JP2009094051A - Manufacturing method of transparent conductive film, and the transparent conductive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive film in which both high gas barrier performance and high initial performance (light-emission of high efficiency and low resistance) can be made compatible, when it is used in a display element. <P>SOLUTION: In the manufacturing method of the transparent conductive film, the transparent conductive layer is installed at least on one side of a base material film, after heat-treatment and/or vacuum-treatment of a gas barrier film that has a gas barrier layer having at least an organic region and an inorganic region. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a transparent conductive film and a transparent conductive film produced by the method. Moreover, it is related with the display element using this transparent conductive film, especially an organic EL element.

  Conventionally, a transparent conductive film has been studied. In Patent Document 1, a transparent gas barrier thin film mainly composed of a metal oxide and a protective film mainly composed of an organic crosslinked material are sequentially formed on at least one surface of the transparent polymer film, and further on at least one surface of the protective film. A transparent conductive film is disclosed in which a transparent conductive thin film is formed.

Japanese Patent No. 3855307

However, the above transparent conductive film does not necessarily have sufficient gas barrier performance. Therefore, when such a transparent conductive film is used for a display element such as an organic EL element, the initial performance (high efficiency, low resistance light emission) of the display element tends to be inferior. On the other hand, when a gas barrier film having high gas barrier properties is used, the gas barrier performance is improved, but the resistance of the transparent conductive film cannot be reduced.
The object of the present invention is to provide a transparent conductive film having a high gas barrier performance. In particular, when used in a display element, an object is to provide a transparent conductive film capable of achieving both high gas barrier performance and high initial performance (high efficiency and low resistance light emission).

As a result of the inventor's earnest study based on the above problems, a gas barrier layer having both an organic region and an inorganic region is used as a gas barrier layer of the gas barrier film, and after a specific pretreatment, a transparent conductive layer is provided. It has been found that the above problems can be solved. Specifically, it was achieved by the following means.
(1) A gas barrier film having a gas barrier layer having at least an organic region and an inorganic region on at least one surface of a base film is subjected to heat treatment and / or vacuum treatment, and then a transparent conductive layer is provided, A method for producing a transparent conductive film.
(2) The method for producing a transparent conductive film according to (1), wherein the gas barrier layer comprises at least one organic layer and at least one inorganic layer.
(3) The method for producing a transparent conductive film according to (1), wherein the gas barrier layer comprises at least one organic layer and at least two inorganic layers.
(4) The manufacturing method of the transparent conductive film of any one of (1)-(3) whose surface roughness (Ra) of the said transparent conductive layer surface is 10 nm or less.
(5) The method for producing a transparent conductive film according to any one of (1) to (4), wherein the heat treatment and / or vacuum treatment is a heat vacuum treatment.
(6) The method for producing a transparent conductive film according to any one of (1) to (5), further comprising providing a bus line on the transparent conductive layer.
(7) The method for producing a transparent conductive film according to any one of (1) to (6), further comprising UV / ozone treatment and / or plasma treatment of the gas barrier film.
(8) The transparent conductivity according to any one of (1) to (7), wherein the UV / ozone treatment or the plasma treatment is performed after the heat treatment and / or vacuum treatment and before the transparent conductive layer is provided. For producing a conductive film.
(9) The transparent conductive material according to any one of (1) to (8), wherein the organic layer or the organic region is formed by applying and curing a composition containing a (meth) acrylate compound having a bisphenol skeleton. For producing a conductive film.
(10) The transparent conductive film manufactured by the manufacturing method of the transparent conductive film of any one of (1)-(9).
(11) A display element using the transparent conductive film according to (10).
(12) The display element according to (11), wherein the display element is an organic EL element.

