JP2020055640A - Packaging material and packaging container - Google Patents

Abstract

To provide a packaging material having a gas barrier property and capable of reducing an environmental load.SOLUTION: A packaging material comprises a vapor deposition film and a sealant layer located inside the vapor deposition film. The vapor deposition film has a first plastic film, a transparent vapor deposition layer containing aluminum oxide, and a gas barrier coating film. The first plastic film contains polyester derived from biomass. The transparent vapor deposition layer includes a transition region. The transition region is a region between a peak position of an element bind AlOH to be converted to aluminum hydroxide and an interface between the transparent vapor deposition layer and the first plastic film, which can be detected by etching the vapor deposition film using the flight time type secondary ion mass spectrometry from the gas barrier coating film side. A ration of a thickness of the transition region to a thickness of the transparent vapor deposition layer ranges from 5% to 60%.SELECTED DRAWING: Figure 1

Description

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

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

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

  Furthermore, in recent years, on a plastic substrate, for example, a silicon oxide, a transparent barrier film having a configuration in which a vapor deposition layer of an inorganic oxide such as aluminum oxide is provided, or a vapor deposition layer of a metal such as aluminum is provided. Further, barrier films and the like have been proposed. For example, Patent Document 1 proposes that a barrier film is produced by forming a vapor-deposited layer of an inorganic oxide on a nylon film.

JP 2007-303000 A

  In recent years, with the increasing demand for the establishment of a recycling-based society, in the materials field, it has been desired to break away from fossil fuels as well as energy. For example, it is desired to reduce the amount of fossil fuel used by using biomass-derived raw materials for the production of packaging materials.

  An object of the present invention is to provide a packaging material that can effectively solve such a problem.

The present invention is a packaging material including a vapor-deposited film and a sealant layer positioned on the inner side of the vapor-deposited film, wherein the vapor-deposited film has a stretched first plastic film and a stretched first plastic film. Provided, a transparent vapor-deposited layer containing aluminum oxide, and a gas barrier coating film provided on the transparent vapor-deposited layer, wherein the first plastic film contains biomass-derived polyester, and the transparent vapor-deposited layer is The transition region is detected by etching the vapor-deposited film from the gas barrier coating film side using time-of-flight secondary ion mass spectrometry (TOF-SIMS). the position of the peak of the element coupling Al ₂ O ₄ H which transformed into aluminum, the transparent deposition layer and said first plastic film A region between the interface, the ratio of the thickness of the transition region to the thickness of the transparent deposition layer is 60% or less than 5%, a packaging material.

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

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

  The packaging material according to the present invention may further include an adhesive layer located between the vapor-deposited 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 include a second plastic film located between the first plastic film and the sealant layer.

  The present invention is a packaging container composed of the packaging material described above.

  According to the present invention, it is possible to provide a packaging material having gas barrier properties and capable of reducing environmental load.

It is sectional drawing which shows an example of the packaging material by embodiment. It is sectional drawing which shows an example of the packaging material by embodiment. It is sectional drawing which shows an example of the packaging material by embodiment. It is sectional drawing which shows an example of the packaging material by embodiment. It is sectional drawing which shows an example of the packaging material by embodiment. It is sectional drawing which shows an example of the packaging material by embodiment. It is a figure which shows an example of the result of having analyzed the transparent vapor deposition layer with the time-of-flight secondary ion mass spectrometer. It is a figure showing an example of the film-forming device which forms a transparent vapor deposition layer on the 1st plastic film. It is a front view showing an example of a packaging container. It is a front view showing an example of a packaging container. It is a front view showing an example of a packaging container. It is a front view showing an example of a packaging container. It is a front view showing an example of a packaging container. It is a front view showing an example of a packaging container. It is sectional drawing which shows an example of a packaging container. It is a front view showing an example of a packaging container. It is sectional drawing which shows the sample for measuring the peeling strength of a packaging material. It is a figure showing signs that a peeling strength of a sample of a packaging material is measured. FIG. 6 is a diagram showing a change in tensile force with respect to a distance between a pair of grips for pulling a part of a sample to measure peel strength. It is a figure which shows the measurement result of Examples A1-A3 and Reference Example A1. It is a figure showing the measurement result of comparative examples A1-A4. It is a figure which shows the layer constitution of the packaging material of Examples B1-B10.

<Packaging materials>
The laminate constituting the packaging material according to the present invention includes a vapor deposition film and a sealant layer located inside the vapor deposition film. The inner side means the side of the content contained in the packaged product in the packaged product formed from the packaging material. Further, the outer side means a side away from the contents contained in the packaged product.

  In the present invention, the biomass degree described below is preferably 3% or more, more preferably 5% or more and 60% or less, and still more preferably 10% or more and 60% or less in the entire laminate constituting the packaging material. . When the biomass degree is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

  FIG. 1 is a sectional view showing an example of a packaging material 10 according to an embodiment of the present invention. The packaging material 10 includes, in order from the outside to the 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 has a first plastic film 111, a transparent vapor deposition layer 112, and a gas barrier coating film 113 in this order from the outside to the inside. The first plastic film 111 forms the outer surface 10y of the packaging material 10, and the sealant layer 12 forms the inner surface 10x of the packaging material 10.

  In the present application, the outer surface is the outermost surface of the packaging material 10, and the inner surface is the innermost surface of the packaging material 10. In the present application, the term “order” in descriptions such as “provide in this order” and “laminated in order” indicates an order in a direction from the outside to the inside unless otherwise specified.

  FIG. 2 is a sectional view showing an example of the packaging material 10 according to the embodiment of the present invention. The packaging material 10 includes a vapor deposition film 11, a printing layer 18, an anchor coat layer 17, a first adhesive layer 13, and a sealant layer 12 in this order. The vapor deposition film 11 has 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 forms the outer surface 10y of the packaging material 10, and the sealant layer 12 forms the inner surface 10x of the packaging material 10.

  FIG. 3 is a cross-sectional view illustrating an example of the packaging material 10 according to the embodiment of the present invention. The packaging material 10 includes a vapor deposition film 11, a printing layer 18, a first adhesive layer 13, and a sealant layer 12 in this order. The vapor deposition film 11 has 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 forms the outer surface 10y of the packaging material 10, and the sealant layer 12 forms the inner surface 10x of the packaging material 10.

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

  FIG. 5 is a cross-sectional view illustrating an example of the packaging material 10 according to the embodiment of the present invention. The packaging material 10 includes 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 in this order. The vapor deposition film 11 has a gas barrier coating film 113, a transparent vapor deposition layer 112, and a first plastic film 111 in this order. The second plastic film 14 forms the outer surface 10y of the packaging material 10, and the sealant layer 12 forms the inner surface 10x of the packaging material 10.

  FIG. 6 is a cross-sectional view illustrating an example of the packaging material 10 according to the embodiment of the present invention. The packaging material 10 includes 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 in this order. The vapor deposition film 11 has 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 forms the outer surface 10y of the packaging material 10, and the sealant layer 12 forms the inner surface 10x of the packaging material 10.

  Hereinafter, a film and a layer constituting the packaging material 10 will be described.

[Evaporated film]
The vapor deposition film 11 has a first plastic film 111, a transparent vapor deposition layer 112 provided on the first plastic film 111, and a gas barrier coating film 113 provided on the transparent vapor deposition layer 112. Hereinafter, each layer will be described.

(1st 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 the transverse direction (TD) orthogonal to the machine direction.

  The first plastic film 111 is a resin composition containing 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 dicarboxylic acid derived from fossil fuel. Examples of the polyester contained in the resin composition of the first plastic film 111 include 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 to 95% by mass of biomass polyester, preferably 50% by mass to 90% by mass, based on the entire resin composition of the first plastic film 111. Including.

  Since biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol, a polyester film synthesized using biomass-derived ethylene glycol is mechanically different from a conventional fossil fuel-derived polyester film. There is no inferiority in physical properties such as characteristics. Therefore, since the first plastic film 111 and the packaging material 10 including the same have the layer made of the carbon neutral material, the first plastic film 111 and the packaging material including the same are manufactured as compared with the stretched plastic film manufactured from the raw material obtained from the conventional fossil fuel. As a result, the amount of fossil fuel used can be reduced, and the environmental burden can be reduced.

  Ethylene glycol derived from biomass is derived from ethanol (biomass ethanol) produced from biomass such as sugarcane and corn. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, for example, by producing ethylene glycol via ethylene oxide. Further, commercially available biomass ethylene glycol may be used. For example, biomass ethylene glycol commercially available from Indiaglycol Co., Ltd. can be suitably used.

  As the dicarboxylic acid unit of the polyester, a dicarboxylic acid derived from a fossil fuel is used. As the dicarboxylic acid, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and a derivative thereof can be used. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl esters of the aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl. Esters and the like. Of these, terephthalic acid is preferred, and dimethyl terephthalate is preferred as the derivative of the aromatic dicarboxylic acid.

  The resin composition forming the first plastic film 111 may be a fossil fuel-derived polyester, a fossil fuel-derived polyester product recycled polyester, a biomass-derived polyester product recycled polyester, or the like at a ratio of 5% by mass to 45% by mass. One or more kinds may be included.

Since carbon dioxide in the atmosphere contains ¹⁴ C at a constant rate (105.5 pMC), plants that take in carbon dioxide in the atmosphere and grow, for example, corn, also have a ¹⁴ C content of about 105.5 pMC. It is known that It is also known that fossil fuels hardly contain ¹⁴ C. Therefore, the ratio of carbon derived from biomass can be calculated by measuring the ratio of ¹⁴ C contained in all the carbon atoms in the polyester.

The biomass degree can be used as an index indicating the ratio of the biomass-derived raw material. In the present embodiment, the “degree of biomass” indicates the weight ratio of the biomass-derived component. Taking polyethylene terephthalate as an example, polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1. Is used, since the weight ratio of the biomass-derived component in polyethylene terephthalate is 31.25%, the biomass degree is 31.25% (molecular weight of ethylene glycol derived from biomass / molecular weight of 1 unit of polyester polymerization). = 60/192).
Since the weight ratio of the biomass-derived component is 0% in the fossil fuel-derived polyester, the biomass degree of the fossil fuel-derived polyester is 0%. In the present embodiment, the degree of biomass in the first plastic film 111 is preferably 5.0% or more, more preferably 10.0% or more, in order to exhibit the effect as a carbon offset material. preferable. In addition, the degree of biomass in the first plastic film 111 may be 30.0% or less from the viewpoint of the film manufacturing process and physical properties.

