JP2012206380A - Transparent gas barrier film, method of forming transparent gas barrier film, organic electroluminescence element, solar battery, and thin film battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent gas barrier film which suppresses the deterioration of a gas barrier property caused by degassing from a resin substrate, and exhibits a high gas barrier property, and to provide a method of forming the same.SOLUTION: The transparent gas barrier film includes a transparent gas barrier layer having the gas barrier property and formed on the resin substrate. The transparent gas barrier layer is a lamination having a suboxide inorganic layer and an inorganic layer. The suboxide inorganic layer and the inorganic layer are laminated in this order on the resin substrate. The suboxide inorganic layer is formed by a sputtering method. The inorganic layer is formed by a vapor deposition method, and contains at least one of metal and semimetal, and at least one kind selected from oxygen, nitrogen, and carbon.

Description

  The present invention relates to a transparent gas barrier film, a method for producing a transparent gas barrier film, an organic electroluminescence element, a solar battery, and a thin film battery.

  In recent years, various electronic devices such as a liquid crystal display element, an organic electroluminescence (EL) element, electronic paper, a solar battery, and a thin film lithium ion battery have been reduced in weight and thickness. Many of these devices are known to be altered and degraded by water vapor in the atmosphere.

  Conventionally, a glass substrate or a silicon substrate has been used as a support substrate for these devices. However, because of excellent properties such as lightness, impact resistance, and flexibility, resin substrates can be used instead of these substrates. Use is under consideration. In general, a resin substrate has a property that gas permeability such as water vapor is remarkably large as compared with a substrate formed of an inorganic material such as glass. Therefore, in the above application, it is required to improve the gas barrier property of the resin substrate while maintaining its light transmittance.

  Therefore, the formation of a gas barrier layer for improving the gas barrier property of a resin substrate has been studied, and a vacuum deposition method or sputtering for forming a dense inorganic layer such as an oxide or nitride in a vacuum with few particles. A dry process such as a method has been proposed (for example, Patent Documents 1, 2, and 3).

  In addition, it has been proposed to form a polymer undercoat layer as a gas barrier layer in order to impart flatness and stress relaxation properties to improve gas barrier properties (for example, Patent Documents 4 and 5). Although the undercoat layer can impart flatness and stress relaxation properties, as in the case of a resin substrate, degassing occurs in a vacuum, so that the barrier property of the inorganic layer formed immediately above is also reduced. is there. Further, the adhesion between the polymer and the inorganic layer is low, and peeling is likely to occur, and as a result, the gas barrier property may be lowered.

JP 2004-148893 A JP 2005-178087 A JP 2007-90681 A JP 2006-281505 A International Publication No. 2006/025356

  As a result of our studies, in such a layer formation process in a vacuum, degassing of moisture and the like occurs from the resin substrate surface and the vicinity of the surface. Even if an inorganic layer is formed on this, these degassing components As a result, it was found that the layer density was lowered and as a result, the gas barrier property was lowered.

  The present invention provides a transparent gas barrier film having a high gas barrier property and a method for producing the same, by suppressing deterioration of the gas barrier property due to degassing from a resin substrate.

The transparent gas barrier film of the present invention is
A transparent gas barrier film in which a transparent gas barrier layer having gas barrier properties is formed on a resin substrate,
The transparent gas barrier layer is a laminate including a suboxide inorganic layer and an inorganic layer,
On the resin substrate, the suboxide inorganic layer and the inorganic layer are laminated in this order,
The suboxide inorganic layer is a layer formed by a sputtering method,
The inorganic layer is a layer formed by a vapor deposition method and including at least one of a metal and a semimetal and at least one selected from oxygen, nitrogen, and carbon.

