JP2019150993A - Barrier laminate film and package - Google Patents

Abstract

To provide a barrier laminate film having excellent durability of barrier performance.SOLUTION: A barrier laminate film 100 in the present invention has a substrate layer (A), and an inorganic layer (B) having fibrous inorganic particles and a binder phase. When an average major axis of the fibrous inorganic particle is X[nm] and an average minor axis of it is X[nm], an aspect ratio represented by X/Xis 100 or more and 1000 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a barrier laminate film and a package.

As a barrier film, a barrier laminated film in which an inorganic layer containing inorganic particles and a binder phase is formed on a base material layer is known. The inorganic layer containing the inorganic particles and the binder phase can be formed not by a dry coating method such as a vapor deposition method or a sputtering method but by a wet coating method in which a coating liquid is formed on the base material layer. Therefore, since such a barrier laminate film is excellent in productivity, it has an advantage that manufacturing cost can be reduced and manufacturing equipment can be simplified.
As a technique regarding such a barrier laminate film, for example, the one described in Patent Document 1 (International Publication No. 2011/122036) can be mentioned.

Patent Document 1 is a composite structure having a base material (X) and a layer (Y) laminated on the base material (X), and the layer (Y) includes a reaction product (R), The reaction product (R) is a reaction product obtained by reacting at least the metal oxide (A) and the phosphorus compound (B), and the infrared absorption spectrum of the layer (Y) in the range of 800 to 1400 cm ^−1. Discloses a composite structure in which the wave number (n ¹ ) at which infrared absorption is maximum is in the range of 1080 to 1130 cm ⁻¹ .

International Publication No. 2011/122036

The level of technology required for various properties of barrier films is increasing.
In consideration of such a development environment, the present inventors have examined the barrier laminated film including the inorganic layer as described in Patent Document 1, for example, the barrier property is likely to be lowered when stress is applied from the outside. It became clear. That is, it has been found that the conventional barrier laminate film having the inorganic layer has room for improvement in terms of durability of the barrier performance.

  This invention is made | formed in view of the said situation, and provides the barrier property laminated | multilayer film excellent in durability of barrier performance.

  The present inventor has intensively studied to solve the above problems. As a result, the present invention was completed by obtaining the knowledge that the durability of the barrier performance can be improved by using an inorganic layer containing fibrous inorganic particles having an aspect ratio in a specific range as the barrier layer.

  That is, according to the present invention, the following barrier laminate film and package are provided.

[1]
A barrier laminate film comprising a base material layer (A) and an inorganic layer (B) containing fibrous inorganic particles and a binder phase,
When the average major axis of the fibrous inorganic particles is X ₁ [nm] and the average minor axis is X ₂ [nm], the barrier laminate film having an aspect ratio represented by X ₁ / X ₂ of 100 or more and 1000 or less. .
[2]
In the barrier laminate film according to the above [1],
Barrier laminate film average major axis _{X 1} of the fibrous inorganic particles is 1000nm or 5000nm or less.
[3]
In the barrier laminate film according to the above [1] or [2],
In the X-ray diffraction spectrum of the inorganic layer (B) obtained by X-ray diffraction using CuKα rays as a radiation source,
A barrier laminate film in which a diffraction peak is observed within a diffraction angle range of 2θ = 10 ° to 18 °.
[4]
In the barrier laminate film according to any one of the above [1] to [3],
A barrier laminate film in which the fibrous inorganic particles include one or more inorganic materials selected from the group consisting of aluminum oxide, zirconium oxide, tin oxide, titanium oxide, zinc oxide, and silicon oxide.
[5]
In the barrier laminate film according to the above [4],
A barrier laminate film in which the fibrous inorganic particles contain aluminum oxide.
[6]
In the barrier laminate film according to any one of the above [1] to [5],
A barrier laminate film in which the binder phase is formed of at least one inorganic compound selected from the group consisting of phosphorus compounds and boron compounds.
[7]
In the barrier laminate film according to any one of the above [1] to [6],
The barrier laminate film in which the fibrous inorganic particles and the binder phase are covalently bonded.
[8]
In the barrier laminate film according to any one of the above [1] to [7],
The total content of aluminum element, zirconium element, tin element, titanium element, zinc element and silicon element contained in the inorganic layer (B) is Y ₁ [mol],
A barrier laminate film in which Y ₁ / Y ₂ is 0.8 or more and 3.0 or less when the total content of phosphorus element and boron element contained in the inorganic layer (B) is Y ₂ [mol].
[9]
In the barrier laminate film according to any one of the above [1] to [8],
In the infrared absorption spectrum of the inorganic layer (B) by the total reflection measurement method,
Barrier laminate film having an absorption peak in the range of less absorption band 1080 cm ^-1 or 1130 cm ^-1.
[10]
In the barrier laminate film according to any one of the above [1] to [9],
A barrier laminate film having no inorganic layer (C) other than the inorganic layer (B) between the substrate layer (A) and the inorganic layer (B).
[11]
In the barrier laminate film according to any one of the above [1] to [10],
A barrier laminate film having a parallel light transmittance of 50% or more at a wavelength of 600 nm.
[12]
In the barrier laminate film according to any one of the above [1] to [11],
A barrier laminate film having a water vapor permeability of 10.0 g / (m ² · 24 h) or less at 40 ° C. and 90% RH.
[13]
In the barrier laminate film according to any one of the above [1] to [12],
A barrier laminate film that is a packaging film.
[14]
A package comprising the barrier laminate film according to any one of [1] to [13].

  ADVANTAGE OF THE INVENTION According to this invention, the barrier property laminated | multilayer film excellent in durability of barrier performance can be provided.

It is sectional drawing which showed typically an example of the structure of the barriering laminated film of embodiment which concerns on this invention.

  Embodiments of the present invention will be described below with reference to the drawings. In addition, the figure is a schematic diagram and does not match the actual dimensional ratio. In addition, "-" between the numbers in a sentence represents the following from the above, unless there is particular notice.

