JP7097720B2 - Barrier laminated film and packaging - Google Patents

Description

The present invention relates to a barrier laminated 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 by a wet coating method such as applying a coating liquid on the substrate layer, instead of a dry coating method such as a vapor deposition method or a sputtering method. Therefore, since such a barrier laminated film is excellent in productivity, it has advantages that the manufacturing cost can be reduced and the manufacturing equipment can be simplified.
Examples of the technique relating to such a barrier laminated film include those described in Patent Document 1 (International Publication No. 2011/122030).

Patent Document 1 describes a composite structure having a base material (X) and a layer (Y) laminated on the base material (X), wherein the layer (Y) contains a reaction product (R). The reaction product (R) is a reaction product formed 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 number of waves (n ¹ ) at which infrared absorption is maximized is in the range of 1080 to 1130 cm ^-1 .

International Publication No. 2011/122030

The technical level required for various properties of barrier films is becoming higher and higher.
Based on such a development environment, the present inventors have examined and found that the barrier-type laminated film provided with the inorganic layer as described in Patent Document 1 tends to have a reduced barrier property when, for example, external stress is applied. It became clear. That is, it was found that the conventional barrier laminated film provided with the inorganic material has room for improvement in terms of durability of the barrier performance.

The present invention has been made in view of the above circumstances, and provides a barrier laminated film having excellent durability of barrier performance.

The present inventor has diligently studied to solve the above problems. As a result, the present invention was completed with the finding 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 barrier laminated film and the package shown below are provided.

[1]
Fibrous inorganic particles and phosphorus compounds and boron containing the substrate layer (A) and one or more inorganics selected from the group consisting of aluminum oxide, zirconium oxide, tin oxide, titanium oxide, zinc oxide and silicon oxide. A barrier laminated film comprising an inorganic layer (B) containing a binder phase formed of at least one inorganic compound selected from the group consisting of compounds .
When the average major axis of the fibrous inorganic particles is X ₁ [nm] and the average minor axis is X ₂ [nm], the aspect ratio indicated by X ₁ / X ₂ is 100 or more and 1000 or less.
In the X-ray diffraction spectrum of the inorganic layer (B) obtained by X-ray diffraction using CuKα ray as a radiation source,
A barrier laminated film in which a diffraction peak is observed in the range of diffraction angle 2θ = 10 ° to 18 ° .
[2]
In the barrier laminated film according to the above [1],
A barrier laminated film having an average major axis X ₁ of the fibrous inorganic particles of 1000 nm or more and 5000 nm or less.
[3]
In the barrier laminated film according to the above [1] or [2] ,
A barrier laminated film in which the fibrous inorganic particles contain aluminum oxide .
[4]
In the barrier laminated film according to any one of the above [1] to [3] ,
A barrier laminated film in which the fibrous inorganic particles and the binder phase are covalently bonded.
[5]
In the barrier laminated film according to any one of the above [1] to [4] ,
The total content of the aluminum element, the zirconium element, the tin element, the titanium element, the zinc element and the silicon element contained in the inorganic layer (B) is defined as Y ₁ [mol].
A barrier laminated 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 material layer (B) is Y ₂ [mol].
[6]
In the barrier laminated film according to any one of the above [1] to [5] ,
In the infrared absorption spectrum of the inorganic layer (B) by the total reflection measurement method,
Absorption band A barrier laminated film having an absorption peak in the range of 1080 cm ^-1 or more and 1130 cm ^-1 or less.
[7]
In the barrier laminated film according to any one of the above [1] to [6] ,
A barrier laminated film having no inorganic layer (C) other than the inorganic layer (B) between the base material layer (A) and the inorganic layer (B).
[8]
In the barrier laminated film according to any one of the above [1] to [7] ,
A barrier laminated film having a parallel light transmittance of 50% or more at a wavelength of 600 nm.
[9]
In the barrier laminated film according to any one of the above [1] to [8] ,
A barrier laminated film having a water vapor transmission rate of 10.0 g / ( ^m 2.24 h) or less at 40 ° C. and 90% RH.
[10]
In the barrier laminated film according to any one of the above [1] to [9] ,
Barrier laminated film that is a packaging film.
[11]
A package containing the barrier laminated film according to any one of the above [1] to [10] .

According to the present invention, it is possible to provide a barrier laminated film having excellent durability of barrier performance.

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

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The figure is a schematic view and does not match the actual dimensional ratio. Unless otherwise specified, the "~" between the numbers in the text indicates the following from the above.