Moreover, the method for producing the transparent gas barrier film of the present invention comprises:
A method for producing a transparent gas barrier film for forming a transparent gas barrier layer having gas barrier properties on a resin substrate,
A suboxide inorganic layer forming step for forming a suboxide inorganic layer on the resin substrate by a sputtering method;
Including an inorganic layer forming step of forming, on the suboxide inorganic layer, an inorganic layer containing at least one of metal and metalloid and at least one selected from oxygen, nitrogen, and carbon by a vapor deposition method. It is characterized by.

  The transparent gas barrier film of another aspect of the present invention is manufactured by the method for manufacturing a transparent gas barrier film of the present invention.

In addition, the organic electroluminescence element of the present invention is
An organic electroluminescence device having a laminate in which an anode layer, an organic light emitting layer and a cathode layer are provided in this order on a substrate, wherein the substrate is the transparent gas barrier film of the present invention. To do.

In addition, the organic electroluminescence element of the present invention is
An organic electroluminescence device having a laminate in which an anode layer, an organic light emitting layer and a cathode layer are provided in this order on a substrate,
Furthermore, it has a back sealing member,
At least a part of the laminate is covered with the back sealing member,
At least one of the substrate and the back sealing member is the transparent gas barrier film of the invention.

The solar cell of the present invention is
A solar battery including a solar battery cell, wherein the solar battery cell is covered with the transparent gas barrier film of the present invention.

The thin film battery of the present invention is
A current collecting layer, an anode layer, a solid electrolyte layer, a cathode layer, and a current collecting layer are thin film batteries having a laminate provided in this order, and the laminate is covered with the transparent gas barrier film of the present invention. It is characterized by.

  ADVANTAGE OF THE INVENTION According to this invention, even when a resin substrate is used, the transparent gas barrier film which can acquire favorable gas barrier property, and its manufacturing method can be provided.

FIG. 1 is a schematic diagram showing an example of the configuration of an apparatus for producing a transparent gas barrier layer according to the present invention by a continuous production method. FIG. 2 is a schematic diagram showing an example of the configuration of an apparatus for producing a transparent gas barrier layer according to the present invention by a batch production method.

  In the transparent gas barrier film of the present invention, the inorganic layer is preferably a laminate in which a plurality of layers are laminated.

  In the transparent gas barrier film of the present invention, the inorganic suboxide layer preferably contains silicon suboxide or aluminum suboxide.

  In the transparent gas barrier film of the present invention, the inorganic layer preferably contains at least one of aluminum and silicon.

  In the method for producing a transparent gas barrier film of the present invention, the inorganic layer forming step is preferably a step of forming a plurality of inorganic layers.

  Next, the present invention will be described in detail. However, the present invention is not limited by the following description.

  The first layer directly formed on the resin substrate is a suboxide inorganic layer formed by sputtering. The sputtering method is a method of forming a layer by striking particles with argon ions ionized by applying a high voltage to the target and colliding with the target. For this reason, particles having relatively high kinetic energy are involved in the layer formation, so that a very dense layer is formed. When the high kinetic energy particles collide with the resin substrate, adsorbed moisture and contaminants on the surface of the resin substrate or in the vicinity of the resin substrate that cause degassing are removed, so that a dense inorganic layer can be formed. In the present invention, as the target, at least one selected from metals, metalloids, metal oxides, and metalloid oxides can be used.

  The “suboxide” in the suboxide inorganic layer is an oxide having a lower oxygen state than the stoichiometric composition. For example, according to Japanese Patent No. 3192249, it is known that the suboxide layer has a higher gas barrier property than the stoichiometric oxide layer. In the present invention, the material of the suboxide is not limited. For example, silicon oxide (SiOx, where X <2), aluminum oxide (AlOx, where X <1.5), titanium oxide (TiOx, where X <2), niobium oxide (NbOx, where X <2.5), indium suboxide (InOx, where X <1.5), and the like, but it is preferable that silicon oxide or aluminum oxide is included from the viewpoint of transparency. Moreover, when the value of X in the composition of the suboxide is large, the gas barrier property is lowered. On the other hand, when it is small, the transparency is lowered. The thickness of the suboxide inorganic layer is preferably in the range of 5 to 100 nm, more preferably in the range of 10 to 50 nm.

