compared to conventional methods, and reduces the environmental impact. Furthermore, in the vapor deposition film 11 of the packaging material 10, the adhesion between the first plastic film 111 and the transparent vapor deposition layer 112 is improved compared to conventional methods. This allows the barrier properties of the tube body 47 to be improved compared to conventional methods.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the description of the following examples as long as it does not deviate from the gist of the invention.

[Example A1]
First, a biomass-derived PET film having a thickness of 12 μm was prepared as the first plastic film 111. The biomass-derived PET film was obtained by the following method.

83 parts by mass of terephthalic acid derived from fossil fuels and 62 parts by mass of ethylene glycol derived from biomass (manufactured by India Glycol) were subjected to an esterification reaction by a conventional direct polymerization method, and then a condensation polymerization reaction was carried out under reduced pressure to obtain biomass-derived polyethylene terephthalate. Radiocarbon measurement of the obtained biomass-derived polyethylene terephthalate was performed, and the biomass degree by radiocarbon (C14) measurement was 31.25%.
60 parts by mass of the above biomass-derived polyethylene terephthalate, 30 parts by mass of fossil fuel-derived polyethylene terephthalate, and 10 parts by mass of a master batch containing fossil fuel-derived polyethylene terephthalate were fed to an extruder, extruded into a sheet from a T-die, and cooled and solidified by a cooling roll to obtain an unstretched sheet. The unstretched sheet was then stretched in the longitudinal direction and then in the transverse direction to obtain a biaxially stretched PET film having a thickness of 12 μm. The biomass content of the obtained biaxially stretched PET film was measured to be 18.8%.

Next, using the above-mentioned film forming apparatus 60 shown in Figure 7, an oxygen plasma treatment was performed on the surface of the first plastic film 111 made of the above-mentioned biaxially stretched PET film, and then a transparent vapor deposition layer 112 containing aluminum oxide and having a thickness of 12 nm was formed on the oxygen plasma-treated surface.
(Oxygen plasma pretreatment conditions)
Plasma intensity: 150 W·sec/ ^m2
Mixing ratio of oxygen gas and inert gas: oxygen/argon = 2/1
Voltage applied between pretreatment drum and plasma supply nozzle: 340 V
Pretreatment pressure: 3.8 Pa
(Aluminum oxide film formation conditions)
・Vacuum degree: 8.1×10 ^-2 Pa
Conveying speed: 400 m/min
Oxygen gas supply amount: 20,000 sccm

Subsequently, a gas barrier coating film 113 was formed on the transparent vapor deposition layer 112. 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 a pH of 2.2, and 175 g of tetraethoxysilane as a metal alkoxide and 9.2 g of glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed into the solution while cooling to 10° C. to prepare solution A.
A solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a polymerization degree of 2400 and a saponification value of 99% or more as a water-soluble polymer, 324 g of water, and 17 g of isopropyl alcohol. The solution A and the solution B were mixed in a weight ratio of 6.5:3.5 to obtain a coating agent for a gas barrier coating film.
The above-prepared gas barrier coating film coating agent was applied onto the above-prepared transparent deposition layer 112 by spin coating.
Thereafter, the mixture was heated in an oven at 180° C. for 60 seconds to form a gas barrier coating film 113 having a thickness of about 400 nm on the transparent deposition layer 112. In this manner, a deposition film 11 having the first plastic film 111, the transparent deposition layer 112, and the gas barrier coating film 113 was obtained.

[Example A2]
Except for changing the thickness of the transparent vapor deposition layer 112 to 10 nm, the transparent vapor deposition layer 112 was formed on the first plastic film 111, and the gas barrier coating film 113 was formed on the transparent vapor deposition layer 112 in the same manner as in Example A1. In this manner, a vapor deposition film 11 having the first plastic film 111, the transparent vapor deposition layer 112, and the gas barrier coating film 113 was obtained.

