JP2007083493A - Gas-barrier film and organic device using the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier film which has high barrier properties and transparency and is excellent in stability with the passage of time of gas-barrier performance and an organic device using the film. <P>SOLUTION: The gas-barrier film 1 has a transparent, flexible support substrate 2, the outermost gas-barrier layer 3 made of an inorganic membrane, and an inorganic membrane protecting layer 6 of a metal nitride or a metal carbide which are arranged in turn. Between the support substrate 2 and the gas-barrier layer 3, intermediate layers 4A and 4B and an intermediate gas-barrier layer 5 made of an inorganic membrane are arranged. The inorganic membrane protecting layer 6 is contacted with the surface of the outermost gas barrier layer 3. The hydrogen and oxygen contents of the inorganic membrane protecting layer 6 are each 20 atom% or below in relation to the metal atom of the metal nitride or the metal carbide of the layer 6. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film excellent in gas barrier properties and an organic device using the same, and particularly relates to a laminated gas barrier film suitable for substrates and coating films of various organic devices. Furthermore, the present invention relates to an organic device excellent in durability and flexibility, particularly an organic EL element, using the gas barrier film.

In recent years, in organic devices such as liquid crystal display elements, solar cells, and electroluminescence (EL) elements, it has been studied to use a thin, light, and flexible plastic film as a substrate instead of a heavy and fragile glass substrate. ing. Transparent plastic substrates are easy to increase in area and can be applied to a roll-to-roll production method, so they are more productive than glass and advantageous in terms of cost reduction. .
However, the transparent plastic substrate has a problem that the gas barrier property is inferior to that of glass. In general, organic devices are likely to be deteriorated or altered by water or air in the constituent materials. For example, when a base material having inferior gas barrier properties is used for the substrate of the liquid crystal display element, the liquid crystal in the liquid crystal cell is deteriorated, and the deteriorated portion becomes a display defect, which deteriorates the display quality.

In order to solve such a problem, the above-mentioned plastic film substrate itself may be given a gas barrier function, or the entire device may be sealed with a transparent plastic film having gas barrier properties. As a gas barrier film, a film obtained by forming a metal oxide thin film on a plastic film is generally known. As a gas barrier film used for a liquid crystal display element, for example, a film obtained by vapor-depositing silicon oxide on a plastic film (for example, see Patent Document 1) or a film obtained by vapor-depositing aluminum oxide (for example, see Patent Document 2). is there. All of these have a water vapor barrier property with a water vapor permeability of about 1 g / m ² / day. However, in recent years, organic EL displays and high-definition color liquid crystal displays that require higher barrier properties have been developed, maintaining transparency that can be used for these, and having high barrier properties, particularly water vapor barrier properties. There is a demand for a substrate having a transmittance of less than 0.1 g / m ² / day.

  In order to meet such demands, as a means for expecting higher barrier performance, studies are being made on film formation by sputtering or CVD, in which a thin film is formed using plasma generated by glow discharge under low pressure conditions. In addition, a technique for producing a barrier film having an alternately laminated structure of organic layers / inorganic layers by a vacuum deposition method has been proposed (for example, see Patent Document 3 and Non-Patent Document 1).

In the formation of the inorganic layer by the CVD method, a thin film that is transparent to the sputtering method and has little film stress can be formed, but hydrogen and oxygen are easily taken up due to the source gas. In addition, incorporation of hydrogen and oxygen into the inorganic layer lowers the barrier performance and makes the inorganic layer susceptible to oxidation. The latter has a problem that barrier performance deteriorates with time due to moisture and oxygen in the outside world. Sputtering can reduce the uptake of hydrogen and oxygen, but it becomes a rough film to some extent in relation to the film stress, and is also a film that is also susceptible to oxidation. As a method for preventing oxidation, a technique for forming a polycondensate protective layer of a silicon compound on a barrier layer has been proposed, but the film formation of the inorganic layer and the protective layer is a separate process. There is a possibility of being affected by oxidation (see, for example, Patent Document 4). In addition, methods for forming an inorganic layer on a barrier layer have been disclosed, but these are improvements in adhesion to a sealant and chemical resistance, and are techniques for solving the problem of deterioration in barrier performance over time. Development has been desired (see, for example, Patent Documents 5 and 6).
Japanese Examined Patent Publication No. 53-12953 (pages 1 to 3) JP 58-217344 A (pages 1 to 4) US Pat. No. 6,413,645 B1 (page 4 [2-54] to page 8 [8-22]) JP 2001-7368 A (page 1 to page 26) JP 2003-245996 A (pages 1 to 4) Japanese Patent Application Laid-Open No. 10-58585 (pages 1 to 10) “Thin Solid Films” (1996), Affinito et al. 290-291 (pages 63-67)

  In order to solve the above-mentioned problems, the present invention aims to provide a gas barrier film having high barrier properties and transparency and excellent in stability over time of barrier performance, and further using this film. An object of the present invention is to provide an organic device (for example, an organic EL element or a dye-sensitized solar cell) that hardly deteriorates even when used for a long time.

The above problem can be solved by the following means.
[1] A transparent flexible support substrate, an outermost gas barrier layer (A) made of an inorganic thin film, and an inorganic thin film protective layer (D) made of a metal nitride or a metal carbide in this order, and Between the flexible support substrate and the outermost gas barrier layer (A), at least one intermediate layer (B) and at least one intermediate gas barrier layer (C) composed of an inorganic thin film are provided. A gas barrier film having
The inorganic thin film protective layer (D) is provided in contact with the surface of the outermost gas barrier layer (A), and the inorganic thin film protective layer (D) contains hydrogen and oxygen in the inorganic thin film. A gas barrier film, wherein the content is 20 atom% or less with respect to metal atoms of the metal nitride or metal carbide constituting the protective layer (D).

[2] The outermost gas barrier layer (A) is made of an inorganic thin film composed of at least one nitride and oxynitride selected from Si, Al, In, Sn, Ti, and Zn. The gas barrier film according to [1], which is characterized.

[3] The intermediate gas barrier layer (C) is made of an inorganic thin film composed of at least one oxide selected from Si, Al, In, Sn, Ti and Zn, nitride and oxynitride. The gas barrier film according to [1] or [2], wherein

[4] The intermediate layer (B) is composed of an inorganic thin film composed of at least one oxide selected from Si, Al, In, Sn, Ti, and Zn and oxynitride. The gas barrier film according to any one of [1] to [3].

[5] In any one of [1] to [4], the inorganic thin film protective layer (D) is composed of at least one kind of nitride and carbide selected from Si and Ti. The gas barrier film as described.

[6] The inorganic thin film protective layer (D) is composed of any one of Si nitride and carbide, and the content of hydrogen and oxygen is 10 atomic% or less with respect to Si atoms. The gas barrier film according to any one of [1] to [5].

[7] The gas barrier film according to any one of [1] to [6], wherein the inorganic thin film protective layer (D) has a thickness of 30 nm to 100 nm.

