JP2008034142A - Organic electroluminescent light emitting device, and organic electroluminescent lighting system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent light emitting device high in blocking performance of moisture from the outside, capable of suppressing degradation of element performance of an organic electroluminescent element over a long time, and high in reliability of the element performance. <P>SOLUTION: This application provides an organic electroluminescent element 5 formed by stacking a translucent base material 1, a transparent conductive layer 2, an organic luminescent layer 3, and a negative electrode layer 4 in that order. The application also provides a photo-curing resin sealing layer 7 formed to directly contact a surface of a stacked material 6 to cover the stacked material 6 with the organic luminescent layer 3 and the negative electrode layer 4 stacked therein and to reach a surface of the translucent base material 1 in the circumference of the stacked material 6. The application still also provides a moisture-proof layer 8 formed on the outside of the photo-curing resin sealing layer 7. The application further provides a thermosetting resin adhesive layer 9 sticking the moisture-proof layer 8 to the translucent base material 1 and the transparent conductive layer 2 at a position surrounding the stacked material 6. This organic electroluminescent light emitting device is formed by comprising them. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an organic electroluminescence light emitting device and an organic electroluminescence illumination device used for a flat panel display, a sign light source, an illumination light source, a backlight for a liquid crystal display, and the like.

  In general, an organic electroluminescence light-emitting element has a structure in which a light-transmitting substrate such as glass or plastic, a transparent conductive layer of an anode made of a transparent electrode film, an organic light-emitting layer made of an organic thin film, and a cathode layer made of a metal electrode are laminated. In recent years, research has been conducted energetically for such reasons as high luminance surface emission at a low voltage of several volts, and the ability to emit light in any color tone by selecting a light emitting material. Development aimed at practical use is being conducted.

  The organic electroluminescence light-emitting device comprising this organic electroluminescence light-emitting element can be used for sign light sources, lighting applications, backlights for liquid crystal displays, flat panel displays, etc. In order to reduce the size and thickness of the electronic equipment provided, or to liberalize the shape, the appearance of lighter and more efficient devices is desired.

  However, when the organic electroluminescence light emitting device is driven for a certain period, a non-light emitting portion called a dark spot occurs and grows, and there is a problem that the light emission characteristics deteriorate. The cause of the occurrence of such a dark spot is considered to be the largest influence of moisture such as water vapor and oxygen, and particularly the moisture is considered to have a great influence even in a very small amount. Therefore, it is necessary to seal the organic light emitting layer by some method to shield the action of moisture and oxygen.

  Means for solving this problem is disclosed in Patent Document 1, Patent Document 2, and the like. In Patent Document 1, a light-emitting element is formed by laminating an electrode, an organic light-emitting layer, or the like on a light-transmitting substrate, and a photo-curable resin is applied so as to cover the light-emitting element. A non-water-permeable substrate is bonded with a photo-curable resin layer by overlaying a small water-permeable substrate and curing the photo-curing resin by light irradiation. The resin layer is sealed with a water-impermeable substrate.

  However, in this case, since the water-impermeable substrate is bonded with the photocurable resin layer, there is a problem in adhesion, and moisture may permeate from the interface between the two, and the moisture blocking effect is not sufficient. There was no problem.

  On the other hand, in Patent Document 2, a light emitting element is formed by laminating an electrode or an organic light emitting layer on a translucent substrate, and an epoxy resin is applied so as to cover the light emitting element, and on the epoxy resin. The moisture-proof layer is stacked and the epoxy resin is cured to bond the moisture-proof layer with the epoxy resin layer, and the light-emitting element is sealed with the epoxy resin layer and the moisture-proof layer.

In the thing of this patent document 2, when using a light-impermeable thing as a moisture-proof layer, since it cannot make photocuring, it is necessary to use a thermosetting thing as an epoxy resin, and a thermosetting resin hardens | cures In this case, the organic light-emitting layer and the aluminum vapor deposition forming the cathode may be destroyed due to the flow of the resin melted by heating and the curing shrinkage of the resin, and the reliability and yield of the device performance are reduced. There was a problem to do.
JP-A-5-182759 JP 2004-119317 A

  The present invention has been made in view of the above points, and has a high ability to block moisture from the outside, can suppress deterioration of the element performance of the organic electroluminescence element over a long period of time, and can be trusted in element performance. It is an object of the present invention to provide an organic electroluminescence light-emitting device and an organic electroluminescence lighting device with high performance.

  An organic electroluminescence light emitting device according to claim 1 of the present invention includes an organic electroluminescence element 5 formed by laminating a translucent substrate 1, a transparent conductive layer 2, an organic light emitting layer 3, and a cathode layer 4 in this order. The light formed in direct contact with the surface of the laminate 6 so as to cover the laminate 6 in which the organic light emitting layer 3 and the cathode layer 4 are laminated and to reach the surface of the translucent substrate 1 around the laminate 6 The curable resin sealing layer 7, the moisture-proof layer 8 provided outside the photo-curable resin sealing layer 7, and the moisture-proof layer 8 at the position surrounding the laminate 6, the translucent substrate 1 and the transparent conductive layer. 2 is provided with a thermosetting resin adhesive layer 9 that adheres to 2.