[Example A3]
Except for changing the thickness of the transparent vapor deposition layer 112 to 14 nm, the transparent vapor deposition layer 112 was formed on the first plastic film 111, and the gas barrier coating film 113 was formed on the transparent vapor deposition layer 112 in the same manner as in Example A1. In this manner, a vapor deposition film 11 having the first plastic film 111, the transparent vapor deposition layer 112, and the gas barrier coating film 113 was obtained.

[Reference Example A1]
A transparent deposition layer ¹¹² was formed on a first plastic film 111, and a gas barrier coating film 113 was formed on the transparent deposition layer 112 in the same manner as in Example A1, except that the plasma intensity in the oxygen plasma treatment was set to 1200 W·sec/m2. In this manner, a deposition film 11 having the first plastic film 111, the transparent deposition layer 112, and the gas barrier coating film 113 was obtained.

[Comparative Example A1]
Except for changing the thickness of the transparent vapor deposition layer 112 to 7 nm, the transparent vapor deposition layer 112 was formed on the first plastic film 111, and the gas barrier coating film 113 was formed on the transparent vapor deposition layer 112 in the same manner as in Example A1. In this manner, a vapor deposition film 11 having the first plastic film 111, the transparent vapor deposition layer 112, and the gas barrier coating film 113 was obtained.

[Comparative Example A2]
Except for not carrying out the oxygen plasma pretreatment, a transparent deposition layer 112 was formed on a first plastic film 111, and a gas barrier coating film 113 was formed on the transparent deposition layer 112 in the same manner as in Example A1. In this manner, a deposition film 11 having the first plastic film 111, the transparent deposition layer 112, and the gas barrier coating film 113 was obtained.

[Comparative Example A3]
A transparent deposition layer 112 was formed on a first plastic film 111, and a gas barrier coating film 113 was formed on the transparent deposition layer 112 in the same manner as in Example A1, except that the mixing ratio of oxygen gas and inert gas in the oxygen plasma treatment was oxygen/argon = 4/1. In this manner, a deposition film 11 having the first plastic film 111, the transparent deposition layer 112, and the gas barrier coating film 113 was obtained.

[Comparative Example A4]
A transparent deposition layer 112 was formed on a first plastic film 111, and a gas barrier coating film 113 was formed on the transparent deposition layer 112 in the same manner as in Example A1, except that the pretreatment pressure in the oxygen plasma treatment was set to 50 Pa. In this manner, a deposition film 11 having the first plastic film 111, the transparent deposition layer 112, and the gas barrier coating film 113 was obtained.

The conversion rate was measured for the vapor-deposited films 11 of the above-mentioned Examples A1 to A3 and Comparative Examples A1 to A4. The color tone was also measured for the vapor-deposited films 11 of the above-mentioned Example A1 and Reference Example A1. The oxygen permeability, water vapor permeability, and adhesion strength were also measured for the packaging materials including the vapor-deposited films 11 of the above-mentioned Examples A1 to A3 and Comparative Examples A1 to A2. In the evaluation of adhesion strength, normal peel strength and water-exposed peel strength were measured.

(Metamorphism rate)
While repeatedly performing soft etching at a constant rate on the surface of the gas barrier coating film 113 of the deposition film 11 using a Cs (cesium) ion gun, ions originating from the gas barrier coating film 113, ions originating from the transparent deposition layer 112, and ions originating from the first plastic film 111 were measured using time-of-flight secondary ion mass spectrometry (TOF-SIMS). As a result, a graph was obtained in which the unit of the vertical axis (intensity) is the intensity of the measured ions and the unit of the horizontal axis (cycle) is the number of etchings, as shown in Fig. 7 described above.

