JP5740179B2 - Transparent gas barrier film, method for producing transparent gas barrier film, organic electroluminescence element, solar cell and thin film battery - Google Patents

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, 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 1 to 3). 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. In addition, there is a problem that the adhesion between the inorganic layer and the polymer layer is low, and deterioration due to aging or bending easily occurs.

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

  The present invention provides a transparent gas barrier film having high gas barrier properties even when the number of laminated layers is small. Moreover, this invention provides the manufacturing method which can manufacture efficiently the transparent gas barrier film which has high gas barrier property by the same formation process in the same vacuum chamber.

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 laminated transparent gas barrier layer in which an inorganic layer and a carbon-containing layer are laminated,
The inorganic layer is a layer formed by an evaporation method using arc discharge plasma, and containing at least one of a metal and a metalloid, and at least one of oxygen and nitrogen;
The carbon-containing layer is formed by a vapor deposition method using arc discharge plasma, and is a layer containing at least one of a metal and a metalloid and carbon.

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 having gas barrier properties on a resin substrate,
Metal, metalloid, metal or metalloid oxide, or metal or metalloid nitride in the presence of a reaction gas that generates arc discharge plasma and contains at least one of oxygen gas, nitrogen gas and oxygen-nitrogen mixed gas An inorganic layer forming step of forming an inorganic layer by depositing at least one of
Arc discharge plasma is generated, and in the presence of a reaction gas containing at least one of hydrocarbon gas and oxygen hydrocarbon mixed gas, metal, metalloid, metal or metalloid oxide, or metal or metalloid nitride A carbon-containing layer forming step of forming a carbon-containing layer by depositing at least one kind on a substrate;
It is characterized by having.

  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.

  Further, the organic electroluminescence element of the present invention is an organic electroluminescence element 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 book. It is a 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.

  The transparent gas barrier film of the present invention has high gas barrier properties even when the number of laminated layers is small. Moreover, according to the manufacturing method of the transparent gas barrier film of this invention, the transparent gas barrier film which has high gas barrier property can be manufactured efficiently in the same formation process in the same vacuum chamber.

FIG. 1 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. 2 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, it is preferable that the carbon-containing layer further contains oxygen.

  In the organic electroluminescent element of the present invention, it is preferable that at least a part of the laminate is further covered with the transparent gas barrier film of the present invention.

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

  The laminated transparent gas barrier layer in the transparent gas barrier film of the present invention is formed using a vapor deposition method using arc discharge plasma. The vapor deposition method is a process with a very high film formation rate and a high productivity. Arc discharge plasma is known 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.

  The laminated transparent gas barrier layer in the present invention is a laminate of an inorganic layer and a carbon-containing layer formed by the vapor deposition method. The inorganic layer is a layer containing at least one of metal and metalloid and at least one of oxygen and nitrogen. Oxygen and nitrogen may be included in the form of a compound or may be included in an atomic state. In the case of a compound, for example, it can be at least one of metal oxide, metalloid oxide, metal nitride, metalloid nitride, metal oxynitride, and metalloid oxynitride. By containing oxygen, the transparency of the inorganic layer can be improved.

  The carbon-containing layer contains at least one of a metal and a semimetal and carbon. The carbon-containing layer may further contain oxygen. By including oxygen, the transparency of the carbon-containing layer can be improved. Carbon and oxygen may be contained in the form of a compound or may be contained in an atomic state. In the case of a compound, for example, it can be at least one of metal carbide, metalloid carbide, metal oxide carbide and metal oxide carbide. Since the carbon-containing layer contains a carbon component, the carbon-containing layer has smoothness and stress relaxation properties like the polymer layer used in the prior art. However, unlike the polymer layer, the carbon-containing layer itself also has a gas barrier property, so that a high gas barrier property can be exhibited even with a small number of layers. Furthermore, since the formation process of this carbon-containing layer can be the same as that of the inorganic layer, a laminate can be formed in the same vacuum atmosphere.

Examples of the inorganic layer include SiO ₂ , Al ₂ O ₃ , TiO ₂ , Nb ₂ O ₂ , Ta ₂ O ₅ , In ₂ O ₃ , oxides such as ITO, Si ₃ N ₄ , AlN, GaN, and TiN. A nitride such as SiON or an oxynitride such as AlON can be used. In addition, as the carbon-containing layer, carbides such as SiC, AlC, and TiC, and oxide carbides such as SiOC, AlOC, and TiOC can be used.

