JP5348869B2 - Hot melt type member for organic electronic device, barrier film sealing member, organic electronic device sealing panel using them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin type organic electronic device sealing panel especially capable of maintaining stable device characteristics free from adverse effects of moisture and oxygen for a long period of time, as well as an organic electronic device sealing panel responding to request for a larger area in addition to thinning. <P>SOLUTION: The organic electronic device sealing panel, which includes (1) a substrate, (2) an organic electronic device formed on the substrate, and (3) a barrier film for sealing the organic electronic device, has a hot melt type member for an organic electronic device including a moisture scavenger and wax arranged between the organic electronic device and the barrier film. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a hot-melt type member for organic electronic devices, a barrier film sealing member, and an organic electronic device sealing panel using them. In particular, the present invention relates to a sealing member for an organic electronic device and an organic electronic device sealing panel using the same, and in particular, a thin organic electronic device sealing capable of maintaining stable device characteristics without being affected by moisture and oxygen over a long period of time. This is related to an improved technology that enables mass production of stop panels with high reliability.

  As organic electronic devices, for example, organic EL elements, organic solar cells, organic semiconductors, and the like are known. Such an organic electronic device is vulnerable to moisture, oxygen, heat, and organic gas, and thus it is necessary to protect the organic electronic device from these.

  For example, an organic EL element is configured by forming an ITO (Indium Tin Oxide) transparent electrode (anode), an organic film (organic hole transport layer, organic light emitting layer, etc.), and a metal electrode (cathode) on a glass substrate. Yes. In such an organic EL element, it is known that an organic film or a metal electrode is weak against moisture, oxygen, heat, or an organic gas generated from a constituent member (hereinafter also referred to as “outgas”). Therefore, in order to extend the life of the organic EL element, the organic EL element is placed in an atmosphere that excludes moisture and oxygen, the outgas from the constituent members is reduced as much as possible, or the heat generated when the organic EL element emits light. Attempts have been made to prevent deterioration by adopting a structure that can efficiently escape.

  Specifically, an organic EL element (anode 2, organic layer 3, cathode 4) is laminated on a substrate 1 such as glass as shown in FIG. The sealing cap 5 is put on and bonded to the substrate 1 with a sealing agent 6 and sealed, and the organic EL element is sealed in a sealed container constituted by the substrate 1 and the sealing cap 5. And in the sealed container, a method of enclosing barium oxide (BaO), calcium oxide (CaO) for capturing moisture or a sheet-like moisture scavenger 7 using these is adopted.

As an organic EL display panel using such a moisture scavenger, for example, a transparent electrode formed of a transparent electrode material on a transparent substrate surface, a light emitting layer made of an EL material laminated on the transparent electrode, A back electrode laminated on the light emitting layer and formed to face the transparent electrode, a water repellent film covering the entire surface of the light emitting layer and the back electrode, and an insulating property for sealing the light emitting layer together with the water repellent film An organic EL element characterized by comprising a protective member is known (Patent Document 1).
JP 2000-68047 A

  In the organic EL display panel shown in FIG. 1, the sealing cap 5 for sealing the organic EL element on the substrate 1 is generally made of glass. When glass is used as the sealing cap 5, since the glass is thick, the thickness of the entire panel is about 2 mm, and it is difficult to make use of the thin characteristics (about 200 nm) of the organic EL element. This is because sealing is performed using cavity glass provided with counterbore (concave portions) in order to prevent the glass from coming into direct contact with the organic EL element.

  Moreover, since the cavity glass provided with counterbore is used, there is a problem that a hollow portion exists in the sealing structure and the physical strength of the entire panel is insufficient. Therefore, it is difficult to produce a large area cavity glass, and accordingly, it is difficult to easily produce a large area organic EL display panel. Moreover, when sealing an organic EL element using a flat glass plate, it is necessary to seal under vacuum so as not to trap air, and there is a problem that a manufacturing apparatus becomes large. On the other hand, a technique has been reported in which an inorganic thin film is directly deposited on an organic electronic device by a method such as vapor deposition, sputtering, or CVD without using a cavity glass or a flat glass plate. However, there is a problem that mass production is difficult. Such a problem is not limited to organic EL elements, but is common to organic solar cells and organic semiconductors having a similar sealing structure.