  According to the present invention, it has become possible to provide a transparent conductive film having a high gas barrier property. In particular, when used in a display element, it is possible to suppress deterioration of the display element due to moisture ingress and to improve the initial performance of the display element.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In the method for producing a transparent conductive film of the present invention, a gas barrier film having a gas barrier layer having at least an organic region and an inorganic region on at least one surface of a base film is subjected to heat treatment and / or vacuum treatment, and then transparent conductive A layer is provided. When the transparent conductive film produced by such a method is used for a display element, low resistance can be realized and the life of the element can be extended.
In the present invention, the gas barrier film is subjected to a heat treatment and / or a vacuum treatment, preferably a heat vacuum treatment. Here, as heat processing, it is preferable to heat at 60-120 degreeC and 0.5 to 50 hours, and it is more preferable to heat at 70 to 90 degreeC and 1 to 12 hours. In particular, it is preferable to heat at 80 ° C. for 2 hours or more. As vacuum processing, it is preferable to perform vacuum processing in the range of 10 ^<-2 > ^{-10 < -6>} Pa, and it is more preferable to perform vacuum processing in the range of 10 < ^-3 > Pa or less. A heating vacuum treatment, the are those subjected to both heat treatment and vacuum treatment, specifically, 10 ^-3 Pa or less, preferably by treatment with 70 ° C. or higher, 10 ^-3 Pa or less, 80 ° C. It is more preferable to process by the above. The heating vacuum processing time can be appropriately determined according to the degree of vacuum or the like, but can be set to, for example, one hour or longer. By adopting such means, when the obtained transparent conductive film is used as a display element, the durability of the display element is greatly improved. In particular, the device can have a longer lifetime compared to a conventional gas barrier film provided with a transparent conductive layer, and the present invention is superior in terms of realizing low resistance.

The gas barrier film in the present invention is preferably further subjected to UV / ozone treatment or plasma treatment. By adopting such means, the lifetime of the display element can be further increased. Here, the UV / ozone treatment or the plasma treatment is preferably performed after the heat treatment and / or vacuum treatment and before providing the transparent conductive layer.
The UV / ozone treatment is performed by irradiating the substrate with ultraviolet light in the presence of oxygen. Specifically, for example, the UV / ozone treatment is performed by arranging the substrate in the decompression chamber and then exhausting the air in the decompression chamber, supplying oxygen gas, and irradiating the substrate with ultraviolet light. . The UV / ozone treatment may be performed in the atmosphere. As the ultraviolet light source, for example, a mercury lamp and a deuterium lamp that can emit ultraviolet light having a wavelength of 150 nm to 350 nm can be used. When the substrate is irradiated with ultraviolet light, oxygen is decomposed by the ultraviolet light to generate ozone and active oxygen, and the ozone and active oxygen react with contaminants such as organic substances on the transparent conductive layer. The reaction removes contaminants. Further, the transparent conductive layer is modified such that the ozone and active oxygen react with the anode material to oxidize the transparent conductive layer. Such oxidation increases the ionization potential of the transparent conductive layer.
The plasma processing is, for example, oxygen plasma processing performed in a parallel plate type plasma apparatus. The oxygen plasma treatment uses a mixed gas of nitrogen, argon, helium, neon, or xenon and oxygen, or a mixed gas of oxygen containing a halogen gas as an atmospheric gas, and generates a plasma discharge in the atmospheric gas. It is a process to fix. Specifically, for example, a mixed gas as described above is introduced into a chamber in which a substrate is disposed and is in a reduced pressure state, and a high frequency voltage is applied to the chamber. As a result, oxygen plasma is generated, and the oxygen plasma reacts with contaminants such as organic substances on the transparent conductive layer, thereby removing the contaminants. The oxygen plasma also reacts with the transparent conductive layer, and the transparent conductive layer is modified.