  According to this invention, the organic light emitting layer 3 of the organic electroluminescence element 5 can be sealed with the photocurable resin sealing layer 7 and the moistureproof layer 8, and the moistureproof layer 8 with the thermosetting resin adhesive layer 9. Can be adhered with high adhesion, and a high barrier property to moisture from the outside can be obtained. The organic light emitting layer 3 and the cathode layer 4 are covered with a photocurable resin sealing layer 7 so that the organic light emitting layer 3 and the cathode layer 4 can be protected by the photocurable resin sealing layer 7. In this case, the organic light emitting layer 3 and the cathode layer 4 can be prevented from being destroyed due to the influence of curing the thermosetting resin adhesive layer 9. As a result, deterioration of the element performance of the organic electroluminescence element 5 can be suppressed over a long period of time, and the reliability of the element performance can be increased.

  The invention of claim 2 comprises the hygroscopic agent-containing sealing layer 10 formed so as to cover the entire surface of the photocurable resin sealing layer 7 in claim 1, and the hygroscopic agent-containing sealing. The moisture-proof layer 8 is formed so as to cover the layer 10.

  According to the present invention, moisture absorption by the hygroscopic agent-containing sealing layer 10 can more effectively block moisture from the outside and suppress deterioration of the element performance of the organic electroluminescence element 5 to a higher level.

  Further, the invention of claim 3 comprises the hygroscopic agent-containing sealing layer 10 formed so as to cover the outer periphery of the photocurable resin sealing layer 7 at a position surrounding the periphery of the laminate 6 in claim 1. In addition, the moisture-proof layer 8 is formed so as to cover the hygroscopic agent-containing sealing layer 10.

  According to the present invention, moisture absorption by the hygroscopic agent-containing sealing layer 10 can more effectively block moisture from the outside and suppress deterioration of the element performance of the organic electroluminescence element 5 to a higher level.

  The invention of claim 4 is characterized in that, in claim 2 or 3, the hygroscopic agent-containing sealing layer 10 comprises a photocurable resin as a base resin.

  According to the present invention, the hygroscopic agent-containing sealing layer 10 can be formed by photocuring, workability can be improved, and the thermal history for the organic electroluminescence element 5 can be reduced. is there.

  The invention of claim 5 is characterized in that in any one of claims 1 to 4, it comprises a moisture absorbent sheet 13 laminated between the photo-curable resin sealing layer 7 and the moisture-proof layer 8. Is.

  According to this invention, moisture absorption by the moisture absorbing sheet 13 can more effectively block moisture from the outside, and the deterioration of the element performance of the organic electroluminescence element 5 can be further suppressed.

  The invention of claim 6 is characterized in that in any one of claims 1 to 5, the thermosetting resin adhesive layer 9 contains 15% by mass or more of an electrically insulating inorganic filler. is there.

  According to this invention, the electrical insulation between the transparent conductive layer 2 and the moisture-proof layer 8 can be ensured by the electrically insulating inorganic filler.

  The invention according to claim 7 is the moisture-proof layer 8 according to any one of claims 1 to 6, wherein the moisture-proof layer 8 is a metal film, a base film made of plastic, and at least one inorganic oxide selected from silicon oxide and aluminum oxide. A laminated sheet obtained by laminating at least one of at least one inorganic nitride selected from silicon nitride and aluminum nitride, and a laminated sheet obtained by vapor-depositing metal on a plastic base film. It is characterized by.

  According to this invention, the moisture-proof layer 8 having high moisture-proof performance can be formed with a thin sheet-like material, and the organic electroluminescence light-emitting device can be formed thin and lightweight.

  The invention of claim 8 is characterized in that in any one of claims 1 to 7, the thermosetting resin adhesive layer 9 contains a hygroscopic agent.

  According to the present invention, moisture absorption by the moisture absorbent in the thermosetting resin adhesive layer 9 can more effectively block moisture from the outside and suppress deterioration of the element performance of the organic electroluminescence element 5 to a higher level. It can be done.

  The invention of claim 9 is characterized in that, in any of claims 2 to 8, the hygroscopic agent is at least one selected from calcium, barium, oxides thereof, and silica gel. is there.

  According to this invention, moisture from the outside can be more effectively blocked by the hygroscopic agent having high moisture absorption performance.

  According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the moisture-proof layer 8 is bonded to the translucent substrate 1 by bending an end so as to cover the periphery of the laminate 6. It is characterized by that.

  According to the present invention, the entire organic light emitting layer 3 can be covered with the moisture-proof layer 8 and the translucent substrate 1, and the gap between the moisture-proof layer 8 and the translucent substrate 1 is reduced. Therefore, it is possible to block moisture and oxygen from the outside more effectively, and to suppress deterioration of the element performance of the organic electroluminescence element 5 to a higher level.

  An organic electroluminescent lighting device according to an eleventh aspect of the present invention is an organic electroluminescent light emitting device A according to any one of the first to tenth aspects, and an endothermic device that absorbs heat generated by the organic electroluminescent light emitting device A. It comprises a body 11 and a heat radiating body 12 for radiating the heat absorbed by the heat absorbing body 11 to the outside.

  According to the present invention, the organic electroluminescence light emitting device A can emit light while dissipating heat, and can be prevented from being deteriorated by heat even when light is emitted with a large area and high illuminance. A long-life organic electroluminescence lighting device can be obtained.

