JP2012211373A - Transparent gas barrier film, method for manufacturing transparent gas barrier film, organic electroluminescence element, solar cell, and thin film cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent gas barrier film excellent in a gas barrier property even if the number of its laminates is small, and having a high transparency, and a method for manufacturing the same.SOLUTION: The transparent gas barrier film includes a transparent gas barrier layer having a gas barrier property formed on a resin substrate. The transparent gas barrier layer is a laminated body formed by laminating a first inorganic layer and a second inorganic layer, wherein the first inorganic layer contains at least one kind selected from metals and semi-metals, and nitrogen, and the second inorganic layer is formed with a sputtering method using a target containing at least one kind of carbides selected from metal carbides and semi-metal carbides, and contains at least one of metals and semi-metals, carbon, and hydrogen.

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 Document 1). 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.

  On the other hand, as a means for obtaining a gas barrier effect with a single layer without heating to a high temperature, it has been proposed to form a thin film formed by sputtering silicon carbide. The silicon carbide thin film is colored because of its large light absorption, but it is said that light transmittance can be imparted by adding nitrogen or oxygen during sputtering (see, for example, Patent Document 2).

Japanese Patent No. 2999616 JP 2004-151528 A

  However, according to the study by the present inventors, by adding nitrogen during sputtering, a gas barrier property is improved but a layer having low light transmittance is formed, and by adding oxygen, light transmittance is improved. A problem has been found that the gas barrier properties are lowered. That is, the gas barrier property and the light transmittance are in a trade-off relationship in the gas barrier layer forming conditions.

  Accordingly, an object of the present invention is to provide a transparent gas barrier film having excellent gas barrier properties and high transparency even when the number of laminated layers is small, and a method for producing the same.

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 in which a first inorganic layer and a second inorganic layer are laminated,
The first inorganic layer is a layer containing nitrogen and at least one selected from metals and metalloids;
The second inorganic layer is formed by a sputtering method using a target including at least one carbide selected from a metal carbide and a metal carbide, and at least one of the metal and the metal, carbon, hydrogen It is a layer containing these.

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 first inorganic layer forming step of forming a first inorganic layer containing at least one selected from metals and metalloids and nitrogen on the resin substrate;
At least one of metal and metalloid is formed on the first inorganic layer by sputtering using a target containing at least one carbide selected from metal carbide and metalloid carbide and using a hydrogen-containing gas as a reaction gas. And a second inorganic layer forming step of forming a second inorganic layer containing carbon and hydrogen.

  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.

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 if there are few laminated | stacked transparent gas barrier layers using a resin substrate, it can provide the transparent gas barrier film which is excellent in gas barrier property, and has high transparency, and its manufacturing method.

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 continuous 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 batch production method.

  In the transparent gas barrier film of the present invention, it is preferable that the first inorganic layer contains silicon nitride or aluminum nitride.

  In the transparent gas barrier film of the present invention, it is preferable that the metal carbide is aluminum carbide and the semimetal carbide is silicon carbide.

  In the transparent gas barrier film of the present invention, it is preferable that the second inorganic layer further contains nitrogen.

  In the method for producing a transparent gas barrier film of the present invention, it is preferable that the reaction gas further contains nitrogen.

  In the method for producing a transparent gas barrier film of the present invention, it is preferable that the metal carbide is aluminum carbide and the semimetal carbide is silicon carbide.

  In the method for producing a transparent gas barrier film of the present invention, the target may further include at least one of a metal and a metalloid, and the metal and the metalloid may be a simple substance, a mixture, or an alloy.

  In the method for producing a transparent gas barrier film of the present invention, the sputtering method is preferably a pulse DC (direct current) sputtering method or an RF (high frequency) sputtering method.

  In the method for producing a transparent gas barrier film of the present invention, the first inorganic layer forming step is preferably performed by at least one of a vapor deposition method, a sputtering method, and a chemical vapor deposition method (CVD).

  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.

  In the above description, it has been described that, in sputtering of a metal carbide or a semimetal carbide, by using oxygen as a reaction gas, a transparent layer having a low gas barrier property is formed. Furthermore, the present inventors have found that a layer having a low gas barrier property is formed when oxygen or moisture is present on the resin substrate during the formation of the layer. Therefore, a first inorganic layer containing at least one selected from metals and metalloids and nitrogen is formed on a resin substrate, and a second inorganic layer is formed on the first inorganic layer. It was found to have a high gas barrier property. Here, the second inorganic layer is formed by a sputtering method using a target containing at least one carbide selected from a metal carbide and a semimetal carbide, and at least one of the metal and the semimetal, carbon And a layer containing hydrogen.