The time-of-flight secondary ion mass spectrometer used in the TOF-SIMS was a TOF.SIMS5 manufactured by ION TOF, Inc., and the measurements were performed under the following measurement conditions.
(TOFSIMS measurement conditions)
Primary ion type: _Bi3 ++ (0.2 pA, 100 μs), measurement area: 150×150 ^μm2
Et gun type: Cs (1 keV, 60 nA), Et area: 600×600 μm ² , Et rate: 3 sec/Cycle
In the analysis, it is important to distinguish the ions derived from aluminum oxide from those derived from other components, to select ions with sufficient strength, and in particular to obtain a depth distribution that can be approximately converted into the concentration distribution of elemental bond Al ₂ O ₄ H. Taking these factors into consideration, Cs ions were selected as the ion gun for measuring the ions derived from aluminum oxide, which were the subject of measurement.

Using Cs, etching was performed from the outermost surface of the gas barrier coating film 113, and analysis was performed on the element bonds at the interfaces between the gas barrier coating film 113, the transparent deposition layer 112, and the first plastic film 111, and on the element bonds of the deposition film, and a graph of the measured elements and element bonds was obtained. In the graph, the position where the strength of SiO ₂ (mass number 59.96), a constituent element of the gas barrier coating film 113, is half the strength in the gas barrier coating film 113, was specified as the interface between the gas barrier coating film 113 and the transparent deposition layer 112. In addition, the position where the strength of C ₆ (mass number 72.00), a constituent material of the first plastic film 111, is half the strength in the first plastic film 111, was specified as the interface between the first plastic film 111 and the transparent deposition layer 112. In addition, the distance in the thickness direction between the two interfaces was adopted as the thickness of the transparent deposition layer 112.

Next, a peak representing the measured element bond _Al2O4H (mass number _118.93 ) was obtained, and the region from the peak to the interface was defined as a transition region. However, if the gas barrier coating film ₁₁₃ is composed of a material with the same mass number as _Al2O4H (mass number 118.93), it is necessary to separate the waveform of 118.93.

When the reactants _AlSiO4 and _{hydroxide Al2O4H are} generated at the interface between the gas barrier coating film 113 and the transparent vapor deposition layer 112, they can be separated from the _Al2O4H present at the interface between the first plastic film ₁₁₁ and the transparent vapor deposition layer 112. In this way, the separation of the corrugations can be dealt with appropriately depending on the material of the gas barrier coating film 113.

In waveform separation, for example, the profile of mass number 118.93 obtained by TOF-SIMS can be nonlinearly curve-fitted using a Gaussian function, and overlapping peaks can be separated using the least squares Levenberg Marquardt algorithm.

The transformation rate of the transparent vapor-deposited layer 112 of the vapor-deposited films 11 of Examples A1 to A3 and Comparative Examples A1 to A4 was calculated as (thickness of the transition region W ₁ /thickness of the transparent vapor-deposited layer 112)×100(%). The results are shown in FIGS. 20A and 20B.

(Color)
Using a spectrophotometer (manufactured by Konica Minolta, Inc. [model name: CM-700d]), the L* value, a* value, and b* value in the L*a*b* color system were measured for one measurement sample (first plastic film 111/transparent vapor deposition layer 112/gas barrier coating film 113) made from the vapor deposition film 11. The results are shown in FIG. 20A.

(Adhesion strength)
A 70 μm thick non-oriented polypropylene film (CPP film) and a 15 μm thick stretched nylon film were bonded together by a dry lamination method via a two-component curing polyurethane adhesive to prepare a laminate. In addition, a two-component curing polyurethane adhesive was applied to the gas barrier coating film 113 side of the deposition film 11 of Examples A1 to A3 and Comparative Examples A1 to A2, and a drying treatment was performed to form an adhesive layer on the gas barrier coating film 113. Next, a laminate including a CPP film and a stretched nylon film was bonded to the deposition film 11 via the adhesive layer on the gas barrier coating film 113 of the deposition film 11 by a dry lamination method to prepare a packaging material for evaluation (hereinafter also referred to as a packaging material for evaluation before retort treatment). The layer structure of the packaging material is expressed as follows, from the outside to the inside.
PET film/transparent deposition layer/gas barrier coating film/adhesive layer/stretched nylon film/adhesive layer/CPP film

[Adhesion after retort treatment]
A B5-sized four-sided sealed pouch was produced using the packaging material for evaluation before retort treatment. Then, 100 mL of water was poured into the four-sided sealed pouch from the opening 31b of the upper portion 31, and the upper seal portion 31a was formed to seal the four-sided sealed pouch. Then, the four-sided sealed pouch was subjected to a hot water retort treatment at 135°C for 40 minutes. In the following description, the packaging material constituting the pouch subjected to the hot water retort treatment at 135°C for 40 minutes is also referred to as the packaging material for evaluation after retort treatment.