  The first plastic film 111 can be formed by using the resin composition described above and forming a film by a T-die method, for example. Specifically, after drying the above-described resin composition, the resin composition is supplied to a melt extruder heated to a temperature of from the melting point of the resin composition (Tm) to Tm + 70 ° C. to melt the resin composition. For example, a film can be formed by extruding a sheet from a die such as a T-die, and rapidly cooling and solidifying the extruded sheet with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

  The film obtained as described above is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known 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 machine direction to form a machine-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. or more and 100 ° C. or less. Further, the magnification of the longitudinal stretching is preferably 2.5 times or more and 4.2 times or less, 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 and it is difficult to obtain a good film.

  The longitudinally stretched film is successively subjected to transverse stretching, heat fixation, and heat relaxation processing steps to form a biaxially stretched film. The transverse stretching is usually performed in a temperature range of 50 ° C or more and 100 ° C or less. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, though it depends on the required characteristics of the application. If the ratio is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film. If the ratio exceeds 5.0 times, breakage tends to occur during film formation.

  After the transverse stretching, a heat setting treatment is performed. The preferable temperature range of the heat setting is Tg of PET + 70 to Tm-10 ° C. Further, the heat fixing time is preferably from 1 second to 60 seconds. Further, for applications requiring a reduction in the heat shrinkage, a heat relaxation treatment may be performed as necessary.

The thickness of the first plastic film 111 obtained as described above is arbitrary depending on its use. The thickness of the first plastic film 111 is, for example, 5 μm or more, and may be 8 μm or more. Further, the thickness of the first plastic film 111 is, for example, 100 μm or less, may be 50 μm or less, may be 30 μm or less, or may be 25 μm or less. The range of the thickness of the first plastic film 111 can be determined by any combination of the above-described lower limit candidate value and upper limit candidate value. Further, the breaking strength of the film in the MD direction 5 kgf / mm ₂ or more 40 kgf / mm ² or less, at 35 kgf / mm ² or less 5 kgf / mm ² or more in the TD direction, elongation at break, 50% MD direction Not less than 350% and not less than 50% and not more than 300% in the TD direction. The shrinkage when left in a temperature environment of 150 ° C. for 30 minutes is 0.1% or more and 5% or less.

(Transparent evaporation layer)
The transparent deposition layer 112 is a thin film of an inorganic oxide containing aluminum oxide as a main component. The transparent vapor-deposited layer 112 may include an aluminum compound such as aluminum oxide, aluminum nitride, carbide, hydroxide alone or a mixture thereof. Further, the transparent evaporation layer 112 contains an aluminum compound as a main component, and includes silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, zirconium oxide, and the like. Or a metal oxide, a metal nitride, a carbide thereof, a mixture thereof, or the like.

(Gas barrier coating film)
The gas barrier coating film 113 is for mechanically and chemically protecting the transparent vapor-deposited layer 112 and improving the barrier properties of the vapor-deposited film 11, and is laminated so as to be in contact with the transparent vapor-deposited layer 112. The gas barrier coating film 113 is a cured film formed by a coating agent for a gas barrier coating film made of a resin composition containing a metal alkoxide, a hydroxyl group-containing water-soluble resin, and a silane coupling agent added as needed. is there.

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

  The thickness of the gas barrier coating film 113 is preferably 100 nm or more and 800 nm or less. When the thickness is smaller than the above range, the barrier effect of the gas barrier coating film 113 tends to be insufficient, and when the thickness is larger than the above range, rigidity and brittleness are likely to increase.

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

  Specific examples of the metal atom represented by M in the metal alkoxide include silicon, zirconium, titanium, aluminum, tin, lead, borane, and the like. For example, an alkoxy group in which M is Si (silicon) Preference is given to using silanes.

In general formula (I), specific examples of OR _2, a hydroxyl group, a methoxy group, an ethoxy group, n- propoxy group, n- butoxy group, i- propoxy group, a butoxy group, 3-methacryloxy groups. Examples include an alkoxy group such as a 3-acryloxy group and a phenoxy group, and a phenoxy group.

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, and a γ-glycol. Examples include a sidoxypropyl group, a methacryl group, and a γ-aminopropyl group.

  Specific examples of alkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyltributoxysilane, methyltriphenoxysilane, phenylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxy Silane, isopropyltriethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyl Methoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, 1,6-bis Various alkoxysilanes such as (trimethoxysilyl) hexane, and phenoxysilanes are exemplified. In the present embodiment, polycondensates of these alkoxysilanes can also be used, and specifically, for example, polytetramethoxysilane, polytetraethoxysilane, and the like can be used.

  The silane coupling agent is used to adjust the cross-link density of the cured film made of the metal alkoxide and the hydroxyl group-containing water-soluble resin to obtain a film having barrier properties and heat-resistant water treatment properties.

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

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

In the general formula (II), R ₄ is, for example, an organic functional group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms which may have a branch, or 3 to 4 carbon atoms. 7 is an alkoxyalkyl group. 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 methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, ethyl propyl ether, ethyl isopropyl ether, methyl butyl ether, ethyl butyl ether, methyl sec-butyl ether, and ethyl sec. And a group in which one hydrogen atom has been removed from a linear or branched ether such as -butyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, and the like. (OR ₄ ) may be the same or different.

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

  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 in the system using trialkoxysilane. Become. Therefore, while being excellent as a film having gas barrier properties and heat-resistant water treatment properties, it becomes a flexible cured film and also has excellent flex resistance, so that a packaging material using the barrier film has gas barrier properties even after the Gelboflex test. Hard to deteriorate.

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

  The hydroxyl group-containing water-soluble resin can be dehydrated and co-condensed with a metal alkoxide, and has a saponification degree of preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, and more preferably 99% or more and 100% or less. % Is more preferable. If the saponification degree is smaller than the above range. The hardness of the barrier coating layer tends to decrease.

  Specific examples of the hydroxyl group-containing water-soluble resin include, for example, a polyvinyl alcohol resin, an ethylene-vinyl alcohol copolymer, a polymer of a bifunctional phenol compound and a bifunctional epoxy compound, and the like. They may be used, or two or more kinds may be used as a mixture, or may be used after copolymerization. Among these, polyvinyl alcohol is particularly preferable because of its excellent flexibility and affinity, and polyvinyl alcohol-based resin is preferable.

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

(Preferred configuration of vapor-deposited film)
Next, a preferred configuration of the vapor deposition film 11 in the thickness direction will be described with reference to FIG. FIG. 7 shows a time-of-flight secondary ion mass spectrometry (TOF-SIMS) while repeatedly soft-etching the surface of the vapor-deposited film 11 on the gas barrier coating film 113 side by a Cs (cesium) ion gun at a constant speed. FIG. 6 is a diagram showing the results of measuring ions originating from the transparent vapor deposition layer 112 and ions originating from the first plastic film 111, using FIG. The transparent vapor-deposited layer 112 of the vapor-deposited film 11 includes a transition region specified by a graph analysis diagram shown in FIG.

The transition region is a position T _{2 of} a peak T _{2 of} an element-bonded Al ₂ O ₄ H converted into aluminum hydroxide, which is detected by etching the vapor-deposited film 11 from the gas barrier coating film 113 side using TOF-SIMS. When a region between the interface T ₁ of the transparent deposition layer 112 and the first plastic film 111. Interface T ₁ of the transparent deposition layer 112 and the first plastic film 111, the intensity of the graph element C ₆ is identified as a position that is half the strength of the element C ₆ in the first plastic film 111. 7, reference numeral W ₁ represents the thickness of the transition region.

Transparent ratio of thickness W ₁ of the transition region to the thickness of the deposited layer 112 (hereinafter, referred to as modified rate of the transition region) is desirably 60% or less than 5%. By setting the transformation rate to 5% or more and 60% or less, when the packaging material including the vapor deposition film 11 is subjected to a sterilization treatment such as a boil treatment or a retort treatment, the barrier property of the vapor deposition film 11 against water vapor is reduced. Can be suppressed. The retort process is a process of filling the contents in a packaging container, sealing the packaging container, and then heating the packaging container in a pressurized state. The temperature of the retort treatment is, for example, 120 ° C. or higher. The boiling process is a process of filling the contents into a packaging container, sealing the packaging container, and then immersing the packaging container in hot water at atmospheric pressure. The temperature of the boiling process is, for example, 90 ° C. or more and 100 ° C. or less. In addition, even if the packaging material containing the vapor deposition film 11 in which the transformation rate of the transition region is 5% or more and 60% or less is used in a packaging container that is not subjected to a sterilization treatment such as a boil treatment or a retort treatment, It can function effectively in maintaining barrier properties against gases such as oxygen and water vapor. The metamorphic rate may be 30% or less, 25% or less, or 20% or less. Moreover, the metamorphosis rate may be 10% or more, and may be 15% or more. The range of the metamorphic rate can 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 deposition layer 112 is subjected to mechanical and chemical stress by heat. Therefore, in order to suppress a decrease in adhesion and barrier properties, it is important to firmly cover 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 a plastic film due to its chemical structure, and has a high water vapor barrier property because it forms a network itself and is dense. However, the bonding structure based on hydrogen bonding between the aluminum hydroxide and the plastic film is liable to be broken microscopically due to thermal stress. Further, the aluminum hydroxide network easily penetrates into the film due to the affinity of the water molecule and the aluminum hydroxide at the grain interface.

In this embodiment mode, in order to minimize the transition region at the interface between the aluminum oxide and the plastic film formed by aluminum hydroxide in the deposited aluminum oxide film, attention should be paid to element-bonded Al ₂ O ₄ H, and the amount of Al ₂ O ₄ H should be controlled. Therefore, aluminum hydroxide generated from element-bonded Al ₂ O ₄ H due to thermal stress is suppressed, and the ratio of the aluminum oxide film containing relatively little aluminum hydroxide is increased, so that a microscopic vapor deposition film is formed by water molecules due to thermal stress. It is intended to suppress destruction and interfacial destruction with plastic films. Thereby, it is possible to provide the vapor deposition film 11 having unprecedented adhesion and barrier properties.

  The aluminum oxide vapor-deposited film can be formed by forming a vapor-deposited film on the surface of a plastic film that has been pretreated with oxygen plasma. As a vapor deposition method for forming a vapor deposition film, various vapor deposition methods among physical vapor deposition and chemical vapor deposition can be applied. The physical vapor deposition method can be selected from the group consisting of a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, and a cluster ion beam method, and the chemical vapor deposition method includes a plasma CVD method, a plasma polymerization method, and a thermal polymerization method. It can be selected from the group consisting of a CVD method and a catalytic reaction type CVD method. In this embodiment mode, a physical vapor deposition method is preferable.