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

As described above, according to the study by the present inventors, the barrier laminated film in which the inorganic layer containing the inorganic particles and the binder phase is formed on the base material layer has a barrier property, for example, when stress is applied from the outside. It became clear that the amount was likely to decrease. That is, it was found that the conventional barrier laminated film provided with the inorganic material has room for improvement in terms of durability of the barrier performance.
Therefore, as a result of diligent studies by the present inventor, the barrier performance is improved by using the inorganic layer (B) containing the fibrous inorganic particles whose aspect ratio represented by X ₁ / X ₂ is in the above range as the barrier layer. We have found that durability can be improved.
That is, in the barrier laminated film 100 according to the present embodiment, 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 not clear why the durability of the barrier performance can be improved by setting the aspect ratio indicated by X ₁ / X ₂ within the above range, but the aspect ratio indicated by X ₁ / X ₂ is within the above range. If there is, it is considered that the fibrous inorganic particles are densely oriented and the structure of the inorganic layer (B) becomes denser, and as a result, the pores through which water and gas pass become smaller and the barrier property is improved. Further, since the fibrous inorganic particles are densely oriented, it is considered that the interaction between the fibrous inorganic particles is enhanced and the followability of the inorganic layer (B) to the external stress is improved.
From the above, 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 in the barrier laminated film 100 according to the present embodiment. Be done.

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

The barrier laminated film 100 according to the present embodiment has a water vapor permeability of 10.0 g / ( ^m 2.24 h) measured under the 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, 1.0 g / (m). It is even ^more preferably 2.24 h) or less, and particularly preferably 0.5 g / ( ^m 2.24 h) or less.
The water vapor transmission rate can be controlled, for example, by appropriately adjusting the constituent materials of the inorganic layer (B), manufacturing conditions, thickness, and the like.

In the barrier laminated film 100 according to the present 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 doing so, transparency can be imparted to the barrier laminated film 100, and when a package or the like is formed using the barrier laminated film 100 according to the present embodiment, the visibility of the contents is improved. be able to.

Hereinafter, each layer constituting the barrier laminated 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 may contain 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 resin, unsaturated polyester resin, phenol resin, urea / melamine resin, polyurethane resin, silicone resin, and polyimide.

Examples of the thermoplastic resin include polyolefins (polyethylene, polypropylene, poly (4-methyl-1-pentene), poly (1-butene), etc.), polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), and polyamides. (Nylon-6, Nylon-66, Polymethoxylen adipamide, etc.), Polyvinyl chloride, Polyvinylidene chloride, Polyethylene, Polyethylene vinyl acetate copolymer or its saponified product, Polyvinyl alcohol, Polyacrylonitrile, Polycarbonate, Polystyrene, Ionomer , A known thermoplastic resin such as a 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 is preferable, and polyethylene terephthalate and polyethylene naphthalate are selected. At least one is more preferred.
Further, the base material layer (A) made of the thermoplastic resin may be a single layer or two or more layers depending on the use of the barrier laminated film 100.

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

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

Further, one side or both sides of the base material layer (A) may be surface-treated in order to improve the adhesiveness with the inorganic material layer (B). Specifically, surface activation treatments such as corona treatment, flame treatment, plasma treatment, primer coating treatment, ozone treatment, undercoat treatment, and coupling agent treatment may be performed.
Further, from the viewpoint of improving the interlayer adhesiveness between the base material layer (A) and the inorganic material layer (B), an adhesive layer may be provided between the base material layer (A) and the inorganic material layer (B). The adhesive constituting the adhesive layer is not particularly limited, and a known adhesive 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 further preferably 1 μm or more and 300 μm or less from the viewpoint of obtaining good film characteristics.

[Inorganic layer (B)]
The inorganic layer (B) according to the present embodiment is a layer containing the fibrous inorganic particles and the binder phase, and is, for example, a fibrous inorganic oxide sol (B1) which is a precursor of the fibrous inorganic particles and a precursor of the binder phase. It is formed by heating a mixture containing the body inorganic compound (B2) and causing a sol-gel reaction. That is, the inorganic layer (B) according to the present embodiment contains, for example, a three-dimensional crosslinked product of a fibrous inorganic oxide sol (B1) and an 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 laminated film 100 can be improved.

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. From the viewpoint of improving the durability of the barrier performance, the aspect ratio is preferably 200 or more, more preferably 300 or more, still more preferably 350 or more, and 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 further preferably 800 or less.

The average major axis X ₁ of the fibrous inorganic particles according to the present embodiment is preferably 1000 nm or more, more preferably 1100 nm or more, still more preferably 1200 nm or more, and is an inorganic layer, from the viewpoint of improving the durability of the barrier performance. 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. ..

The inorganic substance constituting the fibrous inorganic substance particles according to the present embodiment is, for example, one or more kinds of inorganic substances selected from the group consisting of aluminum oxide, zirconium oxide, tin oxide, titanium oxide, zinc oxide, silicon oxide and the like. Can be mentioned. The inorganic substance constituting the fibrous inorganic substance particles may be one kind or two or more kinds. Among these, the inorganic substances constituting the fibrous inorganic particles are selected from the viewpoints that the production of the fibrous inorganic particles can be facilitated and the barrier properties of the obtained barrier laminated film 100 can be improved. It is preferably one or more selected from the group consisting of aluminum oxide, titanium oxide, zinc oxide and zirconium oxide, and more preferably aluminum oxide.
Further, the surface of the fibrous inorganic particles contained in the inorganic layer (B) according to the present embodiment may be bonded with an inorganic substance bonded to the surface of other inorganic particles.

