JP2009123690A - Organic electronics element winding to past drying agent film after forming coated layer or after forming coupled electrode layer and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electronics element formed on a flexible support and having high productivity and durability when considering mass production, and its manufacturing method. <P>SOLUTION: In the organic electronics element having at least one layer of a gas barrier layer on the flexible support, an electrode layer, and an organic material layer formed by coating, after forming the organic material layer, a film forming the coupled electrode layer having a drying agent containing layer is pasted. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a durable and highly productive organic electronics element formed on a flexible support and a method for producing the same.

  In recent years, development of various organic electronics elements such as organic electroluminescence elements, organic photoelectric conversion elements, organic photoconductors for electrophotography, and organic transistors has been studied.

  Organic electronics devices are devices that perform electrical operations using organic materials, and are expected to exhibit features such as energy saving, low cost, and flexibility, and are attracting attention as a technology that can replace conventional inorganic semiconductors based on silicon. ing.

  These organic electronic elements are elements that emit light, generate power, charge, or control current and voltage by passing a current through an electrode through a very thin film of an organic substance.

  An organic electroluminescence (EL) element is an element that emits light when a current is supplied between electrodes, in which a light emitting layer made of a thin film of an organic compound is sandwiched between electrodes. Therefore, when a thin-film organic EL element is used as a light source, it is easy to reduce the size and weight, and the light emitting response speed is higher than that of a fluorescent lamp, and the amount of light immediately after lighting is relatively stable.

  Here, when the organic EL element is used as a light source for a liquid crystal display device or an illumination device for various displays, the emission color is preferably white. However, the organic EL element is very sensitive to substances such as moisture and oxygen that interfere with electrochemical processes from formation of excitons in the light emitting layer to light emission. If these substances are present as impurities or diffuse from the outside, the light emission efficiency and drive life are remarkably shortened, and practical illumination and display performance cannot be obtained.

  In addition, water, oxygen, etc. may change the electrical and chemical characteristics of the electrode surface and inside, and may interfere with the movement of electrons and holes, and as a result, the practical characteristics are greatly deteriorated. Therefore, as disclosed in Patent Document 1, the organic EL element is encapsulated with a desiccant and enclosed in a structure sealed with glass or a metal can, or as disclosed in Patent Document 2, moisture or oxygen It has been studied to form a layer having a barrier performance on a base material or a sealing material to ensure performance against gas components such as the above.

  An organic photoelectric conversion element is an element that generates electricity when irradiated with light in a configuration in which a power generation layer made of a thin film of an organic compound is sandwiched between electrodes. Therefore, if a thin-film organic photoelectric conversion element is used as a solar cell, it is easy to reduce the size and weight, and the output is relatively stable even in low illuminance and constant temperature environments compared to existing inorganic semiconductor solar cells. The solar cell can be obtained.

  Similarly to the organic EL element, the organic photoelectric conversion element also forms a carrier trap in the power generation layer due to the influence of moisture, oxygen, and the like, thereby inhibiting the collection of carriers generated by charge separation. As a result, not only the power generation efficiency is lowered, but also the life of the element is affected. Therefore, in the organic photoelectric conversion element, as disclosed in Patent Document 3, it is considered to secure the performance by using a sealing material having a barrier performance against gas components such as moisture and oxygen. Has been.

However, in the conventional disclosed technique, a small amount of sample is produced by spending a lot of work time, and it is very difficult to produce it in a large amount at a low cost so as to be economically suitable. For this reason, we are looking for processing methods near atmospheric pressure that can be used for organic EL device materials, such as film formation in vacuum, coating film formation from the coating liquid state at atmospheric pressure, and ink-jet method. Has been. These are advantageous in terms of cost compared to the case where the entire manufacturing process is evacuated, but conversely, it becomes difficult to suppress the influence of moisture, oxygen, etc. contained in the gas in the atmosphere or in an inert atmosphere. . As an example, it is very difficult to maintain a high purity nitrogen gas, for example, a moisture content of about -85 ° C. in terms of dew point in all the steps constituting the manufacturing process for mass production of organic EL elements. However, it is practically impossible to maintain the gas tightness, gas adsorption / separation device for dehydration, and high purity inert gas to be reflected in equipment cost and raw material cost from various points. is there.
JP 2007-18497A JP 2007-83644 A JP 2004-165512 A

  An object of the present invention is to provide an organic electronic device which is formed on a flexible support and has high productivity and good durability when mass production is taken into consideration, and a method for manufacturing the same.

  1. A counter electrode having a desiccant-containing layer after forming the organic material layer in an organic electronic device having at least one gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support. An organic electronic device comprising a film in which a layer is formed.

  2. In an organic electronic device having a gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support, a counter electrode layer is formed after the formation of the organic material layer, and An organic electronics element comprising a film having a desiccant-containing layer bonded thereto.

3. In a method for producing an organic electronic element having at least one organic material layer formed by gas barrier layer, electrode layer and coating on a flexible support,
After forming the organic material layer by coating,
A method for producing an organic electronic element, comprising: bonding a film on which a counter electrode layer having a desiccant-containing layer is formed, and further heat aging.

4). In a method for producing an organic electronic element having at least one organic material layer formed by gas barrier layer, electrode layer and coating on a flexible support,
After forming the organic material layer by coating,
A method for producing an organic electronic device, comprising: forming a counter electrode layer; and bonding a film having a desiccant-containing layer, followed by further heat aging.

  5). 3. The organic electronic device as described in 1 or 2 above, wherein the film having the desiccant-containing layer has a surface roughness of 20 nm or less in terms of arithmetic average roughness (Ra).

6). 6. The gas barrier property of the flexible support is 10 ⁻⁵ g / (m ² · 24 h) or less in terms of water vapor permeability as defined in JIS K7129-1992. Organic electronics elements.

  7. 5. The method for producing an organic electronic element according to 3 or 4, wherein the coating step and the drying step of the organic material layer are an inert gas atmosphere, and the moisture concentration in the inert gas atmosphere is 1 ppm or more and 200 ppm or less. An oxygen concentration is 30 ppm or less, The manufacturing method of the organic electronics element characterized by the above-mentioned.

  8). 7. The organic electronic device according to 1, 2, 5, or 6, wherein the organic electronic device is an organic electroluminescence device, and at least one of the organic material layers includes a phosphorescent material.