[8] The gas barrier film according to any one of [1] to [7], wherein the intermediate gas barrier layer (C) and the intermediate layer (B) are alternately laminated.

[9] The gas barrier film according to any one of [1] to [8], wherein a plurality of the intermediate gas barrier layers (C) and the intermediate layers (B) are alternately laminated.

[10] The gas barrier film according to any one of [1] to [9], wherein the water vapor permeability is 0.01 g / m ² / day or less at 40 ° C. and 90% relative humidity.

[11] An organic device using the gas barrier film according to any one of [1] to [10].

[12] An organic device sealed with the gas barrier film according to any one of [1] to [10].

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier film which has the characteristic that it has high barrier property and transparency, and is excellent in the temporal stability of barrier performance can be provided. Moreover, according to this invention, the organic device which cannot be easily deteriorated even if used for a long period of time can be provided.

  Hereinafter, the gas barrier film of the present invention which has high barrier properties and transparency and excellent barrier performance over time will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

<Gas barrier film>
The gas barrier film of the present invention comprises a transparent flexible support substrate, an outermost gas barrier layer (A) made of an inorganic thin film, and an inorganic thin film protective layer (D) made of a metal nitride or metal carbide in this order. And an intermediate gas barrier layer (C) comprising at least one intermediate layer (B) and at least one inorganic thin film between the flexible support substrate and the outermost gas barrier layer (A). A gas barrier film comprising:
The inorganic thin film protective layer (D) is provided in contact with the surface of the outermost gas barrier layer (A), and the inorganic thin film protective layer (D) contains hydrogen and oxygen in the inorganic thin film. It is characterized by being 20 atomic% or less for each metal atom of the metal nitride or metal carbide constituting the protective layer (D).
The gas barrier film of the present invention can achieve both the initial high barrier performance and the stability of the barrier performance over time by laminating the inorganic thin film protective layer (D) on the outermost gas barrier layer (A). .
The gas barrier film of the present invention can have a water vapor transmission rate at 40 ° C. and a relative humidity of 90% of 0.01 g / m ² / day or less, more preferably 0.005 g, by adopting the above configuration. / M ² / day or less.
In the gas barrier film of the present invention, a hygroscopic layer, an antistatic layer, a conductive layer and the like can be provided on a transparent flexible support substrate in addition to the gas barrier layer and the inorganic thin film protective layer.

(Configuration of gas barrier film)
First, the structure of the gas barrier film of this invention is demonstrated. FIG. 1 is a cross-sectional view showing the structure of the gas barrier film of the present invention. In FIG. 1, a gas barrier film 1 of the present invention has a transparent flexible support substrate 2, an outermost gas barrier layer 3, and an inorganic thin film protective layer 6 in this order. 2 and the outermost gas barrier layer 3, an intermediate layer 4A, an intermediate gas barrier layer 5, and an intermediate layer 4B are provided in this order from the substrate side.

  The transparent flexible support substrate 2 can be composed of a transparent flexible plastic film or the like, and is used for holding each layer provided thereon. The outermost gas barrier layer 3 and the intermediate gas barrier layer 5 are layers made of an inorganic thin film and are layers that suppress the permeation of gas molecules. The outermost gas barrier layer 3 is a layer formed on the outermost side (the side farthest from the transparent flexible support substrate 2) among the gas barrier layers. The intermediate gas barrier layer 5 is a layer provided at least one layer between the transparent flexible support substrate 2 and the outermost gas barrier layer 3. As shown in FIG. 1, only one layer of the intermediate gas barrier layer 5 may be provided, or a plurality of intermediate gas barrier layers 5 may be provided depending on the purpose.

The intermediate layers 4A and 4B are layers provided at least one layer between the transparent flexible support substrate 2 and the outermost gas barrier layer 3 in the same manner as the intermediate gas barrier layer 5, and improve the brittleness and barrier properties of the gas barrier layer. It is provided to make it. As shown in FIG. 1, two or more intermediate layers can be provided, and each intermediate layer can be provided between each gas barrier layer or between the intermediate gas barrier layer 5 and the transparent flexible support substrate 2. preferable.
Further, the intermediate layer 4A or 4B and the intermediate gas barrier layer 5 are preferably laminated alternately from the viewpoint of improving the gas barrier property and improving the mechanical strength of the gas barrier film. As shown in FIG. A configuration in which intermediate layers and intermediate gas barrier layers are alternately stacked is preferable. Here, although the gas barrier film 1 of the present invention shown in FIG. 1 has one intermediate gas barrier layer, the gas barrier film is configured so that a plurality of intermediate layers and a plurality of intermediate gas barrier layers are alternately laminated. You can also.
Further, a mode in which each gas barrier layer and intermediate layer are laminated on both surfaces of the flexible support substrate is also suitable.

The inorganic thin film protective layer 6 is made of metal nitride or metal carbide, and is provided in contact with the outermost gas barrier layer 3 as shown in FIG. According to the present invention, by providing the inorganic thin film protective layer 6 on the outermost gas barrier layer 3, it is possible to improve the gas barrier capability and prevent moisture and oxygen from being taken into the gas barrier layer from the outside. It is possible to suppress the gas barrier performance from decreasing with time.
Hereinafter, each layer will be described in detail.

(Gas barrier layer)
The “outermost (intermediate) gas barrier layer comprising an inorganic thin film” in the present invention means a layer that is a thin film having a dense structure capable of suppressing the permeation of gas molecules composed of an inorganic material. And a thin film (metal compound thin film). Here, in the present invention, the “outermost gas barrier layer (A)” is a layer that is laminated at a position farthest from the flexible support substrate among the gas barrier layers provided on the same side of the flexible support substrate. Yes, an inorganic thin film protective layer (D) is provided on the outermost gas barrier layer (A). The intermediate gas barrier layer (C) is a gas barrier layer provided between the outermost gas barrier layer and the flexible support substrate, and a plurality of layers may be provided. In this specification, the term “gas barrier layer” simply includes both the outermost gas barrier layer (A) and the intermediate gas barrier layer (C).

As the formation of the gas barrier layer, any method can be used as long as it can form a target thin film. As the formation method, for example, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method and the like are suitable. Specifically, Japanese Patent Registration No. 3430344, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-322561. The formation method described in 2002-361774 gazette etc. is employable.
The component contained in the inorganic thin film constituting the gas barrier layer is not particularly limited as long as it satisfies the above performance. For example, the group consisting of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like An oxide, nitride, or oxynitride containing at least one metal selected from the group consisting of Si, Al, In, Sn, Ti, and Zn is preferably used. Selected from metals. In particular, the outermost gas barrier layer (A) is preferably made of an inorganic thin film composed of the metal nitride or oxynitride.
Since the gas barrier layer is a thin film having a dense structure capable of suppressing the permeation of gas molecules, the film density of the thin film is preferably in the range of 2.6 g / m ^{3 to} 7.0 g / cm ³ . and more preferably in the range of ^{6g / cm 3 ~6.0g / cm 3} . The measurement of the film density of the thin film can be calculated, for example, from the X-ray reflectivity measurement of the thin film formed on the Si wafer.

