JP2013022820A - Transparent gas barrier film, method for manufacturing the same, organic electroluminescent element, solar cell, and membrane battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent gas barrier film which is excellent in gas barrier properties even if the number of the laminations of transparent gas barrier layers is low, has high transparency, and further has an extremely low internal stress of the transparent gas barrier layers, and to provide a method of manufacturing the same.SOLUTION: The transparent gas barrier film is constituted by forming the transparent gas barrier layer 120 on a resin substrate 110 and the transparent gas barrier layer 120 contains at least one kind of a metal and a semimetal. The transparent gas barrier layer 120 contains a discharge treatment layer 120b subjected to discharge treatment and a non-discharge treatment layer 120a not subjected to discharge treatment and a ratio of the density of the discharge treatment layer 120b to that of the non-discharge treatment layer 120a is within a range of 1.0-2.0 and a ratio of the thickness of the discharge treatment layer 120b to that of the transparent gas barrier layer 120 is within a range of 0.05-0.3.

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 has been used as a supporting substrate for these devices. However, the use of a resin substrate instead of a glass substrate has been studied because of its excellent characteristics such as lightness, impact resistance, and flexibility. ing. 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.

Incidentally, the gas barrier properties of electronic devices are required to be orders of magnitude higher than those of food packaging. The gas barrier property is expressed, for example, by a water vapor transmission rate (hereinafter referred to as WVTR). The value of WVTR in conventional food packaging applications is about ¹ to 10 g · m ⁻² · day ⁻¹ , whereas the WVTR required for substrates for thin film silicon solar cells and compound thin film solar cells is 0. 01g ^· m -2 ^{· day -1} or less, more is it believed that ^{1 × 10 -5 g · m -2} · day -1 or less required for a substrate of the organic EL applications. Various methods for forming a gas barrier layer on a resin substrate have been proposed in response to such a demand for extremely high gas barrier properties.

  For example, as a means for obtaining a gas barrier effect without heating to a high temperature (temperature exceeding the heat resistance of the resin substrate), it has been proposed to form a thin film sputtered with silicon carbide. Although the silicon carbide thin film is colored due to its large light absorption, it is said that light transmittance can be imparted by adding nitrogen or oxygen during sputtering (see, for example, Patent Document 1). However, the gas barrier property of the inorganic film formed by the vacuum process represented by this technique does not satisfy the above requirements.

  Thus, it has been proposed to improve gas barrier properties by alternately laminating a plurality of inorganic layers and polymer layers to form a hybrid (see, for example, Patent Documents 2 to 4). However, since layers of different materials are formed by different processes, it is not preferable from the viewpoint of production efficiency and cost. Further, in order to obtain a sufficient gas barrier property, it is necessary to increase the number of laminated layers or to form each layer thickly, which causes a problem that the production efficiency is lowered. Further, there is a problem that the optical absorption increases depending on the material of the layers to be stacked and the number of stacked layers, and the transparency is easily lowered.

JP 2004-151528 A Japanese Patent No. 2999616 JP 2007-230115 A JP 2009-23284 A

  Moreover, although not pointed out in the prior art document, there is a problem of a crack in the gas barrier layer, and this problem of the crack affects the gas barrier property. Therefore, the present invention provides a transparent gas barrier film that has excellent gas barrier properties even when the number of laminated transparent gas barrier layers is small, has high transparency, and has a very low internal stress in the transparent gas barrier layer, and a method for producing the same. The purpose is to provide.

The transparent gas barrier film of the present invention is a transparent gas barrier film in which a transparent gas barrier layer is formed on a resin substrate,
The transparent gas barrier layer includes at least one of a metal and a metalloid;
The transparent gas barrier layer includes a discharge treatment layer subjected to a discharge treatment and a non-discharge treatment layer not subjected to a discharge treatment,
The ratio of the density of the discharge treatment layer to the density of the non-discharge treatment layer is in the range of more than 1.0 and 2.0 or less,
A ratio of the thickness of the discharge treatment layer to the thickness of the transparent gas barrier layer is in a range of 0.05 to 0.3.