  9. The organic electronic device described in the above 1, 2, 5, or 6 is an organic photoelectric conversion device, and at least one of the organic material layers includes a p-type semiconductor material and an n-type semiconductor material, and generates a photocurrent. An organic electronic device characterized by that.

  According to the present invention, the productivity of the organic electronics element is improved and the driving life of the element is also improved.

  The best mode for carrying out the present invention will be described below, but the present invention is not limited thereto.

  The present invention relates to an organic electronic device designed to improve the dehydration / deoxygenation level and prolong the life when manufacturing the organic electronic device in a practical production line for the organic electronic device, and to the organic electronic device It relates to the manufacturing method.

  Since organic electronic devices are easily deteriorated by gas such as water and oxygen, a small amount of sample is manufactured by spending a lot of work time. That is, when this is manufactured at a low cost and in a large amount to be economically compatible, in all processes constituting the manufacturing process for mass production of organic electronics elements, high-purity nitrogen gas, for example, the moisture content is -85 ° C in dew point display. It is very difficult to maintain to the extent. In the manufacturing process, the above level is substantially maintained to reflect the equipment cost and raw material cost from various points such as maintaining gas tightness, gas adsorption separation device for dehydration, supplied inert gas, etc. It is impossible to do.

  The present invention provides an internal atmosphere of an organic electronics element in a range that can be maintained in production at a factory level, for example, in an atmosphere of an inert gas (for example, nitrogen) atmosphere having a moisture concentration of 1 ppm to 200 ppm and an oxygen concentration of about 30 ppm or less. The present invention relates to a method for producing an organic electronic element that can be bonded and sealed at a degassing level that is practically sufficient, and an organic electronic element obtained thereby.

  The present invention relates to an organic electronic device having at least one electrode layer and an organic material layer formed by coating on a flexible support, and the desiccant-containing layer after the organic material layer is formed. An organic electronic element characterized in that a film on which an electrode layer is formed is bonded, and a gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support. An organic electronics element having one layer, wherein after forming the organic material layer, a counter electrode layer is formed, and a film having a desiccant-containing layer is further bonded. .

  Accordingly, in one embodiment, a desiccant-containing material in which a counter electrode layer is separately provided on an anode film (base material A) in which an organic material layer is formed by coating on one base material, a gas barrier layer, an electrode layer, and the like. A resin film having a layer is bonded and bonded as a sealing film (base material B) to seal the organic electronics element.

  As another embodiment, a gas barrier layer, an electrode layer, and an organic material layer are formed on the base material by coating, and the anode film (base material A) on which the counter electrode layer is further formed has a desiccant-containing layer. A resin film is bonded and bonded as a sealing film (base material B) to seal the organic electronics element.

  In addition, an organic material layer may be separately formed on the base material A and the base material B so that the organic material layer may constitute each functional layer of the organic electronics element after bonding.

  Moreover, it is preferable that the gas barrier layer is formed in the base material B (sealing film) on the surface side opposite to a counter electrode layer of the resin film which has a desiccant content layer.

  The structure of the organic electroluminescent element (henceforth an organic EL element) manufactured by the bonding of this invention in FIG. 4 (a) was shown with sectional drawing. A base material on which a gas barrier layer 2, an electrode layer 3 and an organic material layer 4 formed by coating are formed on a flexible support 1, a counter electrode layer 5, and an organic material layer 4 'formed thereon. The base material which consists of the film (drying agent containing film) 6 which has an agent content layer is bonded and adhere | attached, and the organic EL element is comprised. Reference numeral 8 denotes a sealing material (adhesive). A gas barrier layer 2 ′ is formed here on the uppermost layer of the desiccant-containing film.

  FIG. 1 shows a process for manufacturing the organic EL device of the present invention.

  The production of the substrate A (anode film) will be described.

  A gas barrier layer formation process is a process of forming a gas barrier layer on flexible supports, such as polyethylene terephthalate and polyethylene naphthalate, for example.

The gas barrier layer is, for example, an inorganic vapor deposition film such as silicon oxide, and is a layer having a water vapor transmission coefficient of 1 × 10 ⁻¹⁴ g · cm / (cm ² · sec · Pa) or less. It is also formed by sputtering or plasma CVD. A moisture-proof layer having a thickness of about 20 nm to 50 μm is preferable. By using a resin support having these gas barrier layers, gas permeability such as water vapor permeability of the resin is lowered.

  After the gas barrier layer is formed, ITO is then patterned as an anode on the gas barrier layer in an ITO patterning step. For example, an ITO film is patterned by sputtering using an ITO target with a thickness of 110 nm. A transparent conductive film is used to extract light from the anode film side. It does not have to be ITO.

  Next, in the resin film on which the ITO film is patterned, an organic material layer serving as each functional layer constituting the organic EL element is laminated and formed on the ITO in the organic material layer coating step. As described later, there are various configurations of the organic EL element. Here, the anode (ITO) and the cathode are connected between the anode (ITO) / hole injection layer / hole transport layer / light emitting layer / electron transport. An organic EL element composed of a layer / cathode will be described as an example.

  In the organic material layer coating step, a coater (not specifically limited, such as a die coater or an inkjet coating device), a dryer or the like is disposed (not shown in the figure), and the organic material layer coating step includes at least an inert gas ( For example, it is a process in which the water concentration is 1 ppm or more and 200 ppm or less and the oxygen concentration is maintained at about 30 ppm or less. It is preferable that the moisture concentration and the oxygen concentration be kept low as the inside of the organic EL element, but it is reasonable to maintain this process in this atmosphere from the viewpoint of manufacturing in large quantities at an economically reasonable cost. It can be said that it is suitable.

  In the organic material layer coating step, a hole injection layer, a hole transport layer, and a light emitting layer are sequentially coated on an anode made of ITO and dried to be laminated. In order to form by application | coating, it is preferable to laminate | stack an organic material layer after performing superposition | polymerization, bridge | crosslinking, etc. suitably so that a lower layer (dried organic layer) may not melt | dissolve by lamination | stacking application | coating.

  After drying the light emitting layer, an anode film (base material A) is obtained.

  Next, the sealing film (base material B) will be described.

  The sealing film is a resin film having a desiccant-containing layer (desiccant-containing film), and is not limited. For example, a resin film having a layer in which desiccant fine particles described in JP-A-2005-38661 are kneaded is used. Is preferred.

  FIG. 2 schematically shows the configuration of the desiccant-containing film in a cross-sectional view.