  According to the present invention, the organic light-emitting layer 3 of the organic electroluminescence element 5 can be sealed with the photocurable resin sealing layer 7 and the moisture-proof layer 8, and the moisture-proof layer 8 with the thermosetting resin adhesive layer 9. The organic light-emitting layer 3 and the cathode layer 4 are covered with a photo-curable resin sealing layer 7 on the surface. The organic light-emitting layer 3 and the cathode layer 4 can be protected by the photo-curing resin sealing layer 7, and the organic light-emitting layer 3 and the cathode layer 4 are affected by the effect of curing the thermosetting resin adhesive layer 9. The aluminum vapor deposition forming the cathode layer 4 can be prevented from being destroyed, the deterioration of the element performance of the organic electroluminescence element 5 can be suppressed over a long period, and the reliability of the element performance is increased. It is something that can be done.

  Hereinafter, the best mode for carrying out the present invention will be described.

  FIG. 1 shows an example of an embodiment of an organic electroluminescence light emitting device according to the present invention. A transparent conductive layer 2 serving as an anode is laminated on the surface of a translucent substrate 1, and the transparent conductive layer 2 is The organic electroluminescent element 5 is formed by laminating the organic light emitting layer 3 and the cathode layer 4 on the organic light emitting layer 3. In the embodiment of FIG. 1, the transparent conductive layer 2 forms the anode 20 and the cathode extraction electrode 21 separated from the anode 20, and the cathode layer 4 is connected to the cathode extraction electrode 21. . If necessary, a hole transport layer or hole injection layer is provided between the organic light emitting layer 3 and the transparent conductive layer 2, and an electron transport layer or electron injection layer is provided between the organic light emitting layer 3 and the cathode layer 4. It can be provided by stacking. As materials for forming these members, materials conventionally used for organic electroluminescence light-emitting elements can be used. In the organic electroluminescence element 5, the light emitted from the organic light emitting layer 3 is extracted through the translucent substrate 1 formed of a translucent glass plate or plastic plate.

  In the embodiment of FIG. 1, a photocurable resin sealing layer 7 is formed so as to cover the laminate 6 composed of the organic light emitting layer 3 and the cathode layer 4. In addition, the laminated body 6 includes these layers, when a hole transport layer, a hole injection layer, an electron transport layer, and an electron injection layer are provided. The photocurable resin sealing layer 7 is formed so as to be in direct contact with the surface of the organic light emitting layer 3 or the cathode layer 4 and the outer peripheral portion of the photocurable resin sealing layer 7 is a laminate. The surface of the translucent substrate 1 is reached at a position that surrounds 6, and the entire outer surface of the laminate 6 is covered with the photocurable resin sealing layer 7. Here, the transparent conductive layer 2 is formed in a band shape on a part of the surface of the translucent substrate 1, and the outer peripheral portion of the photocurable resin sealing layer 7 is the upper surface of the transparent conductive layer 2, and It is made to adhere to the upper surface of the translucent base material 1 in which the transparent conductive layer 2 is not provided.

  The photocurable resin for forming the photocurable resin sealing layer 7 may be anything as long as it can be cured by irradiation with light such as UV without damaging the organic film such as the organic light emitting layer 3. Although not limited, for example, a photocationically polymerizable compound is suitable. The photocationically polymerizable compound may be a compound having at least one photocationically polymerizable functional group in the molecule, for example, at least one epoxy group, oxetane group, hydroxyl group, vinyl ether group in the molecule. A compound having a photocationically polymerizable functional group such as an episulfide group or an ethyleneimine group is preferred. For example, a photo-curing adhesive resin made of an epoxy resin, an acrylic resin, a silicone resin, or the like can be given. In particular, an epoxy resin-based photocurable resin which is excellent in moisture resistance and water resistance and has little shrinkage upon curing is preferable.

  Further, a moisture-proof layer 8 is disposed outside the photo-curable resin sealing layer 7, and the moisture-proof layer 8 is bonded to the light-transmitting substrate 1 with a thermosetting resin adhesive layer 9. As described above, the transparent conductive layer 2 is formed in a band shape on a part of the surface of the translucent substrate 1, and the thermosetting resin adhesive layer 9 includes the upper surface of the transparent conductive layer 2 and the transparent conductive layer. 2 is formed on the upper surface of the translucent substrate 1 where the moisture-proof layer 8 is not in contact with the transparent conductive layer 2. Further, a part of the anode 20 and cathode extraction electrode 21 formed of the transparent conductive layer 2 is not covered with the thermosetting resin adhesive layer 9, and a power source is connected to the exposed end of the anode 20 and cathode extraction electrode 21. I can do it. In the embodiment of FIG. 1, a thermosetting resin adhesive layer 9 is formed by applying an adhesive to the entire outer surface of the photocurable resin sealing layer 7 and thermosetting it, and this thermosetting resin adhesive layer 9. The moisture-proof layer 8 is stuck on the outer surface of the laminate.

  The moisture-proof layer 8 is not particularly limited as long as it has a high performance for blocking moisture such as moisture. For example, for the purpose of sealing in the field of organic electroluminescence elements. A commonly used recess that accommodates the laminate 6 by digging into one side of a glass plate or a recess that accommodates the laminate 6 is formed by pressing a metal plate such as SUS. A case-like thing such as a thing can be used.

