JP2012096431A - Barrier film, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film with a moisture vapor transmission rate that is on the order of 10 to the minus fourth power or less, and to provide a method of manufacturing the same.SOLUTION: The barrier film 10 includes a base material 11, a primary coat 12, a first barrier layer 13, and a second barrier layer 14. The base material 11 is formed of a plastic film. The primary coat 12, which is formed on the base material 11, is made of an ultraviolet curing resin. The first barrier layer 13, which is formed on the primary coat 12, is made of a first inorganic material having water vapor barrier properties. The second barrier layer 14, which is formed on the first barrier layer 13 by an atomic layer deposition method, is made of a second inorganic material having water vapor barrier properties.

Description

  The present invention relates to a barrier film having a barrier property against water vapor and the like and a method for producing the same.

  A barrier film in which a metal oxide thin film such as aluminum oxide or silicon oxide is formed on the surface of a plastic film is known. This type of barrier film is widely used for packaging of articles that need to block oxygen or water vapor, and for packaging applications for preventing the deterioration of food, industrial products, pharmaceuticals, and the like. In recent years, in addition to packaging applications, the application of barrier films has become widespread in the field of electronics such as display elements such as organic EL and solar cells.

For example, in the following Patent Document 1, an organic material layer 1, an inorganic material layer 1, an organic material layer 2, and an inorganic material layer 2 are laminated in this order on a resin substrate, and the water vapor permeability is smaller than 30 g / m ² / day, and is transparent. A barrier film is described. Further, Patent Document 2 listed below discloses a gas barrier film having a structure in which an inorganic barrier layer formed by using at least one atomic layer deposition method (ALD method) and at least one organic layer are alternately laminated on a plastic substrate. Is disclosed.

Japanese Patent No. 4254350 JP 2007-90803 A

In recent years, for example, in barrier films for use in electronics, in order to prevent the performance of elements vulnerable to moisture from deteriorating for a certain period of time, the water vapor transmission rate is, for example, 1E-4 (1 × 10 ⁻⁴ ) [g / m ² / day] or less is required. However, Patent Documents 1 and 2 do not describe a gas barrier film having a water vapor transmission rate of the order of minus fourth power or less.

  In view of the circumstances as described above, an object of the present invention is to provide a barrier film having a water vapor transmission rate of the order of minus fourth power or less and a method for producing the same.

In order to achieve the above object, a barrier film according to one embodiment of the present invention includes a base material, a base layer, a first barrier layer, and a second barrier layer.
The base material is formed of a plastic film.
The foundation layer is formed on the substrate.
The first barrier layer is formed on the base layer and is made of a first inorganic material having a water vapor barrier property.
The second barrier layer is formed on the first barrier layer by an atomic layer deposition method and is made of a second inorganic material having a water vapor barrier property.

  In the barrier film, the underlayer smoothes the surface of the base material and enhances the coverage of the base material surface with the first barrier layer. Since the second barrier layer is formed by an atomic layer deposition method (also referred to as an ALD (Atomic Layer Deposition) method), a dense film with high coverage can be obtained. Therefore, according to the said barrier film, the barrier film which has the water-vapor-permeation rate below a minus fourth power order can be obtained.

  The underlayer is formed for the purpose of improving the surface flatness of the substrate. For the underlayer, an organic material such as an ultraviolet curable resin is used. In addition, an inorganic material such as aluminum oxide formed by the ALD method is used for the base layer.

  The first and second inorganic materials are not particularly limited, and examples thereof include oxides and nitrides containing at least one metal element such as Al, Zn, Si, Cr, Zr, Cu, and Mg. The first inorganic material and the second inorganic material may be made of the same kind of material, or may be made of different materials. The thicknesses of the first and second barrier layers are not particularly limited, and are, for example, 10 nm or more and 100 nm or less.

The barrier film according to another embodiment of the present invention includes a base material, a base layer, a first barrier layer, and a second barrier layer.
The base material has a first surface and a second surface facing the first surface, and is formed of a plastic film.
The underlayer is formed on each of the first surface and the second surface.
The first barrier layer is formed on each of the foundation layers and is made of a first inorganic material having a water vapor barrier property.
The second barrier layer is formed by an atomic layer deposition method on each of the first barrier layers and is made of a second inorganic material having a water vapor barrier property.