Hereinafter, the case where the transparent conductive film manufactured by the manufacturing method of this invention is used for an organic EL element is demonstrated in detail. Needless to say, the present invention is not limited to these examples.
FIG. 1 is an example in which a transparent conductive film produced by the production method of the present invention is used for an organic EL device, wherein 1 is a base film, 2 is a gas barrier layer, 3 is a transparent conductive layer, Reference numeral 4 denotes a bus line, 5 denotes an organic compound layer, 6 denotes an electrode layer, and 7 denotes a sealing material. In the present embodiment, the transparent conductive film of the present invention includes a base film 1, a gas barrier layer 2, a transparent conductive layer 3, and a bus line 4, but the bus line 4 is provided. It does not have to be. However, providing a bus line is advantageous from the viewpoint of reducing the applied voltage. Such a transparent conductive film becomes a substrate of an organic EL element, and an organic compound layer 5 and an electrode layer 6 are further provided thereon, with the transparent conductive layer 3 as one of the electrodes. In the present embodiment, the organic EL element is sealed with the sealing material 7.
The thickness of the transparent conductive film in the present invention is preferably 5 to 500 μm, and more preferably 2 to 200 μm.
In the present invention, “transparent” means that the light transmittance is 60% or more.

(Gas barrier film)
The gas barrier film in the present invention is a film having a barrier layer having a function of blocking oxygen and moisture in the atmosphere. The barrier layer in the present invention is an organic-inorganic laminated type in which organic regions and inorganic regions or organic layers and inorganic layers are alternately laminated. Hereinafter, it may be referred to as “organic-inorganic laminated gas barrier film”.
Organic regions and inorganic regions or organic layers and inorganic layers are usually laminated alternately. In the case of an organic region and an inorganic region, a so-called gradient material layer in which each region continuously changes in the film thickness direction may be used. Examples of the gradient materials include a paper by Kim et al. “Journal of Vacuum Science and Technology A Vol. 23 p971-977 (2005 American Vacuum Society) Journal of Vacuum Science and Technology A Vol. , American Vacuum Society) ”, or a continuous layer in which the organic layer and the inorganic layer do not have an interface as disclosed in US Published Patent Application No. 2004-46497. Hereinafter, for simplification, the organic layer and the organic region are described as “organic layer”, and the inorganic layer and the inorganic region are described as “inorganic layer”.
Although there is no restriction | limiting in particular regarding the number of layers which comprises a cas barrier film, Typically 2-30 layers are preferable, and 3-20 layers are more preferable.
In the present invention, in particular, it is preferably composed of at least one organic layer and at least two inorganic layers. By setting it as such a structure, the effect of this invention is exhibited notably.

Base film The gas barrier film in the present invention usually uses a plastic film as the base film. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a laminate such as an organic layer and an inorganic layer, and can be appropriately selected according to the purpose of use. Specifically, as the plastic film, metal support (aluminum, copper, stainless steel, etc.) polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin , 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 Examples thereof include thermoplastic resins such as filn copolymers, fluorene ring-modified polycarbonate resins, alicyclic ring-modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  As for the gas barrier film in this invention, it is preferable that a plastic film consists of a raw material which has heat resistance. Specifically, it is preferable that the glass transition temperature (Tg) is 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. As such a thermoplastic resin, for example, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate ( PAr: 210 ° C., polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: Japanese Patent Application Laid-Open No. 2001-150584 compound: 162 ° C.), polyimide (for example, Mitsubishi Gas Chemical) Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A) : 205 ° C), acryloyl compound (Compound described in JP-A 2002-80616: 300 ° C. or more) (the parenthesized data are Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  When the gas barrier film according to the present invention is used in combination with a polarizing plate, it is preferable that the gas barrier film has a barrier laminate that faces the inside of the cell and is arranged on the innermost side (adjacent to the element). At this time, since the gas barrier film is disposed inside the cell from the polarizing plate, the retardation value of the gas barrier film is important. The usage form of the gas barrier film in such an embodiment includes a gas barrier film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (1/4 wavelength plate + (1/2 wavelength plate) + linearly polarizing plate. ) Or a linear barrier plate combined with a gas barrier film using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate.