Next, the packaging materials for evaluation after retort treatment were visually inspected for the presence or absence of delamination. As a result, delamination did not occur in the packaging materials provided with the vapor-deposited film 11 of Examples A1 to A3 and Comparative Example A1, but delamination did occur in the packaging material provided with the vapor-deposited film 11 of Comparative Example A2.

[Normal peel strength after retort treatment]
The packaging material for evaluation after the retort treatment was cut into a 15 mm wide strip to prepare a sample for measuring the normal peel strength after the retort treatment. Then, the adhesion strength between the first plastic film 111 and the transparent deposition layer 112 of the sample was measured in accordance with JIS K6854-2. A tensile tester (manufactured by Orientec Co., Ltd. [model name: Tensilon universal material testing machine]) was used as the measuring device.

In the measurement, first, as shown in FIG. 17, the first sample was peeled off at the interface between the first plastic film 111 and the transparent deposition layer 112 from the end of the long side direction of the sample 100 to a position 15 mm away along the long side direction. Next, as shown in FIG. 18, the first plastic film 111 side and the transparent deposition layer 112 side of the sample 100 were gripped by the grips 81 and 82 of the measuring device, respectively, and pulled at a speed of 50 mm/min in opposite directions (180° peeling: T-shaped peeling method) perpendicular to the surface direction of the part where the first plastic film 111 and the transparent deposition layer 112 are still laminated, and the average value of the tensile force in the stable region (see FIG. 19) was measured. When the pulling started, the distance S between the grips 81 and 82 was 30 mm, and when the pulling ended, the distance S between the grips 81 and 82 was 60 mm. FIG. 19 is a diagram showing the change in tensile force with respect to the distance S between the grips 81 and 82. As shown in FIG. 19, the change in tensile force relative to the distance S passes through a first region and then enters a second region (stable region) where the rate of change is smaller than in the first region.

Peeling of the packaging material for evaluation is believed to occur between the first plastic film 111 and the transparent vapor deposition layer 112, which have the weakest adhesion strength. The average tensile strength in the stable region was measured for five samples 100, and this average was used as the normal peel strength of the packaging material for evaluation. The environment during measurement was a temperature of 23°C and a relative humidity of 50%. The measurement results are shown in Figures 20A and 20B.

[Water-soaked peel strength after retort treatment]
In the same manner as in the measurement of normal peel strength, the packaging material for evaluation after retort treatment was cut into a strip of 15 mm width to prepare a sample for measuring the water-exposed peel strength after retort treatment. Next, the adhesion strength between the first plastic film 111 and the transparent deposition layer 112 of the sample was measured in accordance with JIS K6854-2. A tensile tester (manufactured by Orientec Co., Ltd. [model name: Tensilon universal material testing machine]) was used as the measuring device. In the measurement, the sample 100 was pulled using the grippers 81 and 82 in a state where water was dropped with a dropper on the boundary between the part where the first plastic film 111 and the transparent deposition layer 112 maintain their bonding and the part where the first plastic film 111 and the transparent deposition layer 112 are peeled off. The other measurement methods and the calculation method of the peel strength are the same as in the case of normal peel strength. The measurement results are shown in Figures 20A and 20B.