The manufacturing method of the barrier film which concerns on one form of this invention includes the process of forming the base layer which consists of ultraviolet curable resin on a plastic film.
A first barrier layer made of a first inorganic material having a water vapor barrier property is formed on the underlayer by a sputtering method.
A second barrier layer made of a second inorganic material having a water vapor barrier property is formed on the first barrier layer by an atomic layer deposition method.

  The underlayer smoothes the surface of the substrate and enhances the coverage of the substrate surface by the first barrier layer. Since the second barrier layer is formed by an atomic layer deposition method (ALD method), a dense film with high coverage can be obtained. Therefore, according to the method for producing a barrier film, a barrier film having a water vapor transmission rate of minus fourth power or less can be produced.

  According to the present invention, a barrier film excellent in water vapor barrier properties can be obtained.

It is sectional drawing which shows typically the barrier film which concerns on the 1st Embodiment of this invention. It is process drawing explaining the formation method of the 2nd barrier layer which comprises the said barrier film. It is sectional drawing which shows typically the film-forming apparatus which forms the said 2nd barrier layer. It is sectional drawing which shows typically the various samples of a barrier film. It is sectional drawing which shows typically the barrier film which concerns on the 2nd Embodiment of this invention. It is sectional drawing which shows typically the barrier film which concerns on the 3rd Embodiment of this invention. It is sectional drawing which shows typically the film-forming apparatus which forms the 2nd barrier layer which comprises the barrier film of FIG.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

<First Embodiment>
[Barrier film]
FIG. 1 is a cross-sectional view schematically showing a barrier film according to an embodiment of the present invention. The barrier film 10 of this embodiment has a laminated structure of a base material 11, an underlayer 12, a first barrier layer 13, and a second barrier layer 14.

(Base material)
The base material 11 can be formed of a flexible plastic film. As this type of plastic film, a light-transmitting plastic material is used. For example, polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polystyrene (PS) ), Aramid, triacetyl cellulose (TAC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA), and the like.

  The thickness of the base material 11 is not specifically limited, For example, they are 10 micrometers or more and 1000 micrometers or less. When the thickness is 10 μm or less, handling properties and reliability may be lowered. On the other hand, when the thickness exceeds 1000 μm, the light transmittance is significantly reduced. A preferable thickness of the substrate 11 is, for example, not less than 50 μm and not more than 200 μm. In particular, when the thickness is set to 200 μm or less, it becomes easy to apply a film-forming process by a roll-to-roll method described later.

(Underlayer)
The underlayer 12 is formed on the surface of the base material 11 and is formed for the purpose of increasing the smoothness of the surface of the base material 11. The constituent material of the underlayer 12 is not particularly limited, but typically a translucent resin material is used. As this type of resin material, an energy ray curable resin such as an ultraviolet curable resin is suitable, and desired transparency and surface flatness can be obtained. As the ultraviolet curable resin, for example, an acrylic ultraviolet curable resin is used.

  The thickness of the foundation layer 12 is not particularly limited, and a thickness that can improve the flatness of the surface of the substrate 11 is sufficient, and is, for example, 5 μm or more and 50 μm or less. The thickness of the foundation layer 12 can be 10 μm or more and 30 μm or less depending on the surface roughness of the substrate 11 used, the viscosity of the ultraviolet curable resin, or the like.

  The underlayer 12 is formed by irradiating an uncured ultraviolet curable resin applied to the surface of the substrate 11 with ultraviolet rays. The coating method of the ultraviolet curable resin is not particularly limited, and an appropriate coating technique such as a spin coating method, a roll coating method, or a bar coating method can be used.

(First barrier layer)
The first barrier layer 13 is formed of an inorganic material having water vapor barrier properties and translucency. Examples of this type of inorganic material include oxides and nitrides containing at least one metal element such as Al, Zn, Si, Cr, Zr, Cu, and Mg.