<Barrier laminated film>
FIG. 1 is a cross-sectional view schematically showing an example of the structure of a barrier laminate film 100 according to an embodiment of the present invention.
The barrier laminate film 100 is a barrier laminate film comprising a base material layer (A) and an inorganic layer (B) containing fibrous inorganic particles and a binder phase, and the average major axis of the fibrous inorganic particles is determined. When X ₁ [nm] and the average minor axis are X ₂ [nm], the aspect ratio represented by X ₁ / X ₂ is 100 or more and 1000 or less.

As described above, according to the study by the present inventors, a barrier laminated film in which an inorganic layer containing inorganic particles and a binder phase is formed on a base material layer has a barrier property when, for example, external stress is applied. It became clear that it is easy to fall. That is, it has been found that the conventional barrier laminate film having the inorganic layer has room for improvement in terms of durability of the barrier performance.
Therefore, as a result of intensive studies, the present inventor has obtained barrier performance by using an inorganic layer (B) containing fibrous inorganic particles having an aspect ratio of X ₁ / X ₂ in the above range as the barrier layer. It has been found that durability can be improved.
That is, in the barrier laminate film 100 according to this embodiment, the durability of the barrier performance can be effectively improved by setting the aspect ratio indicated by X ₁ / X ₂ within the above range.
Although it is not clear why the durability of the barrier performance can be improved by setting the aspect ratio represented by X ₁ / X ₂ within the above range, the aspect ratio represented by X ₁ / X ₂ is within the above range. When it exists, it is thought that fibrous inorganic particle | grains orientate densely and the structure of an inorganic layer (B) becomes denser, As a result, the hole which water and gas pass becomes small, and barrier property improves. Further, since the fibrous inorganic particles are densely oriented, the interaction between the fibrous inorganic particles is increased, and the followability of the inorganic layer (B) to external stress is considered to be improved.
From the above, in the barrier laminate film 100 according to the present embodiment, it is considered that the durability of the barrier performance can be effectively improved by setting the aspect ratio represented by X ₁ / X ₂ within the above range. It is done.

The average major axis X ₁ and the average minor diameter X ₂ of the fibrous inorganic particles by transmission electron microscopy (TEM) can be measured by observing the cross section of the inorganic substance layer (B).
For example, in the cross-sectional observation image of the inorganic layer (B) obtained by a transmission electron microscope (TEM), the maximum length on the longest axis of each inorganic particle is the major axis, and the maximum length on the axis perpendicular thereto is the minor axis. The average major axis X ₁ and the average minor axis X ₂ can be determined by averaging the major axis and minor axis of 10 particles arbitrarily selected in the cross-sectional observation image.

The barrier laminate film 100 according to the present embodiment has a water vapor permeability of 10.0 g / (m ² · 24 h) measured under conditions of a temperature of 40 ° C. and a humidity of 90% RH from the viewpoint of further improving the water vapor barrier property. ) Or less, more preferably 5.0 g / (m ² · 24 h) or less, further preferably 2.0 g / (m ² · 24 h) or less, and 1.0 g / (m ² · 24h) or less, and more preferably 0.5g / (m ² · 24h) or less.
The water vapor permeability can be controlled, for example, by appropriately adjusting the constituent material, manufacturing conditions, thickness, and the like of the inorganic layer (B).

  In the barrier laminate film 100 according to this embodiment, the parallel light transmittance at a wavelength of 600 nm is preferably 50% or more, more preferably 75% or more, and particularly preferably 80% or more. By carrying out like this, transparency can be provided to the barriering laminated film 100, and when the packaging body etc. are formed using the barriering laminated film 100 which concerns on this embodiment, the visibility of the content is improved. be able to.

  Hereinafter, each layer constituting the barrier laminate film 100 will be described.

[Base material layer (A)]
The base material layer (A) is formed of, for example, an organic material such as a thermosetting resin, a thermoplastic resin, or paper, and includes at least one resin selected from a thermosetting resin and a thermoplastic resin. preferable.

  Examples of the thermosetting resin include known thermosetting resins such as epoxy resins, unsaturated polyester resins, phenol resins, urea / melamine resins, polyurethane resins, silicone resins, and polyimides.

Examples of the thermoplastic resin include polyolefin (polyethylene, polypropylene, poly (4-methyl-1-pentene), poly (1-butene), etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide, and the like. (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyvinylidene chloride, polyimide, ethylene vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer , Known thermoplastic resins such as fluororesin or a mixture thereof.
Among these, from the viewpoint of improving transparency, one or more selected from polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, and polyimide are preferable, and selected from polyethylene terephthalate and polyethylene naphthalate More preferred is at least one of the above.
Further, the base material layer (A) composed of the thermoplastic resin may be a single layer or two or more layers depending on the application of the barrier laminate film 100.

  Further, a film composed of at least one resin selected from thermosetting resins and thermoplastic resins may be stretched in at least one direction, preferably in a biaxial direction, to form the base material layer (A).

  As the base material layer (A), one or more thermoplastic resins selected from polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide and polyimide are used from the viewpoint of excellent transparency, rigidity and heat resistance. A biaxially stretched film composed of at least one thermoplastic resin selected from polyethylene terephthalate and polyethylene naphthalate is more preferred.

Moreover, in order to improve the adhesiveness with an inorganic substance layer (B) on the single side | surface or both surfaces of a base material layer (A), you may surface-treat. Specifically, surface activation treatment such as corona treatment, flame treatment, plasma treatment, primer coating treatment, ozone treatment, undercoat treatment, and coupling agent treatment may be performed.
Moreover, you may provide an adhesive bond layer between a base material layer (A) and an inorganic substance layer (B) from a viewpoint of improving the interlayer adhesiveness of a base material layer (A) and an inorganic substance layer (B). The adhesive which comprises an adhesive bond layer is not specifically limited, A well-known adhesive agent can be used.

  The thickness of the base material layer (A) is preferably 1 μm or more and 1000 μm or less, more preferably 1 μm or more and 500 μm or less, and even more preferably 1 μm or more and 300 μm or less from the viewpoint of obtaining good film properties.