Further, the method for producing a transparent gas barrier film of the present invention is a method for producing a transparent gas barrier film for forming a transparent gas barrier layer on a resin substrate,
A transparent gas barrier layer forming step of forming a transparent gas barrier layer containing at least one selected from metals and metalloids;
A discharge treatment step in which a part of the transparent gas barrier layer is a discharge treatment layer by performing a discharge treatment on a part of the transparent gas barrier layer, and a non-discharge treatment layer is a part other than the discharge treatment. It is characterized by including.

  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.

  The organic electroluminescence device of the present invention is an organic electroluminescence device having a laminate in which an anode layer, an organic electroluminescence (EL) 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.

The organic electroluminescence device of the present invention is an organic electroluminescence device having a laminate in which an anode layer, an organic electroluminescence (EL) 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 battery 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 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 characterized by being covered with a transparent gas barrier film.

  According to the present invention, a transparent gas barrier film having excellent gas barrier properties even when the number of laminated transparent gas barrier layers is small, having high transparency, and having very low internal stress in the transparent gas barrier layer, and a method for producing the same Can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the transparent gas barrier film of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the transparent gas barrier film of the present invention. FIG. 3 is a schematic view showing an example of the configuration of an apparatus for producing the transparent gas barrier film of the present invention by a batch production method. FIG. 4 is a schematic view showing an example of the configuration of an apparatus for producing the transparent gas barrier film of the present invention by a continuous production method.

In the transparent gas barrier film of the present invention,
The transparent gas barrier layer is formed in the order of a non-discharge treatment layer and a discharge treatment layer from the resin substrate side,
It is preferable that a barrier layer is further formed on the discharge treatment layer of the transparent gas barrier layer.

In the transparent gas barrier film of the present invention,
It is preferable that at least one of the metal and the metalloid is at least one selected from the group consisting of oxides, nitrides, carbides, oxynitrides, oxycarbides, nitride carbides, and oxynitride carbides.

In the method for producing a transparent gas barrier film of the present invention,
It is preferable that a part of the transparent gas barrier layer is a surface layer portion of the transparent gas barrier layer.

In the method for producing a transparent gas barrier film of the present invention,
The discharge treatment is preferably performed by plasma beam irradiation or ion beam irradiation.

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

  The transparent gas barrier layer in the transparent gas barrier film of the present invention includes a discharge treatment layer that has been subjected to a discharge treatment and a non-discharge treatment layer that has not been subjected to a discharge treatment.

  The discharge treatment layer and the non-discharge treatment layer contain at least one of a metal and a semimetal. It is preferable that at least one metal or metalloid is at least one selected from the group consisting of oxides, nitrides, carbides, oxynitrides, oxycarbides, nitride carbides, and oxynitride carbides. Examples of the metal include aluminum, titanium, indium, and magnesium. Examples of the metalloid include silicon, bismuth, and germanium. In order to improve the gas barrier properties, it is preferable to contain carbon and nitrogen that make the network structure (network structure) in the transparent gas barrier layer dense. Furthermore, in order to improve transparency, it is preferable to contain oxygen.

  The transparent gas barrier layer is formed by a dry process using a vacuum such as vapor deposition, sputtering, or chemical vapor deposition (CVD). Thereby, a very dense thin film having a high gas barrier property can be obtained. Among these, a vapor deposition method is preferable. This is because the vapor deposition method is a process with a very high film formation rate and is a highly productive process, and thus has high production efficiency.

  In the transparent gas barrier film of the present invention, the discharge treatment layer is formed by subjecting a part of the transparent gas barrier layer to a discharge treatment. The other part that is not subjected to the discharge treatment is a non-discharge treatment layer. The discharge treatment layer has a higher layer density than the non-discharge treatment layer and has excellent gas barrier properties. It is preferable that a part of the transparent gas barrier layer is a surface layer portion of the transparent gas barrier layer. Since the discharge treatment layer is a layer formed by surface treatment, the layer thickness is thin and the transparency is high. The thickness of the layer varies depending on conditions such as discharge output and processing time, but can be in the range of 2.5 nm to 150 nm, and preferably in the range of 7.5 nm to 105 nm. Examples of the discharge treatment include irradiation with an ionizing active gas such as corona discharge, atmospheric pressure plasma, high frequency plasma, direct current plasma, arc discharge plasma, and ion beam. Among these, arc discharge plasma and ion beam are preferable, and arc discharge plasma is more preferable. Arc discharge plasma has been found to have a very high electron density, unlike normally used glow discharge plasma. By using arc discharge plasma for the vapor deposition method, the reactivity can be increased and a very dense transparent gas barrier layer can be formed.