The fibrous inorganic oxide sol (B1), which is a precursor of the fibrous inorganic particles, is, for example, hydrolyzed and condensed with a compound (B1-1) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded. Things etc. can be mentioned.
Examples of the metal atom (M) constituting the fibrous inorganic oxide sol (B1) include metal atoms having a valence of 2 or more (for example, 2 to 4 valence), and specifically, magnesium. Metals of Group 2 of the Periodic Table such as calcium; Metals of Group 12 of the Periodic Table such as zinc; Metals of Group 13 of the Periodic Table such as aluminum; Metals of Group 14 of the Periodic Table such as silicon; Transitions of titanium, zirconium, etc. Metals and the like can be mentioned. Silicon may be classified as a metalloid, but in this embodiment, silicon is included in the metal.
The metal atom (M) constituting the fibrous inorganic oxide sol (B1) may be one kind or two or more kinds. Among these, the fibrous inorganic oxide can be produced more easily and the barrier property of the obtained barrier laminated film 100 can be 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), the production efficiency, and the like, those produced by the liquid phase synthesis method are preferable.

When the liquid phase synthesis method is used, a compound (B1-1) containing a metal atom (M) to which a hydrolyzable characteristic group (functional group) is bonded is hydrolyzed and condensed to form a compound (B1-1). A fibrous inorganic oxide sol (B1) can be synthesized as a hydrolysis condensate.
In the present 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). , A part of the complete hydrolyzate of the compound (B1-1) condensed, and a mixture of two or more of these are also included.
The type of the property group that can be hydrolyzed 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, a nitro group, and the like. Among these, a halogen atom or an alkoxy group is preferable, and an alkoxy group is more preferable, because the reaction controllability is excellent.

Examples of the compound (B1-1) include aluminum chloride, aluminum triethoxydo, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tris-butoxide, aluminum trit-butoxide, and aluminum triacetate. , Aluminum acetylacetonate, aluminum compounds such as aluminum nitrate; titanium tetraisopropoxide, titanium tetranormalbutoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxyde, titanium tetraethoxydo, titanium acetylacetonate, etc. Titanium compounds; examples thereof include zirconium compounds such as zirconium tetranormal propoxide, zirconium tetrabutoxide, and zirconium tetraacetylacetonate.
Among these, as the compound (B1-1), at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide is preferable. One type of the compound (B1-1) 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 replaced with a hydroxyl group. Then, the hydrolyzate of the compound (B1-1) is condensed to form a compound in which a metal atom (M) is bonded via an oxygen atom (O). Then, by repeating this condensation, a fibrous inorganic oxide sol (B1) is obtained. A hydroxyl group is usually present on the surface of the fibrous inorganic oxide sol (B1).

The binder phase according to the present embodiment exists between the fibrous inorganic particles and is a phase that binds the fibrous inorganic particles to each other.
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). Examples of the inorganic compound (B2) include phosphorus compounds and boron compounds.
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 be hydrolyzed and condensed with a hydroxyl group existing on the surface of the 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, subboric 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 material layer (B) is formed by using the coating liquid (B) described later, and the barrier property of the obtained barrier laminated film 100. Phosphoric acid or boric acid is preferable, and phosphoric acid is more preferable, because the balance with and is more excellent.

As described above, the inorganic layer (B) according to the present embodiment is a layer containing fibrous inorganic particles and a binder phase, and is, for example, three-dimensionally composed of a fibrous inorganic oxide sol (B1) and an inorganic compound (B2). It contains a crosslinked product.
That is, the inorganic layer (B) according to the present embodiment includes, for example, a fibrous inorganic oxide sol (B1) which is a precursor of fibrous inorganic particles, and an inorganic compound (B2) which is a precursor of a binder phase. The coating liquid (B) containing the above is applied onto the base material layer (A), and then heated to form a fibrous inorganic oxide sol (B1) and an inorganic compound (B2) by sol-gel reaction. be able to.

In the barrier laminated film 100 according to the present embodiment, the total content of the aluminum element, the zirconium element, the tin element, the titanium element, the zinc element and the silicon element contained in the inorganic material layer (B) is set to Y ₁ [mol], and the inorganic material is used. When the total content of the phosphorus element and the 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 laminated film 100. It is preferably 0.8 or more and 3.0 or less, and more preferably 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 material layer (B) are, for example, elements derived from the fibrous inorganic oxide sol (B1), and the inorganic material layer (B). ), The phosphorus element and the boron element are, for example, elements derived from the inorganic compound (B2).
When Y ₁ / Y ₂ is within the above range, the ratio of the fibrous inorganic oxide sol (B1) to the inorganic compound (B2) becomes appropriate, and the fibrous inorganic oxide sol (B1) or the inorganic compound (B2) Can be suppressed from becoming excessive, and as a result, the amount of unreacted hydroxyl groups can be reduced. As a result, the amount of hydroxyl groups present on the surface of the inorganic layer (B) can be reduced, so that the water vapor barrier property of the barrier laminated film 100 according to the present embodiment can be improved.