  FIG. 2 shows a laminated film composed of, for example, a polyethylene naphthalate layer (40 μm) / barium oxide-containing polyethylene naphthalate layer (containing 5% by mass of barium oxide) (30 μm) / polyethylene naphthalate layer (20 μm).

  It is preferable to form a gas barrier layer on the surface of the sealing film opposite to the surface facing the substrate A. The gas barrier layer is not essential, but the effect of the present invention is improved by preventing the penetration of moisture and gas from the outside. After the gas barrier layer is formed on the sealing film, a counter electrode layer, for example, an aluminum vapor deposition layer is preferably (patterned) formed on the side of the sealing film opposite to the gas barrier layer. Further, here, an electron injection layer (lithium fluoride layer (0.3 nm deposition)) is formed on the aluminum deposition layer (counter electrode layer), and further an electron transport layer is formed.

  Here, the electron injection layer and the electron transport layer are formed by vacuum deposition, but for example, the electron transport layer and the like are formed by a coating process in the same atmosphere as the organic material layer coating process of the substrate A. May be.

  In this example, the substrate A is formed up to the light-emitting layer, but after forming up to the electron transport layer, the substrate A is transferred to a vacuum, and the electron injection layer and further the counter electrode are formed to form the substrate A. May be. In this case, a film having a desiccant-containing layer is used only as a sealing film.

  Then, it goes into the bonding process.

  FIG. 3 schematically shows a process of bonding and sealing the base material A and the base material B formed by the above-described process with a pair of pressure rolls R, using a cross-sectional view and a perspective view. is there. In the figure, prior to bonding, the pattern of the sealing material 8 is provided on the base material A so as to surround the periphery of the organic material layer (4) surface (light emitting surface) on the electrode layer 3.

  The sealing material 8 may use an adhesive, for example, a photo-curing or thermosetting adhesive itself, and has a predetermined thickness in consideration of the thickness when bonded, water, gas, for example, oxygen permeability Alternatively, a sealing material made of a low material (resin or metal) may be formed into a pattern and adhered to the base material with an adhesive.

  As shown in FIG. 3, the sealing material pattern has a predetermined thickness (for example, a thickness) by, for example, a screen printing method on the outer peripheral surface of the organic material layer 4 of the base material A, except for an external extraction portion of the electrode. Pattern placement at 0.1 mm). As the adhesive, for example, UV resin XNR5516 manufactured by Nagase Chemtech Co., Ltd. can be used.

  Cross-sectional views of the base materials A and B when pasting are shown in FIG.

  In the substrate A, a gas barrier layer 2, an electrode layer 3 (ITO), and an organic material layer 4 are formed on a flexible support 1, and a sealing material pattern is formed around the light emitting surface. In the base material B, the counter electrode layer 5 and the organic material layer 4 ′ are formed on the desiccant-containing film 6, and the gas barrier layer 2 ′ is formed on the opposite surface side of the base material.

In the bonding step, after the pattern of the sealing material 8 is applied on the base material A by the adhesive, the base material A is made of the base material B, the electrode layer 3, and the counter electrode layer 5 as shown in FIG. It is made to face, organic material layer 4, 4 'is pinched | superposed, it overlaps | stacks, it is crimped | bonded and bonded by a pair of pressurizing roll R, light irradiation is carried out, an adhesive agent is hardened and sealed. For light irradiation, for example, an irradiation energy of 6000 mJ / cm ² or more is given and cured by a handy high-pressure mercury lamp (OHD-110M-ST) manufactured by Oak Manufacturing Co., Ltd. and sealed. In addition, when bonding base materials, it aligns sufficiently and it adjusts so that it may become the range of 0.01-5 Mpa as a bonding pressure. The pressure roll is preferably one that can be heated simultaneously at a temperature of 40 ° C. or higher and 100 ° C. or lower. When the gas barrier layer is formed on the base material B, the side on which the gas barrier layer is not always formed is opposed to the base material A and bonded.

  In the bonding step, at least in an inert gas (for example, nitrogen) atmosphere, the water concentration is maintained at 1 ppm to 200 ppm and the oxygen concentration is about 30 ppm, and the base material A and the base material B are in this atmosphere. Is pasted.

  Even in the bonding step, it can be said that it is reasonable to maintain this step in this atmosphere from the viewpoint of manufacturing in large quantities at an economically reasonable cost.

  Accordingly, the inside of the sealed organic EL element bonded and bonded has the same atmosphere as the atmosphere of the bonding process at the time of bonding and bonding. However, after sealing, the desiccant-containing film constituting the base material B gradually absorbs gas such as moisture inside the organic EL element that permeates through the resin film. Therefore, immediately after sealing by bonding and adhesion, the moisture concentration inside the element gradually decreases. Accordingly, since the dehydration and degassing level inside the organic EL element is improved as compared with the manufacturing process, the nitrogen content of high purity, for example, the moisture content is substantially maintained at about −85 ° C. in the dew point display. In the production conditions with a low moisture content, the level is equivalent to that produced.

  In particular, when the sealing film (base material B), that is, the desiccant-containing film is covered with a gas barrier layer on the outermost surface (FIGS. 3 and 4), the desiccant deteriorates due to the penetration of moisture from the outside. The dehydration effect is high and lasts.

  It is preferable to perform heat aging after winding up after bonding, adhesion, and sealing. Thereby, the moisture inside the element is quickly absorbed by the desiccant, and the moisture concentration inside the element can be rapidly reduced.

  The aging (process) is a temperature range of 40 ° C. to 100 ° C., preferably in a temperature range of 60 ° C. to 90 ° C. What is necessary is just to store for about 72 hours, for example in the state of the roll wound up.

  Moreover, after winding up, you may perform aging, after cutting a roll into each element.

  The cut organic EL element is shown in a sectional view in FIG.

  The present invention is sealed in the bonding step in the above gas atmosphere, but immediately after sealing, in the internal space where the organic EL element is sealed, the desiccant-containing film of the base material B and the base material A Since it is sealed by the gas barrier layer, the degassing level of moisture and the like is gradually improved from a state equivalent to the surrounding atmosphere in the bonding process. For this reason, in the manufacturing process for mass production, for example, a strict manufacturing condition that the moisture content is maintained at about −85 ° C. with dew point display is not required, and it becomes possible to manufacture an organic EL element having a stable lifetime. .

  In particular, when the desiccant-containing film as the sealing film has a gas barrier layer as the outermost layer, the diffusion of gas such as moisture and oxygen from the outside air to the desiccant-containing film is greatly reduced, so the effect can be maintained more. High dehydration effect can be obtained.