[Inorganic layer (B)]
The inorganic layer (B) according to the present embodiment is a layer containing fibrous inorganic particles and a binder phase. For example, the fibrous inorganic oxide sol (B1) that is a precursor of the fibrous inorganic particles and the precursor of the binder phase. It is formed by heating a mixture containing the inorganic compound (B2) as a body to cause a sol-gel reaction. That is, the inorganic layer (B) according to the present embodiment includes, for example, a three-dimensional cross-linked product of the fibrous inorganic oxide sol (B1) and the inorganic compound (B2). In this case, in the inorganic layer (B) according to the present embodiment, the fibrous inorganic particles and the binder phase are bonded by a covalent bond. Thereby, the barrier property of the obtained barrier laminate film 100 can be made better.

The fibrous inorganic particles according to the present embodiment are fibrous inorganic particles, and are represented by X ₁ / X ₂ when the average major axis is X ₁ [nm] and the average minor axis is X ₂ [nm]. The aspect ratio is 100 or more and 1000 or less. The aspect ratio is preferably 200 or more, more preferably 300 or more, and still more preferably 350 or more, from the viewpoint of improving the durability of the barrier performance. The film forming property of the inorganic layer (B) and the inorganic layer From the viewpoint of the orientation of the fibrous inorganic particles in (B), it is preferably 900 or less, more preferably 850 or less, and still more preferably 800 or less.

The average major axis _{X 1} of the fibrous inorganic particles according to the present embodiment, from the viewpoint of more improving the durability of the barrier properties, preferably 1000nm, more preferably at least 1100 nm, even more preferably 1200nm or more, an inorganic layer From the viewpoint of the film-forming property of (B) and the orientation of the fibrous inorganic particles in the inorganic layer (B), it is preferably 5000 nm or less, more preferably 4500 nm or less, still more preferably 4000 nm or less, and particularly preferably 3500 nm or less. .

Examples of the inorganic substance constituting the fibrous inorganic particles according to this embodiment include one or more inorganic substances selected from the group consisting of aluminum oxide, zirconium oxide, tin oxide, titanium oxide, zinc oxide, silicon oxide, and the like. Is mentioned. One kind of inorganic substance constituting the fibrous inorganic particles may be used, or two or more kinds may be used. Among these, the inorganic substance constituting the fibrous inorganic particles from the point that the production of the fibrous inorganic particles can be made easier and the barrier property of the resulting barrier laminate film 100 can be made better. One or more selected from the group consisting of aluminum oxide, titanium oxide, zinc oxide and zirconium oxide are preferable, and aluminum oxide is more preferable.
Moreover, the inorganic substance couple | bonded with the surface of the other inorganic particle may be couple | bonded with the surface of the fibrous inorganic particle contained in the inorganic layer (B) which concerns on this embodiment.

As the fibrous inorganic oxide sol (B1) which is a precursor of the fibrous inorganic particles, for example, hydrolysis condensation of a compound (B1-1) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded. Thing etc. are mentioned.
Examples of the metal atom (M) constituting the fibrous inorganic oxide sol (B1) can include metal atoms having a valence of 2 or more (for example, 2 to 4), specifically, magnesium, Periodic Table Group 2 metals such as calcium; Periodic Table Group 12 metals such as zinc; Periodic Table Group 13 metals such as aluminum; Periodic Table Group 14 metals such as silicon; Transitions such as titanium and zirconium A metal etc. can be mentioned. Silicon may be classified as a semimetal, but in this embodiment, silicon is included in the metal.
The metal atom (M) constituting the fibrous inorganic oxide sol (B1) may be one type or two or more types. Among these, the fibrous inorganic oxide sol (B1) can be produced more easily, and the barrier property of the resulting barrier laminate film 100 can be further improved. The metal atom (M) constituting the sol (B1) is preferably one or more selected from the group consisting of aluminum, titanium, zinc and zirconium, and more preferably aluminum.

  The fibrous inorganic oxide sol (B1) can be produced, for example, by a method such as a liquid phase synthesis method, a gas phase synthesis method, or a solid pulverization method. Considering the controllability of the shape and size of the obtained fibrous inorganic oxide sol (B1), production efficiency, and the like, those produced by a liquid phase synthesis method are preferable.

When the liquid phase synthesis method is used, the compound (B1-1) containing a metal atom (M) to which a hydrolyzable characteristic group (functional group) is bonded is hydrolyzed and condensed, whereby the compound (B1-1) A fibrous inorganic oxide sol (B1) can be synthesized as a hydrolysis condensate.
In this embodiment, the compound (B1-1) includes a partial hydrolyzate of the compound (B1-1), a complete hydrolyzate of the compound (B1-1), and a partial hydrolysis condensate of the compound (B1-1). In addition, a product obtained by condensing a part of the complete hydrolyzate of compound (B1-1), a mixture of two or more of these, and the like are also included.
The type of the hydrolyzable characteristic group is not particularly limited, and examples thereof include a halogen atom (F, Cl, Br, I, etc.), an alkoxy group, an acyloxy group, a diacylmethyl group, and a nitro group. Among these, since it is excellent in controllability of reaction, a halogen atom or an alkoxy group is preferable, and an alkoxy group is more preferable.

Examples of the compound (B1-1) include aluminum chloride, aluminum triethoxide, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tris-butoxide, aluminum tri-t-butoxide, and aluminum triacetate. , Aluminum compounds such as aluminum acetylacetonate and aluminum nitrate; titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxide, titanium tetraethoxide, titanium acetylacetonate, etc. Titanium compounds such as zirconium tetranormal propoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate Onium compounds, and the like.
Among these, as the compound (B1-1), at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide is preferable. As the compound (B1-1), one type may be used alone, or two or more types may be used in combination.

  By hydrolyzing the compound (B1-1), at least a part of the hydrolyzable characteristic group of the compound (B1-1) can be substituted with a hydroxyl group. And the compound by which the metal atom (M) was couple | bonded through the oxygen atom (O) is formed when the hydrolyzate of a compound (B1-1) condenses. Next, the fibrous inorganic oxide sol (B1) is obtained by repeating this condensation. In addition, a hydroxyl group usually exists on the surface of the fibrous inorganic oxide sol (B1).

The binder phase according to the present embodiment is a phase that exists between the fibrous inorganic particles and binds the fibrous inorganic particles.
The binder phase according to the present embodiment is formed of, for example, at least one inorganic compound (B2) selected from the group consisting of a phosphorus compound and a boron compound.