  The method for forming the first barrier layer 13 is not particularly limited, and various thin film forming techniques such as a sputtering method, a vacuum evaporation method, a CVD method, and a sol-gel method can be used. The thickness of the 1st barrier layer 13 is not specifically limited, For example, they are 10 nm or more and 100 nm or less. Considering film formation uniformity and productivity, the first barrier layer 13 has a thickness of 10 nm to 50 nm, for example.

  In the present embodiment, the first barrier layer 13 is formed of a Si—Cr—Zr-based oxide, and is formed on the surface of the base layer 12 by a sputtering method. Since the base layer 12 is formed on the surface of the base material 11, even when the surface roughness of the base material 11 is relatively large, the first barrier layer 13 has a high coverage ( (Coverability).

As a sputtering target for forming the first barrier layer 13 by sputtering, a sintered body of Si—Cr—Zr-based oxide is typically used. In addition, the first barrier layer can be obtained by simultaneously sputtering each target of SiO ₂ , Cr ₂ O ₃ and ZrO ₂ , or simultaneously sputtering each target of Si, Cr and Zr in an oxygen atmosphere. 13 may be formed.

(Second barrier layer)
The second barrier layer 14 is formed of an inorganic material having water vapor barrier properties and translucency. Examples of this type of inorganic material include oxides and nitrides containing at least one metal element such as Al, Zn, Si, Cr, Zr, Cu, and Mg. The inorganic material constituting the second barrier layer 14 may be formed of the same material as the inorganic material constituting the first barrier layer 13, or may be formed of a different material.

  In the present embodiment, the second barrier layer 14 is formed of aluminum oxide (alumina). The second barrier layer 14 is formed on the surface of the first barrier layer 13 by the ALD method. The second barrier layer 14 exhibits higher water vapor barrier properties as its thickness increases. However, if the thickness is too large, there is a risk of warping or cracking due to internal stress. From such a viewpoint, the thickness of the second barrier layer 14 is, for example, not less than 10 nm and not more than 100 nm, preferably not less than 20 nm and not more than 60 nm.

(Method for forming second barrier layer)
Here, a method of forming the second barrier layer 14 will be described. As described above, the second barrier layer 14 is formed by the ALD method. The ALD method is a thin film forming method in which a plurality of kinds of source gases (precursor gases) are alternately introduced into a chamber, and reaction products are deposited one atomic layer on the surface of a substrate installed in the chamber. In order to promote the reaction of the source gas, a method of forming plasma in the chamber (plasma ALD method), a method of heating the substrate (thermal ALD method), and the like are known, and any method can be applied.

When the second barrier layer 14 is formed of an aluminum oxide thin film, a first precursor gas and a second precursor gas are used. Examples of the first precursor gas include TMA (trimethylaluminum; (CH ₃ ) ₃ Al). Examples of the second precursor gas include water (H ₂ O).

In addition, for example, the following materials can be used as these precursor gases.
Bis (ter-butylimino) bis (dimethylamino) tungsten (VI); ((CH ₃ ) ₃ CN) ₂ W (N (CH ₃ ) ₂ ) ₂ , tris (ter-butoxy) silanol; ((CH ₃ ) ₃ CO) ₃ SiOH, diethyl zinc; (C ₂ H ₅ ) ₂ Zn, tris (diethylamide) (ter-butylimido) tantalum (V); (CH ₃ ) ₃ CNTa (N (C ₂ H ₅ ) ₂ ) ₃ , tris (Ter-pentoxy) silanol; (CH ₃ CH ₂ C (CH ₃ ) ₂ O) ₃ SiOH, trimethyl (methylcyclopentadienyl) platinum (IV); C ₅ H ₄ CH ₃ Pt (CH ₃ ) ₃ , bis (ethyl cyclopentadienyl) ruthenium _{(II); C 7 H 9} RuC 7 H 9, (3- aminopropyl) _{triethoxysilane; H 2 N (CH 2)} 3 Si (OC 2 H 5) 3, tetrachloride Silicon; SiC l ₄ , titanium tetrachloride; TiCl ₄ , titanium (IV) isopropoxide; Ti [(OCH) (CH ₃ ) ₂ ] ₄ , tetrakis (dimethylamido) titanium (IV); [(CH ₃ ) ₂ N] ₄ Ti, tetrakis (dimethylamide) zirconium _{(IV); [(CH 3} ) 2 N] 4 Zr, tris [N, N-bis (trimethylsilyl) amide] _{yttrium; [[(CH 3) 3} Si] 2] N) ₃ Y