  Accordingly, the main object of the present invention is to overcome the above-described problems, and in particular, a thin organic electronic device sealing panel that can maintain stable device characteristics without being affected by moisture and oxygen over a long period of time. Is to provide. It is another object of the present invention to provide an organic electronic device sealing panel that meets the demand for a large area in addition to thinning.

  As a result of repeated studies in view of the problems of the prior art, the present inventor has found that a specific member can achieve the above object, and has completed the present invention.

That is, this invention relates to the following hot-melt-type member for organic electronic devices, a barrier film sealing member, and an organic electronic device sealing panel using them.
1. Including a moisture scavenger and wax,
In sealed organic electronic device with a barrier film, the barrier film and are found using between the organic electronic device,
The moisture scavenger includes an organometallic compound,
A hot-melt member for an organic electronic device , wherein the wax content is 1 to 8% by weight .
2. Item 2. The hot melt type member according to Item 1, wherein the moisture scavenger further contains a powdered inorganic oxide having an average particle size of 90 µm or less.
3. Item 3. The hot melt type member according to Item 1 or 2, wherein a moisture scavenger is contained in the hot melt type member in an amount of 50 to 99% by weight.
4 . Item 4. The hot melt member according to any one of Items 1 to 3 , wherein the weight loss after drying under reduced pressure at 150 ° C for 4 hours under vacuum is 0.1% or less.
5 . Item 5. The hot-melt member according to any one of Items 1 to 4 , wherein the hot-melt member is a thin film having a thickness of 100 µm or less.
6 . Item 6. The hot-melt member according to any one of Items 1 to 5 , wherein the organic electronic device is an organic EL element, an organic solar cell, or an organic semiconductor.
7 . Barrier film sealing member obtained by laminating a hot melt-type member according to any one of items 1 to 6 on the barrier film.
8 . 1) a substrate, 2) an organic electronic device formed on the substrate, and 3) an organic electronic device sealing panel comprising a barrier film for sealing the organic electronic device,
The organic electronic device sealing panel in which the hot melt type member according to any one of Items 1 to 6 is disposed between the organic electronic device and the barrier film.
9 . Item 9. The organic electronic device sealing panel according to Item 8 , wherein the entire space between the organic electronic device and the barrier film is occupied by the hot melt type member.
10 . Item 10. The organic electronic device sealing panel according to Item 8 or 9 , wherein the substrate is a transparent film.

  Since the hot-melt type member of the present invention has hot-melt properties, it can be arranged with an arbitrary thickness and pattern on a barrier film for sealing an organic electronic device or an organic electronic device. Then, by bonding the barrier film and the organic electronic device through the hot melt type member, a hot melt type member layer containing a water-capturing agent having no space and in close contact with the organic electronic device can be formed. Since generation of outgas can also be suppressed, an organic electronic device sealing panel (for example, an organic EL display panel) that can maintain stable device characteristics without being affected by moisture, oxygen, and outgas for a long period of time can be provided.

  In particular, unlike the case where the organic moisture scavenger is used alone, the hot melt type member of the present invention can alleviate or eliminate problems such as bending and cracking due to moisture absorption. In this respect as well, it is possible to contribute to long-term stability of device characteristics.

  As a preferred form, powdered inorganic oxides or organometallic compounds (including organometallic complexes, such as BaO and CaO) having a small particle size, or a sheet-like (thin film) hot-melt type using these. By using the member, it is not necessary to use a thick sealing cap (sealing housing) 5 having a recess, and the organic electronic device can be sealed with a flat thin plate-like barrier film. Thereby, the request | requirement of thickness reduction of an organic electronic device sealing panel can be responded. Also, by preparing a barrier film sealing member obtained by laminating a hot melt type member on the barrier film in advance and sealing it on the organic electronic device by tangential bonding, air can be removed in the atmosphere without employing vacuum conditions. Sealing can be performed while sufficiently suppressing the holding-in.