  The first inorganic layer preferably contains silicon nitride or aluminum nitride. These materials are preferable in terms of improving the gas barrier property of the transparent gas barrier layer because the network structure (network-like structure) in the layer can be densely formed and the gas barrier property is high. When the first inorganic layer is formed on the resin substrate, oxygen molecules and water molecules from the resin substrate are difficult to permeate. Therefore, oxygen and moisture due to these exist on the surface of the first inorganic layer. It becomes difficult. By forming the second inorganic layer on such a first inorganic layer, high gas barrier properties can be obtained. The first inorganic layer preferably does not contain oxygen, but the effect of the present invention is not hindered if the elemental composition of oxygen in the first inorganic layer is 20% or less. The elemental composition of oxygen in the first inorganic layer is more preferably 10% or less.

The first inorganic layer is preferably formed by at least one of vapor deposition, sputtering, and chemical vapor deposition (CVD). By using these methods in which layer formation is performed in a vacuum atmosphere, a layer in which mixing of oxygen is suppressed can be formed. For example, a sputtering method using nitrogen as a reactive gas for a silicon target, a plasma chemical vapor deposition method (PECVD) of silane gas (SiH ₄ ) and nitrogen, or the like can be given.

  The thickness of the first inorganic layer 1 is preferably in the range of 0.01 to 1 μm. By setting the thickness to 0.01 μm or more, sufficient gas barrier properties can be obtained, and by setting the thickness to 1 μm or less, internal stress can be reduced and the occurrence of cracks can be prevented. The thickness is more preferably in the range of 0.02 to 0.2 μm.

  In the present invention, in the second inorganic layer in the transparent gas barrier layer, hydrogen atoms formed in the sputtering atmosphere by using a hydrogen-containing gas as a reaction gas in the forming step act on the chemical structure of the gas barrier layer, The gas barrier layer to be formed becomes transparent, and the stress in the gas barrier layer is relaxed. Furthermore, the introduction of nitrogen improves the barrier properties and transparency of the gas barrier layer. The reaction gas may be a compound gas of hydrogen and nitrogen, such as ammonia gas. In this case, the same effect can be obtained. When using a gas of a compound of hydrogen and nitrogen, it is considered that hydrogen and nitrogen are dissociated from the gas of the compound in a sputtering atmosphere, nitrogen is introduced into the gas barrier layer, and hydrogen performs the above action. The present invention is not limited by this assumption.

  The effect is expressed regardless of the mixing ratio (flow rate ratio) of nitrogen and hydrogen in the reaction gas. However, if the mixing ratio of nitrogen (flow rate ratio) is higher than that of hydrogen, better characteristics may be expressed. It is possible and preferable. The mixing ratio of nitrogen and hydrogen is preferably nitrogen / hydrogen = 0.3 to 3.0, and more preferably 0.5 to 2.0.

  In the method for producing a transparent gas barrier film of the present invention, the second inorganic layer forming step is performed by a sputtering method, and the target includes at least one kind of carbide selected from a metal carbide and a metal carbide carbide. Use. The carbide is preferably aluminum carbide, and the carbide metal is preferably silicon carbide. These materials are preferable in terms of improving the gas barrier property of the transparent gas barrier layer, because the network structure (network structure) in the transparent gas barrier layer can be formed densely. Moreover, it is preferable also from the point that the internal stress at the time of transparent gas barrier layer formation is not high compared with other metal carbide and metal carbide.

  Further, the target may further contain at least one of a metal and a semimetal. The metal and metalloid may be a simple substance, a mixture or an alloy. The mixture may be any of a mixture of a plurality of kinds of metals, a mixture of a plurality of kinds of metalloids, a mixture of metals and metalloids, and a mixture of a simple substance and an alloy, and is not limited. When the target containing at least one of the metal and the semimetal is used, the layer formation speed can be increased and the production efficiency can be improved. For example, in the case of a mixed target of silicon carbide and silicon, a layer having components of silicon carbonitride and silicon nitride is obtained, and good gas barrier properties are obtained. The mixing ratio of a simple substance, a mixture or an alloy containing at least one selected from the metals and metalloids is preferably 80% by weight or less. By setting the mixing ratio to 80% by weight or less, for example, it is possible to prevent the occurrence of cracks at the grain boundaries in the target, and it is possible to prevent the layer formation state during sputtering from deteriorating. The mixing ratio is more preferably 50% by weight or less, and still more preferably 30% by weight or less. The metal and metalloid may be the same or different from the metal carbide and metalloid constituting the metal carbide and metalloid, but are the same in consideration of sputtering efficiency and the like. It is preferable.

