JP5109606B2 - Organic electroluminescence device manufacturing method and protective film - Google Patents

Description

The present invention is a roll-to-roll in durability and has high productivity organic electroluminescent device (hereinafter, also referred to as organic EL device) about the protective film used in the production method and the production method of the.

  In general, incandescent lamps and fluorescent lamps are widely used for consumer use as white illumination light sources.

  Incandescent lamps have a light spectrum close to that of sunlight and are close to natural light, but are not suitable for uniformly brightening the entire wall surface and are difficult to change the emission spectrum. In addition, the efficiency of converting electrical energy into light energy is low.

  At present, fluorescent lamps are widely used because of their efficient use, but fluorescent lamps also have some drawbacks. Since the fluorescent lamp uses the glow discharge of mercury vapor, the lighting time is delayed and the discharge is unstable immediately after the lighting and the light quantity is not stable. In addition, a decrease in the amount of light in a low temperature environment is a problem. Furthermore, since the fluorescent lamp has mercury vapor sealed in a glass tube, it is difficult to reduce the size and environmental pollution due to mercury is also a problem.

  On the other hand, in recent years, organic EL elements have attracted attention as self-luminous elements. An organic EL device is a device in which a light emitting layer made of a thin organic compound is sandwiched between electrodes and emits light when a current is supplied between the electrodes. Therefore, when an organic EL element that is a thin film is used as a light source, it is easy to reduce the size and weight, and has a light emission response speed faster than that of a fluorescent lamp, and a light quantity immediately after lighting is relatively stable. .

  Here, when the organic EL element is used as a light source of a liquid crystal display device or an illumination device for various displays, the emission color is preferably white. However, organic EL elements are very sensitive to substances that form excitons in the light-emitting layer, typified by moisture and oxygen, and interfere with electrochemical processes leading to light emission. If these substances are present as impurities or diffuse from the outside, the light emission efficiency and the driving life are remarkably shortened, and practical illumination and display performance cannot be obtained. In addition, moisture, oxygen, etc. may change the electrical and chemical characteristics of the electrode surface and inside, and may hinder the movement of electrons and holes, and as a result, the practical characteristics are greatly deteriorated.

  Therefore, as disclosed in the figure of 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, It has been studied to secure a performance by forming a layer having a barrier performance on a base material or a sealing material against gas components such as oxygen and oxygen.

  However, in the technology disclosed heretofore, a small amount of sample is produced by spending a lot of time and working time, and it is difficult to produce it in a large amount at a low cost so as to be economically suitable. There is a search for a processing method in the vicinity of normal pressure, in which a material for an organic EL element can be subjected to patterning such as film formation from a vacuum, coating film formation from a coating liquid state at atmospheric pressure, and an ink jet method. These are advantageous in terms of cost compared with the case where the entire 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 processes, which constitutes a manufacturing process for mass production of organic EL elements. However, it is practically impossible to maintain gas confidentiality, gas adsorption / separation apparatus for dehydration, supplied inert gas, etc., because it is reflected in equipment costs and raw material costs.

  In particular, in the case of producing by roll-to-roll, there is a case where it is stored as an intermediate product or a semi-finished product in a roll form at a middle stage of the manufacturing process. This is because, according to the production plan, it is convenient not to process the final product, but to keep an intermediate stock before finalizing as a product having various sizes and standards. Even when troubles or troubles suddenly occur on the downstream process side of the manufacturing process, it may be necessary to continue production of a series of manufacturing lots because a large cost is incurred if all the upstream processes are stopped. In any case, even if the semi-finished product stays in the intermediate stage, if it is not a loss, it can be produced with a high yield, and the manufacturing cost can be greatly reduced. It is also preferable that the material can be diverted between a plurality of processes, and flexibility in mass production can be secured.