  In the present invention, a sheet-like material can be used as the moisture-proof layer 8. By using a sheet-like material as the moisture-proof layer 8, the organic electroluminescence light-emitting device can be made thinner and lighter than the case-like material. As the sheet-shaped moisture-proof layer 8, for example, a metal foil or a laminated sheet can be used.

  As the metal foil, metal materials such as aluminum, copper, and nickel, and alloy materials such as stainless steel and aluminum alloy can be used, but they are flexible and excellent in terms of foil workability and cost. An electrolytic copper foil having a thermal expansion coefficient close to that of the translucent substrate 1 is most preferable.

  In addition, as a laminated sheet, at least one of an inorganic oxide composed of at least one of silicon oxide and aluminum oxide and an inorganic nitride composed of at least one of silicon nitride and aluminum nitride is deposited on a base film made of plastic. Thus, a laminated sheet obtained by laminating one or more layers, or a laminated sheet obtained by vapor-depositing a metal on a base film made of plastic can be used.

  As the adhesive for forming the thermosetting resin adhesive layer 9, a thermosetting adhesive resin, a two-component curable adhesive resin, or the like made of an epoxy resin, an acrylic resin, a silicone resin, or the like is used. be able to. In particular, it is preferable to use an epoxy thermosetting adhesive resin that is excellent in moisture resistance and water resistance and has little shrinkage during curing.

  The thermosetting resin adhesive layer 9 is formed by appropriately adopting a coating method or a printing method such as a roll coating method, a spin coating method, a spray coating method, or a screen printing method according to the type of the adhesive material. It is something that can be done. In order to remove moisture contained in the thermosetting resin adhesive layer 9, it is desirable to mix a desiccant such as barium oxide or calcium oxide.

  In the organic electroluminescence light-emitting device of FIG. 1 produced as described above, the organic light-emitting layer 3 of the organic electroluminescence element 5 is double-sealed with a photocurable resin sealing layer 7 and a moisture-proof layer 8. In addition, the moisture-proof layer 8 can be adhered to the translucent substrate 1 with high adhesiveness by the thermosetting resin adhesive layer 9, and has a high barrier property to moisture from the outside. It can obtain and can suppress degradation of the element performance of the organic electroluminescent element 5 over a long period of time.

  Moreover, the photocurable resin sealing layer 7 on the surface of the organic light emitting layer 3 or the cathode layer 4 is obtained by curing the photocurable resin applied on the surface of the organic light emitting layer 3 or the cathode layer 4 in a short time by light irradiation. Aluminum vapor deposition that forms the organic light emitting layer 3 and the cathode layer 4 under the influence of the flow of the resin melted by heating and the curing shrinkage of the resin as in the case of curing by heating. Etc. will not be destroyed. In adhering the moisture-proof layer 8 with the thermosetting resin adhesive layer 9, when the thermosetting resin adhesive is applied and thermoset, the organic light emitting layer 3 and the cathode layer 4 are the photocurable resin sealing layer 7. The organic light-emitting layer 3 and the cathode layer 4 can be prevented from being destroyed by the influence of curing the thermosetting resin adhesive layer 9. For this reason, the reliability of the element performance of the organic electroluminescent element 5 can be obtained highly.

  Here, in order to ensure electrical insulation between the moisture-proof layer 8 and the transparent conductive layer 2, it is desirable that the thermosetting resin adhesive layer 9 be mixed with an electrically insulating inorganic filler. The content of the inorganic filler varies depending on the type of the inorganic filler, but the inorganic filler is preferably set to a content of 15 parts by mass or more, that is, 15% by mass or more with respect to a total of 100 parts by mass of the adhesive and the inorganic filler. . In the case where the organic electroluminescence element 5 is a small element having an area of about 2 mm × 2 mm, it is possible to ensure insulation with 15% by mass of an insulating inorganic filler, but a large size exceeding 50 mm × 50 mm. In the element 5, good insulating properties can be secured by containing 50 mass% or more. Thus, if the content of the electrically insulating inorganic filler is less than 15% by mass, it is difficult to ensure sufficient electrical insulation, and the upper limit of the content of the inorganic filler is not particularly set, but is 95% by mass or less. It is preferable. If the adhesive contains more than 95% by mass of an electrically insulating inorganic filler, it is not preferable because the workability of coating deteriorates.

The electrically insulating inorganic filler has a resistance value larger than the resistance value of the resin component forming the thermosetting resin adhesive layer 9 and can improve the insulation between the moisture-proof layer 8 and the transparent conductive layer 2 If so, the material is not particularly limited. For example, inorganic fillers such as Al ₂ O ₃ , SiO ₂ , SiC, AlN, BN, MgO, or Si ₃ N ₄ may be used singly or in combination. Can be used in combination. In particular, since inorganic fillers made of Al ₂ O ₃ or SiO ₂ are easy to mix with the adhesive resin, when these are used, the insulating inorganic filler can be mixed with the adhesive resin at a high blending ratio, and high Electrical insulation can be obtained. In addition, when an inorganic filler made of Al ₂ O ₃ , SiC or AlN is used, the thermal conductivity is higher than that of other inorganic fillers, so that the thermosetting resin adhesive layer 9 having high thermal conductivity can be formed. The heat dissipation can be improved.