As a base film having a retardation of 10 nm or less, cellulose triacetate (Fuji Film Co., Ltd .: Fuji Tac), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace, Kaneka: Elmec Co., Ltd.), cycloolefin polymer (JSR Co., Ltd.) ): Arton, Nippon Zeon Co., Ltd .: Zeonoa), cycloolefin copolymer (Mitsui Chemicals Co., Ltd .: Appel (pellet), Polyplastic Co., Ltd .: Topas (pellet)) Polyarylate (Unitika Co., Ltd.): U100 (pellet) )), Transparent polyimide (Mitsubishi Gas Chemical Co., Ltd .: Neoprim) and the like.
Moreover, as a quarter wavelength plate, the film adjusted to the desired retardation value by extending | stretching said film suitably can be used.

In the gas barrier film of the present invention, the plastic film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. be able to.
Even when the gas barrier film of the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
The thickness of the plastic film used for the gas barrier film of the present invention is appropriately selected depending on the application and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. The functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627. Examples of functional layers other than these include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like.

Inorganic layer The inorganic layer is usually a thin film layer made of a metal compound. As a method for forming the inorganic layer, any method can be used as long as it can form a target thin film. For example, a coating method, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, and the like are suitable, and specifically, Japanese Patent No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774. The described forming method can be employed.
The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance, but for example, one or more selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, or the like An oxide containing metal, nitride, carbide, oxynitride, oxycarbide, nitride carbide, oxynitride carbide, or the like can be used. Among these, a metal oxide, nitride, or oxynitride selected from Si, Al, In, Sn, Zn, and Ti is preferable, and a metal oxide, nitride, or oxynitride of Si or Al is particularly preferable. . These may contain other elements as secondary components.
Although it does not specifically limit regarding the thickness of the said inorganic layer, It is preferable to exist in the range of 5 nm-500 nm, More preferably, it is 10 nm-200 nm. Two or more inorganic layers may be laminated. In this case, each layer may have the same composition or a different composition. Further, as described above, a layer whose interface with the organic layer is not clear as disclosed in US Patent Publication No. 2004-46497 and whose composition changes continuously in the film thickness direction may be used.

Organic Layer In the present invention, the polymer is preferably an organic layer composed of a polymer of a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group.
(Polymerizable compound)
The polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond at the terminal or side chain and / or a compound having epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds (acrylates and methacrylates are collectively referred to as (meth) acrylates), acrylamide compounds, styrene compounds, and anhydrous maleic compounds. An acid etc. are mentioned.

As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

Although the specific example of a (meth) acrylate type compound is shown below, this invention is not limited to these.

The organic layer is preferably smooth and has a high film hardness. The smoothness of the organic layer is preferably 10 nm or less, and more preferably 2 nm or less, as an average roughness (Ra value) of 10 μm square. The film hardness of the organic layer preferably has a pencil hardness of HB or higher, and more preferably H or higher.
The film thickness of the organic layer is not particularly limited, but if it is too thin, it will be difficult to obtain film thickness uniformity, and if it is too thick, cracks will be generated by external force and the barrier performance will deteriorate. From this viewpoint, the thickness of the organic layer is preferably 10 nm to 2000 nm, more preferably 100 nm to 1000 nm.

 Examples of the method for forming the organic layer include a normal solution coating method or a vacuum film forming method. Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a hopper described in US Pat. No. 2,681,294. It can apply | coat by the extrusion-coating method which uses-. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable.

The monomer polymerization method is not particularly limited, but heat polymerization, light (ultraviolet ray, visible light) polymerization, electron beam polymerization, plasma polymerization, or a combination thereof is preferably used. When performing heat polymerization, the plastic film used as a base material needs to have appropriate heat resistance. In this case, it is necessary that at least the glass transition temperature (Tg) of the plastic film is higher than the heating temperature.
When carrying out photopolymerization, a photopolymerization initiator is used in combination. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure, commercially available from Ciba Specialty Chemicals. 819), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, commercially available from Sartomer). Etc.).
The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The irradiation energy is preferably 0.5 J / cm ² or more, and more preferably ² J / cm ² or more. Since acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air, it is preferable to lower the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of ² J / cm ² or more under a reduced pressure condition of 100 Pa or less.

 At this time, the polymerization rate of the monomer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. The polymerization rate here means the ratio of the reacted polymerizable groups among all the polymerizable groups (acryloyl group and methacryloyl group) in the monomer mixture.