Conventionally, organic EL elements have been regarded as leading-edge technologies, and the production of organic EL elements for individual wafers has finally been able to meet the market. There are no technical ideas or applications.
JP 2007-18497A JP 2007-83644 A

The present invention has been made in view of the above problems, and its purpose is to protect the intermediate product from oxygen and moisture in the organic EL element manufacturing process, and to reduce the supply capacity of the inert gas and dry gas in the production process. An object of the present invention is to provide a method for producing an organic electroluminescence device capable of stabilizing and reducing costs, improving the performance (driving life) of organic EL devices during mass production, and stabilizing the quality, and a protective film used therefor.

  The above object of the present invention is achieved by the following configurations.

1. On a flexible support, the gas barrier layer, at least 1 Soyu organic material layer formed by the electrode layer and the coating, in the manufacturing method of an organic electroluminescence element by a roll-to-roll, the step of forming the organic material layer and a protective film having a desiccant-containing layer Ri preparative winding superposed on the organic material layer, the method of manufacturing the organic electroluminescent device characterized by comprising the step of obtaining an intermediate product, in this order.

2. After the step of obtaining the intermediate product, a step of peeling the protective film from the organic material layer, a step of forming a counter electrode layer on the organic material layer, and a step of bonding a sealing film to the counter electrode layer, The method for producing an organic electroluminescence element as described in 1 above, further comprising:

3. A process for forming the organic material layer in a roll-to-roll organic electroluminescence device manufacturing method comprising at least one gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support. And a step of forming a counter electrode layer and a step of superposing and winding up a protective film having a desiccant-containing layer to obtain an intermediate product in this order.

4). The step 3 further comprising, in this order, a step of peeling the protective film from the counter electrode layer and a step of bonding a sealing film to the counter electrode layer after the step of obtaining the intermediate product. The manufacturing method of the organic electroluminescent element of description.
5). 5. The method for producing an organic electroluminescence element according to 2 or 4, wherein the sealing film is a film having a gas barrier layer and a sealing material on a desiccant-containing film.

6). 5. The method for producing an organic electroluminescent element according to 2 or 4, further comprising a step of performing heat aging after the step of obtaining the intermediate product and before the step of peeling.
7). 6. The method for producing an organic electroluminescent element according to 5 above, further comprising a step of performing heat aging after the step of bonding a sealing film to the counter electrode layer.

8). 8. The method of manufacturing an organic electroluminescence element according to any one of 1 to 7, wherein the organic material layer coating step and the drying step are performed in an inert gas atmosphere, and moisture in the inert gas atmosphere The manufacturing method of the organic electroluminescent element characterized by having a concentration of 1 to 200 ppm and an oxygen concentration of 30 ppm or less.

9. On at least one organic material layer formed by gas barrier layer, electrode layer and coating on a flexible support, and after forming the organic material layer, a protective film is superimposed on the organic material layer. A protective film used for a roll-to-roll organic electroluminescent element manufacturing method, wherein the protective film has a laminated structure of three or more layers having a gas barrier layer and a desiccant-containing layer, and the desiccant A protective film, wherein the containing layer is an inner layer.

10. Used in a method for producing an organic electroluminescence device produced by roll-to-roll having a gas barrier layer, an electrode layer, at least one organic material layer formed by coating and a counter electrode layer on a flexible support. The protective film has a laminated structure including a gas barrier layer, a desiccant-containing layer, and a smooth layer in this order, and is wound on at least the organic material layer or the counter electrode layer. A protective film characterized by being made.
11. 11. The protective film as described in 9 or 10 above, wherein the film is embossed in the longitudinal direction at the time of winding.
12 The protective film according to any one of 9 to 11, wherein the protective film has a thickness of 30 to 200 μm and a surface roughness Ra of 30 nm or less.

  According to the present invention, protection of intermediate products from oxygen and moisture in the organic EL element manufacturing process, stabilization of the production line by reducing the supply capacity of inert gas and dry gas in the production process, cost reduction, organic EL elements in mass production An organic electroluminescence device capable of improving the performance (driving life) and stabilizing the quality, a method for producing the same, and a protective film used therefor can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

  The present invention provides a method for producing an organic electroluminescence device by roll-to-roll, comprising at least one gas barrier layer, an electrode layer and an organic material layer formed by coating on a flexible support. Then, a protective film having a desiccant-containing layer is superimposed on the organic material layer and wound to obtain an intermediate product.