The sputtering method is preferably performed by a pulse DC (direct current) sputtering method or an RF (high frequency) sputtering method. Compared with the normal DC sputtering method, the pulse DC sputtering method can prevent the formation of an insulating layer such as nitride or oxide on the surface of the target, and the layer formation by sputtering becomes unstable. Can be prevented. In the case of the RF sputtering method, the frequency is preferably in the range of 10 kHz to 30 MHz, and more preferably in the range of 30 kHz to 20 MHz. The discharge output is, for example, in the range of 1 to 10 W / cm ² , and preferably in the range of 3 to 6 W / cm ² . Although there is no particular limitation on the frequency and the duty ratio that becomes a negative bias in the pulse DC sputtering method, the discharge time is preferably short, and is preferably in the range of 30 to 95%.

There is no particular limitation on the sputtering conditions when forming the second 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, and hydrogen gas containing, for example, nitrogen gas is introduced as a reaction gas, and the internal pressure of the system becomes 0.1 to 1 Pa. Thus, the flow control (pressure control) is performed by the mass flow controller. 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 thickness of the second inorganic layer is preferably in the range of 0.01 to 1 μm. By setting the thickness to 0.01 μm or more, sufficient gas barrier properties can be obtained, and by setting the thickness to 1 μm or less, internal stress can be reduced and the occurrence of cracks can be prevented. The thickness is more preferably in the range of 0.1 to 0.3 μm.

  The heating temperature at the time of forming the transparent gas barrier layer in the present invention, which is a laminate obtained by laminating the first inorganic layer and the second inorganic layer, is preferably 120 ° C. or less, more preferably 80 to 110 ° C. Range. 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 thickness of the transparent gas barrier layer is preferably in the range of 0.1 to 0.5 μm. By setting the thickness to 0.1 μm or more, a sufficient gas barrier property can be obtained, and by setting the thickness to 0.5 μm or less, internal stress can be lowered and cracking can be prevented. The thickness is more preferably in the range of 0.1 to 0.3 μm. In the transparent gas barrier layer, the thickness of the second inorganic layer is preferably thicker than the thickness of the first inorganic layer. The first inorganic layer has a role as a base layer, and it is considered that the second inorganic layer greatly contributes to gas barrier properties. Further, it has been found that the effect of the first inorganic layer does not change even if it is thicker than a certain thickness. Therefore, when forming a transparent gas barrier layer having the same thickness, in order to obtain a high gas barrier property, the thickness of the second inorganic layer is made thicker than the thickness of the first inorganic layer from the viewpoint of layer formation efficiency. Is also preferable.

  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 a structure of the apparatus which manufactures the transparent gas barrier film of this invention by a continuous production system is shown. In this example, a case where both the first inorganic layer and the second inorganic layer are formed by a sputtering method is shown, but the present invention is not limited to this. 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 nitrogen and a reactive gas gas cylinder 23 containing hydrogen, so that a reactive gas having an appropriate pressure is introduced into the vacuum chamber 11. It is possible to supply. 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 continuous production by this apparatus, a film is continuously introduced into the apparatus, and sputtering is performed in the presence of a reaction gas while moving the film, thereby continuously forming a transparent gas barrier layer. By switching the reaction gas and the target and repeating 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 is performed while moving the film.

  In FIG. 2, an example of a structure of the apparatus which manufactures the transparent gas barrier film of 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.

  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 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 0.01 g * m ^<-2 > * day ^{< -1} > or more.

(Light transmittance)
The light (visible light) transmittance was measured using an ultraviolet-visible light region spectrophotometer (trade name: MCPD-3700) manufactured by Otsuka Electronics Co., 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, trade name “Lumirror T60”) manufactured by Toray Industries, Inc. was prepared.