Functional layer The gas barrier film of the present invention may have a functional layer on the barrier layer. As an example of the functional layer, a layer similar to that described in the section of the plastic film is used.

(Transparent conductive layer)
The transparent conductive layer in the present invention is not particularly defined as long as it is transparent and conductive, and widely known ones can be adopted, for example, provided as described in JP-A-2003-133080, etc. Can do. As specific examples, antimony is a semiconductive metal oxide such as tin oxide (ATO, FTO) doped with fluorine or the like, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), zinc indium oxide (IZO), Metals such as gold, silver, chromium and nickel, and mixtures and laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, the semiconductive metal oxides or metal compounds And organic conductive materials such as polyanions, polythiophenes and polypyrroles, and laminates of these with ITO. In the case of functioning as an anode, a material having a work function of 4.0 eV or more is preferable. The thickness of the transparent conductive layer in the present invention is preferably 10 nm to 50 μm, and more preferably 50 nm to 20 μm. Further, the total light transmittance of the transparent conductive layer in the present invention is preferably 60% or more, and more preferably 85% or more. The surface roughness of the transparent conductive layer is preferably 10 nm or less, more preferably 5 nm or less, with the centerline average roughness (Ra) measured with a stylus roughness measuring instrument.

(Bus line)
In the present invention, it is preferable to provide a bus line. When the resistance of the transparent conductive layer is high, the organic EL element may generate heat due to the presence of the resistance. In such a case, heat generation can be prevented by providing a bus line. As shown in FIG. 2, the bus line is usually provided in a linear shape, and preferably 1 ≦ b / a ≦ 50 (a is the bus line width, and b is the bus line electrode interval). It is the figure which looked at the organic EL element shown in the said FIG. 1 from the upper direction, Comprising: The transparent conductive layer 3, the organic compound layer 5, the electrode layer 6, and the sealing material 7 are abbreviate | omitted. That is, a state in which the bus line 4 is provided on the gas barrier layer 3 is shown. Further, the bus lines can be arranged in a grid pattern or the like other than the above embodiment. Also in this case, the bus line width and the bus line electrode are preferable. As a method for providing a bus line, a method for forming a vacuum by providing a mask on a transparent conductive layer, a method for using an ACP pattern, a method for providing a silver salt-containing layer by exposure, a method for polishing and the like are adopted. it can. Specifically, methods described in JP2003-133080A, JP2006-12714A, JP2002-229010A, JP2004-221564A, and the like can be preferably employed.

  The transparent conductive film manufactured by the manufacturing method of this invention can be preferably used as a board | substrate with an electrode of a display element. Examples of the display element include an organic EL element, a circularly polarizing plate / liquid crystal display element, and a touch panel.

(Organic EL device)
An organic EL element means an organic electroluminescence element. The organic EL element has a cathode and an anode on a substrate, and an organic compound layer including a light emitting layer between both electrodes. The gas barrier film in the present invention serves as a substrate for an organic EL element, and the transparent conductive layer serves as one of the electrodes of the organic EL element.
As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated 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.

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. , Can be appropriately selected from known electrode materials.

 Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, lithium-aluminum alloys, magnesium-silver alloys, rare earth metals such as indium, ytterbium, and the like. 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, as a material constituting the cathode, a material mainly composed of aluminum is preferable.
The material mainly composed of aluminum refers to aluminum alone or an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a Group 2 metal (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.). The cathode material is described in detail in JP-A-2-15595 and JP-A-5-121172. Further, a dielectric layer made of a fluoride or oxide of an alkali metal or a Group 2 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 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.

Light-Emitting Layer The organic EL 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 Examples of the layer include a block layer, a hole injection layer, and an electron injection layer.

-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 the light emitting material, or may be a mixed layer of the host material and the 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 kind or two or more kinds, 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.