  With this manufacturing method, when producing an organic EL element near atmospheric pressure by roll-to-roll, the moisture and oxygen content standards in the manufacturing process can be made more gradual, and the manufacturing process equipment Costs and operating costs can be reduced. In addition, it is possible to sufficiently accelerate the drying of the coated organic EL material after coating, and the performance of the original organic EL material even in production processes that tend to be more demanding than in the laboratory or a small amount of prototype line Can be pulled out.

  Since the organic EL element is easily deteriorated by a gas such as water or oxygen, a small amount of sample is manufactured by spending a lot of work time. That is, when this is manufactured in a large amount at a low cost to meet economic requirements, in all processes constituting the manufacturing process for mass production of organic EL elements, high-purity nitrogen gas, for example, the moisture content is -85 ° C. in terms of dew point. 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 can be used as an internal atmosphere of an organic EL element in a range that can be maintained in factory-level production, for example, in an atmosphere having an inert gas (for example, nitrogen) atmosphere with a moisture concentration of 1 to 200 ppm and an oxygen concentration of about 30 ppm or less. The present invention relates to a method for producing an organic EL element capable of sealing an organic EL element to a degassing level that is practically sufficient, and an organic EL element obtained thereby.

  The present invention provides a roll-to-roll organic EL device manufacturing method comprising at least one gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support. After forming, a protective film having a desiccant-containing layer is superposed on the organic material layer and wound up to obtain an intermediate product. In the method for producing an organic EL device by roll-to-roll, which has at least one gas barrier layer, an electrode layer, and an organic material layer formed by coating, the counter electrode layer is formed after the organic material layer is formed. It is a method for producing an organic EL device, comprising: a step, a protective film having a desiccant-containing layer superimposed thereon, and a step of obtaining an intermediate product in this order.

  Therefore, in one embodiment, a protective film having a desiccant-containing layer is separately stacked as a release liner film on a film on which a gas barrier layer, an electrode layer, and an organic material layer are formed by coating on a support, and wound. Get an intermediate product. Thereafter, after peeling off the protective film from the intermediate product, an organic material layer is additionally formed as necessary to form a counter electrode layer. Furthermore, the counter electrode layer surface and a separately produced sealing film are bonded to complete an organic EL element.

  In another embodiment, a gas barrier layer, an electrode layer, and an organic material layer are formed on a support by coating, and after forming a counter electrode layer, a protective film having a desiccant-containing layer is overlaid as a release liner film. Winding up and obtaining an intermediate product. Thereafter, the protective film is peeled from the intermediate product, and the counter electrode layer surface and a separately produced sealing film are bonded to complete the organic EL element.

  Moreover, it is preferable that the gas barrier layer is formed in the surface side opposite to the counter electrode layer of a sealing film.

  FIG. 5A is a cross-sectional view showing the configuration of the intermediate product manufactured by the manufacturing method of the present invention. 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, and a protective film 10 having a desiccant-containing layer thereon are overlaid. .

  FIG. 5B is a cross-sectional view showing the configuration of another intermediate product manufactured by the manufacturing method of the present invention. A base material on which a gas barrier layer 2, an electrode layer 3, an organic material layer 4 and a counter electrode layer 5 formed by coating are formed on a flexible support 1, and a protective film 10 having a desiccant-containing layer thereon. Are superimposed.

  5C and 5D are cross-sectional views showing the structure of an organic EL element manufactured using an intermediate product obtained by the manufacturing method of the present invention. A film having a gas barrier layer 2, an electrode layer 3, an organic material layer 4 formed by coating, another organic material layer 4 ′, a counter electrode layer 5, a desiccant-containing layer on a flexible support 1 (desiccant Containing film) 21 is bonded and adhered to constitute an organic EL element. Reference numeral 23 denotes a sealing material (adhesive). A gas barrier layer 22 is formed on one side of the desiccant-containing film 21.