  A specific example of a method for obtaining the graph of FIG. 7 will be described. First, etching is performed from the outermost surface of the gas barrier coating film 113 using Cs, and element bonding at the interface between the gas barrier coating film 113, the transparent vapor deposition layer 112, and the film such as the first plastic film 111, and the element of the vapor deposition film Perform binding analysis. Thereby, the graph shown in FIG. 7 can be obtained.

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

First, in the graph, a position where the intensity of SiO ₂ (mass number 59.96), which is a constituent element of the gas barrier coating film 113, is half of the intensity of the gas barrier coating film 113 is defined by the gas barrier coating film 113 and the transparent vapor deposition. It is specified as an interface of the layer 112. Next, the position where the strength of C ₆ (mass number 72.00), which is a constituent material of the first plastic film 111, becomes half of the strength of the first plastic film 111 is defined by the first plastic film 111 and the transparent evaporation layer 112. Specified as the interface of In addition, the distance in the thickness direction between the two interfaces is adopted as the thickness of the transparent vapor deposition layer 112.

Next, a peak representing the measured element-bonded Al ₂ O ₄ H (mass number 118.93) is determined, and a region from the peak to the interface is defined as a transition region. However, when the component of the gas barrier coating film 113 is made of a material having the same mass number as Al ₂ O ₄ H (mass number 118.93), it is necessary to separate the waveform of 118.93.

When reactants AlSiO ₄ and hydroxide Al ₂ O ₄ H are generated at the interface between the gas barrier coating film 113 and the transparent deposition layer 112, the interface between the first plastic film 111 and the transparent deposition layer 112 is formed. it can be separated Al ₂ O ₄ H present in the. Thus, the separation of the waveform can be appropriately dealt with according to the material of the gas barrier coating film 113.

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

[Sealant layer]
The sealant layer 12 is a layer that forms the inner surface 10x of the packaging material 10 and contains a thermoplastic resin. The sealant layer 12 may be formed by extruding a thermoplastic resin onto another film, or may be formed by bonding 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 deposition film 11. In the examples shown in FIGS. 2 to 6, the sealant layer 12 is a layer formed by bonding a film containing a thermoplastic resin to a film containing the vapor-deposited film 11 or a film containing the second plastic film 14. is there.

  The sealant layer 12 may include a biomass-derived component or may not include 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 using the following biomass polyolefin. When the sealant layer 12 is formed from a material that does not contain a biomass-derived component, the sealant layer 12 can be formed using a conventionally known thermoplastic resin derived from a fossil fuel.

  Biomass polyolefin is a polymer of a monomer containing an olefin such as ethylene derived from biomass. Since an olefin derived from biomass is used as a monomer as a raw material, a polyolefin polymerized is derived from biomass. In addition, the raw material monomer of polyolefin does not need to contain 100 mass% of olefins derived from biomass.

  For example, biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use fermented ethanol derived from biomass obtained from plant raw materials. The plant material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beet, and manioc can be mentioned.

  The biomass-derived fermented ethanol refers to ethanol purified by contacting a culture solution containing a carbon source obtained from a plant material with a microorganism-derived microorganism or a product derived from a crushed product thereof, producing the ethanol, and then purifying the ethanol. For purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method of adding benzene, cyclohexane or the like and causing azeotropic distillation, or removing water by membrane separation or the like can be mentioned.

  The monomer which is a raw material of the biomass polyolefin may further include a monomer of ethylene derived from fossil fuel and / or a monomer of α-olefin derived from fossil fuel, and may further include a monomer of α-olefin derived from biomass.

  The α-olefin is not particularly limited in the number of carbon atoms, but usually one having 3 to 20 carbon atoms can be used, and is preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerizing ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, and therefore can be more flexible than a simple linear one.

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

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

Biomass polyolefin, preferably 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.912 g / cm ³ or more 0.928 g / cm ³ or less, more preferably 0.915 g / cm ³ or more 0 It has a density of 0.925 g / cm ³ or less. The density of the biomass polyolefin is a value measured according to the method specified in Method A of JIS K7112-1980 after performing annealing described in JIS K6760-1995. When 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 packaged product. In addition, when 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 packaged product.

  The biomass polyolefin has a melt flow of from 0.1 g / 10 min to 10 g / 10 min, preferably from 0.2 g / 10 min to 9 g / 10 min, more preferably from 1 g / 10 min to 8.5 g / 10 min. It has a rate (MFR). The melt flow rate is a value measured by the method A at a temperature of 190 ° C. and a load of 21.18 N in a 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. When the MFR of the biomass polyolefin is 10 g / 10 minutes 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 (trade name: SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree 95%) manufactured by Braskem. Biomass-derived low-density polyethylene manufactured by Braskem (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 minutes, biomass degree 95%), biomass-derived linear chain manufactured by Braskem Low-density polyethylene (trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1.0 g / 10 minutes, biomass degree 87%) and the like.

  As the thermoplastic resin derived from the fossil fuel, for example, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, Examples include an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, and an ionomer.

  The sealant layer 12 preferably has a biomass degree of 5% or more, more preferably 5% or more and 60% or less, and still more preferably 10% or more and 60% or less. When the biomass degree is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

  The sealant layer 12 may be a single layer or a multilayer. When the biomass polyolefin as described above is used for the sealant layer, it may be a sealant layer including three layers of an inner layer, an intermediate layer, and an outer layer. In that case, the intermediate layer may be a layer composed of biomass polyolefin or a layer composed of a mixture of biomass polyolefin and a conventionally known polyolefin derived from a fossil fuel, and the inner layer and the outer layer may be a conventionally known polyolefin derived from a fossil fuel. preferable.

  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 still more preferably 30 μm or more and 150 μm or less.

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

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

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

  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, not less than 20 μm and not more than 100 μm. When the second plastic film 14 includes a polyethylene film, the thickness of the second plastic film 14 is, for example, not less than 20 μm and not more than 150 μm.

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

  As shown in FIGS. 4 to 6, the second adhesive layer 15 is a layer for bonding a film including the second plastic film 14 and a film including the vapor deposition film 11.

  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. Further, in the example shown in FIG. 3, the first adhesive layer 13 is an adhesive layer. In the example shown in FIGS. 4 to 6, the first adhesive layer 13 and the second adhesive layer 15 may be an adhesive layer or an adhesive resin layer. Hereinafter, each of the adhesive layer and the adhesive resin layer will be described.

  The adhesive layer can be formed by a conventionally known method, for example, a dry lamination method. When two layers are bonded by a dry lamination method, the adhesive layer is formed by applying an adhesive to the surface of the layer on the side to be laminated and drying. Examples of the adhesive to be applied include one-pack or two-pack hardened or non-hardened vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, and rubber. An adhesive such as a solvent type, an aqueous type, or an emulsion type can be used. As the two-part curable adhesive, a cured product of a polyol and an isocyanate compound can be used. As a coating method of the above-mentioned laminating adhesive, for example, it can be applied by a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, a transfer roll coating method, or another method. . The adhesive layer after drying has a thickness of, for example, 1 μm or more and 10 μm or less, preferably 2 μm or more and 5 μm or less.

  The adhesive layer may include 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. Thereby, the biomass degree of the packaging material 10 can be further improved.

  The adhesive resin layer contains a thermoplastic resin. The adhesive resin layer can be formed by a conventionally known method, for example, a melt extrusion lamination method or a sand lamination method. Examples of the thermoplastic resin that can be used for the adhesive resin layer include a polyethylene resin, a polypropylene resin, or a cyclic polyolefin resin, or a copolymer resin, a modified resin, or a mixture (including alloys) containing these resins as a main component. ) Can be used. Examples of the polyolefin resin include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), polypropylene (PP), and metallocene catalyst. Ethylene-α-olefin copolymer, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene / maleic acid copolymer, ionomer resin, interlayer adhesion To improve the above-mentioned polyolefin resin , It can be used acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and an acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as itaconic acid. In addition, a resin obtained by graft-polymerizing or copolymerizing an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or an ester monomer with the polyolefin resin can be used. These materials can be used alone or in combination of two or more. As the cyclic polyolefin-based resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, and polynorbonene can be used. 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 or more and 50 μm or less, preferably 10 μm or more and 30 μm or less.

  In addition, as the above-mentioned polyethylene-based resin, a resin using ethylene derived from biomass described in the sealant layer 12 as a monomer unit may be used. Thereby, the biomass degree of the packaging material 10 can be further improved.

[Anchor coat layer]
The anchor coat layer 17 is a layer formed by applying and drying an anchor coat agent on a predetermined layer or film. The anchor coat layer can enhance the adhesion between a predetermined layer or film provided with the anchor coat layer and a layer formed by extrusion on the predetermined layer or film. The dried anchor coat layer has a thickness of, for example, 0.1 μm or more and 1 μm or less, preferably 0.3 μm or more and 0.5 μm or less.

When the first adhesive layer 13 is an adhesive resin layer, for example, as shown in FIG. 2, the anchor coat layer 17 can be provided on the vapor deposition film 11 or on a printing layer 18 provided on the vapor deposition film 11. Thereby, the adhesion of the first adhesive layer 13 to the deposition film 11 or the print layer 18 can be improved.
When the sealant layer 12 is formed by extrusion molding, for example, as shown in FIG. 1, the anchor coat layer 17 can be provided on the vapor deposition film 11 or on the printing layer 18 provided on the vapor deposition film 11. Thereby, the adhesiveness of the sealant layer 12 to the deposition film 11 or the printing layer 18 can be improved.

  Examples of the anchor coating agent include any resin having a heat-resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, and a polyethylene imine. An anchor coating agent which is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. Further, a silane coupling agent may be used as an additive thereto, and nitrified cotton may be used in combination to increase heat resistance.

  The anchor coat layer may include 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. Thereby, the biomass degree of the packaging material 10 can be further improved.

[Printing layer]
The print layer 18 includes letters, numbers, pictures, figures, symbols, patterns, and the like for displaying decorations, contents, display of a best-before period, display of a manufacturer, a seller, and the like, and display and aesthetics. To form a desired arbitrary printed pattern. The printing layer 18 can be provided as needed, and can be provided, for example, on a film including the vapor 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 may be provided on a part thereof. The printing layer 18 can be formed using a conventionally known pigment or dye, and the forming method is not particularly limited.

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

  The printing layer 18 may include a biomass-derived component. For example, when the print 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.