  The arc discharge plasma can be formed by, for example, a pressure gradient type plasma gun, a direct current discharge plasma generator, a high frequency discharge plasma generator, etc., and the pressure capable of generating a high-density plasma stably even during vapor deposition. It is preferable to use a gradient plasma gun.

  In the discharge treatment, it is preferable to introduce a gas. The gas is not particularly limited, and examples thereof include inert gases such as helium, neon, argon, and xenon, and reactive gases such as oxygen, nitrogen, hydrogen, and hydrocarbons.

The density of the discharge treatment layer is higher than the density of the non-discharge treatment layer, and the ratio of the density of the discharge treatment layer to the density of the non-discharge treatment layer is in the range of more than 1.0 and not more than 2.0. Due to the presence of the high density discharge treatment layer, the gas barrier property can be improved even if the transparent gas barrier layer is thin. However, if the density ratio is greater than 2.0 or less than 1.0, an internal stress difference is generated, cracks are generated, and the gas barrier property is decreased. The density ratio is preferably in the range of 1.2 to 1.8, and more preferably in the range of 1.5 to 1.8. The density of the non-discharge treated layer varies depending on the material, composition, and film forming method. For example, the silicon oxide layer is 1.6 to 2.2 g · cm ⁻³ , and the silicon nitride layer is 2.3 to 2 0.7 g · cm ⁻³ .

  The discharge treatment layer is formed on a part of the transparent gas barrier layer, and a ratio of the thickness of the discharge treatment layer to the thickness of the transparent gas barrier layer is in a range of 0.05 to 0.3. When the thickness ratio is less than 0.05, the gas barrier property is lowered, which is not preferable. On the other hand, when the ratio is larger than 0.3, optical absorption is likely to occur by the discharge treatment layer, and the transparency of the gas barrier layer is lowered, and the production efficiency is lowered due to the time required for the treatment. The thickness ratio is preferably in the range of 0.07 to 0.25, and more preferably in the range of 0.13 to 0.25.

  The thickness of the transparent gas barrier layer is preferably in the range of 50 to 500 nm in consideration of gas barrier properties, transparency, film formation time, and internal stress of the film. More preferably, it is the range of 150 nm-350 nm.

  FIG. 1 is a schematic cross-sectional view of an example of the configuration of the transparent gas barrier film of the present invention. As illustrated, the transparent gas barrier film 100 has a transparent gas barrier layer 120 on a resin substrate 110. In the transparent gas barrier layer 120, a non-discharge treated layer 120a that has not been subjected to a discharge treatment and a discharge treatment layer 120b that has been subjected to a discharge treatment are formed on the resin substrate 110 in this order. FIG. 2 is a schematic cross-sectional view of another example of the configuration of the transparent gas barrier film of the present invention. In the transparent gas barrier film 200, a transparent gas barrier layer 220 is formed on the resin substrate 110, and a barrier layer 230 is further formed on the transparent gas barrier layer 220. In the transparent gas barrier layer 220, a non-discharge treatment layer 220a and a discharge treatment layer 220b are formed on the resin substrate 110 in this order. The barrier layer 230 preferably contains at least one of the same metals and semimetals as the transparent gas barrier layer, and can be formed in the same manner as the transparent gas barrier layer and the non-discharge treatment layer in the transparent gas barrier layer. it can.

  In the transparent gas barrier layer, the number and order of formation of the non-discharge treatment layers and the discharge treatment layers are not particularly limited as long as at least one of the layers is formed. The order of the formation can be, for example, the order of non-discharge treatment layer / discharge treatment layer, or the order of non-discharge treatment layer / non-discharge treatment layer / discharge treatment layer. It is preferable to form a non-discharge treatment layer as a barrier layer because gas barrier properties can be effectively expressed.