  1 and 2 show the manufacturing process of the organic EL device of the present invention.

  A base material A on which a gas barrier layer, an electrode layer and an organic material layer formed by coating are formed on a support, and a base material A ′ on which an electron transport layer, an electron injection layer, and a cathode (counter electrode layer) are further formed. Production of a protective film (base material B) having a gas barrier layer and a smooth layer on a desiccant-containing film, and a sealing film (base material C) having a gas barrier layer and a sealing material (adhesive) on the desiccant-containing 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 has a water vapor transmission coefficient of 1 × 10 ⁻¹⁴ g · cm / (cm ² · sec · Pa) or less. Moreover, it forms also by sputtering method, plasma CVD method, etc. 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 layer / electron injection 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 to 200 ppm and the oxygen concentration is maintained at about 30 ppm or less. As the inside of the organic EL element, it is preferable that the moisture concentration and the oxygen concentration be kept low. However, from the viewpoint of manufacturing in large quantities at an economically reasonable cost, this process should be maintained in this atmosphere. It can be said that it is reasonable.

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

  Substrate A is obtained after the light emitting layer is dried.

  Further, an electron transport layer, an electron injection layer, and a cathode (counter electrode layer) are formed on the light emitting layer to obtain a base material A ′ (not shown).

  Next, the protective film (base material B) having a desiccant-containing layer will be described.

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

  FIG. 3 schematically shows the configuration of the desiccant-containing film in a cross-sectional view.

  The thickness of the protective film is preferably 30 to 200 μm, and has a laminated structure of three or more layers having a gas barrier layer and a desiccant-containing layer, and the desiccant-containing layer is preferably an inner layer. For example, FIG. 3 shows a laminated film comprising a polyethylene naphthalate (PEN) layer (40 μm) / barium oxide-containing polyethylene naphthalate layer (containing 5% by weight of barium oxide) (30 μm) / polyethylene naphthalate layer (20 μm).

  It is preferable to form a gas barrier layer on the surface of the substrate B opposite to the surface facing the substrate A or 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.

  Further, for the same purpose, it is preferable to provide a smooth layer on the opposite surface of the gas barrier layer and to make the surface roughness Ra 30 nm or less. A photocurable resin or the like is used for the smooth layer.

  Further, the substrate A or the substrate A ′ is overlapped with the substrate A and embossed in the longitudinal direction of the substrate B at the time of winding. It is preferable not to contact the support.

  Subsequently, the sealing film (base material C) which has a gas barrier layer and a sealing material (adhesive) on a desiccant containing film is demonstrated.

  The pattern of the sealing material is provided for bonding on one side of the film in which the gas barrier layer is provided on the same desiccant-containing film as the base material B. The sealing material may be an adhesive, for example, a photo-curing or thermo-curing adhesive itself, and has a predetermined thickness in consideration of the thickness when bonded, water or gas, for example, oxygen permeability. A sealing material made of a low material (resin or metal, etc.) may be formed into a pattern and adhered to the substrate with an adhesive. Next, the sealing material is degassed under vacuum to obtain the substrate C.

  The sealing material pattern has a predetermined thickness (for example, thickness) by, for example, a screen printing method using an adhesive on a portion of the base material A or the base material A ′ that is in contact with the outer peripheral surface of the organic material layer 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.

  As the sealing material, an adhesive, for example, a photo-curing or thermosetting adhesive itself may be used, and water or gas having a predetermined thickness in consideration of the thickness when bonded, 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.

  FIG. 4 shows that the surface of the light-emitting layer 3 of the base material A and the surface of the smooth layer 13 of the base material B, which are produced by the above-described steps, are superposed and adhered by a pair of pressure rolls R under a high-purity nitrogen stream. The winding process is schematically shown by a cross-sectional view. Further, the substrate A ′ can be used instead of the substrate A. In this case, the cathode (counter electrode layer) surface of the substrate A ′ and the surface of the smooth layer 13 of the substrate B are overlapped and wound. .