<Production method of packaging material>
Next, an example of a method for manufacturing the packaging material 10 will be described. First, an example of a method for manufacturing the vapor deposition film 11 will be described.

(Manufacturing process of vapor deposition film)
First, the first plastic film 111 is prepared. Subsequently, a transparent evaporation layer 112 containing aluminum oxide is formed on the surface of the first plastic film 111. FIG. 7 is a diagram illustrating an example of the film forming apparatus 60. Hereinafter, the film forming apparatus 60 and a film forming method using the film forming apparatus 60 will be described.

  As shown in FIG. 7, in the film forming apparatus 60, partitions 85 a to 85 c are formed in the decompression chamber 62. The partition walls 85a to 85c form a substrate transfer chamber 62A, a plasma pretreatment chamber 62B, and a film formation chamber 62C. In particular, the plasma pretreatment chamber 62B and the film formation chamber are defined as spaces surrounded by the partition walls and the partition walls 85a to 85c. 62C is formed, and each chamber is further provided with an exhaust chamber as needed.

  The plasma pretreatment chamber 62B and the plasma pretreatment process in the plasma pretreatment chamber 62B will be described. In the plasma pre-processing chamber 62B, a part of the plasma pre-processing roller 70 that transports the first plastic film 111 on which the pre-processing is performed and enables the plasma processing is provided so as to be exposed to the substrate transport chamber 62A. Have been. The first plastic film 111 moves to the plasma pretreatment chamber 62B while being wound.

  The plasma pretreatment chamber 62B and the film formation chamber 62C are provided in contact with the base material transfer chamber 62A, and can move without contacting the first plastic film 111 with the atmosphere. Further, the pretreatment chamber 62B and the base material transfer chamber 62A are connected by a rectangular hole, and a part of the plasma pretreatment roller 70 protrudes toward the base material transfer chamber 62A through the rectangular hole. A gap is provided between the wall of the transfer chamber and the pretreatment roller 70, and the first plastic film 111 can move from the base material transfer chamber 62A to the film formation chamber 62C through the gap. The structure between the base material transfer chamber 62A and the film formation chamber 62C has the same structure, and the first plastic film 111 can be moved without being exposed to the atmosphere.

  The substrate transfer chamber 62A is used as a winding means for winding the first plastic film 111 having a vapor-deposited film formed on one side thereof, which has been moved to the substrate transfer chamber 12A again by the film forming roller 75, in a roll shape. Is provided so that the first plastic film 111 on which the deposited film is formed can be wound.

  When manufacturing the deposited film 11 having the aluminum oxide deposited film, the plasma pretreatment chamber 62B is configured so that the space where the plasma is generated is separated from other regions, and the opposed space can be efficiently evacuated. In addition, the control of the plasma gas concentration is facilitated, and the productivity is improved. The pretreatment pressure formed by reducing the pressure can be set and maintained at about 0.1 Pa or more and 100 Pa or less, and in particular, the treatment pressure of the oxygen plasma pretreatment in order to obtain a preferable transformation rate of the transition region of the aluminum oxide deposition film. Is preferably 1 Pa or more and 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 above-described lower limit candidate value and upper limit candidate value.

  The transport speed of the first plastic film 111 is not particularly limited, but can be at least 200 to 1000 m / min from the viewpoint of production efficiency. The conveying speed of the pretreatment is preferably 300 to 800 m / min.

  The plasma pre-treatment roller 70 constituting the plasma pre-treatment device prevents the first plastic film 111 from shrinking or being damaged by heat during the plasma treatment by the plasma pre-treatment means, and sends the oxygen plasma P to the first plastic film 111. It is intended to be applied uniformly and widely. It is preferable that the pretreatment roller 70 can be adjusted to a constant temperature between −20 ° C. and 100 ° C. by adjusting the temperature of the temperature adjusting medium circulating in the pretreatment roller.

  The plasma pretreatment unit includes a plasma supply unit and a magnetic forming unit. 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 part of the pretreatment roller 70. Specifically, the plasma supply means 72 and the magnetic 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 for supplying a plasma source gas. The magnetic forming means 73 has a magnet or the like to promote generation of the plasma P. Further, the plasma pretreatment means has an electrode 71 to which a voltage is applied between the plasma pretreatment means 70 and the pretreatment roller 70. Although FIG. 7 shows an example in which the electrode 71 and the plasma supply means 72 are separate members, the present invention is not limited to this. Although not shown, the electrode 71 and the plasma supply means 72 may be formed by an integral member.

  By generating a plasma P in a space sandwiched between the pretreatment roller 70 and the magnetic forming means 73 and forming a region having a high plasma density near the surface of the pretreatment roller 70 and the first plastic film 111, (1) An oxygen plasma pretreatment can be performed on the inner surface of the plastic film 111 to form a plasma-treated surface.

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

  These supplied gases are mixed at a predetermined ratio as necessary, formed into a plasma source gas alone or a mixed gas for plasma formation, and supplied to a plasma supply unit. The single or mixed gas is supplied to the plasma supply nozzle of the plasma supply means, and is supplied to the vicinity of the outer periphery of the pretreatment roller 70 where the supply port of the plasma supply nozzle is open. The nozzle opening is directed to the first plastic film 111 on the pretreatment roller 70, and is arranged and configured so that the oxygen plasma P can be uniformly diffused and supplied to the entire surface of the first plastic film 111. . Thus, a large-area portion of the first plastic film 111 can be subjected to uniform plasma pretreatment.

  In order to set the transformation rate of the transition region of the aluminum oxide vapor-deposited film to 5% or more and 60% or less as described above, the oxygen plasma pretreatment includes a mixture ratio of oxygen gas and inert gas (oxygen gas / inert gas). Is preferably 1/1 or more, and may be 3 / 2.5 or more, or 3/2 or more. The mixing ratio of the oxygen gas to the inert gas (oxygen gas / inert gas) is preferably 6/1 or less, and may be 3/1 or less, or may be 5/2 or less. By setting the mixing ratio to be at least 1/1 and at most 6/1, the film forming energy of the deposited aluminum on the plastic film substrate is increased. Is formed near the interface of the base material, that is, the transformation rate of the transition region decreases. The range of the mixing ratio of the oxygen gas and the inert gas (oxygen gas / inert gas) can be determined by any combination of the above-described lower limit candidate value and upper limit candidate value.

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

  Specifically, the electrode 71 is provided with a plasma pretreatment roller as a plasma power source, applies an AC voltage having a frequency of 10 Hz to 2.5 GHz between the electrode 71 and the counter electrode, and performs input power control or impedance control. And a state in which an arbitrary voltage is applied to the plasma pre-treatment roller 70. The film forming apparatus 60 is provided with a power supply 82 capable of applying a bias voltage for making the oxygen plasma P capable of performing a process of physically or chemically modifying the surface physical properties of the first plastic film 111 to a positive potential.

Plasma intensity per unit area is preferably 50W · sec / m ² or more 8000W · sec / m ² or less. At 50 W · sec / m ² or less, the effect of the plasma pretreatment is not seen, and at 8000 W · sec / m ² or more, the first plastic film 111 due to plasma such as consumption, damage coloring, and firing of the first plastic film 111. Degradation tends to occur. In particular, the plasma intensity per unit area is preferably 100 W · sec / m ² or more. Further, 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 a bias voltage to the first plastic film 111 and applying the above-described plasma intensity to the first plastic film 111, it is possible to stably improve the adhesion to the aluminum oxide deposited film. The range of the plasma intensity per unit area can be determined by any combination of the above-mentioned lower limit candidate value and upper limit candidate value.

  As the magnetic forming means 73, an insulating spacer and a base plate provided in a magnet case and a magnet provided on the base plate can be used. An insulating shield plate is provided on the magnet case, and electrodes can be attached to the insulating shield plate. The magnet case and the electrodes are electrically insulated, and even if the magnet case is installed and fixed in the decompression chamber 62, the electrodes can be electrically at a floating level. By providing the magnet, the reactivity in the vicinity of the surface of the first plastic film 111 is increased, and it becomes possible to form a favorable plasma pretreatment surface at a high speed.

  Preferably, the magnet is configured such that the magnetic flux density at the surface position of the first plastic film 111 is 10 gauss to 10000 gauss. If the magnetic flux density on the surface of the first plastic film 111 is 10 gauss or more, the reactivity near the surface of the first plastic film 111 can be sufficiently increased, and a good pretreatment surface can be formed at high speed. .

  Next, a film forming chamber 62C and a film forming process in the film forming chamber 62C will be described. The film forming apparatus 60 includes a film forming roller 75 disposed in the decompressed film forming chamber 62 </ b> C, and a target of the vapor deposition film forming unit 74 disposed to face the film forming roller 75. The film forming roller 75 winds and transports the first plastic film 111 with the processing surface of the first plastic film 111 pretreated by the plasma pretreatment device facing outward. In the film forming step, the target of the vapor deposition film forming means 74 is evaporated to form an aluminum oxide film on the surface of the first plastic film 111.

  The vapor deposition film forming means 74 is, for example, of a resistance heating type, using an aluminum metal wire with aluminum as an evaporation source, supplying oxygen to oxidize aluminum vapor, and depositing aluminum oxide on the surface of the first plastic film 111. A deposited film is formed.

  The thickness of the transparent evaporation layer 112 including the aluminum oxide evaporation film formed as described above is preferably 3 nm or more, may be 8 nm or more, or may be 10 nm or more. Further, the thickness of the transparent vapor deposition layer 112 is preferably 50 nm or less, may be 30 nm or less, may be 20 nm or less, may be 15 nm or less, or may be 14 nm or less. The range of the thickness of the transparent vapor-deposited layer 112 can be determined by any combination of the above-described lower limit candidate value and upper limit candidate value. Within this range, barrier properties can be maintained. However, when the deposited 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 of forming the gas barrier coating film 113 on the transparent evaporation layer 112 will be described. First, the above metal alkoxide, silane coupling agent, hydroxyl group-containing water-soluble resin, reaction accelerator (sol-gel method catalyst, acid, etc.), and organic solvent such as water, alcohol such as methyl alcohol, ethyl alcohol, isopropanol are used. By mixing, a coating agent for a gas barrier coating film composed of a resin composition is prepared.

  Next, the above-mentioned coating agent for a gas barrier coating film is applied on the transparent vapor-deposited layer 112 by a conventional method, and dried. By this drying step, the condensation or co-condensation reaction further proceeds, and a coating film is formed. A plurality of coating films composed of two or more layers may be formed by repeating the above coating operation on the first coating film.