  Furthermore, the thermosetting resin adhesive layer 9 can contain a hygroscopic agent. In this way, by containing a hygroscopic agent in the adhesive layer 5, moisture that penetrates into the element can be easily and surely removed by absorbing moisture with the hygroscopic agent, and moisture acts on the organic light emitting layer 3. The generation of dark spots can be prevented, or the growth of the generated dark spots can be suppressed, and the effect of suppressing the deterioration of the organic light emitting layer 3 can be enhanced. When the moisture-absorbing agent is contained in the thermosetting resin adhesive layer 9, the content of the moisture-absorbing agent is not particularly limited, but the moisture-absorbing agent 5 with respect to 100 parts by mass of the total amount of the moisture-absorbing agent and the adhesive resin component. The range of -80 mass parts is preferable, More preferably, it is the range of 5-60 mass parts of hygroscopic agents, Most preferably, it is the range of 5-50 mass parts of hygroscopic agents.

  The hygroscopic agent is not particularly limited as long as it has at least a function of adsorbing moisture. In particular, a compound that chemically adsorbs moisture and maintains a solid state even when moisture is absorbed is preferable. Examples of such compounds include metal oxides, metal inorganic acid salts and organic acid salts, and alkaline earth metal oxides and sulfates are particularly preferable. Examples of the alkaline earth metal oxide include calcium oxide, barium oxide, magnesium oxide, and strontium oxide. Examples of the sulfate include lithium sulfate, sodium sulfate, gallium sulfate, titanium sulfate, and nickel sulfate. In addition, hygroscopic organic compounds such as silica gel and polyvinyl alcohol can also be used, but are not limited thereto. Among these, calcium oxide, barium oxide, silica gel and the like are particularly preferable.

  FIG. 2 shows another embodiment of the present invention, in which the hygroscopic agent-containing sealing layer 10 is coated and laminated on the entire outer surface of the photocurable resin sealing layer 7. And after apply | coating and forming this hygroscopic agent containing sealing layer 10, and applying and forming the thermosetting resin contact bonding layer 9 on this, and attaching the moisture-proof layer 8 with the thermosetting resin contact bonding layer 9, The hygroscopic agent-containing sealing layer 10 is covered with the moisture-proof layer 8. Other configurations are the same as those in FIG.

  By covering the entire outer surface of the photocurable resin sealing layer 7 with the hygroscopic agent-containing sealing layer 10 in this way, moisture entering the element is absorbed by the hygroscopic agent and easily and reliably removed. The generation of dark spots due to the action of moisture on the organic light emitting layer 3 can be prevented, or the growth of the generated dark spots can be suppressed, and the deterioration of the organic light emitting layer 3 can be suppressed. It is possible to obtain a high effect.

  The hygroscopic agent-containing sealing layer 10 can be formed by adding a hygroscopic agent to the base resin and applying the hygroscopic agent-containing base resin to the outer surface of the photocurable resin sealing layer 7. As the hygroscopic agent, those described above can be used. The content of the hygroscopic agent in the hygroscopic agent-containing layer 10 is not particularly limited, but the hygroscopic agent is 30 parts by mass or more, that is, 30 masses per 100 parts by mass of the total amount of the hygroscopic agent and the base resin component. It is preferable to set it to% or more. The upper limit of the content of the hygroscopic agent is not particularly set, but is preferably less than 95% by mass so as not to deteriorate the workability of coating.

  The base resin containing the hygroscopic agent is not particularly limited as long as it does not adversely affect the organic electroluminescence element 5, and is made of, for example, an acrylic resin, an epoxy resin, a silicon resin, or the like. A photocurable resin can be used. In particular, an epoxy resin-based photocurable resin which is excellent in moisture resistance and water resistance and has little shrinkage upon curing is preferable.

  The hygroscopic agent-containing sealing layer 10 can be formed by appropriately employing a coating method or a printing method such as a roll coating method, a spin coating method, a spray coating method, or a screen printing method according to the type of the base resin. Is.

  Here, if the organic electroluminescence element 5 is an element having a small area of about 2 mm × 2 mm, the entire surface of the photocurable resin sealing layer 7 is covered with a hygroscopic agent-containing sealing layer 10 as shown in FIG. Although it can be cured, when the organic electroluminescence element 5 is increased to an element size of about 50 mm × 50 mm, the entire surface of the photocurable resin sealing layer 7 is covered with the hygroscopic agent-containing sealing layer 10 and photocured. The element 5 is greatly warped, and if the element size is further increased, the element 5 may be cracked and destroyed. This is because internal stress is generated by the curing shrinkage of the hygroscopic agent-containing sealing layer 10, and the hygroscopic agent-containing sealing layer 10 has a high Young's modulus. As a countermeasure, the shrinkage is suppressed and the Young's modulus is lowered. It is preferable that a filler is mixed in the hygroscopic agent-containing sealing layer 10, and warpage and element destruction can be suppressed.