The barrier laminated film 100 according to the present embodiment has an absorption band of 1080 cm ^- in the infrared absorption spectrum of the inorganic layer (B) by the total reflection measurement method from the viewpoint of further improving the water vapor barrier property of the barrier laminated film 100. 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 in the range of the absorption zone 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 to cause the fibrous inorganic oxide sol. A bond represented by MOP in which a metal atom (M) constituting (B1) and a phosphorus atom (P) derived from a phosphorus compound are bonded via an oxygen atom (O) is formed. Represents.
Here, for the measurement of the infrared absorption spectrum by the total reflection measurement method, for example, a multiple reflection measurement unit ATR PRO410-M (prism: Germanium crystal, incident angle 45 degrees, multiplex) using an FT / IR-300 device manufactured by Nippon Spectral Co., Ltd. The number of reflections = 5) can be attached, and the measurement can be performed at room temperature under the conditions of a resolution of 2 cm ^-1 and a total number of times of 64 times. As for the ATR unit, the multiple reflection method is preferable to the single reflection method in that the quality of the absorption spectrum of the inorganic layer (B) can be improved.

The barrier laminated film 100 according to the present embodiment has a diffraction angle of 2θ = 10 ° to 18 ° in the X-ray diffraction spectrum of the inorganic layer (B) obtained by X-ray diffraction using CuKα ray as a radiation source. It is preferable that a diffraction peak is observed. As a result, the water vapor barrier property of the barrier laminated film 100 according to the present embodiment can be further improved, and the deterioration of the barrier property when stress is applied from the outside can be further suppressed.
It is not clear 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 °, but the diffraction angle 2θ = 10 ° to 18 °. The diffraction peak observed within the range is presumed to be the peak of the 020 plane, 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, it is considered that the presence or absence of the diffraction peak in the diffraction angle 2θ = 10 ° to 18 ° in the inorganic layer (B) represents an index of the degree of orientation of the fibrous inorganic particles.
Therefore, when the diffraction peak is observed in the range of the diffraction angle 2θ = 10 ° to 18 °, the structure of the inorganic layer (B) is finer, and as a result, the pores through which water passes becomes smaller and the water vapor is vaporized. It is thought that the barrier property will be improved.
The diffraction peak in the range of the diffraction angle 2θ = 10 ° to 18 ° of the inorganic layer (B) according to the present embodiment describes, for example, the average major axis of the fibrous inorganic particles and the aspect ratio indicated by X ₁ / X ₂ . It is possible to generate it by adjusting it to the specified range.

Here, in the measurement of the X-ray diffraction spectrum using CuKα ray as the radiation source, for example, the barrier laminated film 100 according to the present embodiment is fixed to a glass plate, and an X-ray diffractometer (manufactured by Rigaku Co., Ltd., product name: It can be obtained by powder X-ray diffraction analysis method using MultiFlex 2kW).

Thickness of the inorganic layer (B) in the present embodiment (when the barrier laminated film 100 according to the present embodiment has two or more inorganic layers (B), the total thickness of each inorganic layer (B)) Can be obtained from an image observed 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 property of the barrier laminated film 100 and the adhesiveness 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 from the viewpoint of economic efficiency, the dimensional change of the inorganic layer (B) can be suppressed, or 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, and further preferably 2.0 μm or less. It is even more preferably 0 μm or less, and particularly preferably 0.9 μm or less.

(Method of forming the inorganic layer (B))
The inorganic layer (B) according to the present embodiment contains, for example, a fibrous inorganic oxide sol (B1) which is a precursor of fibrous inorganic particles and an inorganic compound (B2) which is a precursor of a binder phase. The coating liquid (B) can be formed by applying the coating liquid (B) on the base material layer (A) and then heating the coating liquid (B) to cause a sol-gel reaction.
The method for forming the inorganic layer (B) includes, for example, the following steps (1), (2) and (3).
Step (1): At least one inorganic compound (1) containing a fibrous inorganic oxide sol (B1) and a site capable of reacting with the fibrous inorganic oxide sol (B1) and being a precursor of the binder phase (1). Step of preparing a coating liquid (B) containing a fibrous inorganic oxide sol (B1), an inorganic compound (B2) and a solvent by mixing B2) with a solvent Step (2): Base material layer (A) ) To form a precursor layer of the inorganic layer (B) on the base material layer (A) by applying the coating liquid (B). Step (3): The precursor layer of the inorganic layer (B) is formed. Steps for Forming the Inorganic Material Layer (B) on the Base Material Layer (A) by Heat Treatment Each step will be described below.

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

The solvent in the coating liquid (B) is not particularly limited, but is, for example, water; alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; ether solvents such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; acetone and methyl ethyl ketone. , Methyl vinyl ketone, methyl isopropyl ketone and other ketone solvents; ethylene glycol, propylene glycol and other glycol solvents; methyl cellosolve, ethyl cellosolve, n-butyl cellosolve and other glycol derivative solvents; glycerin; acetonitrile; dimethylformamide, dimethylacetamide And the like; 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. One type of these acid compounds may be used alone, or two or more types may be used in combination.
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 reactants in the coating liquid (B) are suppressed. can do. Therefore, when the coating liquid (B) contains an acid compound, the appearance of the obtained barrier laminated 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, preferably 0.5% by mass, when the total amount of the coating liquid (B) is 100% by mass. It is more preferably mass% or more and 2.0 mass% or less.