Further, the thickness of the gas barrier layer is not particularly limited, but if the thickness is too thick, there is a risk of cracking due to bending stress, and if it is too thin, the film is distributed in an island shape. . For this reason, the thickness of each gas barrier layer is preferably in the range of 5 nm to 1000 nm, more preferably 10 nm to 1000 nm, and most preferably 10 nm to 200 nm.
The two or more intermediate gas barrier layers (C) may have the same composition or different compositions, and are not particularly limited.

  In the present invention, in order to achieve both gas barrier properties and high transparency, it is preferable to use silicon oxide, silicon nitride, or silicon oxynitride as the gas barrier layer. When SiOx, which is a silicon oxide, is used as the gas barrier layer, it is desirable that 1.6 <x <1.9 in order to achieve both good gas barrier properties and high light transmittance. When SiNy, which is silicon nitride, is used as the gas barrier layer, it is preferable that 1.2 <y <1.3. When y <1.2, coloring may increase, which may be a limitation when used in display applications.

  Further, when SiOxNy, which is silicon oxynitride, is used as the gas barrier layer, it is preferable to use an oxygen-rich film if importance is placed on improving adhesion, specifically, 1 <x <2 and 0 < It is preferable that y <1 is satisfied. On the other hand, when importance is attached to the improvement of gas barrier properties, a nitrogen-rich film is preferable, and specifically, it is preferable to satisfy 0 <x <0.8 and 0.8 <y <1.3. .

(Middle layer)
The gas barrier film of the present invention can be provided with an intermediate layer (B) adjacent to each layer in order to improve the brittleness and barrier properties of the gas barrier layer. For the intermediate layer (B), a thin film made of an inorganic compound or a thin film of an organic compound can be used.

When a thin film (inorganic thin film) made of an inorganic compound is used for the intermediate layer, the same film formation method as that for the gas barrier layer can be used. For example, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, or the like is preferably used. As the component contained in the intermediate layer, an oxide or oxynitride containing one or more metals selected from the group consisting of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like is used. Preferably, it is selected from at least one metal selected from the group consisting of Si, Al, In, Sn, Ti and Zn.
The inorganic thin film used for the intermediate layer is preferably a thin film having a rough structure because it requires flexibility and smoothness rather than gas barrier performance. Therefore, the film density of the inorganic thin film of the intermediate layer is preferably in the range of 1.2 g / cm ³ or more and less than 2.6 g / cm ³ , and in the range of 1.5 g / cm ³ or more and less than 2.6 g / cm ^3. More preferably.
In addition, when an inorganic thin film is used for the intermediate layer (B), the film thickness is preferably sufficient to alleviate bending stress and fill defects in the gas barrier layer, and the film thickness ranges from 50 nm to 1000 nm. It is preferable that it is within the range, more preferably 100 nm to 1000 nm, and most preferably 100 nm to 500 nm.
When two or more intermediate layers (B) are provided, each may have the same composition or a different composition, and is not particularly limited. The intermediate layer (B) is preferably made of silicon oxide or silicon oxynitride. When SiOx, which is a silicon oxide, is used for the intermediate layer, it is desirable that 1.6 <x <1.9. When SiOxNy, which is a silicon oxynitride, is used, an improvement in adhesion is emphasized, so an oxygen-rich film Specifically, it is preferable that 1 <x <2 and 0 <y <1 are satisfied.

When a thin film of an organic compound is used for the intermediate layer (B), it may be a layer formed by coating or vapor deposition of an ultraviolet or electron beam curable monomer, oligomer or resin and then curing with ultraviolet or electron beam. preferable. As an example, the intermediate layer (B) will be described using an organic layer formed mainly of a polymer obtained by crosslinking monomers. The monomer is not particularly limited as long as it has a group that can be cross-linked by irradiation with ultraviolet rays or electron beams, but it is preferable to use a monomer having an acryloyl group, a methacryloyl group, or an oxetane group.
The intermediate layer (B) is, for example, epoxy (meth) acrylate, urethane (meth) acrylate, isocyanuric acid (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate. It is preferable that the main component is a polymer obtained by crosslinking a monomer having bifunctional or higher acryloyl group or methacryloyl group among polyester (meth) acrylate and the like. These monomers having a bifunctional or higher functional acryloyl group or methacryloyl group may be used as a mixture of two or more, or may be used as a mixture of a monofunctional (meth) acrylate.

  Moreover, as a monomer which has the said oxetane group, the monomer which has the structure described in General formula (3)-(6) of Unexamined-Japanese-Patent No. 2002-356607 is mentioned suitably, for example. In this case, you may mix these arbitrarily.

  The organic compound thin film used for the intermediate layer (B) is isocyanuric acid having a particularly high degree of crosslinking and a glass transition temperature of 200 ° C. or higher from the viewpoints of heat resistance and solvent resistance required for display applications. More preferably, the main component is acrylate, epoxy acrylate, or urethane acrylate. The thickness of the intermediate layer (B) by the organic compound thin film is also not particularly limited, but if the thickness is too thin, it is difficult to obtain thickness uniformity, and therefore it is possible to efficiently fill structural defects in the gas barrier layer. It is not possible to improve the barrier property. On the other hand, if the thickness of the organic layer is too thick, the intermediate layer is likely to crack due to an external force such as bending, which causes a problem that the barrier property is lowered. From this viewpoint, the thickness of the intermediate layer formed of the organic compound thin film is preferably 10 nm to 5000 nm, more preferably 10 nm to 2000 nm, and most preferably 10 nm to 5000 nm.

  Examples of the method for forming the intermediate layer using the organic compound thin film include a method in which a coating film containing a crosslinkable monomer or the like is first formed, and then the coating film is cured by irradiation with an electron beam or ultraviolet rays. Examples of the method for forming the coating film include a coating method and a vacuum film forming method. Although there is no restriction | limiting in particular as said vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable, and the resistance heating vapor deposition method which is easy to control the film-forming rate of an organic substance monomer is more preferable. There are no particular restrictions on the crosslinking method for the crosslinkable monomer or the like, but crosslinking with an electron beam or ultraviolet rays is desirable in that it can be easily mounted in a vacuum chamber and the high molecular weight by a crosslinking reaction is rapid.

When the coating film is applied by a coating method, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used.
Either a coating method or a vapor deposition method may be used as the method for forming the coating film, but a vacuum film forming method that is difficult to apply mechanical stress after the gas barrier layer is formed directly and is advantageous for forming a thin film is used. Is preferred.