  Examples of the sputtering method for forming the suboxide inorganic layer include a direct current discharge method, a high frequency discharge method, a pulse direct current discharge method, and a direct current / high frequency superimposed discharge method. Any discharge method may be used, but since it is preferable that the impact of particles on the resin substrate is relatively small, it is preferable to use a high frequency discharge method or a direct current / high frequency superimposed discharge method.

There is no particular limitation on the sputtering conditions when forming the suboxide inorganic layer. For example, after evacuating the inside of the vacuum chamber to 10 ⁻⁴ Pa or less, argon gas is introduced as a discharge gas, oxygen-containing gas is introduced as a reaction gas, and the flow rate is adjusted with a mass flow controller so that the internal pressure of the system becomes 0.1 to 1 Pa. Perform control (pressure control). As the discharge output during sputtering, 1 to 10 W / cm ² is applied, and sputtering is performed until a desired thickness is achieved.

  The inorganic layer formed of the second layer or more is formed by a vapor deposition method. In the vapor deposition method, high kinetic energy particles are hardly involved in the layer formation process as compared with the sputtering method, so that defects such as pinholes due to collision of the particles with the layer are less likely to be formed. Therefore, a very uniform layer having a high gas barrier property can be formed.

  The inorganic layer is a layer containing at least one of a metal and a metalloid and at least one selected from oxygen, nitrogen and carbon. Examples of the inorganic layer include oxides, nitrides, oxynitrides, oxycarbides, nitrides, and the like such as silicon, aluminum, titanium, magnesium, titanium, and indium. From the viewpoint of transparency, the inorganic layer preferably contains at least one of aluminum and silicon, and contains at least one of silicon oxide, aluminum oxide, silicon nitride, silicon oxynitride, aluminum oxynitride, and silicon oxide carbide. It is preferable that The thickness of the inorganic layer is preferably 50 nm to 1 μm, more preferably 100 to 300 nm.

There is no restriction | limiting in particular in the vapor deposition conditions at the time of the said inorganic layer formation. As the vapor deposition material (vapor deposition source), metal, metalloid, metal oxide, metalloid oxide, metal nitride, metalloid nitride, metal carbide, metalloid carbide can be used. After evacuating the inside of the vacuum chamber to 10 ⁻⁴ Pa or less, the vapor deposition material installed in the vapor deposition source is evaporated by a method of introducing any one of resistance heating, electron beam, plasma beam, and laser into the vapor deposition material (vapor deposition source). . These methods may be used in combination. In the case of a vapor deposition method using a reactive gas, plasma, an ion beam, or the like may be used as an assist in order to promote the reactivity. Among these, from the viewpoint of production efficiency, electron beam vapor deposition or plasma beam vapor deposition with a relatively high layer formation rate can be preferably used.

  In the present invention, when at least one selected from oxygen, nitrogen and carbon contained in the inorganic layer is not contained in the vapor deposition material (vapor deposition source), it is introduced by performing vapor deposition in the presence of a reactive gas. can do. A single or mixture of oxygen-containing gas, nitrogen-containing gas, or hydrocarbon-containing gas is introduced as a reactive gas, and flow control (pressure control) is performed with a mass flow controller so that the system internal pressure becomes 0.01 to 0.1 Pa. However, vapor deposition is performed on the substrate until a predetermined thickness is reached.

  As the laminated structure of the second layer or more, the material, the order of lamination, and the number of laminations are not particularly limited as long as they are inorganic layers by vapor deposition. From the viewpoint of production efficiency, the number of stacked layers is preferably 1 to 2 layers.