  After winding, the intermediate product is preferably subjected to heat aging. Thereby, the water | moisture content inside an intermediate product is absorbed rapidly by a desiccant, and the fall of the water concentration inside an intermediate product can be performed rapidly.

  The aging (process) is a roll in which the resin film is hardly deformed in a temperature range of 40 to 100 ° C., preferably in a temperature range of 60 to 90 ° C., for about 5 to 72 hours after bonding and bonding, for example. It can be stored in the state of.

  In the present invention, the films are wound in a superposed manner under a high-purity nitrogen stream, but immediately after winding, in the internal space of the intermediate product, the desiccant-containing film of the substrate B and the substrate A or the substrate 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 overlapping process. Therefore, in a manufacturing process for mass production, for example, a strict manufacturing condition that the moisture content is maintained at about −85 ° C. by dew point display is not required, and an organic EL element having a stable life can be manufactured.

  In particular, when the desiccant-containing film as the release liner 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.

  Next, a process for producing the organic EL element of the present invention using the obtained intermediate product will be described.

  After the protective film is peeled off from the intermediate product in which the base material A or the base material A ′ and the base material B are superposed in a high purity nitrogen stream, the electron transport layer, the electron injection layer, the cathode (counter electrode) Layer). As the electron injection layer, for example, a lithium fluoride layer (0.3 nm deposition) is formed. As the counter electrode layer, for example, an aluminum vapor deposition layer is preferably formed (patterning).

  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 the case of the intermediate product in which the base material A ′ and the base material B are overlapped, the electron transport layer, the electron injection layer, and the cathode (counter electrode layer) are already formed on the base material A ′. Peel off.

Then, using the same apparatus as FIG. 4, it overlaps with the sealing film (base material C) produced separately, crimps | bonds and bonds with a pair of pressure rolls, hardens an adhesive agent by light irradiation, and seals. To do. 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 bonding pressure. The pressure roll is preferably one that can be heated simultaneously at a temperature of 40 to 100 ° C. When the gas barrier layer is formed on the substrate C, the side on which the gas barrier layer is not formed is always opposed to the substrate A or the substrate A ′ and bonded.

  In the bonding step, at least in an inert gas (for example, nitrogen) atmosphere, the moisture concentration is maintained at 1 to 200 ppm and the oxygen concentration is about 30 ppm or less, and the substrate A or the substrate A ′ and the substrate C are Bonded in this atmosphere.

  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 substrate C 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 C), that is, the desiccant-containing film is covered with the gas barrier layer, the desiccant does not deteriorate due to the penetration of moisture from the outside, and the dehydrating effect is high. And it 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.

  Aging (process) is a temperature range of 40 to 100 ° C. where deformation of the resin film is less likely to occur, preferably 60 to 90 ° C. What is necessary is just to store in the state of the roll, for example to the extent.

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

  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 substrate C and the substrate A or Since it is sealed by the gas barrier layer of the substrate A ′, the degassing level such as moisture is gradually improved from the same state as the surrounding atmosphere in the bonding process. Therefore, in a manufacturing process for mass production, for example, a strict manufacturing condition that the moisture content is maintained at about −85 ° C. by dew point display is not required, and an organic EL element having a stable life can be manufactured.

  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, the desiccant-containing film used for the base material B (protective film) and the base material C (sealing film) contains a hygroscopic filler as described in, for example, JP-A-2005-38661. What introduce | transduced the layer in resin 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. An appropriate amount is added to the resin so as to have a particle size and particle size distribution that can be scattered and control the surface roughness. A ratio of 1 to 40% by mass is preferred. 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 to 5 μm. A more preferable particle size is 0.1 to 2 μm.