The inorganic compound (B2) has one or more sites capable of reacting with the fibrous inorganic oxide sol (B1). As an inorganic compound (B2), a phosphorus compound, a boron compound, etc. can be mentioned, for example.
As the inorganic compound (B2), for example, a compound having a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom or a boron atom can be used. By using such an inorganic compound (B2), it can couple | bond by hydrolytic condensation with the hydroxyl group which exists on the surface of fibrous inorganic oxide sol (B1).

Examples of the phosphorus compound include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof.
Examples of the boron compound include boric acid, polyboric acid, boric acid, metaboric acid, tetraboric acid, and derivatives thereof.
These inorganic compounds (B2) may be used alone or in combination of two or more. Among these inorganic compounds (B2), the stability of the coating liquid (B) when the inorganic layer (B) is formed using the coating liquid (B) described later, and the barrier property of the resulting barrier laminate film 100 And phosphoric acid or boric acid is preferable, and phosphoric acid is more preferable.

As described above, the inorganic layer (B) according to this embodiment is a layer including fibrous inorganic particles and a binder phase, and for example, a three-dimensional structure of a fibrous inorganic oxide sol (B1) and an inorganic compound (B2). It contains a cross-linked product.
That is, the inorganic layer (B) according to the present embodiment includes, for example, a fibrous inorganic oxide sol (B1) that is a precursor of fibrous inorganic particles, and an inorganic compound (B2) that is a binder phase precursor, It is formed by applying a coating liquid (B) containing a sol-gel reaction between the fibrous inorganic oxide sol (B1) and the inorganic compound (B2) by applying the coating liquid (B) on the substrate layer (A) and then heating. be able to.

In the barrier laminate film 100 according to this embodiment, the total content of aluminum element, zirconium element, tin element, titanium element, zinc element and silicon element contained in the inorganic layer (B) is Y ₁ [mol], and the inorganic substance When the total content of the phosphorus element and boron element contained in the layer (B) is Y ₂ [mol], Y ₁ / Y ₂ is from the viewpoint of further improving the water vapor barrier property of the barrier laminate film 100. Preferably, it is 0.8 or more and 3.0 or less, More preferably, it is 1.0 or more and 2.5 or less.
Here, the aluminum element, zirconium element, tin element, titanium element, zinc element and silicon element contained in the inorganic layer (B) are elements derived from, for example, the fibrous inorganic oxide sol (B1), and the inorganic layer (B The phosphorus element and boron element contained in () are, for example, elements derived from the inorganic compound (B2).
When Y ₁ / Y ₂ is within the above range, the ratio between the fibrous inorganic oxide sol (B1) and the inorganic compound (B2) becomes appropriate, and the fibrous inorganic oxide sol (B1) or the inorganic compound (B2). Can be suppressed, and as a result, the amount of unreacted hydroxyl groups can be reduced. Thereby, since the quantity of the hydroxyl group which exists in the inorganic substance layer (B) surface can be reduced, the water vapor | steam barrier property of the barriering laminated film 100 which concerns on this embodiment can be improved.

From the viewpoint of further improving the water vapor barrier property of the barrier laminate film 100, the barrier laminate film 100 according to this embodiment has an absorption band of 1080 cm ⁻ in the infrared absorption spectrum of the inorganic layer (B) by the total reflection measurement method. It is preferable to have an absorption peak in the range of ¹ or more and 1130 cm ⁻¹ or less.
Here, the fact that the absorption peak is observed within the absorption band of 1080 cm ⁻¹ or more and 1130 cm ⁻¹ or less means that the fibrous inorganic oxide sol (B1) reacts with the phosphorus compound and the fibrous inorganic oxide sol A bond represented by M-O-P in which the metal atom (M) constituting (B1) and the phosphorus atom (P) derived from the phosphorus compound are bonded via an oxygen atom (O) is generated. Represents.
Here, the measurement of the infrared absorption spectrum by the total reflection measurement method uses, for example, an FT / IR-300 apparatus manufactured by JASCO Corporation, a multiple reflection measurement unit ATR PRO410-M (prism: Germanium crystal, incident angle 45 degrees, multiple The number of reflections = 5) can be mounted, and at room temperature, the resolution can be 2 cm ⁻¹ and the number of integrations can be 64. The ATR unit is more preferably the multiple reflection method in that the quality of the absorption spectrum of the inorganic layer (B) can be improved than the single reflection method.

In the X-ray diffraction spectrum of the inorganic layer (B) obtained by X-ray diffraction using CuKα rays as a radiation source, the barrier laminate film 100 according to this embodiment is within a diffraction angle range of 2θ = 10 ° to 18 °. It is preferable that a diffraction peak is observed. Thereby, the water vapor | steam barrier property of the barriering laminated film 100 which concerns on this embodiment can be improved further, or the fall of the barrier property at the time of applying a stress from the outside can be suppressed further.
The reason why the durability of the barrier performance can be further improved by observing the diffraction peak in the range of the diffraction angle 2θ = 10 ° to 18 ° is not clear, but the diffraction angle 2θ = 10 ° to 18 °. The diffraction peak observed within the range is presumed to be a 020-plane peak, and when this peak is observed, it is considered that the fibrous inorganic particles are densely oriented so as to align the 020 plane. That is, the presence or absence of a diffraction peak in the range of diffraction angle 2θ = 10 ° to 18 ° in the inorganic layer (B) is considered to represent an index of the degree of orientation of the fibrous inorganic particles.
Therefore, when a diffraction peak is observed within a diffraction angle range of 2θ = 10 ° to 18 °, the structure of the inorganic layer (B) is more dense. As a result, the pores through which water passes become smaller, and water vapor It is considered that the barrier property is improved.
The diffraction peak within the range of the diffraction angle 2θ = 10 ° to 18 ° of the inorganic layer (B) according to the present embodiment has, for example, the average major axis of the fibrous inorganic particles and the aspect ratio indicated by X ₁ / X ₂ described above. It is possible to generate it by adjusting to the adjusted range.