  Examples of the fluorescent light-emitting material include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatics. Compound, perinone derivative, oxadiazole derivative, oxazine derivative, aldazine derivative, pyralidine derivative, cyclopentadiene derivative, bisstyrylanthracene derivative, quinacridone derivative, pyrrolopyridine derivative, thiadiazolopyridine derivative, cyclopentadiene derivative, styrylamine derivative, di Typical examples include ketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives. Various metal complexes are, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom.
Although it does not specifically limit as said 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 the lanthanoid atom 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.

  Examples of the host material contained in the light emitting layer 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 those 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 described later.

-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.

-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.

-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.
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.

(Encapsulant)
In the present invention, a sealing material may be provided. Examples of the sealing material include a glass substrate and a gas barrier film. As the gas barrier film, in addition to the gas barrier film described above, there are also gas barrier films described in JP-A No. 2004-136466, JP-A No. 2004-148766, JP-A No. 2005-246716, JP-A No. 2005-262529, and the like. It can be preferably used.

  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
(Production of gas barrier film)
A gas barrier film (sample Nos. 101 to 103) in which an inorganic layer and an organic layer were provided on a flexible support substrate was produced according to the following procedure. Details of the structure of each gas barrier film are as shown in Table 1. A PEN (manufactured by Teijin DuPont Co., Ltd., Q65A) film having a thickness of 100 μm was used as the flexible support substrate.

[1] Formation of inorganic layer (X) An inorganic layer of aluminum oxide was formed using a reactive sputtering apparatus. Specific film forming conditions are shown below.
The vacuum chamber of the reactive sputtering apparatus was evacuated to an ultimate pressure 5 × 10 ^-4 Pa by an oil rotary pump and a turbo molecular pump. Next, argon was introduced as a plasma gas, and power of 2000 W was applied from a plasma power source. A high-purity oxygen gas was introduced into the chamber, the film formation pressure was adjusted to 0.3 Pa, and the film was formed for a certain period of time to form an aluminum oxide inorganic layer. The obtained aluminum oxide film had a thickness of 40 nm and a film density of 3.01 g / cm ³ .

[2] Formation of Organic Layer (Y, Z, W) The organic layer is formed by a film formation method (organic layer Y, W) by solvent application under normal pressure and a film formation method (organic layer by flash evaporation under reduced pressure). Z). Specific film formation contents are shown below.
[2-1] Film formation by solvent application under normal pressure (organic layer Y)
As a photopolymerizable acrylate, 9 g of tripropylene glycol diacrylate (TPGDA: manufactured by Daicel Cytec) and 0.1 g of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907) were dissolved in 190 g of methyl ethyl ketone, did. This coating solution is applied to a flexible support substrate using a wire bar, and a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge with an oxygen concentration of 0.1% or less. The organic layer Y was formed by irradiating ultraviolet rays having an illuminance of 350 mW / cm ² and an irradiation amount of 500 mJ / cm ² . The film thickness was about 500 nm.

[2-2] Film formation by flash evaporation under reduced pressure (organic layer Z)
As a photopolymerizable acrylate, 9.7 g of the following composition and 0.3 g of a photopolymerization initiator (Lamberti spa, EZACURE-TZT) were mixed to obtain a vapor deposition solution. This vapor deposition solution was vapor-deposited on the substrate by a flash vapor deposition method under the condition that the internal pressure of the vacuum chamber was 3 Pa. Then the conditions of the same degree of vacuum, thereby forming an organic layer Z and an irradiation dose of 2J / cm ^2. The film thickness was about 1200 nm. The organic layer Z was formed using an organic / inorganic laminated film forming apparatus Guardian 200 (manufactured by Vytex Systems).

[2-3] Film formation by solvent application under normal pressure (organic layer W)
In [2-1], the photopolymerizable acrylate was replaced with 9 g of the following compound, and the others were performed in the same manner.