  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, the surface roughness of the film base B (protective film) and the base C (sealing film) having the desiccant-containing layer has smoothness such that the arithmetic average roughness (Ra) is 20 nm or less. It is preferable. 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 each layer constituting the organic EL element is not damaged, so even if the single film of the desiccant-containing layer greatly exceeds this arithmetic average roughness, In the case of a film, 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. The three-layer structure is not necessarily required, 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 the 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 formed into pellets, dried with hot air or vacuum, then melt extruded, extruded into a sheet from a T-die, 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 draw ratio is usually preferably 2.5 to 6 times.

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

  Further, 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 to 700 μm.

  By co-extrusion with polyester (polyethylene terephthalate or the like) 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, In, Sn, Pb, Au , Cu, Ag, Al, Ti, a metal such as _{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 , SixOy (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 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 oxides such as silicon oxide, silicon nitride, silicon oxynitride, tin oxide and the like having a thickness of about 10 to 1000 nm, preferably about 50 to 300 nm, formed by atmospheric pressure plasma method as described in JP-A-2007-83644 The layer is preferably used as a gas barrier layer. For example, a gas barrier layer having a three-layer structure 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 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 device of the present invention comprises a substrate A or a substrate A ′ using a flexible support having an electrode layer and a substrate B using a resin film having a desiccant-containing layer, which are wound up. Then, the base material B is removed, and the base material C is manufactured by sticking and bonding. Since an organic EL element is formed by bonding two substrates of the substrate A and the substrate C, it is necessary to form an organic EL light emitting element when bonded on each substrate. Such an organic material layer needs to be formed in a properly laminated state.

  For example, in the case of the organic EL device configuration shown in FIGS. 1 and 2, the layer configuration is composed of support / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode. Therefore, the base material A is formed by forming, for example, an electrode layer (anode) / hole injection layer / hole transport layer / light-emitting layer after forming a gas barrier layer on a flexible support.

  Moreover, the base material C becomes what the counter electrode layer (cathode) was formed on the sealing film which has a desiccant content layer.

  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 organic EL element constituent layers are arbitrarily separated at which position (interlayer), and each substrate is produced and bonded. For example, as the substrate A, an electrode layer / hole transport Layer / light emitting layer may be laminated, and electrode layer / hole transporting layer / light emitting layer / electron transporting layer / electron injection layer / cathode may be laminated on the substrate A ′ and bonded to the substrate C.

  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 arranged on the base material A, and the base material C has only the electrode layer.

  Further, various organic layer configurations of the organic EL light emitting device 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. In the simplest form, there is a form composed of a layer structure such as an anode / light-emitting layer / cathode. In any form, the base material A or A ′, the base material B, and the base material C are separated from each other. It can carry out similarly by producing this and bonding this. 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.

  In addition, about each said functional layer, well-known literature can be referred.

  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 arylenes, aromatic condensed polycyclic compounds, aromatic heterocondensed ring compounds, metal complex compounds and the like, and single oligo- or complex oligo-bodies thereof, but the invention is not limited to these and 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 phosphorescent material is easily deteriorated by moisture, oxygen and the like as compared with the fluorescent material. However, the phosphorescent material is preferably used because the manufacturing method of the present invention is less susceptible to moisture and oxygen.

  The phosphorescence emission method has a light-emitting region inside the light-emitting layer, so it is relatively difficult to cause uneven light emission. 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 to several hundred nm.

  Examples of the material used in the hole injection / transport layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylenedioxythiophene / 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 to 80 nm, and preferably about 1 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 from each other, 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, ethylbenze Aromatic hydrocarbon solvents such as hexane, octane, decane, tetralin, and other paraffin solvents, ethyl acetate, butyl acetate, amyl acetate, and other ester solvents, 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, etc. And sulfur-based solvents.

  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 | stacking these by application | coating etc. about the organic material layer which is each component layer of these organic EL elements, it is necessary to select a material and a solvent so that the layer which hits a lower layer may not be dissolved.