  Further, heat treatment is performed for 3 seconds to 10 minutes at a temperature in the range of 20 to 200 ° C., preferably 50 to 180 ° C., and a temperature not higher than the softening point of the resin constituting the base layer. Thereby, the gas barrier coating film 113 made of the coating agent for a gas barrier coating film can be formed on the transparent evaporation layer 112. Thus, the vapor deposition film 11 having the first plastic film 111, the transparent vapor deposition layer 112, and the gas barrier coating film 113 can be manufactured.

(Lamination process of other films or layers)
Next, a method for manufacturing the above-described packaging material 10 by laminating another film or layer on the vapor deposition film 11 will be described.

  An example of a method for manufacturing the packaging material 10 shown in FIG. 1 will be described. First, the vapor deposition film 11 is prepared, and the printing layer 18 is formed on the gas barrier coating film 113 of the vapor deposition film 11 by, for example, a gravure printing method. Subsequently, the anchor coat layer 17 is provided on the print layer 18. Thereafter, the sealant layer 12 is formed on the anchor coat layer 17 by a melt extrusion lamination method. In this case, the sealant layer 12 includes, for example, low-density polyethylene. Thus, the packaging material 10 shown in FIG. 1 can be obtained.

  Next, an example of a method for manufacturing the packaging material 10 shown in FIG. 2 will be described. First, the vapor deposition film 11 is prepared, and the printing layer 18 is formed on the gas barrier coating film 113 of the vapor deposition film 11 by, for example, a gravure printing method. Subsequently, the anchor coat layer 17 is provided on the print layer 18. Further, a film constituting the sealant layer 12 is prepared. Then, the film including the vapor deposition film 11 and the film constituting the sealant layer 12 are bonded to each other by a sand lamination method via the first bonding layer 13 formed of a bonding resin layer. Thus, the packaging material 10 shown in FIG. 2 can be obtained.

  Next, an example of a method for manufacturing the packaging material 10 shown in FIG. 3 will be described. First, the vapor deposition film 11 is prepared, and the printing layer 18 is formed on the gas barrier coating film 113 of the vapor deposition film 11 by, for example, a gravure printing method. Further, a film constituting the sealant layer 12 is prepared. Thereafter, the film including the vapor-deposited film 11 and the film constituting the sealant layer 12 are bonded to each other by a dry lamination method via the first adhesive layer 13 formed of an adhesive layer. Thus, the packaging material 10 shown in FIG. 3 can be obtained.

Next, an example of a method for manufacturing the packaging material 10 shown in FIG. 4 will be described. First, the vapor deposition film 11 is prepared, and the printing layer 18 is formed on the gas barrier coating film 113 of the vapor deposition film 11 by, for example, a gravure printing method. Also, a second plastic film 14 is prepared. Then, the film including the vapor deposition film 11 and the second plastic film 14 are bonded to each other by a dry lamination method via the second adhesive layer 15 formed of an adhesive layer. Further, a film constituting the sealant layer 12 is prepared. Thereafter, the laminate including the vapor-deposited film 11 and the second plastic film 14 and the film constituting the sealant layer 12 are bonded to each other by a dry lamination method via the first adhesive layer 13 formed of an adhesive layer. Thus, the packaging material 10 shown in FIG. 4 can be obtained.
After the vapor deposition film 11 and the film constituting the sealant layer 12 are bonded, the laminate including the vapor deposition film 11 and the sealant layer 12 may be bonded to the second plastic film 14.

Next, an example of a method for manufacturing the packaging material 10 shown in FIG. 5 will be described. First, a second plastic film 14 is prepared, and a printing layer 18 is formed on the second plastic film 14 by, for example, a gravure printing method. Further, a deposition film 11 is prepared. Thereafter, the film including the second plastic film 14 and the vapor-deposited film 11 are adhered to each other by a dry lamination method via the second adhesive layer 15 formed of an adhesive layer. Further, a film constituting the sealant layer 12 is prepared. Thereafter, the laminate including the second plastic film 14 and the vapor-deposited film 11 and the film constituting the sealant layer 12 are adhered to each other by the dry lamination method via the first adhesive layer 13 composed of an adhesive layer. Thus, the packaging material 10 shown in FIG. 5 can be obtained.
After laminating the vapor deposition film 11 and the film constituting the sealant layer 12, the laminate including the vapor deposition film 11 and the sealant layer 12 may be laminated to the second plastic film 14.

Next, an example of a method for manufacturing the packaging material 10 shown in FIG. 6 will be described. First, the vapor deposition film 11 is prepared, and the printing layer 18 is formed on the gas barrier coating film 113 of the vapor deposition film 11 by, for example, a gravure printing method. Also, a second plastic film 14 is prepared. Then, the film including the vapor deposition film 11 and the second plastic film 14 are bonded to each other by a dry lamination method via the second adhesive layer 15 formed of an adhesive layer. Further, a film constituting the sealant layer 12 is prepared. Thereafter, the laminate including the vapor-deposited film 11 and the second plastic film 14 and the film constituting the sealant layer 12 are bonded to each other by a dry lamination method via the first adhesive layer 13 formed of an adhesive layer. Thus, the packaging material 10 shown in FIG. 6 can be obtained.
After bonding the second plastic film 14 and the film constituting the sealant layer 12, the laminate including the second plastic film 14 and the sealant layer 12 may be bonded to the vapor deposition film 11.

<Packaging container>
Examples of the packaged product formed by using the packaging material 10 include a packaging bag, a laminated tube, a lid material, and a sheet molded product.

  Packaging products provided with the packaging material 10 include, for example, liquid soups such as foods and drinks, fruit juices, juices, drinking water, sake, cooked foods, fish paste products, frozen foods, meat products, boiled foods, rice cakes, and pot soups. It can be suitably used as packaging for various foods and beverages such as seasonings, liquid detergents, cosmetics such as shampoos, rinses and conditioners, sanitary articles, daily necessities and chemical products. Specific examples of the food and drink include coffee, coffee beans, coffee powder, ice cream, gummy, side dishes, pasta sauce, curry, jelly, bacon, chocolate, chocolate paste, and the like. Specific examples of daily necessities include absorbent cotton, masks, bath additives, powdered milk, and the like. Further, as exemplified in an example described later, a packaged product including the packaging material 10 configured to have heat resistance is used in a case where contents to be subjected to a heat sterilization treatment such as a retort treatment and a boil treatment are accommodated. Can be used. The retort treatment is a process in which the contents are filled in a packaged product, the packaged product is hermetically sealed, and then the packaged product is heated in a pressurized state using steam or heated hot water. The temperature of the retort treatment is, for example, 120 ° C. or higher. The boiling process is a process of filling the contents into a packaged product, sealing the packaged product, and then boiling the packaged product under atmospheric pressure. The temperature of the boiling process is, for example, 90 ° C. or more and 100 ° C. or less.

  The packaging bag of the packaging product is obtained by folding the packaging material 10 in two or preparing two packaging materials 10 so that the sealant layer 12 of the packaging material 10 on the front side and the sealant layer 12 of the packaging material 10 on the back side face each other. , And further, the peripheral end thereof is, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, a gasket-attached seal type (pillow seal type), a pleated seal type, Various types of packaging bags can be manufactured by heat sealing using a heat sealing mode such as a flat bottom sealing type and a square bottom sealing type. Further, heat sealing may be performed in a state where the folded packaging material 10 is inserted between the front packaging material 10 and the back packaging material 10 to produce a gusset-type packaging bag. Note that not all of the packaging material 10 constituting the packaging bag is the packaging material 10 according to the present invention. That is, at least a part of the packaging material 10 constituting the packaging bag may be a packaging material 10 including the vapor-deposited film 11 having the first plastic film 111 containing the biomass-derived component. May be a packaging material 10 having a deposited film derived from fossil fuel.

  As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high-frequency seal, an ultrasonic seal, or the like can be used.

  FIG. 9 is a diagram illustrating an example in which the packaging container 30 including the packaging material 10 is a packaging bag. The packaging container 30 shown in FIG. 9 includes a front film 34A forming the front surface, a back film 34B forming the back surface, and a lower film 36 forming the lower portion 32. The lower film 36 is disposed between the front film 34A and the back film 34B in a state where the lower film 36 is folded at the folded portion 36f. As described above, the packaging container 30 shown in FIG. 9 is a self-standing standing pouch having a lower portion configured as a gusset portion.

  The inner surfaces of the front film 34A, the back film 34B, and the lower film 36 are joined by a seal portion. In the front view of the packaging container 30 shown in FIG. 9 and the like, the sealing portion is hatched. As shown in FIG. 9, the seal portion has an outer edge seal portion extending along the outer edge of the packaging container 30. The outer edge seal portion includes a lower seal portion 32 a extending to the lower portion 32 and a pair of side seal portions 33 a extending along the pair of side portions 33. Note that, in the packaging container 30 in a state before the contents are filled (a state in which the contents are not filled), the upper part 31 of the packaging container 30 is an opening 31b as shown in FIG. After the contents are stored in the packaging container 30, the inner surface of the front film 34 </ b> A and the inner surface of the back film 34 </ b> B are joined at the upper portion 31, thereby forming an upper seal portion and sealing the packaging container 30.

  Note that the terms “front film”, “back film”, and “lower film” described above are merely a division of each film according to the positional relationship, and the provision of the packaging material 10 when the packaging container 30 is manufactured. The method is not limited by the above terms. For example, the packaging container 30 may be manufactured using one piece of the packaging material 10 in which the front film 34A, the back film 34B, and the lower film 36 are connected, and the front film 34A and the lower film 36 are connected. It may be manufactured using a total of two packaging materials 10, one packaging material 10 and one back film 34B, one front film 34A, one back film 34B, and one lower film 36. May be manufactured using a total of three packaging materials 10.

  At least one of the front film 34A, the back film 34B, and the lower film 36 is formed of the packaging material 10 including the vapor-deposited film 11 having the first plastic film 111 containing a biomass-derived component. As a result, the amount of fossil fuel used can be reduced as compared with the related art, and the environmental load can be reduced. Further, 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 higher than in the past. For this reason, the barrier property of the packaging container 30 can be improved as compared with the related art.

  FIG. 10 is a diagram illustrating another example of the packaging container 30 including the packaging material 10. The packaging container 30 shown in FIG. 12 is different from the packaging container 30 shown in FIG. 9 only in that the packaging container 30 further includes a steam release mechanism 40. In the packaging container 30 shown in FIG. 10, the same parts as those of the packaging container 30 shown in FIG. 9 are denoted by the same reference numerals, and detailed description will be omitted.