  FIG. 2 is a process diagram illustrating a thin film formation method using ALD. Here, a method for forming the second barrier layer 14 will be described by taking a batch process as an example, but it is also possible to apply a film-forming process by a roll-to-roll method as will be described later.

  As shown in FIGS. 2A to 2D, the base film 15 is sequentially exposed to the first precursor gas 16A, the purge gas 16P, the second precursor gas 16B, and the purge gas 16P, so that a single aluminum oxide film is obtained. A molecular layer 14C is formed. The base film 15 corresponds to a laminate of the base material 11, the base layer 12, and the first barrier layer 13 shown in FIG.

  The base film 15 is carried into a chamber that is evacuated to a predetermined pressure. As shown in FIG. 2A, the first precursor gas 16A introduced into the chamber is adsorbed on the surface of the base film 15, so that the first precursor layer 14A made of the precursor gas 16A is based. It is formed on the surface of the material film 15.

  Next, as shown in FIG. 2B, the purge gas 16P is introduced into the chamber. As a result, the surface of the base film 15 is exposed to the purge gas 16P, and the unbonded precursor gas 16A remaining on the surface of the base film 15 is removed. An example of the purge gas 16P is argon (Ar) when an aluminum oxide thin film is formed. In addition to this, for example, nitrogen, hydrogen, oxygen, carbon dioxide, or the like can be used as the purge gas.

  Subsequently, as shown in FIG. 2C, the second precursor gas 16B is introduced into the chamber. The second precursor gas 16B is adsorbed on the surface of the base film 15 to form a second precursor layer 14B made of the precursor gas 16B on the first precursor layer 14A. As a result, a monomolecular layer 14C of aluminum oxide is formed by a mutual chemical reaction between the first precursor layer 14A and the second precursor layer 14B. Thereafter, as shown in FIG. 2D, the purge gas 16P is again introduced into the chamber, and the unbonded precursor gas 16B remaining on the surface of the base film 15 is removed.

  By repeating the above process, the second barrier layer 14 having a predetermined thickness is formed on the surface of the base film 15.

  FIG. 3 is a cross-sectional view schematically showing an example of a film forming apparatus for forming the second barrier layer 14 by a roll-to-roll method.

  The film forming apparatus 100 includes a vacuum chamber 101 that is evacuated to a predetermined pressure, an internal chamber 102 that is filled with a purge gas 16P, and a transport mechanism that transports the base film 15 inside the vacuum chamber 101. . The film forming apparatus 100 further includes ALD heads 105A and 105B that discharge the precursor gases 16A and 16B onto the surface of the base film 15 transported inside the vacuum chamber 101, and temperature control installed outside the vacuum chamber 101. Part 106.

  The transport mechanism includes an unwinding roller for unwinding the belt-shaped base film 15, a winding roller for winding the base film 15, and a plurality of guide rolls 103 and 104 installed between these two rollers. . A plurality of guide rolls 103 and 104 are arranged outside the opposing side wall portions of the internal chamber 102, and the base film 15 is conveyed while being alternately guided by the guide roll 103 and the guide roll 104. In this example, both guide rolls 103, such that the surface (film formation surface) of the base film 15 is in contact with the guide roll 103 and the back surface (non-film formation surface) of the base film 15 is in contact with the guide roll 104. 104 is arranged. Each of the guide rolls 103 and 104 is configured such that the surface temperature can be adjusted according to a command from the temperature control unit 106.

  On the other hand, a plurality of slots through which the base film 15 can pass are formed on both side walls of the internal chamber 102. Each of these slots is formed in a passage region of the base film 15 that is linearly bridged between the guide roll 103 and the guide roll 104. Thereby, the base film 15 can enter and exit the internal chamber 102 every time it passes between the guide roll 103 and the guide roll 104.