(Inorganic thin film protective layer)
The gas barrier film of the present invention has an inorganic thin film protective layer (inorganic thin film protective layer (D)) on the outermost gas barrier layer (A). Since the present invention has the protective layer, it is possible to prevent the gas barrier film from being deteriorated by oxidation with water or oxygen immediately after film formation or over time. The inorganic thin film protective layer (D) is made of metal nitride or metal carbide, is in contact with the outermost gas barrier layer (A) located on the outermost side, and the contents of hydrogen and oxygen constitute the inorganic thin film protective layer (D) 20 atomic% or less with respect to the metal atom (for example, Si atom) of the metal nitride or metal carbide. In the present invention, desired performance can be achieved by forming such a protective layer.
The inorganic thin film protective layer (D) can be formed by any method as long as the target thin film can be formed, but a sputtering method, a vacuum deposition method, and an ion plating method are preferable. Although the component contained in the said inorganic thin film protective layer (D) will not be specifically limited if the said performance is satisfy | filled, For example, from the group which consists of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, etc. A nitride or carbide containing at least one selected metal can be used, and preferably selected from at least one metal selected from the group consisting of Si and Ti.

The thickness of the inorganic thin film protective layer (D) is not particularly limited, but if it is too thick, there is a risk of cracking due to bending stress, and if it is too thin, the film is undesirably distributed in an island shape. For this reason, the thickness of each gas barrier layer is preferably in the range of 30 nm to 100 m, more preferably 30 nm to 80 nm, and most preferably 40 nm to 80 nm.
In order to provide a desired protective function in the present invention, it is preferable to reduce the contents of hydrogen and oxygen in the inorganic thin film protective layer (D) as much as possible. The hydrogen and oxygen contents of the protective layer are both 20 atomic% or less with respect to Si atoms, preferably 10 atomic% or less, and most preferably 5 atomic% or less. The content of hydrogen and oxygen in the inorganic thin film protective layer (D) is, for example, hydrogen content by hydrogen forward scattering spectroscopy (HSF), by Rutherford backscattering spectroscopy (RBS) or X-ray photoelectron spectroscopy (ESCA). The oxygen content can be measured.

(Flexible support substrate)
The transparent flexible support substrate used in the gas barrier film of the present invention can be used without particular limitation as long as it is transparent and flexible, and can be any substrate that can hold the above-mentioned layers. There is no restriction | limiting in particular, For example, a transparent film etc. can be suitably selected according to a use purpose. Specific examples of the material constituting the transparent flexible support substrate include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, and polyamide. Resin, Polyamideimide resin, Polyetherimide resin, Cellulose acylate resin, Polyurethane resin, Polyetheretherketone resin, Polycarbonate resin, Alicyclic polyolefin resin, Polyarylate resin, Polyethersulfone resin, Polysulfone resin, Cycloolefin resin And thermoplastic resins such as a fluorene ring-modified carbonate resin, an alicyclic modified polycarbonate resin, and an acryloyl compound. Among these resins, preferred examples include polyester resins such as polyethyl naphthalate resin (PEN), polyarylate resin (PAr), polyethersulfone resin (PES), and fluorene ring-modified carbonate resin (BCF-PC: JP Example -4 of JP-A 2000-227603), alicyclic modified polycarbonate resin (IP-PC: compound of Example -5 of JP-A 2000-227603), acryloyl compound (JP-A 2002-80616) The film which consists of compounds, such as the compound of Example-1 of these, is mentioned.
The flexible support substrate used in the present invention is transparent to visible light because it is used as a support for organic devices. As for the transparency of the flexible support substrate, it is preferable to transmit 50% or more of visible light having a wavelength of 500 nm. The thickness of the transparent flexible support substrate can be appropriately adjusted in order to ensure transparency.

(Other functional layers)
In the gas barrier film of the present invention, a known primer layer or inorganic thin film layer can be installed between the transparent flexible support substrate and the gas barrier layer. Examples of the primer layer include a resin layer such as an acrylic resin, an epoxy resin, a urethane resin, and a silicone resin, an organic-inorganic hybrid layer formed by a sol-gel reaction in the presence of a hydrophilic resin, an inorganic vapor deposition layer, or a dense sol-gel method. An inorganic layer can be mentioned. As said inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.
Further, in order to improve the water vapor barrier performance, a hygroscopic layer may be inserted between the two gas barrier layers. In this case, the hygroscopic layer may be disposed at a position adjacent to the two gas barrier layers, a position adjacent to the gas barrier layer and the intermediate layer, or a position adjacent to the two intermediate layers. From the viewpoint of reducing the effect of deformation due to fragility and volume expansion after moisture absorption, it is most desirable to dispose between the two gas barrier layers adjacent to the two intermediate layers.

Furthermore, the gas barrier film of the present invention may be provided with various functional layers in addition to the gas barrier layer and the intermediate layer. Examples of the functional layer include an optical functional layer such as an antireflection layer, a polarizing layer, a color filter, and a light extraction efficiency improving layer; a mechanical functional layer such as a hard coat layer and a stress relaxation layer; an antistatic layer and a conductive layer. An electric functional layer such as: an antifogging layer; an antifouling layer; a layer to be printed, and the like. These functional layers may be disposed between any of the transparent flexible support substrate, the gas barrier layer, and the intermediate layer, or on the opposite surface of the flexible support substrate on which the gas barrier layer is disposed.
Furthermore, a gas barrier laminate layer in which at least an inorganic gas barrier layer, an intermediate layer, and an inorganic gas barrier layer are laminated in this order can be provided on the side opposite to the base film. The gas barrier laminate layer suppresses the dimensional change of the film substrate by preventing intrusion of water molecules from the opposite side of the film, thereby preventing stress concentration and destruction to the gas barrier layer, resulting in a highly durable display. can do.

《Organic device》
The organic device of the present invention refers to, for example, an image display element (circular polarizing plate / liquid crystal display element, electronic paper or organic EL element), a dye-sensitized solar cell, a touch panel, and the like. Although the use of the gas barrier film of this invention is not specifically limited, It can use suitably as a board | substrate or sealing film of this organic device.

<Circularly polarizing plate>
The circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate on the gas barrier film of the present invention. In this case, the lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, it is preferable to use what is extended | stretched in the 45 degree direction with respect to the longitudinal direction (MD), For example, what is described in Unexamined-Japanese-Patent No. 2002-865554 can be used suitably.

<Liquid crystal display element>
The liquid crystal display device can be roughly classified into a reflective liquid crystal display device and a transmissive liquid crystal display device. The reflective liquid crystal display device includes a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film of the present invention can be used as the transparent electrode and the upper substrate. When the reflective liquid crystal display device has a color display function, a color filter layer may be further provided between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. preferable.

  Further, the transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, and λ / 4. It has the structure which consists of a board and a polarizing film. Among these, the gas barrier film of the present invention can be used as the upper transparent electrode and the upper substrate. Further, when the transmissive liquid crystal display device has a color display function, a color filter layer is further provided between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. It is preferable to provide it.