  The heating temperature at the time of forming the transparent gas barrier layer in the present invention, which is a laminate including the suboxide inorganic layer and the inorganic layer, is preferably 150 ° C. or lower, more preferably in the range of 80 to 120 ° C. . In this case, it is preferable to heat the resin substrate (resin film) at 120 ° C. or lower when forming the transparent gas barrier layer. The method for producing a transparent gas barrier film of the present invention can form a transparent layer having good gas barrier performance at a low temperature. Therefore, even if the substrate is a resin, for example, the properties and shape of the resin are impaired. It is possible to set no conditions.

  The material of the resin substrate is not limited as long as it is transparent. For example, polyethylene, polypropylene, cycloolefin polymer, polyethylene terephthalate (PET), polyethylene naphthalate, polyphenyl sulfide, polycarbonate, polyimide, polyamide (nylon), polyvinyl alcohol, Examples thereof include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride. Moreover, it is preferable that the thickness of the said resin substrate is the range of 20-200 micrometers, More preferably, it is the range of 50-150 micrometers. The average surface roughness of the resin substrate is preferably 10 nm or less. Here, the average surface roughness is an arithmetic average surface roughness (Ra) based on JIS B 0601 (1994 edition).

  The thickness of the transparent gas barrier layer is preferably in the range of 0.05 to 1 μm. By setting the thickness to 0.05 μm or more, a sufficient gas barrier property can be obtained, and by setting the thickness to 1 μm or less, internal stress can be lowered and occurrence of cracks can be prevented. The thickness is more preferably in the range of 0.01 to 0.05 μm.

  The transparent gas barrier layer can be manufactured by a batch method or a continuous production method. In the case of the continuous production method, the transparent gas barrier layer is formed on the transparent resin film while the transparent resin film is continuously conveyed by a roll in a vacuum chamber when the transparent gas barrier layer is formed.

  In FIG. 1, an example of the structure of the apparatus which manufactures the said suboxide inorganic layer which comprises the transparent gas barrier layer in this invention by a continuous production system is shown. As shown, the manufacturing apparatus 10 includes a vacuum chamber 11, an unwinding roll 13a, a can roll 15, a winding roll 13b, two auxiliary rolls 14a and 14b, a cathode 16, a vacuum pump 20, a sputtering gas supply means 18, A reactive gas supply means 19 is provided as a main constituent member. An unwinding roll 13a, a can roll 15, a take-up roll 13b, and two auxiliary rolls 14a and 14b are arranged in the vacuum chamber 11, and the can roll 15 extends from the unwind roll 13a to the take-up roll 13b. The transparent resin film 12 is stretched over the two auxiliary rolls 14a and 14b. The cathode 16 is installed at the bottom of the vacuum chamber 11 so as to face the can roll 15. The target 17 is mounted on the upper surface of the cathode 16. A plurality of targets 17 may be mounted, and the target to be used can be changed according to the composition of the layer to be formed. The vacuum pump 20 is disposed on the side wall (the right side wall in the figure) of the vacuum chamber 11, whereby the inside of the vacuum chamber 11 can be decompressed. The sputtering gas supply means 18 and the reactive gas supply means 19 are arranged on the side wall (right side wall in the figure) of the vacuum chamber 11. The sputtering gas supply means 18 is connected to a sputtering gas cylinder 21, whereby it becomes possible to supply a sputtering gas (for example, argon gas) having an appropriate pressure into the vacuum chamber 11. ing. The reactive gas supply means 19 is connected to a reactive gas gas cylinder 22 containing oxygen, whereby a reactive gas having an appropriate pressure can be supplied into the vacuum chamber 11. A temperature control means (not shown) is connected to the can roll 15. Thereby, the temperature of the transparent resin film 12 can be set to the predetermined range by adjusting the surface temperature of the can roll 15. Examples of the temperature control means include a heat medium circulation device that circulates silicone oil and the like.