  Here, the measurement of the X-ray diffraction spectrum using CuKα rays as a radiation source is performed, for example, by fixing the barrier laminate film 100 according to the present embodiment to a glass plate, and by using an X-ray diffractometer (product name: (MultiFlex 2 kW) can be obtained by powder X-ray diffraction analysis.

In this embodiment, the thickness of the inorganic layer (B) (when the barrier laminate film 100 according to this embodiment has two or more inorganic layers (B), the total thickness of each inorganic layer (B)) Can be obtained from an observation image obtained by a transmission electron microscope or a scanning electron microscope.
The thickness of the inorganic layer (B) is 0.05 μm or more from the viewpoint of improving the barrier properties of the barrier laminate film 100 and the adhesion between the base material layer (A) and the inorganic layer (B). It is preferably 0.1 μm or more, more preferably 0.2 μm or more, and it is possible to suppress the dimensional change of the inorganic layer (B), the inorganic layer (B) From the viewpoint of improving the flexibility and followability of B), it is preferably 5.0 μm or less, more preferably 4.0 μm or less, still more preferably 2.0 μm or less. It is still more preferable that it is 0 micrometer or less, and it is especially preferable that it is 0.9 micrometer or less.

(Formation method of inorganic layer (B))
The inorganic layer (B) according to the present embodiment includes, for example, a fibrous inorganic oxide sol (B1) that is a precursor of fibrous inorganic particles, and an inorganic compound (B2) that is a binder phase precursor. The coating liquid (B) can be formed by applying the coating liquid (B) on the base material layer (A) and then subjecting the coating liquid (B) to a sol-gel reaction by heating.
The method for forming the inorganic layer (B) includes, for example, the following step (1), step (2) and step (3).
Step (1): at least one inorganic compound containing a fibrous inorganic oxide sol (B1) and a site capable of reacting with the fibrous inorganic oxide sol (B1) and being a binder phase precursor ( Step of preparing coating liquid (B) containing fibrous inorganic oxide sol (B1), inorganic compound (B2) and solvent by mixing B2) and solvent Step (2): Base material layer (A ) A step of forming a precursor layer of the inorganic layer (B) on the base material layer (A) by applying the coating liquid (B) thereon Step (3): A precursor layer of the inorganic layer (B) Step of forming inorganic layer (B) on base material layer (A) by heat treatment Hereinafter, each step will be described.

(Process (1))
First, the fibrous inorganic oxide sol (B1), at least one inorganic compound (B2) containing a site capable of reacting with the fibrous inorganic oxide sol (B1) and being a binder phase precursor, The coating liquid (B) containing the fibrous inorganic oxide sol (B1), the inorganic compound (B2) and the solvent is prepared by mixing the solvent.

  Although it does not specifically limit as a solvent in a coating liquid (B), For example, Water; Alcohol solvents, such as methanol, ethanol, n-propanol, isopropanol; Ether-type solvents, such as tetrahydrofuran, dioxane, trioxane, dimethoxyethane; Acetone, methyl ethyl ketone Ketone solvents such as methyl vinyl ketone and methyl isopropyl ketone; glycol solvents such as ethylene glycol and propylene glycol; glycol derivative solvents such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; acetonitrile; dimethylformamide, dimethylacetamide Amide solvents such as dimethyl sulfoxide, sulfolane and the like.

The coating liquid (B) may further contain an acid compound such as an inorganic acid or an organic acid, if necessary. Examples of such an acid compound include acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and the like. These acid compounds may be used alone or in combination of two or more.
When the coating liquid (B) contains an acid compound, the reaction between the fibrous inorganic oxide sol (B1) and the inorganic compound (B2) is suppressed, and the precipitation and aggregation of the reaction product in the coating liquid (B) are suppressed. can do. Therefore, when the coating liquid (B) contains an acid compound, the appearance of the resulting barrier laminate film 100 can be improved.
The content of the acid compound in the coating liquid (B) is preferably 0.1% by mass or more and 5.0% by mass or less when the entire coating liquid (B) is 100% by mass, It is more preferable that the content is not less than mass% and not more than 2.0 mass%.

The coating liquid (B) may further contain a polymer (B3) in order to further improve the coatability. Examples of the polymer (B3) include a polymer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a carboxylate.
In the inorganic layer (B) according to this embodiment, the polymer (B3) is directly or indirectly bonded to one or both of the fibrous inorganic oxide sol (B1) and the inorganic compound (B2) by the functional group. You may do it.

Examples of the polymer (B3) include polyvinyl alcohol, polyvinyl acetate partially saponified products, polyethylene glycol, polyhydroxyethyl (meth) acrylate, starch and other polysaccharides, polysaccharide derivatives derived from polysaccharides, polyacrylic Acid, polymethacrylic acid, poly (acrylic acid / methacrylic acid), polyacrylate, polymethacrylate, salt of poly (acrylic acid / methacrylic acid), ethylene-vinyl alcohol copolymer, ethylene-maleic anhydride copolymer Examples thereof include a polymer, a styrene-maleic anhydride copolymer, an isobutylene-maleic anhydride alternating copolymer, an ethylene-acrylic acid copolymer, and a saponified ethylene-ethyl acrylate copolymer.
As the polymer (B3), at least one heavy selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, polyacrylate, polymethacrylic acid and polymethacrylate. It is preferably a coalescence.

In order to further improve the barrier property, the content of the polymer (B3) in the inorganic layer (B) is preferably 10% by mass or less when the entire inorganic layer (B) is 100% by mass. It is more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.1% by mass or less.
In order to further improve the coating property of the coating liquid (B), the content of the polymer (B3) in the inorganic layer (B) is 100% by mass of the entire inorganic layer (B). Is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.010% by mass or more.
The polymer (B3) may or may not react with other components in the inorganic layer (B). In addition, in this embodiment, also when the polymer (B3) is reacting with another component, it describes with a polymer (B3). For example, when the polymer (B3) is bonded to the fibrous inorganic oxide sol (B1) and / or the inorganic compound (B2), it is also expressed as the polymer (B3). In this case, the content of the polymer (B3) in the inorganic layer (B) is the mass of the polymer (B3) before being combined with the fibrous inorganic oxide sol (B1) and / or the inorganic compound (B2). Calculated by dividing by the mass of the inorganic layer (B).