  The structure of the liquid crystal layer is not particularly limited. For example, a TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB (Electrically Controlled Birefringence) type An OCB (Optically Compensated Bend) type or a CPA (Continuous Pinwheel Alignment) type is preferable.

(Touch panel)
As the touch panel, a substrate in which the gas barrier film of the present invention is applied to a substrate described in JP-A-5-127822, JP-A-2002-48913, or the like can be used.

<Organic EL device>
Hereinafter, an “organic EL element” (hereinafter sometimes simply referred to as “light-emitting element”) will be described in detail as a representative example of the organic device in the present invention. The organic EL element has a cathode and an anode on a substrate, and an organic compound layer including an organic light emitting layer (hereinafter sometimes simply referred to as “light emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.

  As a lamination mode of the organic compound layer, a mode in which a hole transport layer, a light emitting layer, and an electron transport layer are stacked in this order from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Further, the light emitting layer may be a single layer, or the light emitting layer may be divided into a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers.

  Next, elements constituting the light emitting material will be described in detail.

(anode)
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium and nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene and polypyrrole Organic conductive materials, and laminates of these with ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the light-emitting element, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light-emitting element. Is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is described in detail in the book “New Development of Transparent Electrode Films” published by CMC (1999), supervised by Yutaka Sawada, and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

(cathode)
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), Group 2 metal alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloy, lithium-aluminum. Examples include alloys, magnesium-silver alloys, rare earth metals such as indium and ytterbium. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, the material constituting the cathode is preferably an alkali metal or a Group 2 metal alkaline earth metal from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a group 2 metal alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum). Alloy).

  The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the light-emitting element, the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof.
Further, a dielectric layer made of a fluoride, oxide, or the like of an alkali metal or a group 2 metal alkaline earth metal may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

(Organic compound layer)
The organic compound layer in the light emitting element will be described.
The light-emitting element has at least one organic compound layer including a light-emitting layer, and as the organic compound layer other than the organic light-emitting layer, as described above, a hole transport layer, an electron transport layer, a charge blocking layer , Hole injection layer, electron injection layer and the like.

-Formation of organic compound layer-
In the light-emitting element, each layer constituting the organic compound layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

-Organic light emitting layer-
The organic light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, and receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines the holes and electrons. It is a layer having a function of providing light and emitting light. The light emitting layer may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  In the light-emitting element, a light-emitting element of any color can be obtained by using two or three or more different light-emitting materials. Especially, the white light emitting element which is high luminous efficiency and high luminous brightness can be obtained by selecting a luminescent material appropriately. For example, white light can be emitted using a light emitting material that emits a complementary color, such as blue light emission / yellow light emission, light blue light emission / orange light emission, and green light emission / purple light emission. Further, white light can be emitted using a light emitting material of blue light emission / green light emission / red light emission. Note that the host material may function as a light emitting material to emit light. For example, the element may emit white light by light emission of the host material and light emission of the light emitting material.

  In the light emitting element, two or more different kinds of light emitting materials may be included in the same light emitting layer. For example, blue light emitting layer / green light emitting layer / red light emitting layer, or blue light emitting layer / yellow light emitting layer Thus, a structure in which layers each including a light emitting material are stacked may be employed.

  There are the following methods for adjusting the emission color of the light emitting layer. The emission color can be adjusted using one or more of these methods.

1) A method of adjusting by providing a color filter on the light extraction side of the light emitting layer.
The color filter adjusts the emission color by limiting the wavelength to transmit. As the color filter, for example, cobalt oxide is used as a blue filter, a mixed system of cobalt oxide and chromium oxide is used as a green filter, and a known material such as iron oxide is used as a red filter. You may form on a transparent substrate using a well-known thin film forming method.

2) A method of adjusting the emission color by adding a material that promotes or inhibits light emission.
For example, a so-called assist dopant that receives energy from the host material and transfers this energy to the light emitting material can be added to facilitate energy transfer from the host material to the light emitting material. As an assist dopant, it selects from a well-known material suitably, for example, may be selected from the material which can be utilized as a light emitting material and host material mentioned later, for example.

3) A method of adjusting the emission color by adding a wavelength converting material to a layer (including a transparent substrate) on the light extraction side of the light emitting layer.
As this material, a known wavelength conversion material can be used. For example, a fluorescence conversion substance that converts light emitted from the light emitting layer into other light having a low energy wavelength can be used. The type of the fluorescence conversion substance is appropriately selected according to the wavelength of light to be emitted from the target organic EL device and the wavelength of light emitted from the light emitting layer. Further, the amount of the fluorescence conversion substance used can be appropriately selected according to the type within a range in which concentration quenching does not occur. Only one type of fluorescent conversion substance may be used, or a plurality of types may be used in combination. When a plurality of types are used in combination, white light or intermediate color light can be emitted in addition to blue light, green light, and red light.

  Examples of fluorescent light-emitting materials that can be used in the light-emitting element include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, and coumarins. Derivatives, condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, Metal complexes and pyromethene derivatives of styrylamine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives Various metal complexes represented by metal complexes of the body, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of phosphorescent materials that can be used for the light-emitting element include complexes containing transition metal atoms or lanthanoid atoms.
Although it does not specifically limit as a transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum.
Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds,” Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha.
Specific ligands are preferably halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketones Ligand (for example, acetylacetone), carboxylic acid ligand (for example, acetic acid ligand), carbon monoxide ligand, isonitrile ligand, cyano ligand, more preferably nitrogen-containing Heterocyclic ligand. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass.

  Examples of the host material contained in the light emitting layer in the light emitting element include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and Examples thereof include materials having an arylsilane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer, which will be described later.

  Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, It is more preferable that they are 5 nm-200 nm, It is further more preferable that they are 10 nm-100 nm.

--- Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.
The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and further preferably 1 nm to 100 nm.
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

--Electron injection layer, electron transport layer--
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and further preferably 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  Further, in order to alleviate the energy barrier between the cathode and the light emitting layer, the layer adjacent to the cathode may be doped with an alkali metal or an alkali metal compound. Since the organic layer is reduced by the added metal or metal compound to generate anions, the electron injecting property is increased and the applied voltage is decreased. Examples of the alkali metal compound include oxides, fluorides, and lithium chelates.

--Hole blocking layer--
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. In addition, the electron transport layer / electron injection layer may also function as a hole blocking layer.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like. The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm. The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
In addition, a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side can be provided at a position adjacent to the light emitting layer on the anode side. The hole transport layer / hole injection layer may also serve this function.

--EL protective layer--
In the light emitting element, the entire element may be protected by an EL protective layer. As a material contained in the EL protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiNx and SiNxOy, metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide, Copolymerizing polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, and a monomer mixture containing tetrafluoroethylene and at least one comonomer. Copolymer obtained, and a fluorine-containing copolymer having a cyclic structure in the copolymer main chain. Examples thereof include an elemental copolymer, a water-absorbing substance having a water absorption of 1% or more, and a moisture-proof substance having a water absorption of 0.1% or less.