  Examples of the resin substrate in the present invention include transparent films such as cycloolefin polymer, polyethylene naphthalate, polyethylene sulfide, polyphenyl sulfide, polycarbonate, polyimide, and polyamide. The thickness of the resin substrate is preferably 20 to 200 μm, and particularly preferably 50 to 150 μm in terms of handling.

  The surface of the resin substrate in the present invention may be subjected to, for example, corona discharge treatment, plasma discharge treatment or ion etching (RIE) treatment before the formation of the transparent gas barrier layer. Further, an inorganic or polymer layer may be formed as a smooth layer or an adhesive layer by a vacuum process or coating.

  In the present invention, when at least one of the metal and the metalloid is selected from the group consisting of oxide, nitride, carbide, oxynitride, oxycarbide, nitrided carbide, and oxynitride carbide, oxide, nitride Oxygen, carbon, or nitrogen contained in carbide, oxynitride, oxycarbide, nitride carbide, oxynitride carbide, for example, generates an arc discharge plasma in the presence of a reaction gas, so that at least the metal and the semimetal It can introduce | transduce by performing 1 type of vapor deposition. A metal oxide or a semi-metal oxide can also be used as a vapor deposition material in the vapor deposition. As the reaction gas, an oxygen-containing gas, a nitrogen-containing gas, a hydrocarbon-containing gas, or a mixed gas thereof can be used.

The oxygen-containing gas is oxygen (O ₂ ), dinitrogen monoxide (N ₂ O), nitric oxide (NO), and the nitrogen-containing gas is nitrogen (N ₂ ), ammonia (NH ₃ ), nitrogen monoxide (NO ), Hydrocarbon-containing gases include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butane (C ₄ H ₁₀ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ ). H ₂ ).

  As a means for evaporating the vapor deposition material, a method of introducing any one of resistance heating, electron beam, and arc discharge plasma into the vapor deposition material (deposition source) can be used. Among these methods, a method using an electron beam or arc discharge plasma capable of high-speed vapor deposition is preferable. These methods may be used in combination.

  The transparent gas barrier film can be produced by a batch production 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 continuously transporting the transparent resin film by a roll in the vacuum chamber when the transparent gas barrier layer is formed (Roll-to- roll method).

  In FIG. 3, an example of a structure of the apparatus which manufactures the transparent gas barrier film in this invention by a batch production system is shown. As shown, the manufacturing apparatus 300 mainly includes a vacuum chamber 1, a pressure gradient plasma gun 2, a reflective electrode 5, a focusing electrode 6, a vapor deposition source 7, a discharge gas supply unit 11, a reaction gas supply unit 12, and a vacuum pump 20. As a component. A substrate heater 13 is disposed in the vacuum chamber 1, and a resin substrate (for example, a transparent resin film) 3 is installed on the substrate heater 13. The vapor deposition source 7 is installed at the bottom of the vacuum chamber 1 so as to face the substrate heater 13. A vapor deposition material 8 is mounted on the upper surface of the vapor deposition source 7. The vacuum pump 20 is disposed on the side wall (right side wall in the figure) of the vacuum chamber 1, whereby the inside of the vacuum chamber 1 can be decompressed. The discharge gas supply means 11 and the reaction gas supply means 12 are arranged on the side wall (right side wall in the figure) of the vacuum chamber 1. The discharge gas supply means 11 is connected to a discharge gas gas cylinder 21, whereby a discharge gas (for example, argon gas) having an appropriate pressure can be supplied into the vacuum chamber 1. Yes. The reaction gas supply means 12 is connected to a reaction gas gas cylinder 22, and thereby supplies a reaction gas (for example, oxygen gas, nitrogen gas, methane gas) having an appropriate pressure into the vacuum chamber 1. Is possible. A temperature control means (not shown) is connected to the substrate heater 13. Thereby, the temperature of the resin substrate 3 can be set within a predetermined range by adjusting the surface temperature of the substrate heater 13. Examples of the temperature control means include a heat medium circulation device that circulates silicone oil and the like.