[Transparent gas barrier layer forming step]
(First inorganic layer)
Next, the PET film was mounted on the manufacturing apparatus shown in FIG. A polycrystalline silicon 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 nitrogen 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, a silicon nitride layer (first inorganic layer) having a thickness of 50 nm was formed on the PET film by a DC sputtering method under a discharge output of 3 W / cm ² . At this time, the supply amount (flow rate) of argon gas is 50 sccm (50 × 1.69 × 10 ⁻³ Pa · m ³ / sec), and the supply amount (flow rate) of nitrogen gas is 40 sccm (40 × 1.69 ×). 10 ⁻³ Pa · m ³ / sec). At this time, the system internal pressure was 0.05 Pa, and the substrate heater temperature was 80 ° C.

(Second inorganic layer)
Next, a silicon carbide target (purity 5N: 99.999%) 17 was attached as a target. 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 nitrogen gas and hydrogen 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, a silicon nitride silicon carbide layer (second inorganic layer) having a thickness of 150 nm is formed on the first inorganic layer by pulse DC sputtering under the conditions of a DC pulse of 200 kHz and a discharge output of 3 W / cm ^2. A transparent gas barrier film of this example was obtained. At this time, the supply amount (flow rate) of argon gas is 50 sccm (50 × 1.69 × 10 ⁻³ Pa · m ³ / sec), and the supply amount (flow rate) of nitrogen gas is 30 sccm (30 × 1.69 ×). 10 ⁻³ Pa · m ³ / sec), and the supply amount (flow rate) of hydrogen gas was 10 sccm (10 × 1.69 × 10 ⁻³ Pa · m ³ / sec). At this time, the system internal pressure was 0.03 Pa, and the substrate heater temperature was 80 ° C.

[Example 2]
In forming the first inorganic layer, polycrystalline aluminum (purity 4N) was used as a target, and nitrogen gas was introduced as a reaction gas at a flow rate of 50 sccm (50 × 1.69 × 10 ⁻³ Pa · m ³ / sec). Others were carried out similarly to Example 1, and obtained the transparent gas barrier film of a present Example.

[Example 3]
In the formation of the second inorganic layer, aluminum carbide (purity 5N) is used as a target, nitrogen gas is 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec), and hydrogen gas is 20 sccm (reaction gas). 20 × 1.69 × 10 ⁻³ Pa · m ³ / sec) A transparent gas barrier film of this example was obtained in the same manner as in Example 1, except that the flow rate was 20 × 1.69 × 10 ⁻³ Pa · m ³ / sec.

[Example 4]
In the formation of the second inorganic layer, aluminum carbide (purity 5N) is used as a target, nitrogen gas is 30 sccm (30 × 1.69 × 10 ⁻³ Pa · m ³ / sec), and hydrogen gas is 20 sccm (reaction gas). A transparent gas barrier film of this example was obtained in the same manner as in Example 2, except that the flow rate was 20 × 1.69 × 10 ⁻³ Pa · m ³ / sec).

[Example 5]
In the formation of the second inorganic layer, a transparent gas barrier film of this example was obtained in the same manner as in Example 1 except that an alloy of 80 wt% silicon carbide and 20 wt% silicon was used as a target.

[Example 6]
In the formation of the second inorganic layer, a transparent gas barrier film of this example was obtained in the same manner as in Example 2, except that an alloy of silicon carbide 80 wt% and silicon 20 wt% was used as a target.

[Example 7]
In the formation of the second inorganic layer, a transparent gas barrier film of this example was obtained in the same manner as in Example 3 except that an alloy of 70 wt% aluminum carbide and 30 wt% aluminum was used as a target.

[Example 8]
In the formation of the second inorganic layer, a transparent gas barrier film of this example was obtained in the same manner as in Example 4 except that an alloy of 70 wt% aluminum carbide and 30 wt% aluminum was used as a target.

[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 second inorganic layer was formed without forming the first inorganic layer.

[Comparative Example 2]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 3 except that the second inorganic layer was formed without forming the first inorganic layer.

[Comparative Example 3]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 5 except that the second inorganic layer was formed without forming the first inorganic layer.

[Comparative Example 4]
A transparent gas barrier film of this comparative example was obtained in the same manner as in Example 7 except that the second inorganic layer was formed without forming the first inorganic layer.