[Photopolymerizable acrylate composition]
2-Butyl-2--2-ethyl-1,3-propanediol diacrylate (BEPGA) 60% by weight
20% by weight of trimethylolpropane triacrylate (TMPTA)
Ethoxylated pentaerythritol tetraacrylate (PETA-4EO) 20% by weight

[3] Lamination A gas barrier film was prepared by sequentially forming the inorganic layer and the organic layer on a flexible support substrate according to the configuration of each sample described in Table 1. The production method was performed in the following three ways.
[3-1] Method of repeating organic layer formation by solvent coating and inorganic layer formation under reduced pressure (Lamination A)
Organic layers and inorganic layers were alternately laminated on the substrate. When stacking the inorganic layer on the organic layer is placed in a vacuum chamber after forming the organic layer by solution coating under reduced pressure, the inorganic layer was held constant time following the state vacuum of 10 ^-3 Pa Was deposited. When the organic layer was laminated on the inorganic layer, the organic layer was formed by solvent coating immediately after the inorganic layer was formed.
[3-2] Method for consistently forming an organic layer and an inorganic layer under reduced pressure (Lamination B)
The organic layer and the inorganic layer were laminated | stacked using the above-mentioned organic-inorganic laminated film-forming apparatus Guardian200. In this apparatus, both the organic layer and the inorganic layer are formed in a reduced pressure environment, and the organic and inorganic layer forming chambers are connected. Therefore, it is possible to continuously form the film in a reduced pressure environment. Therefore, it is not released to the atmosphere until the barrier layer is completed.
[3-3] Method of forming an organic layer by solvent coating only on the first layer, and forming the remaining layer in a consistent manner under reduced pressure (Lamination C)
A first organic layer was formed on the substrate by a solvent coating method. Subsequently, the substrate having the first organic layer was placed in a vacuum chamber and depressurized, and after maintaining for a certain period of time in a state where the degree of vacuum was 10 ⁻³ Pa or less, inorganic layers and organic layers were alternately formed.

(Production of organic EL element)
Using the gas barrier film or PEN (manufactured by Teijin DuPont Co., Ltd., Q65A) film as a substrate and performing the treatment shown in Table 2, using an ITO target, from a 0.2 μm thick ITO thin film by DC magnetron sputtering A transparent electrode was formed.
Here, in Table 2, “80 ° C., 2 hours” means that heat treatment was performed at 80 ° C. for 2 hours, and “heat vacuum treatment” was about 10 ⁻² to 10 ⁻⁶ Pa. It means that the range is in a vacuum state and left to heat under the atmospheric pressure state, and “80 ° C., 2 hours, heat vacuum treatment” means to leave at 80 ° C., 2 hours, 10 ⁻³ Pa or less. Yes. Furthermore, about the gas barrier film which has an ITO film | membrane after performing these processes, some samples were ultrasonically cleaned in 2-propanol, Then, the UV-ozone process was performed for 30 minutes. Other samples were ultrasonically cleaned in 2-propanol and subjected to oxygen plasma treatment.
The following organic compound layers were sequentially deposited by vacuum deposition on the side of the transparent conductive film on which the ITO electrode (anode) was provided.
(First hole transport layer)
Copper phthalocyanine: film thickness 10nm
(Second hole transport layer)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
Finally, 1 nm of lithium fluoride and 100 nm of metal aluminum were sequentially deposited to form a cathode, and a 3 μm thick silicon nitride film was formed thereon by a parallel plate CVD method to produce an organic EL device.

Sealing of organic EL element The organic EL element produced above was manufactured using a glass substrate (manufacturer: Corning, product number: 1737, 0.7 mm) or the gas barrier film No. 1 produced above. 1 and sealed.
Prior to sealing, the glass substrate and the gas barrier film are bonded to and peeled off from the weak adhesive sheet (EC-310: made by Sumilon, adhesive strength: 0.8 N / 20 mm vs glass plate), and then the foreign matter on the surface is removed. Oxygen gas is introduced into the vacuum chamber, the degree of vacuum is adjusted to about 6 Pa, and the treatment is performed for 2 minutes with an RF plasma apparatus (RFX-500: manufactured by Advanced Energy) with an RF power of 20 W. Was removed.