  The method for forming the EL protective layer is not particularly limited. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method, an MBE (molecular beam epitaxy) method, a cluster ion beam method, an ion plating method, a plasma polymerization method ( High frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

  Furthermore, the light emitting device may be sealed entirely using the barrier film of the present invention and a sealing container. Further, a moisture absorbent or an inert liquid may be enclosed in a space between the sealing container and the light emitting element. The moisture absorbent is not particularly limited, and examples thereof include barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, and chloride. Examples thereof include copper, cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, and magnesium oxide. The inert liquid is not particularly limited, and examples thereof include paraffins, liquid paraffins, fluorine-based solvents such as perfluoroalkane, perfluoroamine, and perfluoroether, chlorine-based solvents, and silicone oils. Can be mentioned.

-Driving of element-
The light emitting element can emit light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. . The driving method of the light emitting element is disclosed in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-241047. The driving methods described in Japanese Patent Publication No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 can be applied.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
Gas barrier films (sample Nos. 1 to 8) in which a gas barrier layer, an intermediate layer and an inorganic thin film protective layer were provided on a base film (transparent flexible support substrate) were produced according to the following procedure. Details of the structure of each gas barrier film are as shown in Table 1. As the substrate film, a 120 μm thick PEN (manufactured by Teijin DuPont Co., Ltd., Q65A) film was used.
In addition, formation of each layer demonstrated below was formed in order from the film | membrane provided in the base film side according to the structure of each sample described in following Table 1.

1. Formation of outermost gas barrier layer (A) The outermost gas barrier layer (A) was formed with a plasma CVD apparatus. Specific film forming conditions are shown below.
The vacuum chamber of the plasma CVD apparatus was depressurized to an ultimate pressure of 4 × 10 ⁻³ Pa with an oil rotary pump and a turbo molecular pump. Next, argon was introduced as a discharge gas, and a discharge power of 500 W was applied from a discharge power source. Silane gas (SiH ₄ ) and nitrogen were introduced into the chamber, the film forming pressure was adjusted to 0.45 Pa, and the film was formed for a certain period of time to form a silicon nitride gas barrier layer (A). The obtained silicon nitride film has a thickness of 100 nm, and from the infrared absorption spectrum, Si—N stretching vibration (830 cm ⁻¹ ), Si—H stretching vibration (2150 cm ⁻¹ ), and N—H (3350 cm ⁻¹ ). Absorption of stretching vibration was observed. The composition of the silicon nitride film obtained from the analysis of ESCA, RBS and HSF was found to contain 80 atomic% of hydrogen relative to Si. The film density was 2.02 g / cm ³ .

2. Formation of the intermediate layer (B) The intermediate layer (B) was formed in the following two ways.
(Intermediate layer (B1))
Similarly to the gas barrier layer (A), an intermediate layer (B1) made of an inorganic compound was formed by a plasma CVD apparatus. Specific film forming conditions are shown below.
The vacuum chamber of the plasma CVD apparatus was decompressed to an ultimate pressure of 4 × 10 ⁻³ Pa, argon was introduced as a discharge gas, and a discharge power of 600 W was applied from a discharge power source. Silane gas (SiH ₄ ), nitrogen and oxygen were introduced into the chamber, the film formation pressure was adjusted to 0.7 Pa, and film formation was performed for a certain period of time, thereby forming an intermediate layer (B) of silicon oxynitride. The resulting nitric oxide silicon film has a thickness of at 500 nm, stretching vibration of Si-N from the infrared absorption spectrum (830 cm ^-1) and Si-O stretching vibration (1050cm ^-1) Si-H stretching vibration (2150 cm ^{- 1} ), absorption of N—H (3350 cm ⁻¹ ) stretching vibration was observed. The composition of the silicon oxynitride film obtained from the analysis of ESCA, RBS, and HSF was found to contain 40 atomic% hydrogen and 150 atomic% oxygen relative to Si. The film density was 2.02 g / cm ³ .

(Intermediate layer (B2))
The intermediate layer (B2) was a thin film layer made of an organic compound. A specific film forming method will be described below. 50.75 mL of tetraethylene glycol diacrylate, 14.5 mL of tripropylene glycol monoacrylate, 7.25 mL of caprolactone acrylate, 10.15 mL of acrylic acid and 10.15 mL of “EZACURE” (Sartomer, benzophenone mixture light The acrylic monomer mixture with the polymerization initiator) is mixed with solid N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine particles 36.25 gm, and about 20 kHz ultrasonic tissue mincer is used. Stir for 1 hour. The mixture, heated to about 45 ° C. and stirred to prevent settling, was pumped through a capillary with an inner diameter of 2.0 mm and a length of 61 mm into a 1.3 mm spray nozzle. Therefore, droplets were sprayed with a 25 kHz ultrasonic sprayer and then UV cured with a high-pressure mercury lamp lamp (accumulated dose of about 2000 mJ / cm ² ) to form the intermediate layer (B2). The film thickness was about 500 nm.

3. Formation of gas barrier layer (C) Gas barrier layer (C) was formed by two methods.

(Intermediate gas barrier layer (C1))
A silicon nitride thin film formed under the same film formation conditions as the gas barrier layer (A) was used.

(Intermediate gas barrier layer (C2))
An inorganic thin film having a composition different from that of the intermediate gas barrier layer (C1) was used. Specific film forming conditions are shown below. The vacuum chamber of the plasma CVD apparatus was decompressed to an ultimate pressure of 4 × 10 ⁻³ Pa, argon was introduced as a discharge gas, and a discharge power of 600 W was applied from a discharge power source. Silane gas (SiH ₄ ), nitrogen and oxygen were introduced into the chamber, the film formation pressure was adjusted to 0.5 Pa, and film formation was performed for a certain period of time to form an intermediate gas barrier layer (C2) of silicon oxynitride. The resulting nitric oxide silicon film has a thickness of at 110 nm, stretching vibration of Si-N from the infrared absorption spectrum (830 cm ^-1) and Si-O stretching vibration (1050cm ^-1) Si-H stretching vibration (2150 cm ^{- 1} ), absorption of N—H (3350 cm ⁻¹ ) stretching vibration was observed. The composition of the silicon oxynitride film obtained from the analysis of ESCA, RBS, and HSF was found to contain 80 atomic% hydrogen and 40 atomic% oxygen relative to Si. The film density was 2.65 g / cm ³ .

5. Formation of inorganic thin film protective layer (D) The inorganic thin film protective layer (D) was formed by the following six methods.