  Further, as a more preferable form, the mechanical strength of the organic electronic device sealing panel can be increased by arranging the hot melt type member of the preferred form of the present invention between the organic electronic device and the barrier film without any gap, and the size of the panel is increased. Can be handled without problems.

  Moreover, as a more preferable embodiment, when a transparent film is used as the substrate, flexibility can be imparted to the organic electronic device sealing panel, and thus a more flexible organic electronic device sealing panel can be provided.

  Hereinafter, the present invention will be specifically described. In addition, as an organic electronic device, an organic EL element is illustrated and demonstrated.

1. Hot Melt Type Member The hot melt type member of the present invention is characterized by containing a moisture scavenger (hereinafter also referred to as “moisture getter agent”) and wax.
(Moisture scavenger)
The moisture trapping agent may be either an inorganic moisture trapping agent or an organic moisture trapping agent as long as it is known as a so-called moisture trapping agent, and is not particularly limited. For example, in addition to powdered inorganic oxides such as barium oxide (BaO), calcium oxide (CaO), and strontium oxide (SrO), organometallic compounds known as transparent moisture getter agents can be used. These moisture scavengers can be used alone or in combination of two or more. A commercial item can also be used for these moisture scavengers.

  In addition, when using a powder-form moisture scavenger as in the case of the powdered inorganic oxide, the average particle diameter may be usually within a range of less than 100 μm, preferably 90 μm or less, more preferably 50 μm or less, Preferably, it may be 0.01 μm or more and 10 μm or less. If the average particle size is less than 100 μm, the possibility of damaging the organic electronic device is reduced. When the particle diameter is less than 0.01 μm, the particles are likely to be scattered and the particle production cost may be increased.

  Among these moisture scavengers, in the present invention, it is desirable to use 1) an organometallic compound and / or 2) a powdered inorganic oxide having an average particle size of 90 μm or less. In particular, from the viewpoint of mixing with a wax and adhesion to an organic electronic device, an organometallic compound that dissolves in the same solvent as the wax is preferable as a moisture scavenger. Further, when the organic electronic device is an organic EL element and the hot melt type member of the present invention is used for an organic EL display panel or the like such as a top emission method that takes out light emitted from the organic EL light emitting layer also from the cathode, It is preferable to use a transparent moisture scavenger, and examples include organic metal compounds in addition to fine powder having a particle size of 100 nm or less. Examples of the organometallic compound include organometallic compounds described in JP-A-2005-298598.

The content of the water scavenger can be appropriately set according to the type of the water scavenger to be used, etc., but is usually about 50 to 99% by weight, particularly 80 to 99% by weight in the hot melt type member of the present invention. preferable. If the content of the water scavenger is less than 50% by weight, the water scavenging performance may be insufficient. If it exceeds 99% by weight, the adhesiveness / adhesiveness of the hot-melt type member to the organic electronic device may be reduced. There is a possibility that the retention of the moisture scavenger may be lowered.
(wax)
The wax is not limited as long as it can impart a hot melt function to the hot melt type member of the present invention, and can be appropriately selected from known or commercially available waxes. For example, paraffin wax, microcrystalline wax or the like can be used. These may be used alone or in combination of two or more. These waxes preferably have a melting point of 60 to 100 ° C. from the standpoint of the production process and the like. If the melting point of the wax is lower than 60 ° C, the organic substance (organic electronic device) may be dissolved and swelled. If the melting point exceeds 100 ° C, heat of 100 ° C or higher is required to soften or melt the hot-melt type member. Therefore, there is a possibility that heat of 100 ° C. or more is applied to the organic matter (organic electronic device), and the organic matter may be deteriorated.

  Further, in the present invention, it is particularly preferable to use microcrystalline wax because it is possible to prevent the generation of outgas that adversely affects the organic electronic device and to have excellent adhesion to substrates such as glass substrates, barrier films, and organic electronic devices. .