  As described above, as a desiccant-containing film used for the base material B (sealing film), for example, a layer containing a hygroscopic filler as described in JP-A-2005-38661 was introduced into the resin. Things can be used. The “hygroscopic filler” referred to in this patent has dehydration / deoxygenation ability and is sometimes called a getter material. A compound such as Compound 1 described in JP-A-2007-197517 can also be used.

As the hygroscopic filler, hygroscopic substances that can be added to the resin layer include oxides such as MgO, BaO, V ₂ O ₅ , CaO, and SrO. Appropriate amounts are added to the resin with a particle size and particle size distribution that can be scattered to control the surface roughness. A ratio of 1% by mass to 40% by mass is preferable. Moreover, in order to give the diffusibility at the time of light extraction, it is preferable that the refractive index of the hygroscopic material itself is 1.30 or more.

  The hygroscopic substance is used by dispersing in an average particle size of 0.08 μm or more and 5 μm or less. A more preferable particle size is 0.1 μm or more and 2 μm or less.

  Usually, the resin layer containing the hygroscopic filler is kneaded as a dispersion in the casting composition when forming the resin layer, or added to the composition to form a film. (Film) can be obtained.

  The resin film may have a laminated structure in which the resin film having the hygroscopic filler is a core layer, and in particular, a thin film and a resin film, or a laminated film composed of a plurality of different resin films. It may be.

  If a resin film containing a hygroscopic filler is used as it is in the present invention, the hygroscopic filler protruding on the surface of the resin film may impair the uniformity of the electrodes and organic material layers constituting the organic EL element composed of a thin layer. In severe cases, the film may penetrate through the film, and uniform light emission characteristics may not be obtained, and after moisture absorption, for example, in the case of barium oxide, which is a strong hygroscopic agent, it is strongly hydrolyzed and generated. Alkali is not preferable because it erodes the electrode and the like.

  Therefore, it is preferable that the surface roughness of the film having the desiccant-containing layer has smoothness such that the arithmetic average roughness (Ra) is 20 nm or less. The arithmetic average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO). The reason why the surface roughness is 20 nm or less is that the layers constituting the organic EL element are not damaged. Therefore, even if the single film of the desiccant-containing layer greatly exceeds the arithmetic average roughness, the laminated film In this case, the surface roughness needs to be 20 nm or less in terms of Ra described above.

  Such a resin film (layer) containing a hygroscopic filler is used as a core layer, and other resin layers such as polyethylene terephthalate, polyethylene naphthalate or glass are used so that the filler is not exposed on the surface. It is particularly preferable to use a laminated film or a laminated film laminated by a co-extrusion method or a co-casting method described later.

  The thickness of the layer containing the hygroscopic filler serving as the core layer is preferably 20 to 500 μm, and this is preferably laminated with a resin layer in the range of 20 to 500 μm not containing the hygroscopic filler. It is not always necessary to have a three-layer structure, and the filler layers may be laminated by combining different resins or those having different hygroscopic substances.

For example, there are the following configurations.
PET / PET (BaO) / PET
PEN / PET (BaO) / PEN
Glass / PES (BaO) / Glass
Etc. is a typical configuration. In the above, PET: polyethylene terephthalate, PEN: polyethylene 2,6-naphthalate, PES: polyethersulfone.

  For film formation of a resin film or a resin layer, for example, a polyester film, a conventionally known method may be used. Usually, the raw material polyester is molded into pellets, dried with hot air or vacuum, melt extruded, extruded into a sheet from a T-die, and brought into close contact with a cooling drum by an electrostatic application method, etc., cooled and solidified, and unstretched Get a sheet.

  A co-extrusion method using a plurality of extruders and a feed block die or a multi-manifold die, a single layer film constituting a laminated body, or other resin constituting the laminated body on the laminated film is melt-extruded from the extruder, and a cooling drum An extrusion laminating method for cooling and solidifying above and a coextrusion method with good adhesion between the layers are preferred. The obtained unstretched sheet is heated through a plurality of roll groups and / or heating devices such as an infrared heater, and stretched in one or more stages. The stretching ratio is usually preferably 2.5 to 6 times.

  In this way, the film is stretched longitudinally and further laterally, and then heat-set.

  Also, when formed by a solvent casting method, the hygroscopic filler may be added in a dispersed state in the dope and then formed into a film. Moreover, the film which has a laminated structure can be similarly obtained by the co-casting method.

  In order to obtain a flexible and lightweight substrate by using a resin film, the thickness of the substrate is 30 μm or more and 700 μm or less.

  By co-extrusion with a polyester (polyethylene terephthalate, etc.) that can obtain a uniform film with a stretchable film at a low price among resins, a film having a desiccant-containing layer can be produced with good productivity and low cost.

  In the present invention, a transparent resin film is used as the flexible support (substrate) constituting the other substrate A. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyesters such as polyvinylidene fluoride, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, polyimide Polyetherimide, polyimide, and a film of polypropylene.

The gas barrier property of the flexible support used in the present invention has a water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K7129-1992. It is preferably 10 ⁻⁵ g / (m ² · 24 h) or less.

  A flexible metal thin plate or the like can also be used when light transmission is not required.

Moreover, as a gas barrier layer (moisture-proof layer), an inorganic vapor deposition film | membrane and metal foil are mentioned. As inorganic vapor deposition films, thin film handbooks p879-p901 (Japan Society for the Promotion of Science), vacuum technology handbooks p502-p509, p612, p810 (Nikkan Kogyo Shimbun), vacuum handbook revised editions p132-p134 (ULVAC Japan Vacuum Technology KK) Inorganic films as described in (1). For example, metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, Fe ₂ O ₃ , Y ₂ O ₃ , TiO ₂ , Cr ₂ O ₃ , Si _x O _y (x = 1, y = 1.5 to 2.0), Ta ₂ O ₃ , ZrN, SiC, TiC, PSG, Si 3 N 4, SiN, single crystal Si, amorphous Si, W, etc. are used.

  As a material of the metal foil, for example, a metal material such as aluminum, copper, or nickel, or an alloy material such as stainless steel or an aluminum alloy can be used, but aluminum is preferable in terms of workability and cost. The film thickness is about 50 nm to 100 μm, preferably about 0.1 μm to 50 μm.

  Further, an inorganic vapor deposition film such as a metal oxide film such as silicon oxide, silicon nitride, silicon oxynitride, or tin oxide can be used as the gas barrier layer. These films can be formed by sputtering, plasma CVD, particularly atmospheric pressure plasma CVD.