  As shown in FIG. 10, the packaging container 30 includes a steam release mechanism 40 for releasing steam generated when heating the content stored in the storage unit 39 to the outside. The steam release mechanism 40 allows the inside and the outside of the packaging container 30 to communicate with each other to release the steam when the pressure of the steam becomes equal to or higher than a predetermined value, and suppresses the occurrence of the steam release from a portion other than the steam release mechanism 40. It is configured to

  In the example shown in FIG. 10, the steam release mechanism 40 includes a steam release seal portion 41 protruding from the side seal portion 33 a toward the inside of the packaging container 30, and a steam release seal portion 41 separated from the storage portion 39 by the steam release seal portion 41. And a seal part 42. The unsealed portion 42 communicates with the outside of the packaging container 30. When the pressure in the housing section 39 is increased by being heated by a microwave oven or the like, the steam release seal section 41 is peeled off. The 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. The configuration of the steam venting mechanism 40 is arbitrary as long as the housing portion 39 and the outside of the packaging container 30 can be communicated when the steam pressure becomes equal to or higher than a predetermined value.

  In the packaging container 30 shown in FIG. 10 as well, at least one of the front film 34A, the back film 34B, and the lower film 36 is made of the packaging material 10 having an adhesive layer containing a biomass-derived component. As a result, the amount of fossil fuel used can be reduced as compared with the related art, and the environmental load can be reduced. Further, 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 higher than in the past. For this reason, the barrier property of the packaging container 30 can be improved as compared with the related art.

  FIG. 11 is a diagram illustrating another example of the packaging container 30 including the packaging material 10. The packaging container 30 shown in FIG. 11 is different from the packaging container 30 shown in FIG. 9 only in that the packaging container 30 further includes a spout 43. In the packaging container 30 shown in FIG. 11, the same parts as those of the packaging container 30 shown in FIG. 9 are denoted 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 pass when the contents stored in the storage section 39 are taken out. In this case, the content is a liquid having fluidity or the like. The width of the spout 43 is smaller than the width of the housing 39. For this reason, the user can determine the pouring direction of the content to be poured out of the packaging container 30 through the pouring port 43 with high accuracy.

  In the example shown in FIG. 11, the spout portion 43 is configured by a part of the front film 34A and the back film 34B. For example, the spout portion 43 includes a spout seal portion 44 that joins the front film 34A and the back film 34B so as to define the spout portion 43 having a smaller width than the storage portion 39. The packaging container 30 provided with such a spout portion 43 is suitably used as a refill pouch for storing contents such as detergent, shampoo, and rinse to be refilled into a bottle.

  Note that the configuration of the spout portion 43 is not limited to the configuration illustrated in FIG. 11 as long as the contents can be appropriately poured out. For example, the spout 43 may be a member other than the front film 34A and the back film 34B, such as a spout.

  In the packaging container 30 shown in FIG. 11 as well, at least one of the front film 34A, the back film 34B, and the lower film 36 is made of the packaging material 10 having an adhesive layer containing a biomass-derived component. As a result, the amount of fossil fuel used can be reduced as compared with the related art, and the environmental load can be reduced. Further, 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 higher than in the past. For this reason, the barrier property of the packaging container 30 can be improved as compared with the related art.

  FIG. 12 is a diagram illustrating another example of the packaging container 30 including the packaging material 10. The packaging container 30 shown in FIG. 12 is a three-side seal pouch formed by joining the front film 34A and the back film 34B along three sides along the outer edge. The upper seal portion is formed on the upper portion 31 after the contents are accommodated in the packaging container 30 through the opening 31b, as in the case of the example shown in FIGS. 9 to 11.

  Also in the packaging container 30 shown in FIG. 12, at least one of the front film 34A and the back film 34B is made of the packaging material 10 having the adhesive layer containing the biomass-derived component. As a result, the amount of fossil fuel used can be reduced as compared with the related art, and the environmental load can be reduced. Further, 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 higher than in the past. For this reason, the barrier property of the packaging container 30 can be improved as compared with the related art.

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

  FIG. 15 is a diagram illustrating an example in which the packaging container 30 including the packaging material 10 is a container with a lid. The lidded container includes a container body 45 made by sheet forming such as drawing, and a lid 46 joined to the container body 45.

  In the example illustrated in FIG. 15, for example, the container body 45 is manufactured by drawing and forming the packaging material 10 including the vapor-deposited film 11 having the first plastic film 111 including the biomass-derived component. As a result, the amount of fossil fuel used can be reduced as compared with the related art, and the environmental load can be reduced. Further, 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 higher than in the past. For this reason, the barrier property of the container main body 45 can be improved as compared with the related art.

  In the example shown in FIG. 15, the lid 46 may be formed of the packaging material 10 including the vapor-deposited film 11 having the first plastic film 111 containing the biomass-derived component. As a result, the amount of fossil fuel used can be reduced as compared with the related art, and the environmental load can be reduced. Further, 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 higher than in the past. For this reason, the barrier property of the lid 46 can be improved as compared with the related art.

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

  In the example shown in FIG. 16, the tube main body 47 is manufactured by processing the packaging material 10 including the vapor-deposited film 11 having the first plastic film 111 containing the biomass-derived component into a cylindrical shape. As a result, the amount of fossil fuel used can be reduced as compared with the related art, and the environmental load can be reduced. Further, 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 higher than in the past. For this reason, the barrier property of the tube main body 47 can be improved as compared with the related art.

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

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

After subjecting 83 parts by mass of terephthalic acid derived from fossil fuel and 62 parts by mass of ethylene glycol derived from biomass (manufactured by Indiaglycol Co.) to an esterification reaction by an ordinary straight-weight method, a condensation polymerization reaction was performed under reduced pressure. As a result, polyethylene terephthalate derived from biomass was obtained. Radiation carbon measurement of the obtained biomass-derived polyethylene terephthalate was performed, and the degree of biomass measured by radiocarbon (C14) was 31.25%.
The above-mentioned biomass-derived polyethylene terephthalate (60 parts by mass), fossil fuel-derived polyethylene terephthalate (30 parts by mass), and a masterbatch containing fossil fuel-derived polyethylene terephthalate (10 parts by mass) are supplied to an extruder, and a sheet is formed from a T die. To obtain an unstretched sheet. Next, the unstretched sheet was stretched in the longitudinal direction and then in the transverse direction to obtain a biaxially stretched PET film having a thickness of 12 μm. When the biomass degree of the obtained biaxially stretched PET film was measured, it was 18.8%.

Subsequently, the surface of the first plastic film 111 made of the above-described biaxially stretched PET film is subjected to oxygen plasma treatment using the above-described film forming apparatus 60 shown in FIG. A transparent evaporation layer 112 containing aluminum and having a thickness of 12 nm was formed.
(Oxygen plasma pretreatment conditions)
Plasma strength: 150W · sec / m ²
Mixing ratio of oxygen gas and inert gas: oxygen / argon = 2/1
・ Applied voltage between pretreatment drum and plasma supply nozzle: 340V
・ Pretreatment pressure: 3.8 Pa
(Aluminum oxide film formation conditions)
-Degree of vacuum: 8.1 × 10 ^-2 Pa
・ Transport speed: 400m / min
・ Oxygen gas supply: 20,000 sccm

Subsequently, a gas barrier coating film 113 was formed on the transparent evaporation layer 112. Specifically, first, 385 g of tetraethoxysilane as a metal alkoxide and glycide as a silane coupling agent were added to a solution prepared by mixing 385 g of water, 67 g of isopropyl alcohol, and 9.1 g of 0.5 N hydrochloric acid to adjust the pH to 2.2. Solution A was prepared by mixing 9.2 g of xylpropyltrimethoxysilane while cooling to 10 ° C.
As the water-soluble polymer, a solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of polymerization of 2400 with a saponification value of 99% or more, 324 g of water, and 17 g of isopropyl alcohol. The solution obtained by mixing the solution A and the solution B at a weight ratio of 6.5: 3.5 was used as a coating agent for a gas barrier coating film.
The coating agent for a gas barrier coating film prepared as described above was coated on the transparent vapor-deposited layer 112 by a spin coating method.
Thereafter, heat treatment was performed 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 vapor deposition layer 112. 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 A2]
Except that the thickness of the transparent evaporation layer 112 was set to 10 nm, a transparent evaporation layer 112 was formed on the first plastic film 111 in the same manner as in Example A1, and a gas barrier coating film was formed on the transparent evaporation layer 112. 113 was formed. 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 that the thickness of the transparent vapor deposition layer 112 was set to 14 nm, a transparent vapor deposition layer 112 was formed on the first plastic film 111 in the same manner as in Example A1, and a gas barrier coating film was formed on the transparent vapor deposition layer 112. 113 was formed. 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]
Except that the plasma intensity in the oxygen plasma treatment was set to 1200 W · sec / m ² , a transparent vapor deposition layer 112 was formed on the first plastic film 111 in the same manner as in Example A1. A gas barrier coating film 113 was formed. 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 A1]
Except that the thickness of the transparent vapor deposition layer 112 was set to 7 nm, a transparent vapor deposition layer 112 was formed on the first plastic film 111 in the same manner as in Example A1, and a gas barrier coating film was formed on the transparent vapor deposition layer 112. 113 was formed. 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 that the oxygen plasma pretreatment was not performed, a transparent vapor deposition layer 112 was formed on the first plastic film 111 and a gas barrier coating film 113 was formed on the transparent vapor deposition layer 112 in the same manner as in Example A1. did. 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 A3]
A transparent vapor deposition layer 112 was formed on the first plastic film 111 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 set to oxygen / argon = 4/1. The gas barrier coating film 113 was formed on the transparent evaporation layer 112. 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 A4]
A transparent vapor deposition layer 112 is formed on a first plastic film 111 in the same manner as in Example A1, except that the pretreatment pressure in the oxygen plasma treatment is set to 50 Pa, and a gas barrier coating film is formed on the transparent vapor deposition layer 112. 113 was formed. 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.

  The conversion rate was measured for the vapor-deposited films 11 of Examples A1 to A3 and Comparative Examples A1 to A4 described above. In addition, the tint was measured for the vapor deposition film 11 of Example A1 and Reference Example A1 described above. Further, for the packaging materials provided with the vapor-deposited films 11 of Examples A1 to A3 and Comparative Examples A1 to A2, the measurement of oxygen permeability, the measurement of water vapor permeability, and the evaluation of adhesion strength were performed. In the evaluation of the adhesion strength, the normal peel strength and the wet peel strength were measured.