  For the transparent gas barrier films obtained in Examples 1 to 8 and Comparative Examples 1 to 4, 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 good gas barrier properties and good visible light permeability (transparency), and are good with a small number of laminated transparent gas barrier layers. It can be seen that a transparent gas barrier film having excellent characteristics was obtained. Moreover, in Examples 5-8 using a mixed target, the layer formation rate by sputtering could be increased compared with other Examples, and the film with a transparent gas barrier layer could be manufactured efficiently. On the other hand, in Comparative Examples 2 to 4, the visible light transmittance was 60 to 65%, and the light transmittance was not sufficient. In addition, although the comparative example 1 is an example which did not provide the 1st inorganic layer in Example 1 and 2, the light transmittance is low compared with these Examples. Similarly, Comparative Example 2 is an example in which the first inorganic layer was not provided in Examples 3 and 4, but the light transmittance was lower than those of these Examples. As a reason for this, in the example, it is conceivable that the light transmittance is improved due to a decrease in reflectance due to a difference in refractive index between the first inorganic layer and the second inorganic layer. In addition, the presence of the first inorganic layer suppresses oxidation during the formation of the second inorganic layer, or promotes nitridation or hydrogenation, so that the chemical composition of the layer is different from that of the comparative example. It is also possible that These are all speculations, and the present invention is not limited by this speculation mechanism. Moreover, in an Example, it turns out that gas barrier property is improving compared with the comparative example which formed the same 2nd inorganic layer, without providing a 1st inorganic layer.

  The transparent gas barrier film of the present invention uses a resin substrate, has a small number of laminated transparent gas barrier layers, is excellent in gas barrier properties, and has high transparency. 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 and transparency can be manufactured efficiently. 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 (nitrogen-containing gas)
23 Gas cylinder for reaction gas (hydrogen-containing gas)
33 Substrate heater

Claims (15)

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 in which a first inorganic layer and a second inorganic layer are laminated,
The first inorganic layer is a layer containing nitrogen and at least one selected from metals and metalloids;
The second inorganic layer is formed by a sputtering method using a target including at least one carbide selected from a metal carbide and a metal carbide, and at least one of the metal and the metal, carbon, hydrogen A transparent gas barrier film characterized by comprising a layer containing: The transparent gas barrier film according to claim 1, wherein the first inorganic layer contains silicon nitride or aluminum nitride. The transparent gas barrier film according to claim 1 or 2, wherein the metal carbide is aluminum carbide and the metal carbide semimetal is silicon carbide. The transparent gas barrier film according to any one of claims 1 to 3, wherein the second inorganic layer further contains nitrogen. 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 first inorganic layer forming step of forming a first inorganic layer containing at least one selected from metals and metalloids and nitrogen on the resin substrate;
At least one of metal and metalloid is formed on the first inorganic layer by sputtering using a target containing at least one carbide selected from metal carbide and metalloid carbide and using a hydrogen-containing gas as a reaction gas. And a second inorganic layer forming step of forming a second inorganic layer containing carbon and hydrogen. A method for producing a transparent gas barrier film, comprising: The method for producing a transparent gas barrier layer according to claim 5, wherein the reaction gas further contains nitrogen. The method for producing a transparent gas barrier film according to claim 5 or 6, wherein the metal carbide is aluminum carbide, and the semimetal carbide is silicon carbide. The said target further contains at least 1 sort (s) of a metal and a metalloid, The said metal and the said metalloid are a single-piece | unit, a mixture, or an alloy, It is any one of Claim 5 to 7 characterized by the above-mentioned. Manufacturing method of transparent gas barrier film. The method for producing a transparent gas barrier film according to any one of claims 5 to 8, wherein the sputtering method is a pulse DC (direct current) sputtering method or an RF (radio frequency) sputtering method. 10. The method according to claim 5, wherein the first inorganic layer forming step is performed by at least one of a vapor deposition method, a sputtering method, and a chemical vapor deposition method (CVD). 11. A method for producing a transparent gas barrier film. A transparent gas barrier film produced by the method for producing a transparent gas barrier film according to any one of claims 5 to 10. 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. 11. An organic electroluminescence device, which is the transparent gas barrier film according to 11. The organic electroluminescence device according to claim 12, wherein at least a part of the laminate is further covered with the transparent gas barrier film according to any one of claims 1 to 4. A solar battery including a solar battery cell, wherein the solar battery cell is covered with the transparent gas barrier film according to any one of claims 1 to 4 or claim 11. 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 11.

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