  Metal oxide such as silicon oxide, silicon nitride, silicon oxynitride, tin oxide, etc. having a thickness of about 10 nm to 1000 nm, preferably about 50 nm to 300 nm formed by atmospheric pressure plasma method as described in JP-A-2007-83644 A physical layer is preferably used as the gas barrier layer. For example, a three-layer gas barrier layer composed of an adhesion layer using a silicon oxide layer, a ceramic layer, and a protective layer described in JP-A-2007-83644 is useful as the barrier layer of the present invention.

  The atmospheric pressure plasma CVD method is preferable because it allows rapid film formation at atmospheric pressure. For example, in the case of a silicon oxide film on a resin film, plasma is generated by applying a high-frequency potential using an inert gas as a discharge gas in the presence of a thin-film forming gas such as tetraalkoxysilane, and 10 nm to 1000 nm by CVD. A range of silicon oxide layers can be formed on the substrate. In addition, ceramic films having different components can be formed by selecting manufacturing conditions, additive gas, and the like.

  In addition, in the anode film (base material A), the ITO patterning for the anode is formed on the resin film on which the gas barrier layer including the electrode (light emitting surface) and the terminal is formed by, for example, applying an ITO target under vacuum. It can be formed by sputtering, but it can also be formed by using a compound such as indium or tin as a thin film forming gas by atmospheric pressure plasma CVD.

  As described above, the formation of the gas barrier layer is a process under vacuum if a vacuum deposition method, a sputtering method, or the like is used.

  In the present invention, since the gas barrier layer on the anode side is the light extraction side of the organic EL element, the light-transmitting inorganic oxide film such as silicon oxide is preferable. As the gas barrier layer formed on the stop film, a layer having a low light transmittance such as a metal thin film or a metal foil can be used.

  Next, an organic material constituting the organic EL element will be described.

  The organic EL element of the present invention is produced by closely bonding and bonding a base material A using a flexible support having an electrode layer and a base material B using a resin film having a desiccant-containing layer. . Since an organic EL element is formed by bonding two substrates, the organic material layer necessary for forming the organic EL light-emitting element is properly formed on each substrate when bonded. It is necessary to be formed in a laminated state.

  For example, in the case of the organic EL element configuration of FIG. 1, the configuration of the organic material layer is anode / hole transport layer / light emitting layer / electron transport layer / cathode. Accordingly, the base material A is formed by forming a gas barrier layer on a flexible support and then forming, for example, an electrode layer (anode) / hole transport layer / light emitting layer.

  Moreover, the base material B becomes what the counter electrode layer (cathode) / electron transport layer / light emitting layer was formed on the sealing film which has a desiccant content layer. The light emitting layer may be on either side.

  An organic EL element having the above-described layer structure is formed by stacking two substrates so that the electrode layers face each other and closely adhering them.

  The organic material layers constituting the respective constituent layers of the organic EL element are arbitrarily determined at which positions (interlayers) to prepare and bond each base material. For example, as the base material A, an electrode layer / hole transport layer The substrate B may be laminated with a counter electrode layer / electron transport layer / light emitting layer / hole transport layer and bonded together.

  In addition, in the above, the same layers are configured to be bonded to each other, but for example, a mode in which different layers are bonded to each other, for example, the electrode layer / hole transport layer is laminated on the substrate A, and the substrate B may be laminated with a cathode layer / electron transport layer / light emitting layer and bonded together.

  Of course, an organic material layer may be formed and bonded only to one of the substrates. In this case, it is preferable that all the organic material layers are disposed on the base material A, and the base material B has a configuration including only the electrode layer.

  Further, various organic layer configurations of the organic EL light emitting element have been proposed in addition to the above, for example, on the support, anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode, etc. Most simply, there is a form consisting of a layer structure such as an anode / light emitting layer / cathode, etc. In any form, it is separated between any of the layers, and a base material A and a base material B are prepared and pasted. It can be similarly implemented by combining. The thickness of each organic layer and each thin film in these organic EL elements is in the range of 1 nm to several μm.

  For each of the above functional layers, known literature can be referred to.

  The organic EL element has a structure in which one or a plurality of organic material layers are laminated between electrodes as described above. In addition to the above, an electron blocking layer, a hole blocking layer, a buffer layer, and other necessary layers are appropriately provided. Are stacked in a predetermined layer order so that carriers such as holes and electrons injected from both poles move smoothly. The main organic material layer constituting the organic EL element will be described below.

  In each of these organic material layers constituting the organic EL element, organic light emitting materials contained in the light emitting layer include aromatic heterocyclic compounds such as carbazole, carboline, diazacarbazole, triarylamine derivatives, stilbene derivatives, poly Examples include arylene, aromatic condensed polycyclic compounds, aromatic heterocondensed ring compounds, metal complex compounds and the like, and single oligo compounds or composite oligo compounds thereof. However, the present invention is not limited thereto, and is widely known. These materials can be used.

  The layer (film forming material) may preferably contain about 0.1 to 20% by mass of a dopant in the light emitting material. Examples of the dopant include known fluorescent dyes such as perylene derivatives and pyrene derivatives, and in the case of phosphorescent light emitting layers, for example, tris (2-phenylpyridine) iridium, bis (2-phenylpyridine) (acetylacetonate). A complex compound such as an orthometalated iridium complex represented by iridium, bis (2,4-difluorophenylpyridine) (picolinato) iridium, and the like is similarly contained in an amount of about 0.1 to 20% by mass.

  The phosphorescence emission method has a light emitting region inside the light emitting layer, so it is relatively difficult to cause uneven light emission, and it is difficult to cause phenomena such as unevenness at the bonding interface, which is the biggest difficulty of the bonding method, and slow carrier movement. Therefore, compatibility with the bonding method is good. The thickness of the light emitting layer ranges from 1 nm to several hundred nm.

  Examples of materials used in the hole injection / transport layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), and the like. Polymer materials such as conductive polymers are also used for the light emitting layer, for example, carbazole-based light emitting materials such as 4,4′-dicarbazolylbiphenyl, 1,3-dicarbazolylbenzene, (di ) Low molecular light emitting materials represented by pyrene-based light emitting materials such as azacarbazoles, 1,3,5-tripyrenylbenzene, polymer light emitting materials represented by polyphenylene vinylenes, polyfluorenes, polyvinyl carbazoles, etc. Etc.