The laminated transparent gas barrier layer may be constructed by mutual lamination of an inorganic layer and a carbon-containing layer. Since the carbon-containing layer can function as a base flat layer and a stress relaxation layer at the interface with the inorganic layer, an inorganic layer having a high barrier property without a pinhole can be formed. The layer formed as the first layer on the resin substrate may be either an inorganic layer or a carbon-containing layer, but it is preferable to form an inorganic layer as the first layer. As a result of investigations by the inventors, it has been found that when an inorganic layer is formed as the first layer, high barrier properties can be obtained. This is thought to be due to the higher barrier properties of the inorganic layer compared to the carbon-containing layer, but the present invention is not limited by this assumption. In addition, when (layers of inorganic layer / carbon-containing layer) are paired as in the case of substrate / (inorganic layer / carbon-containing layer) _n (n ≧ 1), or substrate / (inorganic layer / carbon-containing layer) _n / In the case of an inorganic layer (n ≧ 1), a pair of laminated layers and a single layer may be used.

The inorganic layer and the carbon-containing layer constituting the laminated transparent gas barrier layer in the present invention can be produced by the same formation process in which the reaction gas is different. As a vapor deposition source (vapor deposition material), at least one of metal, metalloid, metal oxide, metal nitride, metalloid oxide, and metalloid nitride is used. The metal, for example, aluminum, titanium, indium, magnesium, and the like, as a metalloid such as silicon, bismuth, etc., as an oxide of a metal or metalloid, for _{example, SiO, SiO 2, TiO 2} , In For example, Si ₃ N ₄ , AlN, or the like can be used as the metal or metalloid nitride such as ₂ O ₃ . Among these, it is preferable to use one containing silicon (Si). Examples of the hydrocarbon gas that is one of the reaction gases when forming the carbon-containing layer include methane (CH ₄ ), ethane (C ₂ H ₆ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ H). ₂ ) etc. are used. In addition, although the vapor deposition source (vapor deposition material) may differ between an inorganic layer and a carbon containing layer, in order to make the adhesiveness of an inorganic layer and a carbon containing layer high, it is preferable to use the same vapor deposition material.

  The thickness of the inorganic layer and the carbon-containing layer is preferably 30 to 300 nm in each layer. In consideration of gas barrier properties, deposition time, and internal stress of the layer, the thickness of each layer is more preferably 50 to 200 nm. Further, the total thickness of the transparent gas barrier layer is preferably 800 nm or less, more preferably in the range of 200 to 500 nm in consideration of the internal stress of the layer.

  The material of the resin substrate is not limited as long as it is transparent. For example, polyethylene, polypropylene, cycloolefin polymer, polyethylene terephthalate, polyethylene naphthalate, polyphenyl sulfide, polycarbonate, polyimide, polyamide (nylon), polyvinyl alcohol, polychlorinated Examples thereof include vinyl, 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.

  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 method or a continuous production method (Roll-to-roll method).

  In FIG. 1, 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 100 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 13 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 a manufacturing process when the manufacturing apparatus shown in FIG. 1 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. This process is repeated to form a predetermined laminate. 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. At this time, the system internal pressure 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. 2, 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. In FIG. 2, the same parts as those in FIG. As shown in the drawing, 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. 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 using this equipment, the film is continuously introduced into the equipment, while the film is moved, vapor deposition is performed by exposure to an arc discharge plasma beam in the presence of a reactive gas, and a transparent gas barrier layer is continuously formed. Except for the above, it can be carried out in the same manner as the apparatus manufactured by the batch production method.

  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.

  In the organic EL device of the present invention, at least a part of the laminate may be further covered with the transparent gas barrier film of the present 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 layer, 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 0.01 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.

(Thickness of transparent gas barrier layer)
The thickness of the transparent gas barrier layer is determined by observing the cross section of the transparent gas barrier film with a transmission electron microscope (TEM, trade name: HF-2000) manufactured by Hitachi, Ltd., from the surface of the substrate (film) to the surface of the transparent gas barrier layer. The length of was measured and calculated.

[Example 1]
[Preparation of transparent resin film]
As a transparent resin film (resin substrate), a polyethylene terephthalate (PET) film (thickness: 100 μm) manufactured by Teijin DuPont Films was prepared.

[Transparent gas barrier layer forming step]
(First layer) Carbon-containing layer Next, the polyethylene terephthalate film was attached to the production apparatus shown in FIG. Argon gas 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) is introduced into the pressure gradient type plasma gun, and a discharge output of 10 kW is applied to the cathode in the plasma gun to generate arc discharge plasma. I let you. Methane gas (purity 99.9%) is introduced as a reaction gas into the vacuum chamber at a flow rate of 18 sccm (18 × 1.69 × 10 ⁻³ Pa · m ³ / sec), and in this state, monoxide which is a deposition material Silicon (99% purity) is evaporated by an electron beam (acceleration voltage 6 kV, applied current 50 mA) to a deposition rate of 100 nm / min, so that a silicon oxide carbide (hereinafter referred to as SiOC) layer has a thickness of 100 nm on the substrate. Vapor deposited. At this time, the system internal pressure was 2.0 × 10 ⁻² Pa, and the substrate heater temperature was 100 ° C.