  The content of the wax can be appropriately set according to the type of wax to be used and the like, but is usually about 1 to 50% by weight, particularly preferably 1 to 10% by weight in the hot melt type member of the present invention. When the content of the wax exceeds 50% by weight, the moisture trapping property may be insufficient. Moreover, when it is less than 1% by weight, there is a risk that the effect of suppressing cracks with time due to moisture trapping when using an organic metal compound as a moisture trapping agent may deteriorate. is there. From the viewpoint of making a transparent hot melt type member, the blending amount of the wax in the hot melt type member is preferably 10% by weight or less.

When the organic electronic device is an organic EL element and the hot melt type member of the present invention is used for a top emission type organic EL display panel that takes out light emitted from the organic EL light emitting layer from the cathode, etc., It is preferable to use a transparent wax. In addition, the blending amount of the wax in the hot melt type member or the thickness of the layer obtained using the hot melt type member may be reduced. Examples include changing the type of wax contained in the hot melt type member, and changing the type and blending amount of the moisture scavenger. In addition, a transparent barrier film or a combination thereof can be applied to a top emission method in which light emitted from the organic EL light emitting layer is also taken out from the cathode.
(Hot melt type member)
The hot-melt type member of the present invention may be a two-component system of the above-described moisture scavenger and wax, but may contain various additives as necessary as other components.

  The shape of the hot melt type member of the present invention is not limited, and the shape can be adopted according to a desired application. For example, any of a thin film shape, a plate shape, an indefinite shape, and the like may be used. In particular, in the present invention, it is preferably used as a thin film. Although the thickness in this case is not limited, it is generally preferably 100 μm or less, particularly about 5 to 50 μm.

  The hot melt type member of the present invention is usually used as a member for an organic electronic device after drying (solvent dilution type) or after cooling (solvent-free type). For example, an organic electronic device, a barrier film, What is necessary is just to use it in a viscous state at the time of use, such as a lamination | stacking operation | work on a releasable base material. That is, it can be used by being softened or melted by heating at the time of use, or dissolved in an organic solvent. For this reason, since the hot-melt type member of the present invention can be adhered and laminated on an organic electronic device, a barrier film, etc., the moisture scavenger is adhered to the organic electronic device and the The organic electronic device can be protected from moisture, outgas, etc. contained in the electronic device. When the organic electronic device is driven (for example, when the organic EL element is caused to emit light), the hot melt type member may be in a liquid state.

  When it is softened or melted by heating at the time of use and is adhered or coated, it is heated until it is softened or melted, and a hot melt type member is adhered or coated on a substrate (organic electronic device laminated surface), a barrier film, etc. It is possible to form the member in a desired shape such as a shape. Further, in the case of the thin film hot melt type member as described above, if a part is softened or melted, it can be adhered (fused) to a substrate or the like.

  For example, when a thin film is formed by coating (coating), for example, the method of softening or melting by heating can be used to efficiently obtain the thin film by heating the coating head to about 70 to 80 ° C. In addition, since the drying time after coating can be shortened, productivity can be further increased, and the risk of outgas generation is also reduced.

From the viewpoint of suppressing the generation of outgas, it is further preferable to soften and melt the following solvent-free hot-melt type member by heating, and to perform a laminating operation on an organic electronic device or a barrier film.
(Transfer film)
In particular, in the present invention, a laminate of a hot-melt member on a thin film on a releasable substrate (release film) is preferable because it can be used as a transfer film. That is, when used as a transfer film, when producing an organic electronic device sealing panel, stock it as a transfer film, take out the transfer film when necessary, and release the hot-melt type member on the releasable substrate. The member can be easily attached to an organic electronic device such as an organic EL element by transferring from the moldable substrate to the organic electronic device such as an organic EL element.

  The thickness of the hot-melt member on the release film is preferably 100 μm or less, particularly about 5 to 50 μm.

As the releasable substrate, a known or commercially available substrate can be used, but preferably, an alkyd type release agent is applied on a resin film. Further, the hot melt type member on the release film may be transferred from the release base material to the barrier film and used.
The transfer film is produced by applying a liquid hot-melt type member dissolved by heating or using an organic solvent on the releasable substrate, and volatilizing the organic solvent by cooling or heating, thereby releasing the releasable substrate. A thin film hot melt type member can be laminated thereon.