  Examples of the electron injection / transport layer material include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinate) zinc, and nitrogen-containing five-membered ring derivatives listed below. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenyl) Asiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  The film thickness of the organic EL element and each organic material layer is required to be about 0.1 nm to 80 nm, and preferably about 1 nm to 50 nm.

  The organic material layer (organic EL functional layer) can be formed by vapor deposition or the like, but application and printing are preferred.

  As the coating, spin coating, transfer coating, extrusion coating and the like can be used. In consideration of material use efficiency, a method capable of applying a pattern such as transfer coating and extrusion coating is preferable, and transfer coating is particularly preferable.

  Moreover, screen printing, offset printing, inkjet printing, etc. can be used for printing. As the display element, a thin film, a small element size, and high-precision high-definition printing such as offset printing and inkjet printing are preferable in consideration of overlapping RGB patterns.

  Each organic material has its own solubility characteristics (solubility parameters, ionization potential, polarity), and there are limitations on the solvents that can be dissolved. In this case, since the solubility is different, the concentration cannot be generally determined. However, the type of the solvent used in the present invention is suitable for the above conditions depending on the organic EL material to be formed. May be selected from known solvents, for example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, dibutyl ether, tetrahydrofuran, Ether solvents such as dioxane and anisole, alcohol solvents such as methanol, ethanol, isopropanol, butanol, cyclohexanol, 2-methoxyethanol, ethylene glycol, glycerin, benzene, toluene, xylene, ethylben Aromatic hydrocarbon solvents such as hexane, paraffin solvents such as hexane, octane, decane and tetralin, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as N-methylpyrrolidone, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, amine solvents such as pyridine, quinoline and aniline, nitrile solvents such as acetonitrile and valeronitrile, thiophene, carbon disulfide And sulfur-based solvents such as

  In addition, the solvent which can be used is not restricted to these, You may mix and use 2 or more types of these as a solvent.

  Among these, preferable examples of the organic EL material are different depending on each functional layer material. However, as a good solvent, for example, an aromatic solvent, a halogen solvent, an ether solvent, and the like are preferable. Aromatic solvents and ether solvents. Examples of the poor solvent include alcohol solvents, ketone solvents, paraffin solvents, and the like. Among them, alcohol solvents and paraffin solvents are used.

  In addition, when laminating these organic EL layers as constituent layers of these organic EL elements by coating or the like, it is necessary to select a material and a solvent so as not to dissolve the lower layer.

  For this reason, these organic material layers have a polymerizable group such as a vinyl group or a cross-linking group as an organic EL material constituting each of the organic material layers. What forms a coalescence can be used. As a result, dissolution of the film due to the multilayer, disturbance of the interface, and the like can be suppressed.

  As the conductive material used as the electrode layer in the base material A, that is, the anode of the organic EL element, those having a work function larger than 4 eV are suitable, such as silver, gold, platinum, palladium and alloys thereof, Metal oxides such as tin oxide, indium oxide and ITO, and organic conductive resins such as polythiophene and polypyrrole are used. It is preferable that it is translucent, and ITO is preferably excellent as the transparent electrode. As a method for forming the ITO transparent electrode, mask vapor deposition, sputtering, photolithography patterning, or the like can be used, but is not limited thereto.

  Moreover, as a conductive substance used as a counter electrode (cathode), those having a work function smaller than 4 eV are suitable, and magnesium, aluminum, and the like are preferable. Typical examples of the alloy include magnesium / silver and lithium / aluminum. The formation method can be mask vapor deposition, photolithography patterning, plating, printing, or the like, but is not limited thereto.

  Moreover, in the manufacturing process of the organic EL element of the present invention, a counter electrode is previously formed on a film having a gas barrier layer and an electrode layer in the substrate A and a desiccant-containing layer as the substrate B. Is preferred. Thus, an optimum process such as sputtering or vapor deposition can be used for electrode formation. The electrode can be formed in a roll-to-roll form using a resin film as a flexible base plate.

  Hereinafter, the present invention will be described specifically by way of examples.

Example 1
<< Production of Substrate A >>
(Process of forming an electrode layer, a hole injection layer, a hole transport layer, and a light emitting layer on a flexible support)
JP-A-2007-83644 described on one side of a 150 μm thick polyethylene naphthalate film previously stored at a dew point of −65 ° C. under an inert gas atmosphere at a pressure of 80 Pa and subjected to dehydration and deoxygenation. By this method, a gas barrier layer was formed.

  That is, the roll electrode type discharge treatment apparatus shown in JP-A-2007-83644 and FIG. 3 was used.

  A gas barrier film was formed on one side of the polyethylene naphthalate film by forming an adhesion layer / ceramic layer / protective layer on the resin film substrate in the following order. Regarding the respective film thicknesses, the adhesion layer is 50 nm, the ceramic layer is 30 nm, and the protective layer is 400 nm. The substrate holding temperature during film formation was 120 ° C.

<Ceramic layer>
Discharge gas: N ₂ gas reaction gas 1: 5% of oxygen gas to the total gas
Reaction gas 2: TEOS (tetraethoxysilane) is 0.1% of the total gas
Low frequency side power supply: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz at 10 W / cm ²
<Adhesion layer>
Discharge gas: N ₂ gas reactive gas 1: 1% of hydrogen gas with respect to the total gas
Reaction gas 2: 0.5% of TEOS with respect to the total gas
Low frequency side power supply: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz at 5 W / cm ²
<Protective layer>
Discharge gas: N ₂ gas reactive gas 1: 1% of hydrogen gas with respect to the total gas
Reaction gas 2: 0.5% of TEOS with respect to the total gas
Low frequency side power supply: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz at 5 W / cm ²
Next, on the polyethylene naphthalate film on which the gas barrier layer is formed, using indium tin oxide (ITO) as a target material, and using argon containing 5% by volume of oxygen as a sputtering gas in a vacuum chamber, An ITO film having a thickness of 110 nm was patterned by sputtering as an electrode layer while continuously feeding at 0.5 Pa. As the ITO pattern, the conductive layer pattern shown in FIG. 3 was used. This was wound around a core in a vacuum chamber, returned to normal pressure under a nitrogen stream, and transferred to a coating process under normal pressure without exposure to the atmosphere (air).