An example of the manufacturing process when the manufacturing apparatus shown in FIG. 3 is used is as follows. After evacuating the inside of the vacuum chamber 1 to 10 ⁻³ Pa or less, argon is introduced as a discharge gas from the discharge gas supply means 11 into the pressure gradient plasma gun 2 which is an arc discharge plasma generation source, and a constant voltage is applied. The plasma beam 4 is irradiated toward the reflective electrode 5 so that the resin substrate 3 is exposed. The plasma beam 4 is controlled by the focusing electrode 6 so as to have a constant shape. The output of the arc discharge plasma is, for example, 1 to 10 kW. On the other hand, the reaction gas is introduced from the reaction gas supply means 12. Further, the vapor deposition material 8 installed in the vapor deposition source 7 is irradiated with an electron beam 9 to evaporate the material toward the substrate 3. In the presence of the reaction gas, vapor deposition is performed to form a predetermined transparent gas barrier layer on the substrate 3. The formation rate (deposition rate) of the transparent gas barrier layer is measured and controlled by a crystal monitor 10 installed near the substrate 3. During the period from the start of evaporation until the deposition rate is stabilized, a shutter (not shown) covering the substrate 3 is closed, and after the deposition rate is stabilized, the shutter is opened to form a transparent gas barrier layer. Is preferred. When a plurality of layers are laminated as the transparent gas barrier layer, this step is repeated to form a predetermined laminate. When the discharge treatment layer is formed, the substrate 3 is irradiated with only the arc discharge plasma without irradiating the deposition material 8 installed in the deposition source 7 with the electron beam. The output of the arc discharge plasma at this time is the same as described above. By controlling the output of the discharge plasma and the irradiation time, the density and thickness of the discharge treatment layer can be controlled. When the discharge plasma is set to a high output, the discharge treatment layer can be made dense, and when the irradiation time is made long, the thickness of the discharge treatment layer can be increased. The system pressure at the time of forming each layer is, for example, in the range of 0.01 Pa to 0.1 Pa, and preferably in the range of 0.02 Pa to 0.05 Pa. The substrate temperature is, for example, in the range of 20 ° C to 200 ° C, and preferably in the range of 80 ° C to 150 ° C. The generation of the arc discharge plasma and the introduction of the reaction gas may be performed simultaneously or before and after, the reaction gas introduction and the plasma generation may be performed simultaneously, or the plasma may be generated after the reaction gas introduction, A reactive gas may be introduced after the plasma generation. The reactive gas may be present in the system when the transparent gas barrier layer is formed.

  In FIG. 4, an example of the structure of the apparatus which manufactures the transparent gas barrier layer of this invention by a continuous production system is shown. The continuous production method is a method in which 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. 4, the same parts as those in FIG. 3 are denoted by the same reference numerals. As shown in the drawing, in this manufacturing apparatus 400, in place of the substrate heater 13, an unwinding roll 33a, a can roll 35, a winding roll 33b, and two auxiliary rolls 34a and 34b are arranged in the vacuum chamber 31. Yes. The transparent resin film 32 is stretched over the take-up roll 33a and the take-up roll 33b through the can roll 35 and the two auxiliary rolls 34a and 34b. Except for these, the configuration is the same as in FIG. A temperature control means (not shown) is connected to the can roll 35. Examples of the temperature control means are the same as those for the substrate heater 13.

  In continuous production by this apparatus, a film is continuously introduced into the apparatus, and the film is moved to be exposed to an arc discharge plasma beam in the presence of a reactive gas to perform deposition, thereby continuously forming a transparent gas barrier layer. A predetermined laminate can be formed by switching this reaction gas and target and repeating this process without irradiating the vapor deposition material with an electron beam. Continuous production by this apparatus can be carried out in the same manner as the apparatus manufactured by the batch production method, except that vapor deposition and discharge treatment are performed while moving the film.

  The organic EL device of the present invention has a laminate in which an anode layer, an organic electroluminescence (EL) layer, and a cathode layer are provided in this order on a substrate, and the substrate is the transparent gas barrier of the present invention. It is a film. 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 electroluminescence (EL) 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.

(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-permeability measuring apparatus is 0.005g * 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.