(Protective layer (D1))
A silicon nitride film was formed by reactive sputtering. The vacuum chamber was decompressed to an ultimate pressure of 4 × 10 ⁻³ Pa, argon was introduced as a discharge gas, and a discharge power of 5 kW was applied from the discharge power source to generate plasma on the Si target. Next, nitrogen was introduced as a reaction gas, and a film was formed at a film forming pressure of 0.1 Pa for a certain period of time. The obtained silicon nitride film had a thickness of 10 nm, and only absorption of Si—N stretching vibration (830 cm ⁻¹ ) was observed from the infrared absorption spectrum. The composition of the silicon nitride film obtained from the analysis of ESCA, RBS and HSF was found to be 15 atomic% of hydrogen relative to Si and no oxygen was detected.

(Protective layer (D2))
A silicon nitride film was formed by reactive sputtering. The vacuum chamber was decompressed to an ultimate pressure of 4 × 10 ⁻³ Pa, argon was introduced as a discharge gas, and a discharge power of 5 kW was applied from the discharge power source to generate plasma on the Si target. Next, nitrogen was introduced as a reaction gas, and a film was formed at a film forming pressure of 0.1 Pa for a certain period of time. The introduction of nitrogen increased 1.5 times with respect to the protective layer (D1). The obtained silicon nitride film had a thickness of 40 nm, and only absorption of Si—N stretching vibration (830 cm ⁻¹ ) was observed from the infrared absorption spectrum. The composition of the silicon nitride film obtained from the analysis of ESCA, RBS and HSF was found to be 5 atomic% of hydrogen relative to Si and no oxygen was detected.

(Protective layer (D3))
A silicon carbide (SiC) film was formed by sputtering. The vacuum chamber was decompressed to an ultimate pressure of 4 × 10 ⁻³ Pa, argon was introduced as a discharge gas, and a discharge power of 5 kW was applied from the discharge power source to generate plasma on the SiC target. Film formation was performed for a certain time at a film formation pressure of 0.1 Pa. The obtained silicon carbide film had a thickness of 20 nm, and absorption of Si—H stretching vibration (2150 cm ⁻¹ ) and Si—O stretching vibration (1050 cm ⁻¹ ) was not observed from the infrared absorption spectrum. The composition of the silicon carbide film obtained from the analysis of ESCA, RBS, and HSF was found not to detect hydrogen and oxygen with respect to Si.

(Protective layer (D4))
As the protective layer (D4), a silicon nitride film having a thickness of 20 nm was formed according to the method of the protective layer (D1). The composition of the silicon nitride film obtained from the analysis of ESCA, RBS and HSF was the same as that of the protective layer (D1).

(Protective layer (D5))
As the protective layer (D5), a silicon nitride film having a thickness of 40 nm was formed according to the method of the protective layer (D1). The composition of the silicon nitride film obtained from the analysis of ESCA, RBS and HSF was the same as that of the protective layer (D1).

(Protective layer (D6))
As the protective layer (D6), a silicon nitride film having a thickness of 60 nm was formed according to the method of the protective layer (D1). The composition of the silicon nitride film obtained from the analysis of ESCA, RBS and HSF was the same as that of the protective layer (D1).

4). Evaluation of Physical Properties of Gas Barrier Film Various physical properties of the gas barrier film were evaluated using the following apparatus.
Layer configuration (film thickness): Measured by observing an ultrathin section of a film sample with a scanning electron microscope “S-900 type” manufactured by Hitachi, Ltd.
Water vapor transmission rate (g / m ² / day): Measured using “PERMATRAN-W3 / 31” (condition: 40 ° C., relative humidity 90%) manufactured by MOCON. Moreover, the value below 0.01 g / m < ² > / day which is the measurement limit of the said MOCON apparatus was supplemented using the following method. First, metal Ca was vapor-deposited directly on the gas barrier film, and the measurement sample was prepared by sealing the film and the glass substrate with a commercially available organic EL sealing material so that the vapor-deposited Ca was inside. Next, the measurement sample was kept under the above temperature and humidity conditions, and the water vapor transmission rate was determined from the change in optical density of the metal Ca on the gas barrier film (the metal gloss decreased due to hydroxylation or oxidation).
Infrared absorption spectrum: When each layer is formed on a substrate film, a similar film is formed on a Si wafer (N-type, crystal axis <100>, thickness 525 μm, manufactured by Shin-Etsu Chemical Co., Ltd.) and evaluated. A sample was prepared and measured. The measurement was performed by a transmission method using a Fourier transform infrared spectrophotometer (manufactured by Nicolet, AVATAR360). Especially used for qualitative analysis of hydrogen content.
ESCA: The composition analysis of the gas barrier layer, the intermediate layer, and the inorganic thin film protective layer was performed by etching the sample with an argon ion gun using an X-ray photoelectron spectrometer (manufactured by Kratos Co., Ltd., ESCA-3400). The composition of the part was determined. As the X-ray source, Mg—Kα was used, and measurement was performed by setting a detector in the normal direction with respect to the sample surface to perform appropriate charge correction. After performing sensitivity coefficient correction on the peak area of each composition obtained, the elemental composition ratio was calculated.
RBS (Rutherford backscattering spectroscopy) and HSF (hydrogen forward scattering spectroscopy): Measurement was performed using He ions as an ion irradiation source.
-Stability test over time: After the sample formed on the substrate film was treated at 80 ° C. and 70% relative humidity for 3 days, the water vapor transmission rate was measured.
X-ray reflectance measurement: Measurement was performed using an ATX-G manufactured by Rigaku Corporation using an evaluation sample formed on a Si wafer. The film density of the thin film was calculated from the measurement result.

  The results of the water vapor transmission rate and the stability test over time are summarized in Table 1. From Table 1, by forming the inorganic protective layer (D) in the present invention in contact with the outermost gas barrier layer (A), the change in water vapor transmission rate over time could be kept low (Sample No. 1, 13-15). Moreover, it turns out that the suppression effect is large when the film thickness of an inorganic protective layer (D) increases (sample No. 1, 3-5). For the inorganic protective layer (D), the effect of the present invention was obtained with either silicon nitride or silicon carbide (Sample Nos. 3 and 9). It can be seen that the lower the hydrogen and oxygen content of the inorganic protective layer (D), the greater the effect of the present invention (sample Nos. 4 and 8).

  The intermediate layer (B) can obtain the effect of the present invention even when the inorganic thin film layer (B1) and the organic thin film layer (B2) are used, but the inorganic thin film layer (B1) is preferable because it has a lower water vapor transmission rate. (Sample Nos. 1 and 2). The effect of the present invention can be obtained even when a plurality of intermediate gas barrier layers (C) and intermediate layers (B) are laminated.