  On this support with conductive layer, a coating solution for a hole injection layer (deoxygenated) having the liquid composition described below is applied by an extrusion coater installed in the first coating chamber, and dried under an inert gas stream. (30 nm thickness after drying). Subsequently, the hole transport layer coating solution (deoxygenated and dehydrated) is applied in the second coating chamber, irradiated with UV rays to crosslink, insolubilized in the coating solvent after this step, and then dried. (The thickness after drying was 40 nm). Further, in the third coating chamber, a light-emitting layer is applied on the cross-linked hole transport layer (the thickness after drying is 50 nm), dried, and a coated original fabric (web W) in which three functional layers are laminated. -1) was produced. The coating process under normal pressure was maintained in an atmosphere having a moisture concentration in a nitrogen atmosphere of 1 ppm to 200 ppm and an oxygen concentration of 30 ppm or less.

(Coating solution for hole injection layer)
A solution obtained by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was used.

(Coating liquid for hole transport layer)
A solution in which 50 mg of the following compound A was contained in 10 ml of toluene was used. After irradiating with ultraviolet light for 90 seconds to carry out photopolymerization and crosslinking, the film was dried under a nitrogen stream while being slowly conveyed through a drying zone at 90 ° C.

(Light emitting layer coating solution)
A solution in which PVK (polyvinylcarbazole) (60 mg) and 1.5 mg of Ir (ppy) ₃ were contained in 6 ml of chlorobenzene was used. After film formation, the film was dried under a nitrogen stream while slowly transporting through a 95 ° C. drying zone to form a light emitting layer having a dry film thickness of 50 nm.

<< Production of Substrate B >>
(Step of forming a surface smooth layer on a film having a layer containing a desiccant)
A desiccant-containing film as a sealing film is a polyethylene 2,6 naphthalate film (A) containing barium oxide in the core layer using the method for producing a laminated substrate described in Example 1 of JP-A-2005-38661. -1) was prepared and used.

  That is, polyethylene-2,6-naphthalate A (containing barium oxide; barium oxide powder (average particle size, 0.5 μm) was mixed and kneaded with polyethylene-2,6-naphthalate chips at 280 ° C. (content 5 mass) ) And polyethylene-2,6-naphthalate chips were each vacuum dried at 170 ° C. for 10 hours, and then extruded from a hopper installed on an extruder while being kept warm in a dry nitrogen stream. Each is supplied to a machine, melt extruded at 290 ° C., passed through a 40 mesh filter, joined in layers so that the thickness ratio is 4: 3: 2 in a T die, and a 60 ° C. cooling drum It was brought into close contact with electrostatic application and rapidly cooled and solidified to obtain a laminated unstretched sheet. At this time, the core layer was made of polyethylene-2,6-naphthalate A (containing barium oxide), and the surface layer was made of polyethylene-2,6-naphthalate. This unstretched sheet was guided to a roll-type longitudinal stretching machine, preheated at 90 ° C., and stretched 2.8 times in the longitudinal direction while being heated with an IR heater between low-speed and high-speed rolls. The obtained uniaxially stretched film was supplied to a tenter-type transverse stretching machine and stretched at 130 ° C. so that the transverse stretching ratio was 2.8 times. The obtained biaxially oriented film was heat-fixed at 210 ° C. for 10 seconds. Subsequently, it was slowly cooled to room temperature over 30 seconds while being subjected to a 5% relaxation treatment in the transverse direction to obtain a biaxially stretched laminated PEN film support having a thickness of 90 μm (desiccant-containing film A-1).

  It was 15 nm or less when the surface roughness was measured using the optical interference type surface roughness meter RST / PLUS (made by WYKO).

  The layer structure of A-1 consists of three layers of polyethylene-2,6-naphthalate (PEN) / PEN and barium oxide / PEN, and the overall thickness is 90 μm and the thickness ratio is 40/30/20.

  This original film roll was stored in an inert gas atmosphere storage with a dew point temperature of −65 degrees (water content of 10 ppm or less).

(Process of forming electrode layer and electron injection layer on desiccant-containing film)
Similarly to the above, on the surface of the desiccant-containing film A-1 whose surface layer polyethylene-2,6-naphthalate (PEN) is 40 μm, a gas barrier layer having the composition described in Examples of JP-A-2007-83644 is similarly formed. A desiccant-containing film was coated. Next, a surface smooth layer made of an acrylate ester is formed on the surface (opposite side) where the surface layer polyethylene-2,6-naphthalate (PEN) is 20 microns, cross-linked and cured with ultraviolet rays, and then passed through a decompression chamber. Then, it was introduced into the vacuum transfer chamber, and aluminum was patterned to a thickness of 120 nm by vapor deposition as a counter electrode layer in the first thin film forming chamber. Subsequently, lithium fluoride (electron injection layer) was deposited by 0.3 nm in the second thin film formation chamber.

(Step of applying a sealing resin to the desiccant-containing film with the counter electrode layer / injection layer formed and laminating with the web with the functional layer formed)
A film in which an electrode layer and an electron injection layer are formed on the desiccant-containing film A-1 in an inert gas stream (in a nitrogen atmosphere, the water concentration is 1 ppm or more and 200 ppm or less, the oxygen concentration is 30 ppm or less). An ultraviolet curable epoxy resin (manufactured by Nagase Chemtech Co., Ltd., UV resin XNR5516) was applied in a predetermined shape using screen printing. Without winding up this sealing film with an electrode, it is continuously sent to the bonding step using the pressure roll shown in FIG. 3 and bonded while controlling the W-1 and the bonding position (bonding pressure). Was 0.2 MPa), and simultaneously cured by irradiation with a mercury lamp (6000 mJ / cm ² or more), and wound around a core having a diameter of 1 m.

  Further, the wound core was stored at 80 ° C. for 48 hours, subjected to aging, and then cut into each element to produce a light emitting device OLED1 composed of an organic EL element.

Example 2
In the same manner except that the gas barrier layer was not formed on the surface of the desiccant-containing film A-1 whose surface layer polyethylene-2,6-naphthalate (PEN) was 40 μm, except that the base material B was prepared, The base material A was pasted and adhered, the sealing material was cured to produce an organic EL element, and wound around a core having a diameter of 1 m. Furthermore, after performing aging similarly, it cut into each element and produced light-emitting device OLED2.

  In FIG. 4, the structure of OLED1 (FIG. 4 (a)) and 2 (FIG.4 (b)) was shown with sectional drawing.