  In the continuous production by this apparatus, the suboxide inorganic that continuously introduces the film into the apparatus, performs sputtering in the presence of the reaction gas while moving the film, and continuously constitutes the transparent gas barrier layer in the present invention. Form a layer. The inorganic layer may be formed in the same vacuum chamber by forming the suboxide inorganic layer and then performing deposition by switching the cathode 16 and the target 17 to a deposition source and a deposition material. Alternatively, a film having the suboxide inorganic layer formed thereon may be introduced into another vapor deposition apparatus. When the inorganic layer is formed in the same vacuum chamber, the reaction gas supply means 19 is preferably connected to a reaction gas gas cylinder 22 containing oxygen and a reaction gas gas cylinder 23 containing nitrogen. By this step, a predetermined laminate can be formed. Continuous production by this apparatus can be carried out in the same manner as the apparatus manufactured by the batch production method described later, except that sputtering and vapor deposition are performed while moving the film.

  In FIG. 2, an example of a structure of the apparatus which manufactures the transparent gas barrier layer in this invention by a batch production system is shown. In FIG. 2, the same parts as those in FIG. As shown in the figure, in this manufacturing apparatus 30, a substrate heater 33 is disposed in a vacuum chamber 31 instead of the various rolls, and a transparent resin substrate (for example, a transparent resin film) 32 is installed on the substrate heater 33. Except for this, the configuration is the same as in FIG. Examples of the substrate heater 33 include those similar to the temperature control means.

  The organic EL device of the present invention has a laminate in which an anode layer, an organic light emitting layer and a cathode layer are provided in this order on a substrate, and the substrate is the transparent gas barrier film of the present invention. It is characterized by. As the anode layer, for example, an ITO (Indium Tin Oxide) or IZO (registered trademark, Indium Zinc Oxide) layer that can be used as a transparent electrode layer is formed. The organic light emitting layer includes, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. As the cathode layer, an aluminum layer, a magnesium / aluminum layer, a magnesium / silver layer, and the like are also formed as a reflective layer. Sealing is performed from above with a metal, glass, resin, or the like so that the laminate is not exposed to the atmosphere.

  The organic EL element of the present invention further has a back surface sealing member, at least a part of the laminate is covered with the back surface sealing member, and at least one of the substrate and the back surface sealing member is a book. It is a transparent gas barrier film of the invention. That is, the transparent gas barrier film of the present invention can also be applied as a back sealing member for organic EL elements. In this case, it is possible to maintain sufficient sealing properties by installing the transparent gas barrier film on the laminate using an adhesive or by heat sealing.

  When the transparent gas barrier film of the present invention is used as the substrate of the organic EL element, the organic EL element can be reduced in weight, thickness and flexibility. Therefore, the organic EL element as a display becomes flexible and can be used like electronic paper by rolling it. Moreover, when the transparent gas barrier film of this invention is used as a back surface sealing member, coating | cover is easy and thickness reduction of an organic EL element is also attained.

  The solar cell of the present invention includes a solar cell, and the solar cell is covered with the transparent gas barrier film of the present invention. The transparent gas barrier film of the present invention can also be suitably used as a light receiving side front sheet and a protective back sheet of a solar cell. As an example of the structure of the solar cell, a solar cell formed by thin film silicon or CIGS (Copper Indium Gallium DiSelenide) thin film is sealed with a resin such as ethylene-vinyl acetate copolymer, and the transparent gas barrier film of the present invention What is comprised by inserting | pinching between is mentioned. You may pinch | interpose directly with the transparent gas barrier film of this invention, without sealing with the said resin.

  The thin film battery of the present invention is a thin film battery having a laminate in which a current collecting layer, an anode layer, a solid electrolyte layer, a cathode layer, and a current collecting layer are provided in this order, and the laminate is the invention of the present invention. It is covered with a transparent gas barrier film. Examples of the thin film battery include a thin film lithium ion battery. The thin film battery typically has a structure in which a current collecting layer using a metal, an anode layer using a metal inorganic film, a solid electrolyte layer, a cathode layer, and a current collecting layer using a metal are sequentially laminated on a substrate. is there. The transparent gas barrier film of the present invention can also be used as a substrate for a thin film battery.