  When the size of the organic electroluminescence element 5 is further increased, a photocurable resin sealing layer is provided at a position surrounding the end face of the laminate 6 of the organic light emitting layer 3 and the cathode layer 4 as in the embodiment of FIG. It is effective to form the moisture-absorbing agent-containing sealing layer 10 only on the outer peripheral portion 7. The hygroscopic agent-containing sealing layer 10 includes an interface between the photocurable resin sealing layer 7 and the surfaces of the translucent substrate 1 and the transparent conductive layer 2, and the thermosetting resin adhesive layer 9 and the translucent group. It is formed in close contact with the surface of the translucent substrate 1 or the transparent conductive layer 2 so as to cover the interface between the material 1 and the surface of the transparent conductive layer 2. The main intrusion route of moisture from the outside is between the thermosetting resin adhesive layer 9 and the translucent substrate 1 and the transparent conductive layer 2, or between the photocurable resin sealing layer 7 and the translucent substrate 1 and Since it is an interface between the transparent conductive layers 2, by providing the hygroscopic agent-containing sealing layer 10 at these interface portions, the moisture that has entered before the moisture reaches the organic electroluminescent element 5 is absorbed by the hygroscopic agent. The inclusion sealing layer 10 can capture and remove moisture.

  FIG. 4 shows another embodiment of the present invention, in which a hygroscopic agent-containing sealing layer 10 is formed on the outer surface of the photocurable resin sealing layer 7, and the hygroscopic agent-containing sealing layer 10 is formed on the outer surface. After the moisture absorbent sheet 13 is pasted, the moisture absorbent sheet 13 is laminated between the photocurable resin sealing layer 7 and the moisture proof layer 8 by forming the thermosetting resin adhesive layer 9 and adhering the moisture proof layer 8. It is. By providing the moisture absorbing sheet 13 in this way, moisture entering the element can be absorbed by the moisture absorbing sheet 13 and easily and reliably removed, and moisture acts on the organic light emitting layer 3. The generation of dark spots can be prevented, or the growth of the generated dark spots can be suppressed, and the effect of suppressing deterioration of the organic light emitting layer 3 can be highly obtained. In this case, the hygroscopic sheet 13 may be laminated without providing the hygroscopic agent-containing sealing layer 10.

  The hygroscopic sheet 8 is not particularly limited, but a sheet formed by mixing the hygroscopic agent with a resin binder component and molding it into a sheet shape can be used. As the resin binder, a hygroscopic agent that can be contained in the form of a powder, that does not interfere with the moisture removing action of the hygroscopic agent, and is made of a polymer material having gas permeability is suitable. Examples of such a polymer include, but are not limited to, fluorine-based, polyolefin-based, polyacrylic-based, polyacrylonitrile-based, polyamide-based, polyester-based, epoxy-based, and polycarbonate-based polymers. It is not a thing.

  The embodiment of FIG. 5 shows an example in which a bendable sheet material such as a metal foil is used as the moisture-proof layer 8, and the outer surface of the photocurable resin sealing layer 7 as in the embodiment of FIG. The light-absorbing agent-containing sealing layer 10 is further formed on the outer surface of the photocurable resin sealing layer 7 and the moisture-absorbing agent-containing sealing layer 10, the surface of the transparent conductive layer 2 and the transparent conductive layer 2 are not provided. The thermosetting resin adhesive layer 9 is formed on the surface of the curable substrate 1, and the moisture-proof layer 8 is adhered by the thermosetting resin adhesive layer 9. Then, the entire surface of the moisture-proof layer 8 is applied to the thermosetting resin adhesive layer 9 in a state where the peripheral end portion of the moisture-proof layer 8 formed of a flexible sheet material is squeezed and bent toward the translucent substrate 1. It is designed to be adhered. In this way, the organic light emitting layer 3 and the light transmissive substrate are bonded to the thermosetting resin adhesive layer 9 with the end of the moisture proof layer 8 bent toward the light transmissive substrate 1 side. 1 can be completely covered, and the gap between the moisture-proof layer 8 and the translucent substrate 1 can be reduced, so that moisture and oxygen from the outside can be effectively blocked and organic. The deterioration of the light emitting layer 3 can be further suppressed.

  In the embodiment of FIG. 5, the end of the moisture-proof layer 8 in the embodiment of FIG. 3 is bonded to the thermosetting resin adhesive layer 9 in a state where the end of the moisture-proof layer 8 is bent toward the translucent substrate 1. 1, FIG. 2, FIG. 4, and FIG. 6 described later, similarly, bonding is performed in a state where the end of the moisture-proof layer 8 is bent toward the translucent substrate 1. It goes without saying that it may be possible to do so.

  In the embodiment of FIG. 6, a coating layer 22 is formed on the outer surface of the moisture-proof layer 8 to display the product name of the organic electroluminescence light-emitting device. Other configurations are the same as those in FIG. As the paint or ink for forming the coating layer 22, an arbitrary one can be selected in consideration of adhesion to the moisture-proof layer 8, corrosion resistance, heat dissipation, and the like. Needless to say, the coating layer 22 may be formed on the moisture-proof layer 8 in each of the embodiments shown in FIGS. 1, 2, 4, and 5.

  FIG. 7 shows an example of an embodiment of an organic electroluminescence lighting device B according to the present invention. This organic electroluminescence light-emitting device A formed as in each of the above embodiments is used, and this organic electroluminescence device A is used. A heat absorber 11 that absorbs heat is provided on the outer surface of the moisture-proof layer 8 of the luminescence light emitting device A, and a heat radiator 12 that dissipates the heat absorbed by the heat absorber 11 is provided on the outer surface of the heat absorber 11. The heat absorber 11 is preferably one having high thermal conductivity and high adhesion to the moisture-proof layer 8, and is not particularly limited, but silicon sheet, silicon grease, carbon graphite sheet and the like can be used. Further, as the heat radiating body 12, a heat radiating plate 24 with fins 23 using an alloy of aluminum or copper, a metal plate whose surface is coated with a paint having a high thermal emissivity, and the like can be used, but are not limited thereto. It is not a thing.