Comparative Example 1
When producing the desiccant-containing film A-1 used in Example 1, the core layer does not contain barium oxide powder as a hygroscopic material, that is, a film of polyethylene-2,6-naphthalate (PEN) having a thickness of 100 μm. In the same manner, except that a gas barrier layer was formed on one side, a base material B was prepared, bonded and adhered to the base material A, an encapsulant was cured to prepare an organic EL element, and a diameter of 1 m. Wound around the core. Furthermore, after performing aging similarly, it cut into each element and produced light-emitting device OLED3. Although it is the same structure as Fig.4 (a), it becomes the structure which replaced the desiccant containing film 6 with the film which does not contain a desiccant.

Comparative Example 2
When producing the desiccant-containing film A-1 used in Example 1, the core layer does not contain barium oxide powder as a hygroscopic material, that is, a film of polyethylene-2,6-naphthalate (PEN) having a thickness of 100 μm. In the same manner except that was used, a base material B was prepared, bonded and adhered to the base material A, an encapsulating material was cured to prepare an organic EL element, and wound around a core having a diameter of 1 m. Furthermore, after performing aging similarly, it cut into each element and produced light-emitting device OLED4. Although it is the same structure as FIG.4 (b), it becomes the structure which replaced the desiccant containing film 6 with the film which does not contain a desiccant.

  The following evaluation was performed about each obtained light-emitting device.

  The results are shown in Table 1.

<Initial brightness>
When a direct current voltage of 10 V was applied at a temperature of 23 ° C. and in the air, the OLED 4 emitted light was measured with a luminance meter in the range of 400 nm to 800 nm, and calculated in units of cd / m ² . With this as 100, the luminance of OLED1, OLED2, OLED3 was displayed as a relative value. For the measurement with the luminance meter, the average value of the values at the center of each part obtained by dividing the light emitting surface into 9 parts was used. It is preferable that the light emitting surface has few dark portions and high luminance.

<Brightness half-life>
After adjusting the applied voltage so that the initial luminance of each sample element was 500 cd / m ² , the time until the luminance decreased by 50% from the initial time was measured. The half life of each of the OLEDs 1 to 4 when the luminance half life of the element of the OLED 4 was 1.0 was evaluated as a relative value.

《Yield (Yield)》
20 elements each of OLED1 to OLED4 are manufactured by the roll-to-roll method of the present invention, and the luminance of one place in the light emitting surface is divided into 9 parts is 25% lower than the average value of 20 initial luminances. Considering it as a defective product, the other products were regarded as non-defective products, and the yield for 20 pieces was calculated.

  From the above results, the organic electroluminescence device of the present invention is superior to the conventional sealing film with a barrier in a process with high moisture and oxygen concentration assuming mass production, and combined with a desiccant-containing sealing film. As a result, it has become apparent that the performance can be greatly improved and the product yield, that is, the manufacturing cost can be reduced.

Example 3
In creating the web W-1 of the light emitting device OLED1, after forming the hole injection layer, the power generation layer having the liquid composition described later is applied (the thickness after drying is 150 nm) in the third coating chamber. The organic photoelectric conversion element OPV1 having a desiccant in the element was produced in the same manner as in the production of the OLED 1 except that -2 was produced.

(Coating liquid for power generation layer)
6 ml of chlorobenzene, regioregular P3HT (poly (3-hexylthiophene)) having a number average molecular weight of 45000 and fullerene derivative PCBM (6,6-phenyl-C ₆₁ -butyric acid methyl ester) in a mass ratio of 1: 1, A solution dissolved so as to be 3% by mass was used. After film formation, the film was dried in a nitrogen stream while slowly transporting through a 140 ° C. drying zone to form a power generation layer having a dry film thickness of 150 nm.

When the organic photoelectric conversion element OPV1 having the obtained desiccant in the element was evaluated for the short circuit current density Jsc when the solar simulator (AM1.5G) was continuously irradiated with light of 100 mW / cm ² , It has become clear that it exhibits high stability over a long period of time and has sufficient light resistance. In addition, as with the organic electroluminescence element, it has become apparent that the yield of the product, that is, the manufacturing cost can be reduced in the process of mass production in the organic photoelectric conversion element.

It is a figure which shows the process of manufacture of the organic EL element of this invention. It is sectional drawing which shows the structure of a desiccant containing film typically. The bonding / adhering step is schematically shown by a cross-sectional view and a perspective view. It is sectional drawing which shows the structure of the organic EL element manufactured by bonding.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 2 Gas barrier layer 3 Electrode layer 4 Organic material layer 5 Counter electrode layer 6 Desiccant containing film 8 Sealing material

Claims (9)

A counter electrode having a desiccant-containing layer after forming the organic material layer in an organic electronic device having at least one gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support. An organic electronic device comprising a film in which a layer is formed. In an organic electronic device having a gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support, a counter electrode layer is formed after the formation of the organic material layer, and An organic electronics element comprising a film having a desiccant-containing layer bonded thereto. In a method for producing an organic electronic element having at least one organic material layer formed by gas barrier layer, electrode layer and coating on a flexible support,
After forming the organic material layer by coating,
A method for producing an organic electronic element, comprising: bonding a film on which a counter electrode layer having a desiccant-containing layer is formed, and further heat aging. In a method for producing an organic electronic element having at least one organic material layer formed by gas barrier layer, electrode layer and coating on a flexible support,
After forming the organic material layer by coating,
A method for producing an organic electronic device, comprising: forming a counter electrode layer; and bonding a film having a desiccant-containing layer, followed by further heat aging. The organic electronic device according to claim 1 or 2, wherein the film having the desiccant-containing layer has a surface roughness of 20 nm or less in terms of arithmetic average roughness (Ra). The gas barrier property of the flexible support is 10 ⁻⁵ g / (m ² · 24 h) or less in terms of water vapor permeability as defined in JIS K7129-1992. The organic electronics element as described. The method for producing an organic electronic element according to claim 3 or 4, wherein the coating step and the drying step of the organic material layer are an inert gas atmosphere, and a moisture concentration in the inert gas atmosphere is 1 ppm or more and 200 ppm. Hereafter, the manufacturing method of the organic electronics element characterized by oxygen concentration being 30 ppm or less. The organic electronic device according to claim 1, 2, 5, or 6, wherein the organic electronic device is an organic electroluminescent device, wherein at least one of the organic material layers contains a phosphorescent material. 7. The organic electronic device according to claim 1, 2, 5 or 6, wherein at least one of the organic material layers includes a p-type semiconductor material and an n-type semiconductor material, and generates a photocurrent. An organic electronic device characterized by that.

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