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 acid anhydride group and a carboxylate salt.
In the inorganic layer (B) according to the present 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 be doing it.

Examples of the polymer (B3) include polyvinyl alcohol, partially saponified products of polyvinyl acetate, polyethylene glycol, polyhydroxyethyl (meth) acrylate, polysaccharides such as starch, polysaccharide derivatives derived from polysaccharides, and polyacrylic acid. Acid, polymethacrylic acid, poly (acrylic acid / methacrylic acid), polyacrylic acid salt, polymethacrylic acid salt, poly (acrylic acid / methacrylic acid) salt, ethylene-vinyl alcohol copolymer, ethylene-maleic anhydride Examples thereof include polymers, styrene-maleic anhydride copolymers, isobutylene-maleic anhydride alternating copolymers, ethylene-acrylic acid copolymers, and saponified products of ethylene-ethyl acrylate copolymers.
The polymer (B3) is at least one weight selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, polyacrylic acid salt, polymethacrylic acid and polymethacrylic acid salt. It is preferably coalesced.

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 total of the 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.
Further, in order to further improve the coatability of the coating liquid (B), the content of the polymer (B3) in the inorganic layer (B) was set to 100% by mass of the entire inorganic layer (B). When, it 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 this embodiment, even when the polymer (B3) reacts with other components, it is referred to as the 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 referred to as a polymer (B3). In this case, the content of the polymer (B3) in the inorganic layer (B) is the mass of the polymer (B3) before binding to 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 coatability 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 2% by mass or more and 15% by mass or less. It is more preferable that it is 3% by mass or more and 10% by mass or less.
Further, from the viewpoint of storage stability and coatability 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. It is more preferably in the range, and even 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, fatty acid, ammonium sulfate and the like. Examples of the basic compound include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, sodium acetate and the like.

(Step (2))
Next, the coating liquid (B) is applied onto the base material layer (A) to form a precursor layer of the inorganic material layer (B) on the base material layer (A).
The coating liquid (B) may be applied directly onto at least one surface of the substrate layer (A). Further, before applying the coating liquid (B), the surface of the base material layer (A) may be treated with a known anchor coating agent, or the surface of the base material layer (A) may be coated with a known adhesive. Alternatively, an adhesive layer may be formed on the surface of the base material layer (A).

Further, the coating liquid (B) may be degassed and / or defoamed, if necessary. Examples of the degassing and / or defoaming treatment method include evacuation, heating, centrifugation, ultrasonic waves and the like.

The method of applying the coating liquid (B) on the base material layer (A) is not particularly limited, and a known method can be used. For example, Mayer bar coater, air knife coater, direct gravure coater, gravure offset, arc gravure coater, gravure coater such as gravure reverse and jet nozzle method, top feed reverse coater, bottom feed reverse coater and reverse roll such as nozzle feed reverse coater. Examples thereof include a method of coating using various known coating machines such as a coater, a 5-roll coater, a lip coater, a bar coater, a bar reverse coater, a die coater, and an applicator.

Then, if necessary, the precursor layer of the inorganic layer (B) can be formed by removing the solvent in the coating liquid (B). The method for removing the solvent is not particularly limited, and a known drying method can be applied.

(Step (3))
Next, the precursor layer of the inorganic layer (B) is heat-treated to form the inorganic layer (B) on the base material layer (A).
The heat treatment method for the precursor layer of the inorganic layer (B) is not particularly limited, and a known method can be used. For example, a method of heat treatment using hot air drying, hot roll drying, microwave irradiation, high frequency irradiation, infrared irradiation, UV irradiation and the like can be mentioned.
By heat-treating the precursor layer of the inorganic layer (B), the fibrous inorganic oxide sol (B1) which is a precursor of the fibrous inorganic particles and the inorganic compound (B2) which is a precursor of the binder phase are used. And, the sol-gel reaction can proceed.
The temperature condition of the heat treatment is preferably in the range of 130 to 220 ° C., and the time condition of 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, the treatment needs to be performed for a long time, and if the heat treatment temperature is high, the treatment may be performed 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 laminated film 100 according to the present embodiment, from the viewpoint of further improving the barrier properties such as water vapor barrier property and oxygen barrier property, the inorganic material layer (B) is placed between the base material layer (A) and the inorganic material layer (B). ) May be further provided. However, since the barrier laminated film 100 according to the present embodiment has excellent barrier properties even if it does not further include the inorganic layer (C) other than the inorganic layer (B), the manufacturing cost can be reduced or the manufacturing equipment can be simplified. The barrier laminated 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 preferable.

Examples of the inorganic substance constituting the inorganic substance layer (C) include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides capable of forming a thin film having a barrier property.
Examples of the inorganic substances constituting the inorganic substance layer (C) include periodic table 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 2B elements; Periodic Table 3A elements such as aluminum, gallium, indium, and tarium; Periodic Table 4A elements such as silicon, germanium, and tin; Periodic Table 6A elements such as selenium and tellurium, oxides , One or more selected from nitrides, fluorides, oxynitrides and the like.
Here, the family name of the periodic table is shown by the old CAS formula.