  Thus, by forming the organic electroluminescent lighting device B including the heat absorbing body 11 and the heat radiating body 12, the heat generated by the organic electroluminescent light emitting device A is absorbed by the heat absorbing body 11 and radiated by the heat radiating body 12. It is possible to suppress deterioration due to heat even if the organic electroluminescence light emitting device A emits light with a large area and high illuminance, and the organic electroluminescence lighting device B can be formed with a long lifetime. It can be done.

  In the embodiment of FIG. 7, the organic electroluminescence light-emitting device B is formed using the organic electroluminescence light-emitting device A of the embodiment of FIG. 3, but the organic electroluminescence light emission of other embodiments is formed. It goes without saying that the organic electroluminescence lighting device B can be similarly formed using the device A.

  Next, the present invention will be specifically described with reference to examples.

(Example 1)
An ITO (indium-tin oxide) film having a thickness of 150 nm is formed by sputtering on a light-transmitting substrate 1 made of a glass substrate of 50 mm × 50 mm × thickness 0.7 mm, and then photolithography and wet etching. The ITO film was patterned by the method to form the transparent conductive layer 2. At this time, as shown in FIG. 8, the transparent conductive layer 2 was patterned so that the anode layer 20 and the cathode extraction electrode 21 were formed. The translucent substrate 1 on which the transparent conductive layer 2 was formed was subjected to ultrasonic cleaning with pure water and isopropyl alcohol for 15 minutes, dried, and further UV ozone cleaned.

Then, set the translucent substrate 1 formed with the transparent conductive layer 2 in a vacuum deposition apparatus, at a reduced pressure of 1 × ¹⁰ -5 Pa, on the anode 20, 4,4'-bis [N -(Naphthyl) -N-phenyl-amino] biphenyl (α-NPD) was deposited to a thickness of 400 mm at a deposition rate of 1 to 2 mm / s, and the hole transport layer was formed into a tris (8-hydroxyquinolinato) aluminum complex. (Alq3) was deposited to a thickness of 400 で at a deposition rate of 1 to 2 １〜 / s to form a layer that also serves as the organic light emitting layer 3 and the electron transport layer in this order. Thereafter, LiF is deposited to a thickness of 5 mm at a deposition rate of 0.5 to 1.0 mm, and further Al is deposited to a thickness of 1000 mm at a deposition rate of 5 mm / s, whereby the organic light emitting layer 3 is formed as shown in FIG. The cathode layer 4 was formed on the cathode take-out electrode 21 from above, and the organic electroluminescence element 5 was produced.

  Then, the organic electroluminescence element 5 is transferred to a nitrogen circulation type glove box having a dew point of −70 ° C., and a UV curable epoxy resin sealant (manufactured by Matsushita Electric Works Co., Ltd.) is applied on the organic light emitting layer 3 and the cathode layer 4. Then, the photocurable resin sealing layer 7 was formed by UV curing and photocuring.

  On the other hand, as a moisture-proof layer 8, a sealing plate formed by digging by blasting at a depth of 0.5 mm on one side of a glass plate 26 of 36 mm × 46 mm × thickness 1.1 mm leaving a periphery of 3 mm. A stop cap 28 was used. Then, a thermosetting epoxy resin (manufactured by Matsushita Electric Works Co., Ltd.) is applied to a 3 mm wide portion around the sealing cap 28 with a dispenser, and the sealing cap 28 is placed on the organic electroluminescence element 5 and fixed with a jig. Removed from the box. Thereafter, the thermosetting epoxy resin is cured by heating, and the sealing cap 23 is bonded and fixed to the translucent substrate 1 with the thermosetting resin adhesive layer 9, whereby organic electroluminescence emission as shown in FIG. 8 is performed. Got the device.

(Example 2)
A 10 mm × 10 mm hygroscopic sheet 13 made by Dynic was used in the concave portion 27 of the sealing cap 23, and thereafter, the organic electroluminescence light emitting device as shown in FIG. 9 was obtained in the same manner as in Example 1.

(Comparative Example 1)
In Example 1, an organic electroluminescence light emitting device as shown in FIG. 10 was obtained in the same manner as in Example 1 except that the photocurable resin sealing layer 7 was not formed.

(Comparative Example 2)
A 10 mm × 10 mm hygroscopic sheet 13 made by Dynic Co. was used in the concave portion 27 of the sealing cap 23. After that, in Example 1, except that the photocurable resin sealing layer 7 was not formed, it was carried out. In the same manner as in Example 1, an organic electroluminescence light emitting device as shown in FIG. 11 was obtained.

  The organic electroluminescence light emitting devices of Example 1 and Comparative Example 1 produced as described above were left in a constant temperature and humidity chamber at 50 ° C. and 90% RH for 300 hours. The organic electroluminescence light emitting devices of Example 2 and Comparative Example 2 were left in a constant temperature and humidity chamber at 50 ° C. and 90% RH for 2400 hours. And the light emission state of the organic electroluminescent light-emitting device for every progress of predetermined time was observed, and the increment of the non-light-emitting part of the organic light emitting layer 3 was dimension-measured with the microscope. The transition of the increment is shown in FIGS.