  Next, examples of the present invention will be described together with comparative examples. The present invention is not limited or restricted by the following examples and comparative examples. In addition, various properties and physical properties in each example and each comparative example were measured and evaluated by the following methods.

(Composition analysis)
The composition of the first layer (suboxide inorganic layer) was measured using an X-ray photoelectron spectroscopy (XPS) apparatus (trade name PHI-5000, manufactured by ULVAC-PHI). The composition ratio (x) of oxygen atom / metal (metalloid) atom was calculated from the ratio of peak intensity.

(Water vapor transmission rate)
The water vapor transmission rate (WVTR) was measured in a water vapor transmission rate measurement device (manufactured by MOCON, trade name PERMATRAN) specified in JIS K7126 under an environment of a temperature of 40 ° C. and a humidity of 90% RH. In addition, the measurement range of the said water-vapor-permeation rate measuring apparatus is 0.05 g * m ^<-2 > * day ^{< -1} > or more.

(Light transmittance)
The light (visible light) transmittance was measured using a UV-visible light spectrophotometer (trade name: U4000) manufactured by Hitachi, Ltd., and represented by a transmittance of 550 nm.

[Example 1]
[Preparation of transparent resin film]
As a transparent resin film (resin substrate), a polyethylene terephthalate (PET) film (thickness 100 μm, average surface roughness Ra = 2 nm, trade name “Lumirror T60”) manufactured by Toray Industries, Inc. was prepared.

[Transparent gas barrier layer forming step]
(First layer: suboxide inorganic layer)
Next, the PET film was mounted on the manufacturing apparatus shown in FIG. An aluminum target (purity 4N: 99.99%) 17 was mounted on the upper surface of the cathode 16. The inside of the vacuum chamber 31 was depressurized with the vacuum pump 20, and an ultimate vacuum of 1.0 × 10 ⁻⁴ Pa or less was obtained. Thereafter, argon gas as a sputtering gas and oxygen gas as a reactive gas were introduced into the vacuum chamber 31 by the sputtering gas supply means 18 and the reactive gas supply means 19. Subsequently, an aluminum suboxide (AlOx) layer having a thickness of 30 nm was formed on the PET film by a DC sputtering method under a discharge output of 10 W / cm ² . At this time, the supply amount (flow rate) of argon gas is 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec), and the supply amount (flow rate) of oxygen gas is 10 sccm (10 × 1.69 ×). 10 ⁻³ Pa · m ³ / sec). At this time, the system internal pressure was 0.5 Pa, and the substrate heater temperature was 60 ° C. In the obtained aluminum suboxide (AlOx) layer, x (element composition ratio O / Al) was 1.2.

(Second layer: Inorganic layer)
An aluminum oxide layer was formed as the second inorganic layer by high-frequency plasma-assisted vapor deposition. Argon gas 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec) was introduced into the vacuum chamber, and oxygen gas (purity 3N: 99.9%) was used as a reaction gas at 20 sccm (20 × 1). .69 × 10 ⁻³ Pa · m ³ / sec), and in this state, aluminum (purity 3N: 99.9%) as an evaporation material is deflected by 270 degrees (acceleration voltage 6 kV, The aluminum oxide layer was evaporated to a thickness of 300 nm on the substrate by evaporating with an applied current of 60 mA) so that the deposition rate was 50 nm / min. At this time, the system internal pressure was 0.05 Pa, and the substrate heater temperature was 60 ° C.

[Example 2]
In the formation of the first suboxide inorganic layer, a silicon suboxide (SiOx) layer is formed using silicon (purity 3N) as a target, and in the formation of the second inorganic layer, silicon (purity) A transparent gas barrier film of this example was obtained in the same manner as in Example 1 except that the silicon oxide layer was formed using 3N). In the obtained silicon suboxide (SiOx) layer, x (element composition ratio O / Si) was 1.5.