(Second layer) Inorganic layer Argon gas 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) was introduced into the pressure gradient type plasma gun, and a discharge power of 10 kW was applied to the cathode in the plasma gun. Applied to generate arc discharge plasma. Nitrogen gas (purity: 99.9%) as a reaction gas is introduced into the vacuum chamber at a flow rate of 20 sccm (20 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Silicon oxide (purity 99%) is evaporated by an electron beam (acceleration voltage 6 kV, applied current 50 mA) so as to have a deposition rate of 100 nm / min. The SiON) layer was deposited to a thickness of 100 nm. At this time, the system internal pressure was 2.0 × 10 ⁻² Pa, and the substrate heater temperature was 100 ° C.

[Example 2]
A transparent gas barrier film of this example was obtained in the same manner as in Example 1 except that the transparent gas barrier layer formed on the substrate was a SiON layer as the first layer and a SiOC layer as the second layer.

[Example 3]
The transparent gas barrier layer of the present example was the same as in Example 1 except that the transparent gas barrier layer formed on the substrate was a SiON layer as the first layer, a SiOC layer as the second layer, and a SiON layer as the third layer. A film was obtained.

[Example 4]
The transparent gas barrier layer of the present example was the same as in Example 1 except that the transparent gas barrier layer formed on the substrate was a SiOC layer as the first layer, a SiON layer as the second layer, and a SiOC layer as the third layer. A film was obtained.

[Comparative Example 1]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 1 except that the transparent gas barrier layer formed on the substrate was only one SiON layer.

[Comparative Example 2]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 1 except that the transparent gas barrier layer formed on the substrate was a SiON layer as the first layer and the second layer.

[Comparative Example 3]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 1 except that the transparent gas barrier layer formed on the substrate was all SiON layers from the first layer to the third layer.

[Comparative Example 4]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 1 except that the transparent gas barrier layer formed on the substrate was only one SiOC layer.

[Comparative Example 5]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 1 except that the transparent gas barrier layer formed on the substrate was a SiOC layer as the first layer and the second layer.

[Comparative Example 6]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 1 except that the transparent gas barrier layer formed on the substrate was all SiOC layers from the first layer to the third layer.

  For the transparent gas barrier films obtained in Examples 1 to 4 and Comparative Examples 1 to 6, the water vapor transmission rate (WVTR) and the light transmittance at a wavelength of 550 nm were measured. The measurement results are shown in Table 1.

  As shown in Table 1, the transparent gas barrier films obtained in the examples have better gas barrier properties than the transparent gas barrier films of the comparative examples. In particular, Examples 3 and 4 have good gas barrier properties below the detection limit of water vapor transmission rate. In addition, Example 2 in which the inorganic layer is formed as the first layer has a low water vapor permeability and good gas barrier properties compared to Example 1 in which the carbon-containing layer is formed as the first layer. ing. Moreover, it turns out that the transparent gas barrier film of an Example has favorable gas barrier property, even if there are few lamination numbers (layer thickness). For example, the transparent gas barrier films of Examples 1 and 2 in which the number of layers is 2 have a lower water vapor transmission rate than the transparent gas barrier films of Comparative Examples 3 and 6 in which the number of layers is 3. Even in the transparent gas barrier film in which only the SiOC layer (carbon-containing layer) or only the SiON layer (inorganic layer) is laminated, the barrier property (water vapor transmission rate) is improved by increasing the number of laminated layers (comparison) By using the laminated transparent gas barrier layer in which the SiOC layer and the SiON layer are laminated as in Examples 4 to 6 and Comparative Examples 1 to 3) and Examples 1 to 4, the gas barrier property is remarkably high and the transparency is excellent. It can be seen that a gas barrier film is obtained.

  The transparent gas barrier film of the present invention has high gas barrier properties even when the number of laminated layers is small. Moreover, according to the manufacturing method of the transparent gas barrier film of this invention, the transparent gas barrier film which has high gas barrier property can be manufactured efficiently in the same formation process in the same vacuum chamber. 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.

1, 31 Vacuum chamber 2 Pressure gradient type plasma gun (arc discharge plasma generation 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 rolls 100, 200 Production apparatus

Claims (1)

A method for producing a transparent gas barrier film for forming a transparent gas barrier layer having gas barrier properties on a resin substrate,
In the presence of a reaction gas that generates an arc discharge plasma and contains at least one of oxygen gas, nitrogen gas, and oxygen-nitrogen mixed gas,
As the evaporation material, and the inorganic layer forming process of forming the inorganic layer by depositing a Si O to the substrate,
In the presence of a reaction gas that generates an arc discharge plasma and contains at least one of a hydrocarbon gas and an oxygen-hydrocarbon mixed gas,
A carbon-containing layer forming step of forming a carbon-containing layer by depositing SiO as a deposition material on a substrate,
The manufacturing method of the transparent gas barrier film characterized by using the same vapor deposition material in both said processes.

Images