  As shown in FIG. 12, in Example 1, the increment of the non-light-emitting portion of the organic light emitting layer 3 is smaller than that in Comparative Example 1, and as shown in FIG. In addition, the increment of the non-light emitting portion of the organic light emitting layer 3 is smaller, and it is confirmed that Examples 1 and 2 have high moisture blocking performance from the outside and can suppress deterioration of device performance.

It is sectional drawing which shows an example of embodiment of the organic electroluminescent light-emitting device concerning this invention. It is sectional drawing which shows another example of embodiment of the organic electroluminescent light-emitting device concerning this invention. It is sectional drawing which shows another example of embodiment of the organic electroluminescent light-emitting device concerning this invention. It is sectional drawing which shows another example of embodiment of the organic electroluminescent light-emitting device concerning this invention. It is sectional drawing which shows another example of embodiment of the organic electroluminescent light-emitting device concerning this invention. It is sectional drawing which shows another example of embodiment of the organic electroluminescent light-emitting device concerning this invention. It is sectional drawing which shows an example of embodiment of the organic electroluminescent illuminating device which concerns on this invention. 1 is a cross-sectional view of an organic electroluminescence light emitting device produced in Example 1. FIG. 3 is a cross-sectional view of an organic electroluminescence light emitting device produced in Example 2. FIG. 6 is a cross-sectional view of an organic electroluminescence light emitting device produced in Comparative Example 1. FIG. 6 is a cross-sectional view of an organic electroluminescence light emitting device produced in Comparative Example 2. FIG. It is a graph which shows transition of the increment of a non-light-emission part in the humidity resistance test of the organic electroluminescent light-emitting device produced in Example 1 and Comparative Example 1. It is a graph which shows transition of the increment of a non-light-emission part in the humidity resistance test of the organic electroluminescent light-emitting device produced in Example 2 and Comparative Example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Translucent base material 2 Transparent conductive layer 3 Organic light emitting layer 4 Cathode layer 5 Organic electroluminescent element 6 Laminate 7 Photocurable resin sealing layer 8 Moisture proof layer 9 Thermosetting resin adhesive layer 10 Hygroscopic agent containing sealing layer 11 Heat absorber 12 Heat radiator 13 Hygroscopic sheet

Claims (11)

  An organic electroluminescence element formed by laminating a light-transmitting substrate, a transparent conductive layer, an organic light emitting layer, and a cathode layer in this order, and a laminate in which the organic light emitting layer and the cathode layer are laminated and covering the periphery of the laminate A photocurable resin sealing layer formed in direct contact with the surface of the laminate so as to reach the surface of the translucent substrate, a moisture-proof layer provided outside the photocurable resin sealing layer, and the above An organic electroluminescence light-emitting device comprising a moisture-proof layer and a thermosetting resin adhesive layer for adhering a moisture-proof layer to a transparent substrate and a transparent conductive layer at a position surrounding the laminate.   It comprises a hygroscopic agent-containing sealing layer formed so as to cover the entire surface of the photocurable resin sealing layer, and the moisture-proof layer is formed so as to cover the hygroscopic agent-containing sealing layer. The organic electroluminescence light-emitting device according to claim 1.   A moisture-absorbing agent-containing sealing layer formed so as to cover the outer peripheral portion of the photocurable resin sealing layer at a position surrounding the periphery of the laminate, and the moisture-proof agent so as to cover the moisture-absorbing agent-containing sealing layer The organic electroluminescence light-emitting device according to claim 1, wherein a layer is formed.   The organic electroluminescence light-emitting device according to claim 2, wherein the hygroscopic agent-containing sealing layer comprises a photocurable resin as a base resin.   The organic electroluminescence light-emitting device according to any one of claims 1 to 4, further comprising a moisture-absorbing sheet laminated between the photo-curable resin sealing layer and the moisture-proof layer.   The organic electroluminescence light-emitting device according to any one of claims 1 to 5, wherein the thermosetting resin adhesive layer contains 15% by mass or more of an electrically insulating inorganic filler.   The moisture-proof layer is a metal film, a base film made of plastic, at least one of at least one inorganic oxide selected from silicon oxide and aluminum oxide, and at least one inorganic nitride selected from silicon nitride and aluminum nitride. The organic electro of any one of claims 1 to 6, which is selected from a laminated sheet obtained by laminating one or more layers, and a laminated sheet obtained by depositing a metal on a plastic base film. Luminescence light emitting device.   The organic electroluminescence light-emitting device according to claim 1, wherein the thermosetting resin adhesive layer contains a hygroscopic agent.   The organic electroluminescence light-emitting device according to any one of claims 2 to 8, wherein the hygroscopic agent is at least one selected from calcium, barium, oxides thereof, and silica gel.   10. The organic material according to claim 1, wherein the moisture-proof layer is bonded to a light-transmitting substrate by bending an end portion so as to cover the periphery of the laminate. Electroluminescence light emitting device.   The organic electroluminescence light emitting device according to any one of claims 1 to 10, a heat absorber that absorbs heat generated by the organic electroluminescence light emitting device, and a heat radiator that dissipates heat absorbed by the heat absorber to the outside. An organic electroluminescent lighting device comprising:

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