Further, among the above-mentioned inorganic substances, one or more kinds of inorganic substances selected from the group consisting of silicon oxide, silicon nitride, silicon nitride, aluminum oxide and aluminum are selected because they have an excellent balance of barrier properties and cost. preferable.
In addition to silicon dioxide, silicon oxide may contain silicon monoxide, silicon suboxide, and the like.

The inorganic substance layer (C) is composed of the above-mentioned inorganic substances. The inorganic layer (C) may be composed of a single inorganic layer or may be composed of a plurality of inorganic layers. When the inorganic layer (C) is composed of a plurality of inorganic layers, it may be composed of the same type of inorganic layer or may be composed of different types 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 the balance of barrier property, adhesion, handleability and the like.
In the present embodiment, the thickness of the inorganic layer (C) can be determined from an observation image by a transmission electron microscope or a scanning electron microscope.

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

[Heat fusion layer]
The barrier laminated 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-sealing properties.
Examples of the heat-sealed layer include homopolymers or copolymers of α-olefins such as ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, and octene-1, which are high-pressure low densities. 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; A layer composed of a resin composition containing one or more kinds of polyolefins selected from propylene / butene-1 random copolymer; etc .; a layer composed of a resin composition containing an ethylene / vinyl acetate copolymer (EVA). Layer to be formed; a layer composed of a resin composition containing EVA and polyolefin can be mentioned.

<Use>
Since the barrier laminated film 100 according to the present embodiment is excellent in water vapor barrier property and oxygen barrier property, for example, foods; chemicals such as pesticides, chemicals and pharmaceuticals; medical equipment; mechanical parts, precision materials and the like. It can be suitably used as an industrial material; daily miscellaneous goods; a packaging film for packaging clothing and the like.
Further, the barrier laminated film 100 according to the present embodiment is, for example, a film for a vacuum heat insulating panel, an electroluminescence element, a sealing film for sealing a solar cell, an electronic device, etc., a substrate film for an LCD, and an organic film. For 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 a fuel cell, various functional films and the like.
Since the barrier laminated film 100 according to the present embodiment is excellent in water vapor barrier property, it can be particularly preferably used as a packaging film.

Further, the barrier laminated film 100 according to the present embodiment can be suitably used as a film constituting a package. The package according to the present embodiment is, for example, a packaging bag itself used for the purpose of accommodating the contents or a package containing the contents in the bag. Further, the packaging bag according to the present embodiment may use the barrier laminated film 100 as a part thereof depending on the intended use, or the barrier laminated film 100 may be used for the entire packaging bag.
Since the package containing the barrier laminated film 100 according to the present embodiment has excellent water vapor barrier properties, it can be suitably used as a food package.

Although the embodiments of the present invention have been described above with reference to the drawings, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the reference form will be added.
1. 1.
A barrier laminated 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 laminated film having an aspect ratio of 100 or more and 1000 or less represented by X ₁ / X ₂ . ..
2. 2.
1. 1. In the barrier laminated film described in 1.
A barrier laminated film having an average major axis X ₁ of the fibrous inorganic particles of 1000 nm or more and 5000 nm or less.
3. 3.
1. 1. Or 2. In the barrier laminated film described in
In the X-ray diffraction spectrum of the inorganic layer (B) obtained by X-ray diffraction using CuKα ray as a radiation source,
A barrier laminated film in which a diffraction peak is observed in the range of diffraction angle 2θ = 10 ° to 18 °.
4.
1. 1. To 3. In the barrier laminated film according to any one of
A barrier laminated film in which the fibrous inorganic particles contain one or more inorganic substances selected from the group consisting of aluminum oxide, zirconium oxide, tin oxide, titanium oxide, zinc oxide and silicon oxide.
5.
4. In the barrier laminated film described in 1.
A barrier laminated film in which the fibrous inorganic particles contain aluminum oxide.
6.
1. 1. ~ 5. In the barrier laminated film according to any one of
A barrier laminated film in which the binder phase is formed of at least one inorganic compound selected from the group consisting of a phosphorus compound and a boron compound.
7.
1. 1. ~ 6. In the barrier laminated film according to any one of
A barrier laminated film in which the fibrous inorganic particles and the binder phase are covalently bonded.
8.
1. 1. ~ 7. In the barrier laminated film according to any one of
The total content of the aluminum element, the zirconium element, the tin element, the titanium element, the zinc element and the silicon element contained in the inorganic layer (B) is defined as Y ₁ [mol].
A barrier laminated film in which Y ₁ / Y ₂ is 0.8 or more and 3.0 or less when the total content of the phosphorus element and the boron element contained in the inorganic layer (B) is Y ₂ [mol] .
9.
1. 1. ~ 8. In the barrier laminated film according to any one of
In the infrared absorption spectrum of the inorganic layer (B) by the total reflection measurement method,
Absorption band A barrier laminated film having an absorption peak in the range of 1080 cm ^-1 or more and 1130 cm ^-1 or less.
10.
1. 1. ~ 9. In the barrier laminated film according to any one of
A barrier laminated film having no inorganic layer (C) other than the inorganic layer (B) between the base material layer (A) and the inorganic layer (B).
11.
1. 1. ~ 10. In the barrier laminated film according to any one of
A barrier laminated film having a parallel light transmittance of 50% or more at a wavelength of 600 nm.
12.
1. 1. ~ 11. In the barrier laminated film according to any one of
A barrier laminated film having a water vapor transmission rate of 10.0 g / (m 2.24 h) or less at ⁴⁰ ° C. and 90% RH .
13.
1. 1. To 12. In the barrier laminated film according to any one of
Barrier laminated film that is a packaging film.
14.
1. 1. ~ 13. A package containing the barrier laminated film according to any one of the above.