  The ALD heads 105 </ b> A and 105 </ b> B are arranged to face the respective guide rolls 103 and discharge precursor gases 16 </ b> A and 16 </ b> B toward the surface of the base film 15 on each guide roll 103. One ALD head 105A discharges the first precursor gas 16A, and the other ALD head 105B discharges the second precursor gas 16B. In this example, the ALD heads 105 </ b> A and 105 </ b> B are alternately arranged along the conveyance direction of the base film 15 so as to face each guide roll 103.

  Although not shown, the film forming apparatus 100 further supplies an exhaust line for exhausting the inside of the vacuum chamber 101, a purge gas introduction line for supplying the purge gas 16P to the internal chamber 102, and a precursor gas to each of the ALD heads 105A and 105B. A precursor gas introduction line and the like are provided.

  In the film forming apparatus 100 having the above configuration, the base film 15 is sequentially transported to the positions of the ALD heads 105A and 105B by the transport mechanism including the guide rolls 103 and 104 as shown in FIG. The base film 15 is exposed to the first precursor gas 16A discharged from the ALD head 105A (FIG. 2A), and then exposed to the purge gas 16P in the internal chamber 102 (FIG. 2B). . Subsequently, the base film 15 is exposed to the second precursor gas 16B discharged from the ALD head 105B (FIG. 2C), and then exposed to the purge gas 16P in the internal chamber 102 (FIG. 2 ( D)). By repeating such a process sequentially, the second barrier layer 14 is formed on the surface of the base film 15.

  The amount of the precursor gas 16A, 16B and the purge gas 16P exposed to the base film 15, the exposure time, etc. are the transport speed of the base film 15, the amount of gas discharged from the ALD heads 105A, 105B, the size of the internal chamber 102. It is adjusted by the etc.

  The barrier film 10 shown in FIG. 1 is manufactured as described above. In the barrier film 10 of the present embodiment, the base layer 12 smoothes the surface of the base material 11 and enhances the coverage of the base material surface by the first barrier layer 13. Since the second barrier layer 14 is formed by the ALD method, a dense film with high coverage can be obtained. Therefore, according to the barrier film 10 of the present embodiment, it is possible to obtain excellent water vapor barrier characteristics with a very low water vapor transmission rate.

  Here, an experimental example performed by the present inventor will be described. A plurality of samples having different configurations were prepared, and the water vapor transmission rate (WVTR) of each sample was compared. The configuration of each sample is as follows.

(Sample 1)
As Sample 1, a substrate made of a single-layer plastic film was used. A polycarbonate film having a thickness of 100 μm was used as the substrate.

(Sample 2)
The structure of Sample 2 is shown in FIG. Sample 2 has a laminated structure of a base material 111 constituting Sample 1 and an inorganic barrier layer 114. The inorganic barrier layer 114 is formed of an aluminum oxide thin film having a thickness of 20 nm formed by the ALD method.

The inorganic barrier layer 114 was formed by the method shown in FIGS. Here, the base pressure in the chamber is a nitrogen atmosphere of 13.3 to 26.6 Pa (0.1 to 0.2 Torr), TMA is used as the first precursor gas, and H ₂ is used as the second precursor gas. Nitrogen was used for O and the purge gas, respectively. The processing times of the steps shown in FIGS. 2A, 2B, 2C, and 2D are T1 (seconds), T2 (seconds), T3 (seconds), and T4 (seconds), respectively, and the total of T1 to T4 Multiple cycles were repeated until the thickness reached 20 nm with one cycle as the time. Moreover, as each value of T1-T4, it was set to T1: 0.01-1 and T2: 5-200, T3: 0.01-2, T4: 5-700.

(Sample 3)
The structure of Sample 3 is shown in FIG. Sample 3 has a laminated structure of a base material 111, a base layer 112 formed on the base material 111, and an inorganic barrier layer 114 having a thickness of 20 nm formed on the base layer 112. The underlayer 112 is made of an ultraviolet curable resin having a thickness of 30 μm.