From the viewpoint of storage stability and coating properties of the coating liquid (B), the solid content concentration of the coating liquid (B) is preferably 1% by mass or more and 20% by mass or less, and preferably 2% by mass or more and 15% by mass or less. It is more preferable that it is 3 mass% or more and 10 mass% or less.
In addition, from the viewpoint of storage stability and coating properties of the coating liquid (B), the pH of the coating liquid (B) is preferably in the range of 0.5 to 6.0, preferably 0.5 to 5.0. More preferably, it is in the range, more preferably in the range of 0.5 to 4.0.
The pH of the coating liquid (B) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound. Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of the basic compound include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, sodium acetate and the like.

(Process (2))
Next, the precursor layer of the inorganic layer (B) is formed on the base material layer (A) by applying the coating liquid (B) on the base material layer (A).
The coating liquid (B) may be applied directly on at least one surface of the base material layer (A). Moreover, before apply | coating coating liquid (B), the surface of a base material layer (A) is processed with a well-known anchor coating agent, or a well-known adhesive agent is apply | coated to the surface of a base material layer (A). In addition, an adhesive layer may be formed on the surface of the base material layer (A).

  In addition, the coating liquid (B) may be degassed and / or defoamed as necessary. Examples of the degassing and / or defoaming treatment include evacuation, heating, centrifugation, and ultrasonic waves.

  The method for applying the coating liquid (B) on the base material layer (A) is not particularly limited, and a known method can be used. For example, reverse rolls such as Mayer bar coater, air knife coater, direct gravure coater, gravure offset, arc gravure coater, gravure reverse and jet nozzle type gravure coater, top feed reverse coater, bottom feed reverse coater and nozzle feed reverse coater Examples of the coating method include various known coating machines such as a coater, a five-roll coater, a lip coater, a bar coater, a bar reverse coater, a die coater, and an applicator.

  Subsequently, the precursor layer of an inorganic material layer (B) can be formed by removing the solvent in a coating liquid (B) as needed. The method for removing the solvent is not particularly limited, and a known drying method can be applied.

(Process (3))
Next, the inorganic layer (B) is formed on the base material layer (A) by heat-treating the precursor layer of the inorganic layer (B).
It does not specifically limit as a heat processing method of the precursor layer of an inorganic substance layer (B), A well-known method can be used. For example, the method of heat-processing using hot air drying, hot roll drying, microwave irradiation, high frequency irradiation, infrared irradiation, UV irradiation etc. is mentioned.
By subjecting the precursor layer of the inorganic layer (B) to heat treatment, a fibrous inorganic oxide sol (B1) that is a precursor of fibrous inorganic particles and an inorganic compound (B2) that is a binder phase precursor The sol-gel reaction can be advanced.
The temperature condition for the heat treatment is preferably in the range of 130 to 220 ° C., and the time condition for the heat treatment is preferably selected in the range of 1 second to 12 hours according to the temperature condition. If the heat treatment temperature is low, it is necessary to carry out the treatment for a long time, and if the heat treatment temperature is high, the treatment may be carried out for a short time. The heat treatment time is preferably 1 second to 1 hour, more preferably 1 second to 15 minutes.

[Inorganic layer (C) other than inorganic layer (B)]
In the barrier laminate film 100 according to the present embodiment, an inorganic layer (B) between the base material layer (A) and the inorganic layer (B) from the viewpoint of further improving barrier properties such as water vapor barrier property and oxygen barrier property. An inorganic layer (C) other than) may be further provided. However, the barrier laminate film 100 according to the present embodiment is excellent in barrier properties without further including an inorganic layer (C) other than the inorganic layer (B), so that the manufacturing cost can be reduced or the manufacturing equipment can be simplified. From the standpoint of making it, the barrier laminate film 100 according to the present embodiment does not have an inorganic layer (C) other than the inorganic layer (B) between the base material layer (A) and the inorganic layer (B). Is preferred.

Examples of the inorganic substance constituting the inorganic layer (C) include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides that can form a thin film having a barrier property.
Examples of inorganic substances constituting the inorganic layer (C) include periodic table group 2A elements such as beryllium, magnesium, calcium, strontium, and barium; periodic table transition elements such as titanium, zirconium, ruthenium, hafnium, and tantalum; zinc and the like Periodic table group 2B elements; periodic table group 3A elements such as aluminum, gallium, indium and thallium; periodic table group 4A elements such as silicon, germanium and tin; simple substances such as group 6A elements of the periodic table such as selenium and tellurium, oxides , Nitrides, fluorides, oxynitrides, or the like.
Here, the family name of the periodic table is shown by the old CAS formula.

Furthermore, among the above inorganic materials, because of excellent balance of barrier properties and cost, one or more inorganic materials selected from the group consisting of silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide and aluminum are used. preferable.
In addition, silicon oxide may contain silicon monoxide, silicon suboxide, etc. in addition to silicon dioxide.

  The inorganic layer (C) is composed of the inorganic material. The inorganic layer (C) may be composed of a single inorganic layer or may be composed of a plurality of inorganic layers. Moreover, when the inorganic layer (C) is composed of a plurality of inorganic layers, it may be composed of the same kind of inorganic layer, or may be composed of different kinds of inorganic layers.

The thickness of the inorganic layer (C) is preferably 1 nm or more and 500 nm or less, more preferably 2 nm or more and 300 nm or less, and further preferably 5 nm or more and 150 nm or less, from the viewpoint of balance between barrier properties, adhesion, and handleability.
In the present embodiment, the thickness of the inorganic layer (C) can be obtained from an observation image obtained by a transmission electron microscope or a scanning electron microscope.

  The method for forming the inorganic layer (C) is not particularly limited. For example, the inorganic layer (C) may be formed on one or both sides of the base layer (A) by a vacuum process such as a vacuum deposition method, a sputtering method, and a plasma vapor deposition method (CVD method). A layer (C) can be formed.