[Example 3]
A transparent gas barrier film of this example was obtained in the same manner as in Example 1 except that an aluminum oxynitride layer was formed as the third inorganic layer on the second layer by high-frequency plasma-assisted vapor deposition. Argon gas 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec) was introduced into the vacuum chamber, and oxygen gas (purity 3N: 99.9%) and nitrogen gas (purity 4N) were used as reaction gases. : 99.99%) at a flow rate of 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) and 10 sccm (10 × 1.69 × 10 ⁻³ Pa · m ³ / sec), respectively. In this state, the evaporation material aluminum (purity 3N: 99.9%) is evaporated to an evaporation rate of 50 nm / min by an electron beam (acceleration voltage 6 kV, applied current 60 mA) deflected 270 degrees. Then, an aluminum oxynitride layer was deposited on the substrate to a thickness of 50 nm. At this time, the system internal pressure was 0.05 Pa, and the substrate heater temperature was 60 ° C.

[Example 4]
A transparent gas barrier film of this example was obtained in the same manner as in Example 1 except that a silicon oxynitride layer was formed as an inorganic layer of the third layer on the second layer by high-frequency plasma assisted vapor deposition. Argon gas 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) was introduced into the vacuum chamber, and oxygen gas and nitrogen gas were respectively 20 sccm (20 × 1.69 ×) as reaction gases. 10 ⁻³ Pa · m ³ / sec) and 10 sccm (10 × 1.69 × 10 ⁻³ Pa · m ³ / sec) were introduced, and in this state, silicon as the deposition material was deflected by 270 degrees. Evaporation was performed with an electron beam (acceleration voltage 6 kV, applied current 100 mA) to a deposition rate of 30 nm / min, and a silicon oxynitride layer was deposited on the substrate to a thickness of 50 nm. At this time, the system internal pressure was 0.05 Pa, and the substrate heater temperature was 60 ° C.

[Comparative Example 1]
Only the 2nd layer (aluminum oxide layer) in Example 1 was formed on the said PET film, and the transparent gas barrier film of this comparative example was obtained.

[Comparative Example 2]
Only the 2nd layer (silicon oxide layer) in Example 2 was formed on the said PET film, and the transparent gas barrier film of this comparative example was obtained.

[Comparative Example 3]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 3 except that oxygen gas was introduced at 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec) in the formation of the first layer. It was. In the obtained aluminum oxide (AlOx) layer, x (element composition ratio O / Al) was 1.5.

[Comparative Example 4]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 4 except that oxygen gas was introduced at 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec) in the formation of the first layer. It was. In the obtained silicon oxide (SiOx) layer, x (element composition ratio O / Si) was 2.0.

  About the transparent gas barrier film obtained in Examples 1-4 and Comparative Examples 1-4, the water vapor transmission rate (WVTR) and the light transmittance were measured. The measurement results are shown in Table 1.

As shown in Table 1 above, the transparent gas barrier films obtained in the examples have favorable gas barrier properties in which the water vapor transmission rate is lower than 0.05 g · m ⁻² · day ⁻¹ and have suitable characteristics. It turns out that the transparent gas barrier film is obtained. On the other hand, in Comparative Examples 1 and 2 in which the first suboxide inorganic layer is not formed, the water vapor transmission rate is as high as 0.1 g · m ⁻² · day ⁻¹ , indicating that the gas barrier property is poor. . In addition, in Comparative Examples 3 and 4 in which the first layer which is an oxide having a stoichiometric composition was used instead of the first suboxide inorganic layer in Examples 3 and 4, the water vapor transmission rate was 0.08 g · It turns out that it is inferior to gas barrier property also compared with Example 1 and 2 which are m- ² * day- ¹ or more and two transparent gas barrier layers.