Hereinafter, this embodiment will be described in detail with reference to Examples and Comparative Examples. The present embodiment is not limited to the description of these examples.

<Evaluation method>
(1) Measurement of water vapor permeability Adhesive (polyurethane adhesive (manufactured by Mitsui Chemicals, trade name:) on one side of an unstretched polypropylene film (manufactured by Mitsui Chemicals Tosero, trade name: RXC-22) with a thickness of 70 μm. Takelac A525S): 9 parts by mass, isocyanate-based curing agent (manufactured by Mitsui Chemicals, trade name: Takenate A50): 1 part by mass and ethyl acetate: 7.5 parts by mass) are applied so that the thickness after drying is 3 μm. Then, it was dried to form a polyurethane-based adhesive layer. Next, the barrier laminated film and the unstretched polypropylene film were formed so that the inorganic layer (B) surface of the barrier laminated film obtained in Examples and Comparative Examples was in contact with the polyurethane adhesive layer of the unstretched polypropylene film. Was laminated (dry laminate) to obtain a multilayer film. The multilayer film was aged at 40 ° C. for 5 days in order to cure the adhesive layer.
The obtained multilayer film was folded back so that the unstretched polypropylene film was on the inner surface, and heat-sealed on both sides to form a bag. Then, calcium chloride was added as the content. Next, the other side was heat-sealed to prepare bags having an internal surface area of 0.01 m ² . Then, the obtained bag was stored at 40 ° C. and 90% humidity for 300 hours. The weight of calcium chloride before and after storage was measured, and the water vapor transmission rate (g / (m ^2.24h )) was calculated from the difference.

(2) Measurement of Moisture Vapor Transmission Rate after Tensile Using a tensile tester, the barrier laminated films obtained in Examples and Comparative Examples were subjected to a chuck distance of 150 mm, a sample width of 120 mm, a chuck width of 100 mm, and a tensile speed of 50 mm / min. Barrier laminated films after 2%, 3% and 5% tensile, 2%, 3% and 5% tensile were obtained under the above conditions. Then, the water vapor transmission rate of the barrier laminated film after 2%, 3% and 5% tension was measured, respectively.

(3) Measurement of the infrared absorption spectrum of the inorganic layer (B) by the total reflection measurement method The measurement of the total reflection infrared absorption spectrum (ATR method) uses an FT / IR-300 device manufactured by Nippon Spectral Co., Ltd. to improve the spectral quality. A multi-reflection measurement unit ATR PRO410-M (prism: Germanium crystal, incident angle 45 degrees, number of multiple reflections = 5) was attached, and measurements were taken at room temperature under the conditions of a resolution of 2 cm ^-1 and an integrated number of 64 times. From the obtained absorption spectrum, the presence or absence of an absorption peak in the absorption band 1080 cm ^-1 or more and 1130 cm ^-1 or less was examined.

(4) X-ray Diffraction Analysis An inorganic layer in the barrier laminated film obtained in Examples and Comparative Examples by an X-ray diffraction analysis method using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., product name: MultiFlex 2 kW). The X-ray diffraction spectra of B) were obtained respectively. Here, the X-ray diffraction spectrum of the inorganic layer (B) was measured with the barrier laminated film fixed to the glass plate. In addition, CuKα ray was used as a radiation source.

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

[Example 1]
(Preparation of coating liquid (B))
For the formation of the inorganic layer (B), fibrous alumina sol (manufactured by Kawaken Fine Chemical Co., Ltd. (abbreviated as Kawaken Co., Ltd. in Table 1), fibrous, trade name: aluminum sol F-1000), phosphoric acid and nitric acid were used. .. Here, each component was blended so that Al element / P element / N element = 1.15 / 1.0 / 1.0 (molar ratio).
The specific compounding procedure is as follows.
9.14 g of purified water, 0.344 g of 60 mass% nitrate aqueous solution, 0.049 g of 5 mass% polyvinyl alcohol (Clarepovar PVA124 ^TM ) aqueous solution and 3.27 g of methanol with respect to 0.378 g of 85 mass% phosphoric acid aqueous solution. Was added and stirred so as to be uniform to obtain a solution [A]. Next, 4.00 g of a 4.8% by mass fibrous alumina sol solution (manufactured by Kawaken Fine Chemical Co., Ltd., trade name: Aluminasol F-1000 ^TM ) was slowly added dropwise with the solution [A] being vigorously stirred, and after the addition was completed. The mixture was further stirred for 30 minutes. After the stirring was completed, the coating liquid (B1) having a pH of 0.85 was obtained by degassing using an aspirator.