As shown in Table 2, the cleaned glass substrate or gas barrier film is a thermosetting adhesive (Epotech 310, Daizonichi Mori Co., Ltd.) or an ultraviolet curable (UV curable) adhesive (XNR5516HV, Nagase Ciba Co., Ltd.). )). Here, the gas barrier layer side of the barrier film and the organic EL element substrate were bonded together.
When a thermosetting adhesive was used, the adhesive was cured by heating at 65 ° C. for 3 hours. In the case of using a UV curable adhesive, the adhesive was cured by being irradiated with high-pressure mercury lamp light cut from ultraviolet rays having a wavelength shorter than 270 nm, and bonded.

[4] Evaluation of organic EL element light emitting surface condition The organic EL element immediately after production was made to emit light by applying a voltage of 7 V using a source measure unit (SMU2400 type, manufactured by Keithley). When the surface of the light emitting surface was observed using a microscope, it was confirmed that all the elements gave uniform light emission without dark spots.
Next, each element was allowed to stand in a dark room at 60 ° C. and a relative humidity of 90% for 48 hours, and then the light emitting surface was observed. The ratio of elements in which dark spots larger than 300 μm in diameter were observed was visually evaluated. The results are shown in Table 2. In Table 2, in Table 1, ◎ indicates less than 1, ◯ indicates less than 5, △ indicates less than 10, and x indicates 10 or more. The practical level is Δ or more.

From the above results, it was confirmed that all the organic EL elements using the transparent conductive film of the present invention were excellent in gas barrier properties and good in initial performance and aging performance.
In addition, it was confirmed that the same result was obtained for these organic EL elements even in the case of elements divided into pixels described in JP-A-2005-26210.
Furthermore, it was confirmed that good results were obtained even when the bus line described in Example 1 of JP-A-2003-133080 was installed in the above sample according to the method.

  By using the transparent conductive film of the present invention for a display element, a display element having both high gas barrier properties and high initial performance can be obtained. Furthermore, the transparent conductive film of the present invention can improve the initial performance of the display element and improve the yield, so that productivity can be improved.

FIG. 1 is a schematic view showing an example in which a transparent conductive film produced by the production method of the present invention is used for an organic EL element. FIG. 2 is a schematic view showing a state in which a bus line is provided on the transparent conductive layer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base film 2 Gas barrier layer 3 Transparent conductive layer 4 Bus line 5 Organic compound layer 6 Electrode layer 7 Sealing material

Claims (12)

A transparent conductive layer characterized in that a transparent conductive layer is provided on a gas barrier film having a gas barrier layer having at least an organic region and an inorganic region on at least one surface of a base film after heat treatment and / or vacuum treatment. A method for producing a film. The method for producing a transparent conductive film according to claim 1, wherein the gas barrier layer comprises at least one organic layer and at least one inorganic layer. The method for producing a transparent conductive film according to claim 1, wherein the gas barrier layer comprises at least one organic layer and at least two inorganic layers. The manufacturing method of the transparent conductive film of any one of Claims 1-3 whose surface roughness (Ra) of the said transparent conductive layer surface is 10 nm or less. The said heat processing and / or vacuum processing are the manufacturing methods of the transparent conductive film of any one of Claims 1-4 which is heat vacuum processing. The manufacturing method of the transparent conductive film of any one of Claims 1-5 including providing a bus line further on a transparent conductive layer. Furthermore, the manufacturing method of the transparent conductive film of any one of Claims 1-6 including performing the UV / ozone process and / or the plasma process for the said gas barrier film. The method for producing a transparent conductive film according to claim 1, wherein the UV / ozone treatment or the plasma treatment is performed after the heat treatment and / or vacuum treatment and before the transparent conductive layer is provided. . The method for producing a transparent conductive film according to any one of claims 1 to 8, wherein the organic layer or the organic region is formed by applying and curing a composition containing a (meth) acrylate compound having a bisphenol skeleton. . The transparent conductive film manufactured by the manufacturing method of the transparent conductive film of any one of Claims 1-9. The display element using the transparent conductive film of Claim 10. The display element according to claim 11, wherein the display element is an organic EL element.

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