(Oxygen permeability)
In the same manner as in the measurement of adhesion strength, the above-mentioned "packaging material for evaluation before retort treatment" and "packaging material for evaluation after retort treatment" including the deposition film 11 of Examples A1 to A3 or Comparative Examples A1 to A2 were prepared. Then, samples for measuring oxygen permeability were produced from each of the evaluation packaging materials.
The evaluation sample before retort treatment was one in which the evaluation packaging material was subjected to aging treatment for 48 hours at 36° C. The evaluation sample after retort treatment was one obtained by, as in the case of measuring the adhesion strength, sealing 100 mL of water in a four-side sealed pouch made from the evaluation packaging material, subjecting the four-side sealed pouch to hot water retort treatment at 135° C. for 40 minutes, and then cutting out the packaging material on one side of the four-side sealed pouch.

Next, the five types of measurement samples of Examples A1 to A3 and Comparative Examples A1 to A2 were each set so that the first plastic film was on the oxygen supply side, and the oxygen permeability was measured in accordance with JIS K 7126 B method under measurement conditions of 23°C and 90% RH atmosphere. The measurement device used was an oxygen permeability measuring device (manufactured by Modern Control (MOCON) [model name: OX-TRAN 2/21]). The results are shown in Figures 20A and 20B.

(Water vapor permeability)
The water vapor permeability was measured using the same samples as those used for the measurement of oxygen permeability. Specifically, each measurement sample was set so that the first plastic film was on the sensor side, and the water vapor permeability was measured in accordance with JIS K 7126 B method under measurement conditions of 40°C and 100% RH atmosphere. As the measurement device, a water vapor permeability measurement device (a measurement device manufactured by MOCON [model name: PERMATRAN 3/33]) was used. The results are shown in Figures 20A and 20B.

As shown in FIG. 20A, in the deposition films 11 of Examples A1 to A3, the conversion rate of the transition region of the transparent deposition layer 112 was in the above-mentioned range of 5% to 60% and specifically in the range of 10% to 25%. The conversion rate tended to decrease as the thickness of the transparent deposition layer 112 increased. On the other hand, as shown in FIG. 20B, in the deposition films 11 of Comparative Examples A1 to A2, the element bond Al ₂ O 4 _H peak was too small to be separated, so the conversion rate of the transition region could not be calculated. In addition, in the deposition films 11 of Comparative Examples A3 to A4, the plasma discharge was not stable and plasma pretreatment could not be performed, so the conversion rate of the transition region could not be calculated. From these facts, in order to produce the deposition films 11 so that the conversion rate of the transition region of the transparent deposition layer 112 is in the range of 5% to 60%, it is preferable to satisfy all of the following manufacturing conditions I to IV.
Manufacturing Condition I
The transparent vapor deposition layer has a thickness of 8 nm or more.
Manufacturing Conditions II
The mixture ratio of oxygen gas to inert gas in the oxygen plasma treatment is 3/2.5 or more and 3/1 or less.
Manufacturing Condition III
The pretreatment pressure in the oxygen plasma treatment is 1 Pa or more and 20 Pa or less.
Manufacturing Condition IV
The plasma intensity in the oxygen plasma treatment is 100 W·sec/m ² or more and 500 W·sec/m ² or less.

As shown in FIG. 20A, the b* value of the vapor-deposited film 11 of Reference Example A1 was greater than the b* value of the vapor-deposited film 11 of Example A1. In addition, in the vapor-deposited film 11 of Reference Example A1, it was visually confirmed that the first plastic film 111 was discolored. The above-mentioned manufacturing conditions I to IV are considered to be useful in suppressing discoloration.

As shown in Fig. 20A, the packaging materials including the deposited films 11 of Examples A1 to A3 had oxygen permeabilities of 0.3 cc/ ^m2 /24 hr/atm or less and water vapor permeabilities of 0.6 g/ ^m2 /24 hr or less both before and after retort treatment. On the other hand, as shown in Fig. 20B, the samples of the packaging materials including the deposited films 11 of Comparative Examples A1 to A2 after retort treatment had oxygen permeabilities of 0.8 cc/ ^m2 /24 hr/atm or more and water vapor permeabilities of 1.0 g/ ^m2 /24 hr or more. In particular, the sample of the packaging material including the deposited film 11 of Comparative Example A1 after retort treatment had oxygen permeabilities of 1.0 cc/ ^m2 /24 hr/atm or more and water vapor permeabilities of 2.0 g/ ^m2 /24 hr or more. From these findings, it can be said that a transformation rate in the transition region of the transparent vapor deposition layer 112 within the range of 5% or more and 60% or less can effectively function in maintaining barrier properties against gases such as oxygen and water vapor.