(Preparation of barrier laminated film)
A 12 μm biaxially stretched polyethylene terephthalate film (manufactured by Unitika Ltd., trade name: Embret PET12) is used as a base material layer, a coating liquid (B1) is applied to the corona surface of PET12, and the film is dried at 110 ° C. for 5 minutes. , A precursor layer of the inorganic layer (B) was formed. Next, a heat treatment was carried out at 200 ° C. for 10 minutes to form an inorganic layer (B) having a thickness of 0.45 μm, and a barrier laminated 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 substance 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 on the longest axis of the alumina sol is the major axis, the maximum length on the axis perpendicular to it is the minor axis, and the major axis and the minor axis of 10 arbitrarily selected alumina sol in TEM observation are averaged. As a result, the average major axis and the average minor axis of the alumina sol were obtained, respectively.
Here, the present inventors have confirmed that in the step of forming the inorganic layer (B) in the present Example / Comparative Example, the grain growth of the alumina sol such that the aspect ratio changes significantly does not occur. That is, the aspect ratio of the alumina sol used in the present examples and comparative examples does not change significantly even after becoming inorganic particles under the above-mentioned conditions for forming the inorganic layer (B). Therefore, in Table 1, the average major axis and the average minor axis of the alumina sol are adopted as the average major axis X ₁ and the average minor axis X ₂ of the inorganic particles, respectively.
Table 1 shows the evaluation results of the obtained barrier laminated film.

<Examples 2 to 3 and Comparative Examples 1 to 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 in Table 1, and the inorganic used. Barrier laminated films were 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 laminated film.

The barrier laminated film of the example using the fibrous inorganic particles having an aspect ratio of 100 or more and 1000 or less represented by X ₁ / X ₂ has an initial (before tension) water vapor barrier property and after tension. Was excellent in water vapor barrier property. That is, it was found that the barrier laminated film of the example was excellent in durability of the barrier performance. On the other hand, the barrier laminated film of the comparative example was inferior in the durability of the barrier performance.

100 Barrier laminated film A Base material layer B Inorganic material layer

Claims (11)

Fibrous inorganic particles and phosphorus compounds and boron containing the substrate layer (A) and one or more inorganics selected from the group consisting of aluminum oxide, zirconium oxide, tin oxide, titanium oxide, zinc oxide and silicon oxide. A barrier laminated film comprising an inorganic layer (B) containing a binder phase formed of at least one inorganic compound selected from the group consisting of compounds .
When the average major axis of the fibrous inorganic particles is X ₁ [nm] and the average minor axis is X ₂ [nm], the aspect ratio represented by X ₁ / X ₂ is 100 or more and 1000 or less.
In the X-ray diffraction spectrum of the inorganic layer (B) obtained by X-ray diffraction using CuKα ray as a radiation source,
A barrier laminated film in which a diffraction peak is observed in the range of diffraction angle 2θ = 10 ° to 18 ° . In the barrier laminated film according to claim 1,
A barrier laminated film having an average major axis X ₁ of the fibrous inorganic particles of 1000 nm or more and 5000 nm or less. In the barrier laminated film according to claim 1 or 2 ,
A barrier laminated film in which the fibrous inorganic particles contain aluminum oxide. The barrier laminated film according to any one of claims 1 to 3 .
A barrier laminated film in which the fibrous inorganic particles and the binder phase are covalently bonded. The barrier laminated film according to any one of claims 1 to 4 .
The total content of the aluminum element, the zirconium element, the tin element, the titanium element, the zinc element and the silicon element contained in the inorganic layer (B) is defined as Y ₁ [mol].
A barrier laminated film in which Y ₁ / Y ₂ is 0.8 or more and 3.0 or less when the total content of the phosphorus element and the boron element contained in the inorganic layer (B) is Y ₂ [mol]. The barrier laminated film according to any one of claims 1 to 5 .
In the infrared absorption spectrum of the inorganic layer (B) by the total reflection measurement method,
Absorption band A barrier laminated film having an absorption peak in the range of 1080 cm ^-1 or more and 1130 cm ^-1 or less. The barrier laminated film according to any one of claims 1 to 6 .
A barrier laminated film having no inorganic layer (C) other than the inorganic layer (B) between the base material layer (A) and the inorganic layer (B). The barrier laminated film according to any one of claims 1 to 7 .
A barrier laminated film having a parallel light transmittance of 50% or more at a wavelength of 600 nm. The barrier laminated film according to any one of claims 1 to 8 .
A barrier laminated film having a water vapor transmission rate of 10.0 g / ( ^m 2.24 h) or less at 40 ° C. and 90% RH. The barrier laminated film according to any one of claims 1 to 9 .
Barrier laminated film that is a packaging film. A package containing the barrier laminated film according to any one of claims 1 to 10 .

Images