(Metamorphosis rate)
While repeating soft etching on the surface of the gas-barrier coating film 113 of the vapor-deposited film 11 by a Cs (cesium) ion gun at a constant rate, gas-barrier coating was performed using time-of-flight secondary ion mass spectrometry (TOF-SIMS). The ions derived from the film 113, the ions derived from the transparent vapor-deposited layer 112, and the ions derived from the first plastic film 111 were measured. As a result, a graph was obtained in which the unit on the vertical axis (intensity) is the measured ion intensity and the unit on the horizontal axis (cycle) is the number of times of etching, as shown in FIG. 7 described above.

As a time-of-flight secondary ion mass spectrometer used in TOF-SIMS, ION TOF, TOF. The measurement was performed using SIMS5 under the following measurement conditions.
(TOFSIMS measurement conditions)
・ Primary ion type: Bi ₃ ++ (0.2 pA, 100 μs), measurement area: 150 × 150 μm ²
・ Et gun type: Cs (1 keV, 60 nA), Et area: 600 × 600 μm ² , Et rate: 3 sec / Cycle
In the analysis, among the ions derived from aluminum oxide, ions separated from other components were selected, those having a sufficient strength were selected, and the concentration distribution of the element-bonded Al ₂ O ₄ H was particularly improved. It is important to obtain a depth distribution that can be approximated. Considering these, Cs ions were selected as an ion gun for measuring ions derived from aluminum oxide to be measured.

Etching is performed from the outermost surface of the gas barrier coating film 113 using Cs, and the element bonding at the interface between the gas barrier coating film 113, the transparent vapor deposition layer 112, and the first plastic film 111 and the element bonding of the vapor deposition film are analyzed. Then, a graph of the measured elements and element bonds was obtained. In the graph, the position where the intensity of SiO ₂ (mass number 59.96), which is a constituent element of the gas barrier coating film 113, becomes half of the intensity in the gas barrier coating film 113 is defined by the gas barrier coating film 113 and the transparent vapor deposition layer 112. Interface. The position where the strength of C ₆ (mass number 72.00), which is a constituent material of the first plastic film 111, becomes half of the strength of the first plastic film 111 is determined by the position of the first plastic film 111 and the transparent evaporation layer 112. Specified as an interface. Further, the distance in the thickness direction between the two interfaces was adopted as the thickness of the transparent vapor deposition layer 112.

Next, a peak representing the measured element-bonded Al ₂ O ₄ H (mass number 118.93) was determined, and the region from the peak to the interface was defined as a transition region. However, when the component of the gas barrier coating film 113 is made of a material having the same mass number as Al ₂ O ₄ H (mass number 118.93), it is necessary to separate the waveform of 118.93.

When reactants AlSiO ₄ and hydroxide Al ₂ O ₄ H are generated at the interface between the gas barrier coating film 113 and the transparent deposition layer 112, the interface between the first plastic film 111 and the transparent deposition layer 112 is formed. it can be separated Al ₂ O ₄ H present in the. Thus, the separation of the waveform can be appropriately dealt with according to the material of the gas barrier coating film 113.

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

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

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

(Adhesion strength)
A non-stretched polypropylene film (CPP film) having a thickness of 70 μm and a stretched nylon film having a thickness of 15 μm were bonded to each other by a dry lamination method via a two-component curable polyurethane-based adhesive to prepare a laminate. In addition, a two-component curable polyurethane-based adhesive is applied to the gas-barrier coating film 113 side of the vapor-deposited films 11 of Examples A1 to A3 and Comparative Examples A1 and A2, and is dried to form a coating on the gas-barrier coating film 113. To form an adhesive layer. Subsequently, the laminate including the CPP film and the stretched nylon film and the vapor-deposited film 11 are attached to each other by a dry lamination method via an adhesive layer on the gas-barrier coating film 113 of the vapor-deposited film 11, and are packaged for evaluation. A material (hereinafter, also referred to as a packaging material for evaluation before the retort treatment) was produced. The layer configuration of the packaging material is expressed as follows in order from the outside to the inside.
PET film / transparent deposited layer / gas barrier coating / adhesive layer / stretched nylon film / adhesive layer / CPP film

(Adhesion after retort treatment)
Using a packaging material for evaluation before the retort treatment, a B5 size four-side seal pouch was produced. Subsequently, after injecting 100 mL of water into the inside of the four-sided seal pouch from the opening 31b of the upper part 31, the upper-side seal part 31a was formed to seal the four-sided seal pouch. Subsequently, the four-side seal pouch was subjected to a hydrothermal retort treatment at 135 ° C. for 40 minutes. In the following description, the packaging material constituting the pouch that has been subjected to the hydrothermal retort treatment at 135 ° C. for 40 minutes is also referred to as a packaging material for evaluation after the retort treatment.

  Subsequently, it was visually confirmed whether or not delamination had occurred in the packaging material for evaluation after the retort treatment. As a result, delamination did not occur in the packaging material including the vapor deposition film 11 of Examples A1 to A3 and Comparative Example A1, but delamination occurred in the packaging material including the vapor deposition film 11 of Comparative Example A2. Was.

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

  In the measurement, first, as shown in FIG. 17, at the interface between the first plastic film 111 and the transparent vapor deposition layer 112 from the end in the long side direction of the sample 100 to a position at a distance of 15 mm along the long side direction. The first sample was peeled off. Subsequently, as shown in FIG. 18, the first plastic film 111 side and the transparent vapor-deposited layer 112 side of the sample 100 are gripped by the grippers 81 and 82 of the measuring device, respectively. Are pulled in opposite directions (180 ° peeling: T-peeling method) at a speed of 50 mm / min in a direction perpendicular to the surface direction of the portion where the layers are still laminated, and a tensile force in a stable region (see FIG. 19). Was measured. The spacing S between the grippers 81 and 82 when starting the pulling was 30 mm, and the spacing S between the grippers 81 and 82 when the pulling was finished was 60 mm. FIG. 19 is a diagram illustrating a change in the tensile force with respect to the interval S between the grippers 81 and 82. As shown in FIG. 19, the change in the tensile force with respect to the interval S enters the second region (stable region) having a smaller change rate than the first region via the first region.

  It is considered that peeling of the packaging material for evaluation occurs between the first plastic film 111 having the weakest adhesion strength and the transparent vapor deposition layer 112. The average value of the tensile force in the stable region was measured for the five samples 100, and the average value was defined as the normal peel strength of the packaging material for evaluation. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. The measurement results are shown in FIGS. 20A and 20B.

(Peeling strength after retort treatment)
In the same manner as in the measurement of the normal peel strength, the packaging material for evaluation after the retort treatment was cut into a strip having a width of 15 mm to prepare a sample for measuring the wet peel strength after the retort treatment. Subsequently, the adhesion strength between the first plastic film 111 and the transparent vapor deposition layer 112 of the sample was measured in accordance with JIS K6854-2. As a measuring instrument, a tensile tester (made by Orientec Co., Ltd. [model name: Tensilon universal material tester]) was used. In the measurement, water was dropped with a dropper at the boundary between the portion where the first plastic film 111 and the transparent vapor deposited layer 112 maintained the bonding and the portion where the first plastic film 111 and the transparent vapor deposited layer 112 were separated. Was dropped, and the sample 100 was pulled using the grippers 81 and 82. Other measurement methods and calculation methods of the peel strength are the same as those of the normal peel strength. The measurement results are shown in FIGS. 20A and 20B.

(Oxygen permeability)
In the same manner as in the case of the measurement of the adhesion strength, the above-described “packaging material for evaluation before retort treatment” and the “evaluation for evaluation after retort treatment”, which include the vapor-deposited films 11 of Examples A1 to A3 or Comparative Examples A1 to A2. Packaging material "was prepared. Subsequently, a sample for measuring oxygen permeability was prepared from each of the packaging materials for evaluation.
As a sample for evaluation before the retort treatment, a packaging material subjected to aging treatment at 36 ° C. for 48 hours was used. As a sample for evaluation after the retort treatment, as in the case of the measurement of adhesion strength, 100 mL of water was sealed in a four-sided seal pouch made from a packaging material for evaluation, and heated at 135 ° C. for 40 minutes in the four-sided seal pouch. After water retort treatment, the one obtained by cutting out the packaging material on one side of the four-side seal pouch was used.

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

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

As shown in FIG. 20A, in the vapor deposition films 11 of Examples A1 to A3, the transformation rate of the transition region of the transparent vapor deposition layer 112 is in the range of 5% or more and 60% or less, specifically, 10%. It was more than 25% or less. As the thickness of the transparent vapor-deposited layer 112 increased, the rate of denaturation tended to decrease. On the other hand, as shown in FIG. 20B, in the vapor-deposited films 11 of Comparative Examples A1 and A2, the elementary Al ₂ O 4 _H peak was too small to be separated, so that the conversion rate of the transition region could not be calculated. In addition, in the deposited films 11 of Comparative Examples A3 to A4, the plasma discharge was not stable, and the plasma pretreatment could not be performed, so that the conversion rate of the transition region could not be calculated. From these facts, in order to produce the vapor-deposited film 11 so that the transformation rate of the transition region of the transparent vapor-deposited layer 112 is in the range of 5% to 60%, all of the following production conditions I to IV must be satisfied. Is preferred.
Manufacturing conditions I
The thickness of the transparent evaporation layer is 8 nm or more.
Manufacturing conditions II
The mixing ratio of the oxygen gas and the inert gas in the oxygen plasma treatment is 3 / 2.5 or more and 3/1 or less.
Manufacturing conditions III
The pretreatment pressure in the oxygen plasma treatment is 1 Pa or more and 20 Pa or less.
Manufacturing conditions 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 deposited film 11 of Reference Example A1 was larger than the b * value of the deposited film 11 of Example A1. Further, in the vapor deposition film 11 of Reference Example A1, it was visually confirmed that the first plastic film 111 was colored. It is considered that the above-mentioned production conditions I to IV are also useful for suppressing coloring.