(Sample 4)
The structure of Sample 4 is shown in FIG. Sample 4 has a laminated structure of a base material 111, the base layer 112 formed on the base material 111, and an inorganic barrier layer 113 formed on the base layer 112. The inorganic barrier layer 113 is formed of a 20-nm-thick SCZ (Si—Cr—Zr-based oxide) thin film formed by sputtering.

For the formation of the inorganic barrier layer 113, a SiO ₂ —Cr ₂ O ₃ —Zr ₂ O ₃ sintered target having a diameter of 150 mm was used. The base pressure (film formation pressure) in the chamber was an argon atmosphere of 0.5 Pa, and the input power to the target was 500 W (13.56 MHz).

(Sample 5)
The structure of Sample 5 is shown in FIG. The sample 5 is formed on the base material 111, the base layer 112 formed on the base material 111, the inorganic barrier layer 113 having a thickness of 20 nm formed on the base layer 112, and the inorganic barrier layer 113. And a laminated structure with an inorganic barrier layer 114 having a thickness of 20 nm. That is, the sample 5 has the same layer structure as the barrier film 10 shown in FIG.

(Sample 6)
The structure of Sample 6 is shown in FIG. Sample 6 has a laminated structure of a base material 111, an inorganic barrier layer 114 having a thickness of 20 nm formed on the base material 111, and an inorganic barrier layer 113 having a thickness of 10 nm formed on the inorganic barrier layer 114. .

(Sample 7)
Sample 7 has a laminated structure of a base material 111 and a 50 nm thick inorganic barrier layer 114 formed on the base material 111. That is, Sample 7 has the same layer structure as Sample 2 shown in FIG. 4A, and the thickness of barrier layer 114 is different.

(Sample 8)
The sample 8 has a laminated structure of a base material 111 and a 60 nm thick inorganic barrier layer 114 formed on the base material 111. Sample 8 also has the same layer structure as Sample 2 shown in FIG. 4A, and the thickness of barrier layer 114 is different.

  The water vapor transmission rate (WVTR) of each of samples 1 to 8 was measured. For measurement, a calcium corrosion observation apparatus “MFB-1000” manufactured by Mitsuwa Frontec Co., Ltd. was used. The measurement conditions were 40 ° C. and 90% RH (relative humidity). The measurement results are shown in Table 1.

Comparing sample 4 and sample 5, it can be seen that sample 5 has a lower WVTR than sample 4, that is, has a higher water vapor barrier property. This is due to the effect of the ALD film that forms the inorganic barrier layer 114. With this configuration, a very excellent water vapor barrier property of 3.5E-5 [g / m ² / day] or less can be realized.

  When sample 4 and sample 6 are compared, both have the same WVTR. From this, it can be seen that even when an ALD film for forming the inorganic barrier layer 114 is used as a base layer, it has a certain water vapor barrier characteristic. In Sample 6, although the inorganic barrier layer 113 is formed thinner than that of Sample 4, it exhibits a WVTR equivalent to that of Sample 4, and therefore, the constituent material of the underlayer is more oxidized than UV curable resin. It is presumed that an aluminum ALD film is superior.

  When comparing sample 3 and sample 4, sample 3 has a higher water vapor barrier property than sample 4. This indicates that the alumina ALD film has higher barrier properties than the SCZ-based sputtered film. On the other hand, from the results of Sample 3 and Sample 4, the ultraviolet curable resin provided as the base of the inorganic barrier layer is effective in improving the surface properties of the base material, and has a water vapor barrier property at the interface between the base material and the inorganic barrier layer. It turns out that it has the function to raise.

  Comparing Sample 2, Sample 7 and Sample 8, it can be seen that the higher the ALD layer thickness, the higher the water vapor barrier property. This indicates that the coverage with respect to the substrate surface is greatly related to the water vapor barrier property, and there is a strong correlation between the ALD film thickness and the coverage. From the result of Sample 8, by setting the ALD film thickness to 60 nm or more, it is possible to realize a water vapor transmission rate of the order of minus fourth power or less. Therefore, by further increasing the thickness of the ALD layer of Sample 5, the barrier property is further increased, and there is a possibility that a water vapor transmission rate of 1E-5 [g / m2 / day] or less can be realized.