As shown in Figure 20A, in the packaging materials including the vapor-deposited films 11 of Examples A1 to A3, no delamination occurred after retort treatment. The normal peel strength was 3.0 N/15 mm or more, and the water-exposed peel strength was 2.0 N/15 mm or more. On the other hand, as shown in Figure 20B, in the packaging materials including the vapor-deposited films 11 of Comparative Examples A1 to A2, delamination occurred after retort treatment. From these findings, it can be said that a transformation rate in the transition region of the transparent vapor-deposited layer 112 in the range of 5% to 60% can be effective in suppressing the occurrence of delamination in packaging materials including the vapor-deposited films 11.

[Example B1]
A deposited film 11 produced as in Example A1 was prepared as the deposited film 11. Then, a printed layer 18 was formed on the gas barrier coating film 113 of the deposited film 11 by gravure printing. Then, an anchor coat layer 17 was formed on the printed layer 18. Then, molten low-density polyethylene was extruded onto the anchor coat layer 17 to form a sealant layer 12 having a thickness of 30 μm. In this manner, a packaging material 10 having the layer structure shown in FIG. 1 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio PET12/Deposition/Barrier/Print/AC/PE(1)30
"Bio-PET" means PET film containing biomass-derived components. "Vapor deposition" means aluminum oxide film. "Barrier" means gas barrier coating film. "Print" means printed layer. "AC" means anchor coat layer. "PE(1)" means polyethylene layer formed by melt extrusion lamination method. Numbers mean layer thickness (unit: μm).

Next, the packaging material 10 was used to produce a three-sided sealed pouch as shown in FIG. 12 and a pillow pouch as shown in FIG. 13. The three-sided sealed pouch and pillow pouch can contain, for example, snacks.

[Example B2]
As in Example B1, a printed layer 18 was formed on the gas barrier coating film 113 of the vapor deposition film 11, and an anchor coat layer 17 was formed on the printed layer 18. In addition, a film including the vapor deposition film 11 and a film constituting the sealant layer 12 were bonded together by a sand lamination method via a first adhesive layer 13 made of an adhesive resin layer. A polyethylene film (thickness 30 μm) was used as the film of the sealant layer 12. Polyethylene was used as the adhesive resin of the first adhesive layer 13. The thickness of the adhesive resin layer was 12 μm. In this way, a packaging material 10 having the layer structure shown in FIG. 2 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio PET 12/Deposition/Barrier/Print/AC/Adhesive resin 15/PE(2)30
"Adhesive resin" means an adhesive resin layer. "PE(2)" means a polyethylene film.

Next, the packaging material 10 was used to produce a three-sided sealed pouch as shown in FIG. 12 and a pillow pouch as shown in FIG. 13. The three-sided sealed pouch and pillow pouch can be used for food, toiletries, medical and pharmaceutical products, etc.

[Example B3]
As in Example B1, a printed layer 18 was formed on the gas barrier coating film 113 of the vapor-deposited film 11. The film including the vapor-deposited film 11 and the film constituting the sealant layer 12 were bonded together by dry lamination via the first adhesive layer 13 made of an adhesive layer. A non-oriented polypropylene film (thickness 25 μm) was used as the film for the sealant layer 12. In this manner, a packaging material 10 having the layer structure shown in FIG. 3 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio-PET12/Deposition/Barrier/Printing/Adhesive/CPP25
"Adhesive" means adhesive layer. "CPP" means unoriented polypropylene film.