  For this reason, these organic material layers have, as organic EL materials constituting each, a polymer having a polymerizable group such as a vinyl group or a crosslinking group, and having the above structural units by heating or light irradiation, for example. 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.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example << Preparation of Sealing Film (Base Material C) >>
The desiccant-containing film on the sealing side is a polyethylene 2,6 naphthalate film (A) containing barium oxide in the inner layer by using the method for producing a laminated substrate described in Example 1 of JP-A-2005-38661. -1) was prepared and used. The layer structure of A-1 is composed of three layers of polyethylene 2,6 naphthalate (PEN) / PEN and barium oxide / PEN, and the total thickness is 90 μm and the thickness ratio is 40/30/20. A sealing agent (ultraviolet curable resin) was patterned and applied on one side.

<< Preparation of Protective Film (Base Material B) >>
Polyethylene 2,6 naphthalate A (containing barium oxide) and polyethylene 2,6 naphthalate chips were vacuum-dried at 170 ° C. for 10 hours each, and then 3 units from the hopper installed on the extruder while being kept warm in a dry nitrogen stream Each was supplied to each of the extruders, melt-extruded at 290 ° C., passed through a 40-mesh filter, and then joined in layers so that the thickness ratio was 4: 3: 2 in a T-die. The sheet was brought into close contact with the cooling drum while being electrostatically applied, and rapidly cooled and solidified to obtain a laminated unstretched sheet. At this time, the inner layer (core, core layer) was polyethylene 2,6 naphthalate A (containing barium oxide), and the surface layer was 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, the film 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 (A-1) having a thickness of 90 μm. This film former roll was used after being stored in a room temperature storage in an inert atmosphere having a dew point temperature of −65 degrees (water content of 10 ppm or less).

(Step of forming a smooth layer)
An acrylic ester-based ultraviolet curable resin layer was formed on both sides of A-1 so as to have a dry thickness of 2 μm. It was 1.0 nm when the surface roughness (Ra) was measured using an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO). This protective film is designated as A-2.

<< Preparation of base material (base material A ') having organic layer and cathode >>
A hole transport layer and a light emitting layer were formed in this order on a polyethylene naphthalate-based ITO surface on which ITO had been formed by coating using a coating solution having the following composition.

(Hole transport layer coating solution)
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 prepared by dissolving 60 mg of PVK (polyvinylcarbazole) and 1.5 mg of Ir (ppy) _{3 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.

  Further, it was introduced into a vacuum chamber, an electron injection layer (lithium fluoride) was formed by vapor deposition of 0.3 nm, and aluminum (counter electrode, cathode) was formed by patterning to a thickness of 120 nm by vapor deposition. This is B-1.

<Production of intermediate products>
Under a dry nitrogen stream, while embossing 80 μm in height at both ends in the width direction of A-2, it overlaps with B-1 to form a chromium-plated metal hollow core with a diameter of 1.2 m The top part was fixed and rolled up. The moisture in the atmosphere of this step was 10 ppm. This original winding is set to D-1.

<< Production of Organic EL Element 1 >>
D-1 is fed out under a nitrogen stream to recover B-1, and continuously sent to a bonding step using a pressure roll, and pressure-bonded while controlling the sealing film and the bonding position (bonding pressure) Was 0.2 MPa), and at the same time irradiated with a mercury lamp (6000 mJ / cm ² or more), cured, adhered, and then punched to produce an organic EL device 1.

<< Production of Organic EL Element 2 >>
In the production of the organic EL element 1, the base material A ′ and the base material C were bonded together without producing an intermediate product, and the organic EL element 2 was produced.

<< Evaluation of organic EL elements >>
When the brightness | luminance and lifetime were measured with the following method, the organic EL element 1 of this invention improved the brightness | luminance 10% and the lifetime about twice with respect to the comparison organic EL element 2. FIG.

(Luminance)
The emission of the organic EL element when a DC voltage of 10 V was applied at a temperature of 23 ° C. in the atmosphere was measured with a luminance meter in the range of 400 to 800 nm, and calculated in units of cd / m ² . The brightness of the organic EL element 2 was determined as 100, and the brightness of the organic EL element 1 was determined 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.