  Furthermore, it can be seen that the water vapor barrier property can be greatly improved by forming the ALD layer at least in the uppermost layer. It is presumed that the water vapor barrier property can be further improved by forming the underlayer of sample 5 with an ALD layer instead of the ultraviolet curable resin layer.

As is clear from the above results, according to the barrier film 10 of the present embodiment shown in FIG. 1, it is possible to realize a water vapor transmission rate [g / m ² / day] of the order of minus fourth power or less and a very high water vapor. Barrier properties can be obtained.

  Moreover, since each layer which comprises the barrier film 10 has translucency, it can use suitably as a barrier film which requires transparency like an organic EL display or a solar cell module use, for example.

  Furthermore, since the barrier film 10 has moderate flexibility, it can be used by being bent into a desired shape.

<Second Embodiment>
FIG. 5 is a cross-sectional view schematically showing a barrier film according to the second embodiment of the present invention. In the present embodiment, the description of the same parts as those of the first embodiment will be omitted or simplified, and different parts from the first embodiment will be mainly described.

  The barrier film 20 of this embodiment is different from that of the first embodiment in that it has a third barrier layer 17 made of an inorganic material having a water vapor barrier property as an underlayer of the first barrier layer 13. The third barrier layer 17 is formed of an ALD film of aluminum oxide, for example, similarly to the second barrier layer 14.

  The thickness of the third barrier layer 17 is sufficient if it can cover the entire surface of the base material 11, and is, for example, 20 nm or more and 60 nm or less. Thereby, the water vapor barrier property can be improved.

<Third Embodiment>
FIG. 6 is a cross-sectional view schematically showing a barrier film according to the third embodiment of the present invention. In the present embodiment, the description of the same parts as those of the first embodiment will be omitted or simplified, and different parts from the first embodiment will be mainly described.

  The barrier film 30 according to the present embodiment includes the base layer 22, the first barrier layer 23, and the second barrier layer not only on the front surface (first surface) side but also on the back surface (second surface) side of the base material 11. It differs from the first embodiment in that it has 24 laminated structures. The underlayer 22, the first barrier layer 23, and the second barrier layer 24 have the same configuration as the underlayer 12, the first barrier layer 13, and the second barrier layer 14 on the surface side of the substrate 11, respectively. . However, the present invention is not limited to this, and the material of each layer may be different between the front surface side and the back surface side.

  According to the barrier film 30 of this embodiment, since various barrier layers are formed on both surfaces of the base material 11, further improvement in water vapor barrier properties can be achieved. Moreover, since it becomes applicable to a product, without distinguishing the surface and the back surface of the base material 11, handling property can be improved.

  Regarding manufacture of the barrier film 30, each layer may be formed on one side of the substrate 11, or each layer may be formed on both sides simultaneously. FIG. 7 shows an example of a film forming apparatus for forming the second barrier layers 14 and 24 on each surface.

  A film forming apparatus 200 shown in FIG. 7 has a configuration in which a plurality of second ALD heads 107A and 107B are added to the film forming apparatus 100 shown in FIG. These ALD heads 107 </ b> A and 107 </ b> B are arranged to face the guide rolls 104, respectively, and discharge precursor gases 16 </ b> A and 16 </ b> B toward the back side of the base film 25 supported by each guide roll 104. One ALD head 107A discharges the first precursor gas 16A, and the other ALD head 107B discharges the second precursor gas 16B. These ALD heads 107 </ b> A and 107 </ b> B are alternately arranged along the conveyance direction of the base film 25 so as to face each guide roll 104.

  As the base film 25, as shown in FIG. 6, a laminate of the base material 11 and the base layers 12 and 22 and the first barrier layers 13 and 23 formed on each surface thereof is used. When the base film 25 is guided by the guide rolls 103, the first barrier layer 13 on the front side faces the ALD heads 105 </ b> A and 105 </ b> B. The first barrier layer 23 faces the ALD heads 107A and 107B, respectively. Thereby, the second barrier layers 14 and 24 can be formed on the front and back surfaces of the base film 25, respectively.