Next, the packaging material 10 was used to produce a three-sided sealed pouch as shown in FIG. 12 and a pillow pouch as shown in FIG. 13. The three-sided sealed pouch and pillow pouch can contain chocolate, rice snacks, etc.

[Example B4]
A packaging material 10 was produced in the same manner as in Example B3, except that a polyethylene film (thickness: 40 μm) was used as the sealant layer 12.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio-PET12/Deposition/Barrier/Printing/Adhesive/PE(2)40

Next, the pillow pouch shown in FIG. 13 and the side gusset pouch shown in FIG. 14 were made using the packaging material 10. The pillow pouch and the side gusset pouch can store wet tissues, pickles, etc.

[Example B5]
As in Example B1, a printed layer 18 was formed on the gas barrier coating film 113 of the vapor deposition film 11. The film including the vapor deposition film 11 and the film constituting the sealant layer 12 were bonded together by a dry lamination method via a first adhesive layer 13 made of an adhesive layer. A polyethylene film (thickness 30 μm) was used as the film of the sealant layer 12. The laminate having the vapor deposition film 11 and the polyethylene film was bonded together with a stretched polypropylene film (thickness 20 μm) functioning as the second plastic film 14 via a second adhesive layer 15 made of an adhesive layer by a dry lamination method. In this way, a packaging material 10 having the layer structure shown in FIG. 4 was produced. In the vapor deposition film 11, the transparent vapor deposition layer 112 is located on the surface of the first plastic film 111 on the stretched polypropylene film side.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP20/adhesive/print/barrier/vapor deposition/bio-PET12/adhesive/PE(2)30
"OPP" means oriented polypropylene film.

Next, the packaging material 10 was used to create the lid 46 of the lidded container shown in FIG. 15. The lidded container can contain, for example, bacon.

[Example B6]
A packaging material 10 was prepared in the same manner as in Example B5, except that a polyethylene film (thickness 150 μm) was used as the second plastic film 14 and a polyethylene film (thickness 150 μm) was used as the sealant layer 12.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PE(2)150/adhesive/printing/barrier/vapor deposition/bio-PET12/adhesive/PE(2)150

Next, the tube shown in FIG. 16 was made using the packaging material 10. The tube can contain, for example, chocolate.

[Example B7]
A stretched nylon film having a thickness of 15 μm was prepared as the second plastic film 14. A non-stretched polypropylene film having a thickness of 60 μm was prepared as the sealant layer 12. The stretched nylon film and the non-stretched polypropylene film were then bonded together by a dry lamination method via a second adhesive layer 15 made of an adhesive layer. A vapor-deposited film 11 was also prepared, and a printed layer 18 was formed on the gas barrier coating film 113 of the vapor-deposited film 11. Then, a film including the vapor-deposited film 11 and a laminate having a stretched nylon film and a non-stretched polypropylene film were bonded together by a dry lamination method via a first adhesive layer 13 made of an adhesive layer. In this manner, a packaging material 10 having a layer structure shown in FIG. 6 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio-PET12/Deposition/Barrier/Printing/Adhesive/Nylon15/Adhesive/CPP60

Next, the packaging material 10 was used to produce a standing pouch as shown in FIG. 9 and a pouch for use in a microwave oven as shown in FIG. 10. The standing pouch and the pouch for use in a microwave oven can contain, for example, prepared foods.

[Example B8]
A non-stretched polypropylene film having a thickness of 60 μm was prepared as the sealant layer 12. Next, the non-stretched polypropylene film and the deposition film 11 were bonded together by a dry lamination method via a first adhesive layer 13 made of an adhesive layer so that the transparent deposition layer 112 was located on the surface of the first plastic film 111 opposite to the sealant layer 12. In addition, a stretched PET film having a thickness of 12 μm was prepared as the second plastic film 14, and a printing layer 18 was formed on the stretched PET film. Then, the stretched PET film and a laminate having the deposition film 11 and the non-stretched polypropylene film were bonded together by a dry lamination method via a second adhesive layer 15 made of an adhesive layer. In this way, a packaging material 10 having a layer structure shown in FIG. 5 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/printing/adhesive/barrier/vapor deposition/bio-PET12/adhesive/CPP60

Next, the packaging material 10 was used to produce a standing pouch as shown in FIG. 9 and a pouch for use in a microwave oven as shown in FIG. 10. The standing pouch and the pouch for use in a microwave oven can contain, for example, prepared foods.