  The transparent gas barrier film of the present invention uses a resin substrate and is excellent in gas barrier properties even if it is a transparent gas barrier layer having a small number of layers. The transparent gas barrier film of the present invention is, for example, various display devices (displays) such as an organic EL display device, a field emission display device or a liquid crystal display device, various electric elements / electrical devices such as a solar cell, a thin film battery, and an electric double layer capacitor. It can be used as a substrate or a sealing material of an element, and its use is not limited, and can be used in all fields in addition to the above-mentioned use.

DESCRIPTION OF SYMBOLS 10, 30 Manufacturing apparatus 11, 31 Vacuum tank 12, 32 Transparent resin film 13a Unwinding roll 13b Winding roll 14a, 14b Auxiliary roll 15 Can roll 16 Cathode 17 Target 18 Sputtering gas supply means 19 Reactive gas supply means 20 Vacuum pump 21 Gas cylinder for sputtering 22 Gas cylinder for reaction gas (oxygen-containing gas)
23 Gas cylinder for reaction gas (nitrogen-containing gas)
33 Substrate heater

Claims (11)

A transparent gas barrier film in which a transparent gas barrier layer having gas barrier properties is formed on a resin substrate,
The transparent gas barrier layer is a laminate including a suboxide inorganic layer and an inorganic layer,
On the resin substrate, the suboxide inorganic layer and the inorganic layer are laminated in this order,
The suboxide inorganic layer is a layer formed by a sputtering method,
The transparent gas barrier film, wherein the inorganic layer is a layer formed by a vapor deposition method and comprising at least one of a metal and a metalloid and at least one selected from oxygen, nitrogen and carbon. The transparent gas barrier film according to claim 1, wherein the inorganic layer is a laminate in which a plurality of layers are laminated. The transparent gas barrier film according to claim 1, wherein the suboxide inorganic layer contains silicon oxide or aluminum oxide. The transparent gas barrier film according to any one of claims 1 to 3, wherein the inorganic layer contains at least one of aluminum and silicon. A method for producing a transparent gas barrier film for forming a transparent gas barrier layer having gas barrier properties on a resin substrate,
A suboxide inorganic layer forming step for forming a suboxide inorganic layer on the resin substrate by a sputtering method;
Including an inorganic layer forming step of forming, on the suboxide inorganic layer, an inorganic layer containing at least one of metal and metalloid and at least one selected from oxygen, nitrogen, and carbon by a vapor deposition method. A method for producing a transparent gas barrier film characterized by the above. The method for producing a transparent gas barrier film according to claim 5, wherein the inorganic layer forming step is a step of forming a plurality of inorganic layers. A transparent gas barrier film produced by the method for producing a transparent gas barrier film according to claim 5. The organic electroluminescent element which has the laminated body in which the anode layer, the organic light emitting layer, and the cathode layer were provided in this order on the board | substrate, Comprising: The said board | substrate is any one of Claims 1-4, or Claim. 7. An organic electroluminescence device, which is the transparent gas barrier film according to 7. An organic electroluminescence device having a laminate in which an anode layer, an organic light emitting layer and a cathode layer are provided in this order on a substrate,
Furthermore, it has a back sealing member,
At least a part of the laminate is covered with the back sealing member,
At least one of the said board | substrate and the said back surface sealing member is the transparent gas barrier film of any one of Claim 1 to 4, or Claim 7, The organic electroluminescent element characterized by the above-mentioned. It is a solar cell containing a photovoltaic cell, Comprising: The said photovoltaic cell is coat | covered with the transparent gas barrier film as described in any one of Claim 1-4, or the solar cell characterized by the above-mentioned. 5. A thin film battery having a laminate in which a current collecting layer, an anode layer, a solid electrolyte layer, a cathode layer, and a current collecting layer are provided in this order, wherein the laminate is any one of claims 1 to 4. Alternatively, a thin film battery which is covered with the transparent gas barrier film according to claim 7.

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