  The embodiment of the present invention has been described above, but the present invention is not limited to this, and various modifications can be made based on the technical idea of the present invention.

  For example, in the above embodiment, the base layer of the barrier film is formed of an ultraviolet curable resin layer or an ALD layer of aluminum oxide, but the base layer may be formed by a laminated structure of these layers. In this case, an ultraviolet curable resin layer is formed on the substrate side, and the ALD layer is formed thereon. Such a structure can also improve the water vapor barrier property.

  In the above embodiment, the uppermost layer (outermost layer) of the barrier film is composed of an ALD layer. However, a protective layer or the like for enhancing the durability of the ALD layer may be further formed thereon.

  Furthermore, in the above embodiment, although the barrier film applied to an organic EL display, a solar cell module etc. was mentioned as an example, the application object is not limited to this, The member of all the products which require water vapor | steam barrier property As applicable. For example, the present invention can be applied to display devices, portable electronic devices, semiconductor devices, batteries, packaging members, and the like. Here, examples of the display device include a liquid crystal display, a plasma display, a touch panel, and electronic paper in addition to the organic EL display described above. Examples of the portable electronic device include a mobile phone, a portable music player, a data card, and the like, and those having a display function are also included. Examples of the semiconductor device include a TFT (Thin Film Transistor), an IC chip, an IC tag, a semiconductor memory, a semiconductor sensor, a MEMS (Micro Electro-Mechanical System) element, a photoelectric conversion element incorporated in a solar cell module, and the like. It is done. Examples of the battery include, in addition to the above-described solar cell module, a secondary battery such as a primary battery or a lithium ion battery, a fuel cell, a storage battery, and the like. The present invention can also be applied to other electric and electronic devices that require water vapor barrier properties. The present invention can also be applied to packaging members such as foods, precision instruments, cards, and artworks that require water vapor barrier properties.

DESCRIPTION OF SYMBOLS 10, 20, 30 ... Barrier film 11 ... Base material 12, 22 ... Underlayer 13, 23 ... 1st barrier layer 14, 24 ... 2nd barrier layer 15, 25 ... Base film 100, 200 ... Film-forming apparatus

Claims (13)

A substrate formed of a plastic film;
An underlayer formed on the substrate;
A first barrier layer formed on the underlayer and made of a first inorganic material having a water vapor barrier property;
A barrier film comprising: a second barrier layer formed on the first barrier layer by an atomic layer deposition method and made of a second inorganic material having a water vapor barrier property. The barrier film according to claim 1,
The underlayer is a barrier film made of an ultraviolet curable resin. The barrier film according to claim 2,
A barrier film having a water vapor transmission rate of 1 × 10 ⁻⁴ [g / m ² / day] or less. The barrier film according to claim 3,
The first inorganic material is a Si—Cr—Zr-based oxide barrier film. The barrier film according to claim 3,
The second inorganic material is an aluminum oxide barrier film. The barrier film according to claim 1,
The underlayer is an aluminum oxide film formed by an atomic layer deposition method. A base material formed of a plastic film having a first surface and a second surface opposite to the first surface;
An underlayer formed on each of the first surface and the second surface;
A first barrier layer formed on each of the underlying layers and made of a first inorganic material having a water vapor barrier property;
A barrier film comprising: a second barrier layer formed on each of the first barrier layers by an atomic layer deposition method and made of a second inorganic material having a water vapor barrier property.   The display apparatus which has a barrier film of any one of Claims 1-7.   The portable electronic device which has a barrier film of any one of Claims 1-7.   The semiconductor device which has a barrier film of any one of Claims 1-7.   A battery comprising the barrier film according to claim 1.   The packaging member which has a barrier film of any one of Claims 1-7. Form a base layer made of UV curable resin on a plastic film,
On the underlayer, a first barrier layer made of a first inorganic material having a water vapor barrier property is formed by a sputtering method,
A method for producing a barrier film, comprising: forming a second barrier layer made of a second inorganic material having a water vapor barrier property on the first barrier layer by an atomic layer deposition method.

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