As shown in FIG. 20A, in the packaging material comprising a vapor deposited film 11 of Example A1 to A3, in or after retort treatment before and retort treatment also oxygen permeability 0.3cc / m ² / 24hr / atm or less There, the water vapor permeability was less than 0.6g / m ² / 24hr. On the other hand, as shown in FIG. 20B, in the sample after retort treatment of the packaging material comprising a vapor deposited film 11 of Comparative Example A1 to A2, and the oxygen permeability 0.8cc / m ² / 24hr / atm or higher, the water vapor transmission degrees is was 1.0g / m ² / 24hr or more. In particular, in the sample after retort treatment of the packaging material comprising a vapor deposited film 11 of Comparative Example A1, and the oxygen permeability 1.0cc / m ² / 24hr / atm or more, a water vapor permeability of 2.0g / m ² / 24hr That was all. From these facts, the fact that the transformation rate of the transition region of the transparent vapor-deposited layer 112 is in the range of 5% or more and 60% or less can function effectively in maintaining the barrier property against gases such as oxygen and water vapor. I can say.

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

[Example B1]
As the vapor deposition film 11, a vapor deposition film 11 produced as in Example A1 was prepared. Subsequently, a printing layer 18 was formed on the gas barrier coating film 113 of the deposition film 11 by a gravure printing method. Subsequently, the anchor coat layer 17 was formed on the print layer 18. Subsequently, a low-density polyethylene in a molten state was extruded onto the anchor coat layer 17 to form a sealant layer 12 having a thickness of 30 μm. Thus, a packaging material 10 having the layer configuration shown in FIG. 1 was produced.

The layer configuration of the packaging material 10 of the present embodiment is expressed as follows.
Bio PET12 / Evaporation / Barrier / Mark / AC / PE (1) 30
"Bio PET" means a PET film containing a biomass-derived component. “Evaporation” means an aluminum oxide film. "Barrier" means a gas barrier coating film. "Mark" means a printed layer. “AC” means an anchor coat layer. “PE (1)” means a layer of polyethylene formed by a melt extrusion lamination method. The number means the thickness of the layer (unit: μm).

  Subsequently, using the packaging material 10, a three-sided seal pouch shown in FIG. 12 and a pillow pouch shown in FIG. 13 were produced. The three-side seal pouch and the pillow pouch can contain, for example, confectionery.

[Example B2]
As in the case of Example B1, the print layer 18 was formed on the gas barrier coating film 113 of the vapor deposition film 11, and the anchor coat layer 17 was formed on the print layer 18. Further, a film including the vapor-deposited film 11 and a film constituting the sealant layer 12 were bonded by a sand lamination method via a first adhesive layer 13 formed of an adhesive resin layer. As the film of the sealant layer 12, a polyethylene film (thickness: 30 μm) was used. Polyethylene was used as the adhesive resin of the first adhesive layer 13. The thickness of the adhesive resin layer was 12 μm. Thus, the packaging material 10 having the layer configuration shown in FIG. 2 was produced.

The layer configuration of the packaging material 10 of the present embodiment is expressed as follows.
Bio PET12 / Evaporation / Barrier / Mark / AC / Adhesive resin 15 / PE (2) 30
“Adhesive resin” means an adhesive resin layer. “PE (2)” means a polyethylene film.

  Subsequently, using the packaging material 10, a three-sided seal pouch shown in FIG. 12 and a pillow pouch shown in FIG. 13 were produced. The three-sided seal pouch and the pillow pouch can be used for applications such as food, toiletry, medicine and medicine.

[Example B3]
As in the case of Example B1, the print layer 18 was formed on the gas barrier coating film 113 of the vapor deposition film 11. Further, a film including the vapor-deposited film 11 and a film constituting the sealant layer 12 were bonded by a dry lamination method via a first adhesive layer 13 formed of an adhesive layer. As a film of the sealant layer 12, a non-stretched polypropylene film (25 μm in thickness) was used. Thus, the packaging material 10 having the layer configuration shown in FIG. 3 was produced.

The layer configuration of the packaging material 10 of the present embodiment is expressed as follows.
Bio PET12 / deposition / barrier / mark / adhesive / CPP25
"Adhesive" means an adhesive layer. "CPP" means unstretched polypropylene film.

  Subsequently, using the packaging material 10, a three-sided seal pouch shown in FIG. 12 and a pillow pouch shown in FIG. 13 were produced. The three-side seal pouch and the pillow pouch can accommodate chocolate, rice confectionery, and the like.

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

The layer configuration of the packaging material 10 of the present embodiment is expressed as follows.
Bio PET12 / deposition / barrier / mark / adhesive / PE (2) 40

  Subsequently, the pillow pouch shown in FIG. 13 and the side gusset pouch shown in FIG. 14 were produced using the packaging material 10. Pillow pouches and side gusset pouches can accommodate wet tissues, pickles, and the like.

[Example B5]
As in the case of Example B1, the print layer 18 was formed on the gas barrier coating film 113 of the vapor deposition film 11. Further, a film including the vapor-deposited film 11 and a film constituting the sealant layer 12 were bonded by a dry lamination method via a first adhesive layer 13 formed of an adhesive layer. As the film of the sealant layer 12, a polyethylene film (thickness: 30 μm) was used. In addition, a laminate having the vapor-deposited film 11 and the polyethylene film and a stretched polypropylene film (thickness: 20 μm) functioning as the second plastic film 14 are dry-laminated via the second adhesive layer 15 made of an adhesive layer. Stuck together. Thus, the packaging material 10 having the layer configuration 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 configuration of the packaging material 10 of the present embodiment is expressed as follows.
OPP20 / Adhesive / Mark / Barrier / Evaporation / Bio PET12 / Adhesive / PE (2) 30
"OPP" means oriented polypropylene film.

  Subsequently, the lid part 46 of the lidded container shown in FIG. For example, bacon can be stored in the lidded container.

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

The layer configuration of the packaging material 10 of the present embodiment is expressed as follows.
PE (2) 150 / Adhesive / Mark / Barrier / Evaporation / Bio PET12 / Adhesive / PE (2) 150

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

[Example B7]
As the second plastic film 14, a stretched nylon film having a thickness of 15 μm was prepared. Further, as the sealant layer 12, an unstretched polypropylene film having a thickness of 60 μm was prepared. Subsequently, the stretched nylon film and the non-stretched polypropylene film were bonded by a dry lamination method via the second adhesive layer 15 made of an adhesive layer. Further, the vapor deposition film 11 was prepared, and the printing layer 18 was formed on the gas barrier coating film 113 of the vapor deposition film 11. Thereafter, a film including the vapor-deposited film 11 and a laminate having a stretched nylon film and a non-stretched polypropylene film were bonded by a dry lamination method via a first adhesive layer 13 formed of an adhesive layer. Thus, the packaging material 10 having the layer configuration shown in FIG. 6 was produced.

The layer configuration of the packaging material 10 of the present embodiment is expressed as follows.
Bio PET12 / Evaporation / Barrier / Mark / Adhesive / Nylon 15 / Adhesive / CPP60

  Subsequently, using the packaging material 10, a standing pouch shown in FIG. 9 and a range pouch shown in FIG. 10 were produced. The standing pouch and the range pouch can contain, for example, prepared foods.

[Example B8]
An unstretched polypropylene film having a thickness of 60 μm was prepared as the sealant layer 12. Subsequently, the unstretched polypropylene film and the vapor-deposited film 11 are combined with the first plastic film 111 such that the transparent vapor-deposited layer 112 is located on the surface of the first plastic film 111 opposite to the sealant layer 12. Lamination was performed via the adhesive layer 13 by a dry lamination method. Further, a stretched PET film having a thickness of 12 μm was prepared as the second plastic film 14, and a printed layer 18 was formed on the stretched PET film. Thereafter, the stretched PET film and the laminate having the vapor-deposited film 11 and the unstretched polypropylene film were bonded by a dry lamination method via the second adhesive layer 15 formed of an adhesive layer. Thus, the packaging material 10 having the layer configuration shown in FIG. 5 was produced.

The layer configuration of the packaging material 10 of the present embodiment is expressed as follows.
PET12 / Mark / Adhesive / Barrier / Evaporation / Bio PET12 / Adhesive / CPP60

  Subsequently, using the packaging material 10, a standing pouch shown in FIG. 9 and a range pouch shown in FIG. 10 were produced. The standing pouch and the range pouch 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 configuration of the packaging material 10 of the present embodiment is expressed as follows.
Bio PET12 / Evaporation / Barrier / Mark / Adhesive / Nylon 15 / Adhesive / PE (2) 50

  Then, the standing pouch shown in FIG. 9 was produced using the packaging material 10. The standing pouch can accommodate, for example, prepared foods.

[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 configuration of the packaging material 10 of the present embodiment is expressed as follows.
Bio PET12 / Evaporation / Barrier / Mark / Adhesive / Nylon 15 / Adhesive / PE (2) 120

  Subsequently, using the packaging material 10, a refill pouch shown in FIG. 11 was produced. The refill pouch can contain a liquid detergent, shampoo, rinse, conditioner, and the like.

  FIG. 21 shows the layer configurations of the packaging materials of Examples B1 to B10.

Reference Signs List 10 packaging material 11 vapor-deposited film 111 first plastic film 112 transparent vapor-deposited 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 print layer 30 packaging container 31 upper part 32 Lower part 33 Side part 34A Surface film 34B Backside film 36 Lower film 36a Lower seal part 38 Joint part 39 Storage part 40 Steam release mechanism 41 Steam release seal part 42 Unsealed part 43 Outlet part 44 Outlet seal part 45 Container body 46 Lid 47 Tube body 48 Cap

Claims (7)

A vapor-deposited film, a packaging material comprising a sealant layer positioned on the inner side than the vapor-deposited film,
The vapor deposition film has a stretched first plastic film, a transparent vapor deposition layer provided on the first plastic film and containing aluminum oxide, and a gas barrier coating film provided on the transparent vapor deposition layer. And
The first plastic film includes a biomass-derived polyester,
The transparent deposition layer includes a transition region,
The transition region is detected by performing etching on the vapor-deposited film from the gas barrier coating film side using time-of-flight secondary ion mass spectrometry (TOF-SIMS). A region between the position of the peak of Al ₂ O ₄ H and the interface between the transparent vapor-deposited layer and the first plastic film,
A packaging material, wherein a ratio of a thickness of the transition region to a thickness of the transparent vapor-deposited layer is 5% or more and 60% or less.   The packaging material according to claim 1, further comprising an anchor coat layer located between the vapor-deposited film and the sealant layer.   The packaging material according to claim 1, further comprising an adhesive resin layer located between the vapor-deposited film and the sealant layer.   The packaging material according to claim 1, further comprising an adhesive layer located between the vapor-deposited film and the sealant layer.   The packaging material according to claim 1, further comprising a second plastic film located outside the first plastic film.   The packaging material according to claim 1, further comprising a second plastic film located between the first plastic film and the sealant layer.   A packaging container comprising the packaging material according to claim 1.