[Heat-fusion layer]
The barrier laminate film 100 according to the present embodiment may be provided with a heat-sealing layer on at least one surface in order to impart heat sealability.
Examples of the heat-fusible layer include homopolymers or copolymers of α-olefins such as ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, octene-1; Polyethylene; Linear low density polyethylene (so-called LLDPE); High density polyethylene; Polypropylene; Polypropylene random copolymer; Low crystalline or amorphous ethylene / propylene random copolymer; Ethylene / butene-1 random copolymer; Propylene / butene-1 random copolymer; a layer composed of a resin composition containing one or two or more polyolefins selected from, etc .; composed of a resin composition containing an ethylene / vinyl acetate copolymer (EVA) A layer composed of a resin composition containing EVA and polyolefin, and the like That.

<Application>
Since the barrier laminate film 100 according to the present embodiment is excellent in water vapor barrier property and oxygen barrier property, for example, foods; chemicals such as agricultural chemicals, chemicals, and pharmaceuticals; medical equipments; mechanical parts, precision materials, etc. Industrial materials; daily goods; can be suitably used as packaging films for packaging clothing and the like.
Moreover, the barrier laminate film 100 according to the present embodiment includes, for example, a film for vacuum insulation panel, an electroluminescent element, a sealing film for sealing a solar cell, an electronic device, and the like, an LCD substrate film, an organic film EL substrate film, electronic paper substrate film, PDP film, LED film, IC tag film, solar cell backsheet, solar cell protective film, optical communication member, electronic device flexible film, fuel cell It can also be used as a diaphragm, a sealing film for fuel cells, various functional films and the like.
Since the barrier laminate film 100 according to this embodiment is excellent in water vapor barrier properties, it can be particularly suitably used as a packaging film.

Moreover, the barrier laminate film 100 according to this embodiment can also be suitably used as a film constituting a package. The package according to the present embodiment is, for example, a packaging bag used for the purpose of containing contents or the contents contained in the bag. Further, the packaging bag according to the present embodiment may use the barrier laminate film 100 for a part of the packaging bag, or may use the barrier laminate film 100 for the entire packaging bag.
Since the package containing the barrier laminate film 100 according to this embodiment is excellent in water vapor barrier properties, it can be suitably used as a food packaging.

  As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

  Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. In addition, this embodiment is not limited to description of these Examples at all.

<Evaluation method>
(1) Measurement of water vapor permeability Adhesive (polyurethane adhesive (manufactured by Mitsui Chemicals, product name) on one side of a 70 μm thick unstretched polypropylene film (trade name: RXC-22, manufactured by Mitsui Chemicals, Inc.). Takelac A525S): 9 parts by weight, isocyanate-based curing agent (Mitsui Chemicals, trade name: Takenate A50): 1 part by weight and ethyl acetate: 7.5 parts by weight) were applied so that the thickness after drying was 3 μm. Then, a polyurethane adhesive layer was formed by drying. Next, the barrier laminate film and the unstretched polypropylene film were brought into contact with the inorganic layer (B) surface of the barrier laminate film obtained in the examples and comparative examples and the polyurethane adhesive layer of the unstretched polypropylene film. Were laminated together (dry lamination) to obtain a multilayer film. The multilayer film was aged at 40 ° C. for 5 days in order to cure the adhesive layer.
About the obtained multilayer film, it turned up so that an unstretched polypropylene film might become an inner surface, and heat sealed two sides and made it into the bag shape. Thereafter, calcium chloride was added as a content. Next, the other one was heat-sealed to prepare bags having an inner surface area of 0.01 m ² . Next, the obtained bags were stored for 300 hours under the conditions of 40 ° C. and humidity 90% RH. The weight of calcium chloride before and after storage was measured, and the water vapor permeability (g / (m ² · 24 h)) was calculated from the difference.

(2) Measurement of water vapor permeability after pulling Using a tensile tester, the barrier laminated films obtained in Examples and Comparative Examples were measured with a chuck distance of 150 mm, a sample width of 120 mm, a chuck width of 100 mm, and a pulling speed of 50 mm / min. Barrier laminated films after 2%, 3% and 5% tension, 2%, 3% and 5% tension were obtained respectively under the conditions described above. Subsequently, the water vapor permeability of the barrier laminate film after 2%, 3% and 5% tension was measured.

(3) Measurement of infrared absorption spectrum of inorganic layer (B) by total reflection measurement method Measurement of total reflection infrared absorption spectrum (ATR method) uses an FT / IR-300 apparatus manufactured by JASCO Corporation to improve spectral quality. A multiple reflection measurement unit ATR PRO410-M (prism: Germanium crystal, incident angle 45 degrees, multiple reflection number = 5) was mounted, and measurement was performed at room temperature under a resolution of 2 cm ⁻¹ and an integration number of 64 times. The presence or absence of an absorption peak in the range of the absorption band from 1080 cm ^{−1 to} 1130 cm ⁻¹ was examined from the obtained absorption spectrum.

(4) X-ray diffraction analysis Using an X-ray diffractometer (manufactured by Rigaku Corporation, product name: MultiFlex 2 kW), an inorganic layer (in the barrier laminate films obtained in Examples and Comparative Examples) by X-ray diffraction analysis ( The X-ray diffraction spectra of B) were determined respectively. Here, the X-ray diffraction spectrum of the inorganic layer (B) was measured with the barrier laminate film fixed to the glass plate. Note that CuKα rays were used as the radiation source.

(5) Light transmittance Parallel light transmittance at a wavelength of 600 nm of the barrier laminate films obtained in Examples and Comparative Examples using a spectrophotometer using parallel light (manufactured by Hitachi High-Technology, model number U-3010). Was measured.

[Example 1]
(Preparation of coating solution (B))
For the formation of the inorganic layer (B), fibrous alumina sol (manufactured by Kawaken Fine Chemical Co., Ltd. (abbreviated as Kawakensha in Table 1), fibrous, trade name: Aluminum Sol F-1000), phosphoric acid and nitric acid were used. . Here, each component was mix | blended so that it might become Al element / P element / N element = 1.15 / 1.0 / 1.0 (molar ratio).
A specific blending procedure is as follows.
9.14 g of purified water, 0.344 g of 60% by weight nitric acid aqueous solution and 0.049 g of 5% by weight aqueous polyvinyl alcohol (Kuraraypoval PVA124 ^™ ) and 3.27 g of methanol with respect to 0.378 g of 85% by weight phosphoric acid aqueous solution Were added and stirred uniformly to obtain a solution [A]. Next, 4.00 g of a 4.8% by mass fibrous alumina sol solution (trade name: Alumina Sol F-1000 ^™ , manufactured by Kawaken Fine Chemical Co., Ltd.) was slowly added dropwise with the solution [A] vigorously stirred. Stir for another 30 minutes. After the completion of stirring, the coating solution (B1) having a pH of 0.85 was obtained by deaeration using an aspirator.