※表１中、水蒸気透過率が<0.005(g/m²/day)を示す場合には、検出限界以下を示す。また、表１における「層構成」中の記号は以下の通りである。「ＰＥＮ」：透明フィルム、「Ａ」：最外ガスバリア層（Ａ）、「Ｂ１」〜「Ｂ２」：中間層（Ｂ１）〜（Ｂ２）、「Ｃ１」〜「Ｃ２」：中間ガスバリア層（Ｃ１）〜（Ｃ２）、「Ｄ１」〜「Ｄ６」：無機薄膜保護層（Ｄ１）〜（Ｄ６）

* In Table 1, when the water vapor transmission rate is <0.005 (g / m ² / day), it indicates below the detection limit. Moreover, the symbols in “Layer structure” in Table 1 are as follows. “PEN”: transparent film, “A”: outermost gas barrier layer (A), “B1” to “B2”: intermediate layers (B1) to (B2), “C1” to “C2”: intermediate gas barrier layer (C1 ) To (C2), “D1” to “D6”: inorganic thin film protective layers (D1) to (D6)

[Example 2]
5. Production of Organic EL Element Each of the gas barrier films (Sample Nos. 1, 3-5, 8 and 14) of Example 1 was introduced into a vacuum chamber, and an IZO target (produced by Idemitsu Kosan Co., Ltd.) was used. A transparent electrode made of an IZO thin film having a thickness of 0.2 μm was formed on the surface on which the inorganic gas barrier layer was laminated by DC magnetron sputtering. An aluminum lead wire was connected from the transparent electrode (IZO) to form a laminated structure.
The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (BAYER, Baytron P: 1.3 mass% solid content), and then vacuum-dried at 150 ° C. for 2 hours. A hole transporting organic thin film layer having a thickness of 100 nm was formed. This was designated as substrate X.

On the other hand, a coating solution for a light-emitting organic thin film layer having the following composition was formed on one surface of a temporary support made of polyethersulfone (Sumitomo Bakelite Co., Ltd., Sumilite FS-1300) having a thickness of 188 μm using a spin coater. The luminescent organic thin film layer having a thickness of 13 nm was formed on the temporary support by applying and drying at room temperature. This was designated as transfer material Y.
〔composition〕
Polyvinylcarbazole: 40 parts by mass (Mw = 63000, manufactured by Aldrich)
・ Tris (2-phenylpyridine) iridium complex: 1 part by mass (orthometalated complex) (manufactured by Chemipro Kasei Co., Ltd.)
・ Dichloroethane: 3200 parts by mass

The luminescent organic thin film layer side of the transfer material Y is superimposed on the upper surface of the hole transporting organic thin film layer of the substrate X, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, A light-emitting organic thin film layer was formed on the upper surface of the substrate X by peeling off the temporary support. This is a substrate XY.
Also, a patterned vapor deposition mask (a mask with a light emission area of 5 mm × 5 mm) is installed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm cut into 25 mm square, Al was vapor-deposited in a reduced pressure atmosphere of 0.1 mPa to form an electrode having a film thickness of 0.3 μm. Al2O3 was deposited in the same pattern as the Al layer by a DC magnetron sputtering method using an Al2O3 target to a thickness of 3 nm. An aluminum lead wire was connected from the Al electrode to form a laminated structure. A coating liquid for electron transporting organic thin film layer having the following composition is coated on the obtained laminated structure with a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, whereby an electron transporting organic thin film having a thickness of 15 nm is obtained. A layer was formed on LiF. This is referred to as a substrate Z.

〔composition〕
Polyvinyl butyral 2000L: 10 parts by mass (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.)
1-butanol: 3500 parts by mass Electron transporting compound having the following structure: 20 parts by mass (synthesized by the method described in JP-A No. 2001-335776)

  Using the substrate XY and the substrate Z, the electrodes were stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and sealed with a commercially available organic EL sealing material.

When a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.) was applied to the obtained organic EL element to emit light, all element samples emitted light well.
Next, after the organic EL element sample was left in an environment of 60 ° C. and 90% relative humidity for 24 hours, the element was made to emit light in the same manner. In the device using No. 1, a dark spot occupies 10% of the light emitting area. In the case of the element No. 3, 5% of the sample No. In the device of 4, the dark spot occupied 1%. Sample No. No dark spots were observed in samples 5 and 8. In the conventional gas barrier film (Sample No. 14, for comparison), dark spots were observed in 20% of the light emitting area of the device. From this, it was recognized that the gas barrier film formed according to the present invention has excellent gas barrier properties and excellent temporal stability, and thus improves the temporal stability of the organic EL.

It is sectional drawing which shows the structure of the gas barrier film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Transparent flexible support substrate 3 Outermost gas barrier layer 4A Intermediate layer 4B Intermediate layer 5 Intermediate gas barrier layer 6 Inorganic thin film protective layer

Claims (12)

A transparent flexible support substrate, an outermost gas barrier layer (A) made of an inorganic thin film, and an inorganic thin film protective layer (D) made of a metal nitride or a metal carbide in this order; A gas barrier film having at least one intermediate layer (B) and at least one intermediate gas barrier layer (C) composed of an inorganic thin film between the flexible support substrate and the outermost gas barrier layer (A). Because
The inorganic thin film protective layer (D) is provided in contact with the surface of the outermost gas barrier layer (A), and the inorganic thin film protective layer (D) contains hydrogen and oxygen in the inorganic thin film. A gas barrier film, wherein the content is 20 atom% or less with respect to metal atoms of the metal nitride or metal carbide constituting the protective layer (D).   The outermost gas barrier layer (A) is composed of an inorganic thin film composed of at least one nitride and oxynitride selected from Si, Al, In, Sn, Ti and Zn. The gas barrier film according to claim 1.   The intermediate gas barrier layer (C) is composed of an inorganic thin film composed of at least one oxide selected from Si, Al, In, Sn, Ti and Zn, nitride and oxynitride. The gas barrier film according to claim 1 or 2.   The said intermediate | middle layer (B) consists of an inorganic thin film comprised by at least 1 sort (s) of oxides and oxynitride chosen from Si, Al, In, Sn, Ti, and Zn. The gas barrier film of any one of 1-3.   The gas barrier according to any one of claims 1 to 4, wherein the inorganic thin film protective layer (D) is composed of at least one kind of nitride and carbide selected from Si and Ti. the film.   The inorganic thin film protective layer (D) is composed of any one of Si nitride and carbide, and the content of hydrogen and oxygen is 10 atomic% or less with respect to Si atoms. Item 6. The gas barrier film according to any one of Items 1 to 5.   The film thickness of the said inorganic thin film protective layer (D) is 30-100 nm, The gas barrier film of any one of Claims 1-6 characterized by the above-mentioned.   The gas barrier film according to any one of claims 1 to 7, wherein the intermediate gas barrier layer (C) and the intermediate layer (B) are alternately laminated.   The gas barrier film according to any one of claims 1 to 8, wherein a plurality of the intermediate gas barrier layers (C) and the intermediate layers (B) are alternately laminated. The gas barrier film according to any one of claims 1 to 9, wherein the water vapor permeability is 0.01 g / m ² / day or less at 40 ° C and 90% relative humidity.   The organic device using the gas barrier film of any one of Claims 1-10.   The organic device sealed with the gas barrier film of any one of Claims 1-10.

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