(Thickness of each layer constituting the transparent gas barrier film)
The thickness d of each layer constituting the transparent gas barrier film is determined by observing the cross section of the transparent gas barrier film with a scanning electron microscope (trade name: JSM-6610) manufactured by JEOL Ltd., and the surface of each layer from the substrate (film) surface. The length up to was measured and calculated.

(Density of each layer constituting the transparent gas barrier film)
The density ρ of each layer constituting the transparent gas barrier film is measured by measuring the X-ray reflectivity of each layer constituting the transparent gas barrier layer with an X-ray diffractometer (trade name: Smart Lab) manufactured by Rigaku Corporation. Calculated.

(Curl of film)
In order to confirm the internal stress of the transparent gas barrier layer and the barrier layer, the presence or absence of curling (warping) of the film on which the transparent gas barrier layer and the barrier layer were formed was determined by the following method. Place the 100 mm square film on a horizontal base and fix one end. If the distance at which the other end was separated from the horizontal base was less than 3 mm, it was determined as “No”, and if it was 3 mm or more, it was determined as “Yes”.

[Example 1]
[Preparation of transparent resin film]
As a transparent resin film (resin substrate), a polyethylene naphthalate film (thickness 100 μm, trade name “Teonex”) manufactured by Teijin DuPont Films was prepared.

[Transparent gas barrier layer forming step]
Next, the polyethylene naphthalate film was attached to the production apparatus shown in FIG. Argon gas 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) was introduced into the pressure gradient plasma gun, and a discharge output of 5 kW was applied to the plasma gun to generate arc discharge plasma. As a reaction gas, nitrogen (purity 5N: 99.999%) was introduced into the vacuum chamber at a flow rate of 40 sccm (40 × 1.69 × 10 ⁻³ Pa · m ³ / sec). A certain silicon grain (purity 3N: 99.9%) is irradiated with an electron beam (acceleration voltage 6 kV, applied current 50 mA) and evaporated to a deposition rate of 100 nm / min to form a transparent gas barrier layer on the substrate. It vapor-deposited so that it might become 80 nm. At this time, the system internal pressure was 2.0 × 10 ⁻² Pa, and the substrate heater temperature was 100 ° C.

[Discharge treatment process]
Thereafter, the irradiation of the electron beam was stopped, and the evaporation of the silicon grains was stopped. In this state, argon gas was vacuumed at a flow rate of 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) and nitrogen at a flow rate of 40 sccm (40 × 1.69 × 10 ⁻³ Pa · m ³ / sec). It was introduced into a bath, a discharge output of 5 kW was applied to the plasma gun, and the discharge gas treatment layer was formed by irradiating the transparent gas barrier layer with arc discharge plasma for 30 seconds.

About the obtained transparent gas barrier layer, the thickness and density of each layer were analyzed. The transparent gas barrier layer had a thickness of 80 nm and a density of 2.4 g · cm ⁻³ . The thickness of the discharge treatment layer was 10 nm, and the density was 3.6 g · cm ⁻³ .

[Example 2]
Until the non-discharge treatment layer and the discharge treatment layer are formed, the barrier layer is formed on the discharge treatment layer under the same conditions as in the transparent gas barrier layer forming step, and the process of the present embodiment is performed. A transparent gas barrier film was obtained.

  When the obtained transparent gas barrier layer was analyzed for thickness and density, it was the same as in the first example.

[Example 3]
A transparent gas barrier film of this example was obtained in the same manner as in Example 2, except that the discharge output when forming the discharge treatment layer was 3 kW.

The obtained transparent gas barrier layer was analyzed for thickness and density. Example 2 was the same as Example 2 except that the density of the discharge treatment layer was 2.9 g · cm ⁻³ .

[Example 4]
A transparent gas barrier film of this example was obtained in the same manner as in Example 2 except that the discharge output when forming the discharge treatment layer was 7 kW.

The obtained transparent gas barrier layer was analyzed for thickness and density. Example 2 was the same as Example 2 except that the density of the discharge treatment layer was 4.3 g · cm ⁻³ .