(lifespan)
After adjusting the applied voltage so that the initial luminance of the organic EL element was 500 cd / m ² , the time until the luminance decreased by 50% from the initial time was measured. The half life of the organic EL element 1 when the luminance half life of the organic EL element 2 was 1.0 was evaluated as a relative value.

It is a figure which shows the process of manufacture of the organic EL element of this invention. 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 process of superimposing and winding up is schematically shown by a sectional view. It is sectional drawing which shows the structure of the intermediate product and the organic EL element which were manufactured with the manufacturing method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 2, 12, 22 Gas barrier layer 3 Electrode layer 4, 4 'Organic material layer 5 Counter electrode layer 6, 11, 21 Desiccant containing film 10 Protective film 13 Smooth layer 23 Sealing material

Claims (12)

In a method for producing a roll-to-roll organic electroluminescence device, comprising a gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support,
Wherein the step of forming the organic material layer, and a protective film having a desiccant-containing layer Ri preparative winding superposed on the organic material layer, to obtain an intermediate product,
In this order, the manufacturing method of the organic electroluminescent element characterized by the above-mentioned. After the step of obtaining the intermediate product,
Peeling the protective film from the organic material layer,
Forming a counter electrode layer on the organic material layer; and
A step of bonding a sealing film to the counter electrode layer;
The organic electroluminescence element manufacturing method according to claim 1, further comprising: In a method for producing a roll-to-roll organic electroluminescence device, comprising a gas barrier layer, an electrode layer, and an organic material layer formed by coating on a flexible support,
Forming the organic material layer ;
Obtaining the step, and superposed protective film having a desiccant-containing layer Ri preparative winding, the intermediate product to form a counter electrode layer,
In this order, the manufacturing method of the organic electroluminescent element characterized by the above-mentioned. After the step of obtaining the intermediate product,
Peeling the protective film from the counter electrode layer; and
A step of bonding a sealing film to the counter electrode layer;
The organic electroluminescence element manufacturing method according to claim 3, further comprising: The method for producing an organic electroluminescence element according to claim 2, wherein the sealing film is a film having a gas barrier layer and a sealing material on a desiccant-containing film. The method of manufacturing an organic electroluminescence element according to claim 2, further comprising a step of performing heat aging after the step of obtaining the intermediate product and before the step of peeling. The method for producing an organic electroluminescence element according to claim 5, further comprising a step of performing heat aging after the step of bonding a sealing film to the counter electrode layer. It is a manufacturing method of the organic electroluminescent element of any one of Claims 1-7, Comprising: The application | coating process and drying process of an organic material layer are performed in inert gas atmosphere, In this inert gas atmosphere A method for producing an organic electroluminescence device, wherein the moisture concentration is 1 to 200 ppm and the oxygen concentration is 30 ppm or less. On at least one organic material layer formed by gas barrier layer, electrode layer and coating on a flexible support, and after forming the organic material layer, a protective film is superimposed on the organic material layer. A protective film used for a method for producing a roll-to-roll organic electroluminescence element by winding ,
The protective film has a laminated structure of three or more layers having a gas barrier layer and a desiccant-containing layer, wherein the desiccant-containing layer is an inner layer. Used in a method for producing an organic electroluminescence device produced by roll-to-roll having a gas barrier layer, an electrode layer, at least one organic material layer formed by coating and a counter electrode layer on a flexible support. A protective film,
The protective film has a laminated structure having a gas barrier layer, a desiccant-containing layer, and a smooth layer in this order, and is wound at least on the organic material layer or the counter electrode layer. Protective film. The protective film according to claim 9 or 10 , wherein embossing is performed in a longitudinal direction at the time of winding. The protective film according to any one of claims 9 to 11, wherein the protective film has a thickness of 30 to 200 µm and a surface roughness Ra of 30 nm or less.

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