[Example B9]
A packaging material 10 was produced in the same manner as in Example B7, except that a polyethylene film having a thickness of 50 μm was used as the sealant layer 12.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio-PET12/Deposition/Barrier/Printing/Adhesive/Nylon15/Adhesive/PE(2)50

Next, a standing pouch as shown in FIG. 9 was made using the packaging material 10. The standing pouch can contain, for example, prepared food.

[Example B10]
A packaging material 10 was produced in the same manner as in Example B7, except that a polyethylene film having a thickness of 120 μm was used as the sealant layer 12.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio-PET12/Deposition/Barrier/Printing/Adhesive/Nylon15/Adhesive/PE(2)120

Next, the refill pouch shown in FIG. 11 was made using the packaging material 10. The refill pouch can contain liquid detergent, shampoo, rinse, conditioner, etc.

Figure 21 shows the layer structure of the packaging materials for Examples B1 to B10.

Reference Signs List 10 Packaging material 11 Deposition film 111 First plastic film 112 Transparent deposition layer 113 Gas barrier coating film 12 Sealant layer 13 First adhesive layer 14 Second plastic film 15 Second adhesive layer 17 Anchor coat layer 18 Printed layer 30 Packaging container 31 Upper portion 32 Lower portion 33 Side portion 34A Surface film 34B Back surface film 36 Lower film 36a Lower seal portion 38 Joint portion 39 Storage portion 40 Steam release mechanism 41 Steam release seal portion 42 Unsealed portion 43 Spout portion 44 Spout seal portion 45 Container body 46 Lid portion 47 Tube body 48 Cap

Claims (9)

A packaging material comprising a vapor-deposited film and a sealant layer located on an inner side of the vapor-deposited film,
the deposition film comprises a stretched first plastic film, a transparent deposition layer provided on the first plastic film, the transparent deposition layer containing aluminum oxide and having a thickness of 10 nm or more, and a gas barrier coating film provided on the transparent deposition layer;
the first plastic film comprises a biomass-derived polyester;
the transparent deposition layer includes a transition region;
the transition region is a region between the position of a peak of elemental bond Al 2 O 4 H transformed into _aluminum hydroxide, detected by etching the vapor-deposited film from the gas barrier coating film side using time-of-flight secondary ion mass spectrometry (TOF _- SIMS), and the interface between the transparent vapor-deposited layer and the first plastic film;
A packaging material, wherein the ratio of the thickness of the transition region to the thickness of the transparent vapor deposition layer is 10% or more and 25% or less. The packaging material according to claim 1, further comprising an anchor coat layer located between the vapor deposition film and the sealant layer. The packaging material according to claim 1, further comprising an adhesive resin layer located between the vapor deposition film and the sealant layer. The packaging material of claim 1, further comprising an adhesive layer located between the vapor deposition film and the sealant layer. The packaging material according to claim 1, further comprising a second plastic film positioned outside the first plastic film. The packaging material of claim 1, further comprising a second plastic film positioned between the first plastic film and the sealant layer. The packaging material according to claim 1 , wherein the transparent vapor deposition layer has a thickness of 10 nm or more and 14 nm or less. The thickness of the transition region of the transparent deposition layer is 7.89 nm or more and 12.11 nm or less;
The packaging material according to claim 1 , wherein the transparent vapor deposition layer has a thickness of 1.89 nm or more and 2.35 nm or less in a portion other than the transition region. A packaging container made from the packaging material according to any one of claims 1 to 8 .