[Example 5]
Example 2 except that a discharge output of 5 kW was applied to the plasma gun, the discharge gas treatment layer was formed by irradiating the transparent gas barrier layer with an arc discharge plasma for 10 seconds, and the thickness of the discharge treatment layer was 6 nm. In the same manner as above, a transparent gas barrier film of this example was obtained.

[Example 6]
Example 2 except that a discharge output of 5 kW was applied to the plasma gun, the discharge gas treatment layer was formed by irradiating the transparent gas barrier layer with arc discharge plasma for 90 seconds, and the thickness of the discharge treatment layer was 20 nm. In the same manner as above, a transparent gas barrier film of this example was obtained.

[Comparative Example 1]
Only the non-discharge treated layer was formed on the substrate under the same conditions as in Example 1 to obtain a transparent gas barrier film of this comparative example.

[Comparative Example 2]
A non-discharge treated layer was formed under the same conditions as in Example 1, and a barrier layer was formed thereon under the same conditions as the non-discharge treated layer to obtain a transparent gas barrier film of this comparative example.

[Comparative Example 3]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 2 except that the discharge output when forming the discharge treatment layer was 2 kW.

The obtained transparent gas barrier layer was analyzed for thickness and density. Example 2 was the same as Example 2 except that the density of the discharge treatment layer was 1.9 g · cm ⁻³ .

[Comparative Example 4]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 2 except that the discharge output upon forming the discharge treatment layer was 10 kW.

The obtained transparent gas barrier layer was analyzed for thickness and density. Example 2 was the same as Example 2 except that the density of the discharge treatment layer was 5.3 g · cm ⁻³ .

[Comparative Example 5]
A discharge power of 5 kW was applied to the plasma gun, an arc discharge plasma was irradiated to the transparent gas barrier layer for 4 seconds to form a discharge treatment layer, and the thickness of the discharge treatment layer was 2.5 nm. In the same manner as in Example 2, a transparent gas barrier film of this comparative example was obtained.

[Comparative Example 6]
Example 2 except that a discharge output of 5 kW was applied to the plasma gun, the discharge gas treatment layer was formed by irradiating the transparent gas barrier layer with arc discharge plasma for 120 seconds, and the thickness of the discharge treatment layer was 30 nm. In the same manner, a transparent gas barrier film of this comparative example was obtained.

  For the transparent gas barrier films obtained in Examples 1 to 6 and Comparative Examples 1 to 6, the water vapor transmission rate (WVTR), the light transmittance at a wavelength of 550 nm, and the presence or absence of curling of the film were measured. The measurement results are shown in Table 1.

As shown in Table 1, all of the transparent gas barrier films obtained in the examples have good gas barrier properties with a water vapor transmission rate of 0.01 g · m ⁻² · day ⁻¹ or less, and good light rays of 83% or more. It turns out that the transparent gas barrier film which has the transmittance | permeability and has a suitable characteristic is obtained. Moreover, the curvature of a film is not seen and it turns out that the internal stress of a transparent gas barrier layer is low. On the other hand, in Comparative Examples 1 and 2 having no discharge treatment layer, the water vapor transmission rate is as high as 0.12 g · m ⁻² · day ⁻¹ or more, indicating that the gas barrier property is poor. In Comparative Example 3 in which the ratio of the density of the discharge treatment layer to the density of the non-discharge treatment layer is less than 1.0, the density of the discharge treatment layer is not sufficiently high, so that the gas barrier property is 0.04 g · m ⁻² · day- ¹ and it was not good. In Comparative Example 4 in which the density ratio was larger than 2.0, curling of the film was observed, and the gas barrier property was not as good as 0.03 g · m ⁻² · day ⁻¹ . This is presumably because an internal stress difference occurs between the layers, cracks are generated, and gas barrier properties are lowered. Further, due to the occurrence of optical absorption by the high-density discharge treatment layer, the light transmittance was 80%, and the light transmittance was not sufficient. In Comparative Example 5 in which the ratio of the thickness of the discharge treatment layer to the density of the non-discharge treatment layer is less than 0.05, the thickness of the discharge treatment layer is not sufficient, so that the gas barrier property is 0.04 g · m ⁻² · day- ¹ and it was not good. In Comparative Example 6 in which the thickness ratio was greater than 0.3, the light transmittance was 80% and the light transmittance was not sufficient due to the occurrence of optical absorption by the discharge treatment layer. Moreover, the curl of a film is seen and it turns out that the internal stress of a transparent gas barrier layer is high. Therefore, it is considered that the gas barrier property is lowered to 0.03 g · m ⁻² · day ⁻¹ .