(Preparation of barrier laminated film)
As a base material layer, a 12 μm biaxially stretched polyethylene terephthalate film (trade name: Emblet PET12, manufactured by Unitika Co., Ltd.) is used, and the coating liquid (B1) is applied to the corona surface of PET12 and dried at 110 ° C. for 5 minutes. The precursor layer of the inorganic layer (B) was formed. Next, heat treatment was performed at 200 ° C. for 10 minutes to form an inorganic layer (B) having a thickness of 0.45 μm, and a barrier laminate film was obtained.
Here, as the average major axis X ₁ and the average minor axis X ₂ of the inorganic particles in the inorganic layer (B) in Table 1, the average major axis and the average minor axis of the alumina sol were adopted, respectively. The average major axis and the average minor axis of the alumina sol were measured by observing a dilute solution of the alumina sol with a transmission electron microscope (TEM).
Specifically, the maximum length of the longest axis of the alumina sol is defined as the major axis, the maximum length along the axis perpendicular thereto is defined as the minor axis, and the major axis and minor axis of 10 alumina sols arbitrarily selected in the TEM observation are averaged. Thus, the average major axis and the average minor axis of the alumina sol were determined.
Here, the present inventors have confirmed that in the step of forming the inorganic layer (B) in the present examples and comparative examples, grain growth of alumina sol that causes a large change in the aspect ratio does not occur. That is, the aspect ratio of the alumina sol used in the present example / comparative example does not change greatly even after the formation of the inorganic layer (B) as described above. Therefore, in Table 1, an average major axis X ₁ and the average minor diameter X ₂ of inorganic particles was employed alumina sol having an average major diameter and average minor diameter, respectively.
Table 1 shows the evaluation results of the obtained barrier laminate film.

<Examples 2-3 and Comparative Examples 1-6>
The ratio of each raw material was adjusted so that the ratio Y ₁ / Y ₂ of the content Y ₁ [mol] of the aluminum element to the content Y ₂ [mol] of the phosphorus element was the value shown in Table 1, and the inorganic used A barrier laminate film was prepared in the same manner as in Example 1 except that the oxide sol was changed to that shown in Table 1, and each evaluation was performed. Table 1 shows the evaluation results of the obtained barrier laminate film.

The barrier laminate film of the example using the fibrous inorganic particles having an aspect ratio of 100 to 1000 in the fibrous inorganic particles represented by X ₁ / X ₂ is an initial (before tension) water vapor barrier property and after tension It was excellent in water vapor barrier property. That is, it turned out that the barriering laminated film of an Example is excellent in durability of barrier performance. On the other hand, the barrier laminate film of the comparative example was inferior in durability of the barrier performance.

100 Barrier laminated film A Base material layer B Inorganic layer

Claims (14)

A barrier laminate film comprising a base material layer (A) and an inorganic layer (B) containing fibrous inorganic particles and a binder phase,
When the average major axis of the fibrous inorganic particles is X ₁ [nm] and the average minor axis is X ₂ [nm], the barrier laminate film having an aspect ratio represented by X ₁ / X ₂ of 100 or more and 1000 or less. . The barrier laminate film according to claim 1,
Barrier laminate film average major axis _{X 1} of the fibrous inorganic particles is 1000nm or 5000nm or less. In the barrier laminate film according to claim 1 or 2, in the X-ray diffraction spectrum of the inorganic layer (B) obtained by X-ray diffraction using CuKα rays as a radiation source,
A barrier laminate film in which a diffraction peak is observed within a diffraction angle range of 2θ = 10 ° to 18 °. In the barrier laminate film according to any one of claims 1 to 3,
The barrier laminate film, wherein the fibrous inorganic particles include one or more inorganic materials selected from the group consisting of aluminum oxide, zirconium oxide, tin oxide, titanium oxide, zinc oxide, and silicon oxide. In the barrier laminate film according to claim 4,
A barrier laminate film in which the fibrous inorganic particles contain aluminum oxide. In the barrier laminate film according to any one of claims 1 to 5,
A barrier laminate film in which the binder phase is formed of at least one inorganic compound selected from the group consisting of phosphorus compounds and boron compounds. In the barrier laminate film according to any one of claims 1 to 6,
The barrier laminate film in which the fibrous inorganic particles and the binder phase are covalently bonded. In the barrier laminate film according to any one of claims 1 to 7,
The total content of aluminum element, zirconium element, tin element, titanium element, zinc element and silicon element contained in the inorganic layer (B) is Y ₁ [mol],
A barrier laminate film in which Y ₁ / Y ₂ is 0.8 or more and 3.0 or less when the total content of phosphorus element and boron element contained in the inorganic layer (B) is Y ₂ [mol]. In the barrier laminate film according to any one of claims 1 to 8,
In the infrared absorption spectrum of the inorganic layer (B) by the total reflection measurement method,
Barrier laminate film having an absorption peak in the range of less absorption band 1080 cm ^-1 or 1130 cm ^-1. In the barrier laminate film according to any one of claims 1 to 9,
A barrier laminate film having no inorganic layer (C) other than the inorganic layer (B) between the substrate layer (A) and the inorganic layer (B). In the barrier laminate film according to any one of claims 1 to 10,
A barrier laminate film having a parallel light transmittance of 50% or more at a wavelength of 600 nm. The barrier laminate film according to any one of claims 1 to 11,
A barrier laminate film having a water vapor permeability of 10.0 g / (m ² · 24 h) or less at 40 ° C. and 90% RH. In the barrier laminate film according to any one of claims 1 to 12,
A barrier laminate film that is a packaging film.   A package comprising the barrier laminate film according to any one of claims 1 to 13.

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