  The transparent gas barrier film of the present invention is excellent in gas barrier properties even when the number of laminated transparent gas barrier layers is small, has high transparency, and has an extremely low internal stress in the transparent gas barrier layer. 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.

100, 200 Transparent gas barrier film 110 Resin substrate 120, 220 Transparent gas barrier layer 120a, 220a Non-discharge treatment layer 120b, 220b Discharge treatment layer 230 Barrier layer 300, 400 Production apparatus 1, 31 Vacuum chamber 2 Pressure gradient plasma gun (arc discharge) Plasma source)
3 Resin substrate 4 Plasma beam 5 Reflective electrode 6 Focusing electrode 7 Deposition source 8 Deposition material 9 Electron beam 10 Crystal monitor 11 Discharge gas supply means 12 Reactive gas supply means 13 Substrate heater 20 Vacuum pump 21 Discharge gas gas cylinder 22 Reactive gas Gas cylinder 32 Transparent resin film 33a Unwinding roll 33b Winding rolls 34a, 34b Auxiliary roll 35 Can roll

Claims (11)

A transparent gas barrier film having a transparent gas barrier layer formed on a resin substrate,
The transparent gas barrier layer includes at least one of a metal and a metalloid;
The transparent gas barrier layer includes a discharge treatment layer subjected to a discharge treatment and a non-discharge treatment layer not subjected to a discharge treatment,
The ratio of the density of the discharge treatment layer to the density of the non-discharge treatment layer is in the range of more than 1.0 and 2.0 or less,
A ratio of the thickness of the discharge treatment layer to the thickness of the transparent gas barrier layer is in a range of 0.05 to 0.3. The transparent gas barrier layer is formed in the order of a non-discharge treatment layer and a discharge treatment layer from the resin substrate side,
The transparent gas barrier film according to claim 1, further comprising a barrier layer formed on the discharge treatment layer of the transparent gas barrier layer. At least one of the metal and the metalloid is at least one selected from the group consisting of oxide, nitride, carbide, oxynitride, oxycarbide, nitride carbide, and oxynitride carbide, The transparent gas barrier film according to claim 1 or 2. A transparent gas barrier film manufacturing method for forming a transparent gas barrier layer on a resin substrate,
A transparent gas barrier layer forming step of forming a transparent gas barrier layer containing at least one selected from metals and metalloids;
A discharge treatment step in which a part of the transparent gas barrier layer is a discharge treatment layer by performing a discharge treatment on a part of the transparent gas barrier layer, and a non-discharge treatment layer is a part other than the discharge treatment. A method for producing a transparent gas barrier film, comprising: The method for producing a transparent gas barrier film according to claim 4, wherein a part of the transparent gas barrier layer is a surface layer portion of the transparent gas barrier layer. The method for producing a transparent gas barrier film according to claim 4 or 5, wherein the discharge treatment is performed by plasma beam irradiation or ion beam irradiation. A transparent gas barrier film produced by the method for producing a transparent gas barrier film according to any one of claims 4 to 6. The organic electroluminescent element which has the laminated body in which the anode layer, the organic electroluminescent layer, and the cathode layer were provided in this order on the board | substrate, Comprising: The said board | substrate is any one of Claims 1-3, or Claim Item 8. An organic electroluminescence device, which is the transparent gas barrier film according to Item 7. An organic electroluminescence device having a laminate in which an anode layer, an organic electroluminescence 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 3, 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 to 3, or the solar cell characterized by the above-mentioned. The current collector layer, the anode layer, the solid electrolyte layer, the cathode layer, and the current collector layer are thin film batteries having a laminate provided in this order, and the laminate is any one of claims 1 to 3. Alternatively, a thin film battery which is covered with the transparent gas barrier film according to claim 7.

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