  When storing the transfer film in roll form, a cover film may be laminated on the hot melt mold member on the release film so that the hot melt mold member does not stick to the back surface of the release film. Good. As the cover film, a film made of polyethylene, polypropylene, polycarbonate, polyester, or the like can be used. More preferably, the surface of the cover film that is in contact with the hot melt type member has a slight adhesiveness. Specifically, using adhesive films or adhesives with little adhesive residue will prevent misalignment when the transfer film and cover film are bonded, and transfer films during storage and transportation From the viewpoint of preventing the displacement of the cover film.

  The transfer film and the cover film may be bonded by tangential bonding in which the film is bonded in the tangential direction while being pressed with a rubber roll or the like. By performing tangential bonding, it is possible to bond the two while suppressing air entrapment at the bonded portion.

  The transfer film has a three-layer structure of a release sheet, a hot melt type member, and a cover film, and is preferably wound into a roll and stored, transported, or the like.

  In addition, when storing and / or transporting a transfer film (regardless of the presence or absence of a cover film) from the atmosphere such as a glove box substituted with nitrogen gas to the atmosphere, the transfer film has a gas barrier property. It is preferable that it is hermetically sealed and packaged, and for example, hermetically packaged in a nitrogen-substituted bag made of an aluminum foil film (a laminate of an aluminum foil and a polyester film) is preferable. Lamination of the hot melt type member on the releasable substrate, lamination of the cover film, and hermetic packaging are preferably performed in a nitrogen gas atmosphere or a vacuum in which moisture and oxygen are not present.

When transferring a hot melt type member to a barrier film, an organic electronic device or the like, the transfer sheet wrapped in a glove box substituted with nitrogen gas is put again, opened, and a transfer operation is performed.
(Barrier film sealing member)
In the present invention, in addition to using a hot melt type member as the transfer film, it can also be used as a barrier film sealing member in which a hot melt type member is laminated on a barrier film for sealing an organic electronic device. That is, if used as a barrier film sealing member, when producing an organic electronic device sealing panel, it is stocked as a barrier film sealing member, and when necessary, the barrier film sealing member is taken out to obtain a hot melt type member. By sticking the side to the organic electronic device side such as an organic EL element, an organic electronic device sealing panel can be easily produced.

  The manufacturing method of the barrier film sealing member is a method of applying a liquid hot melt type member dissolved by heating or using an organic solvent on the barrier film, and volatilizing the organic solvent by cooling or heating, thereby forming a thin film on the barrier film. Can be laminated.

  When storing the barrier film sealing member in a roll shape, a cover film is further provided on the hot melt type member on the barrier film so that the hot melt type member does not stick to the back surface of the barrier film sealing member. You may laminate. As the cover film, a film made of polyethylene, polypropylene, polycarbonate, polyester, or the like can be used. More preferably, the surface of the cover film that is in contact with the hot melt type member has a slight adhesiveness. Specifically, using a film with adhesive or a pressure-sensitive adhesive with a small amount of adhesive residue prevents misalignment when the barrier film sealing member and the cover film are bonded, and is being stored or transported. From the viewpoint of preventing the deviation of the barrier film sealing member and the cover film.

  Bonding of the barrier film sealing member and the cover film may be performed by tangential bonding in which the film is bonded in the tangential direction while being pressed with a rubber roll or the like. By performing tangential bonding, it is possible to bond the two while suppressing air entrapment at the bonded portion.

  The barrier film sealing member may have a three-layer structure of a barrier film, a hot melt type member, and a cover film, and may be wound, stored, transported, etc. in a roll shape.

  Also, when storing and / or transporting a barrier film sealing member (regardless of the presence or absence of a cover film) from the atmosphere such as a glove box substituted with nitrogen gas to the atmosphere, seal the barrier film. The stopper member is preferably sealed and packaged with a high gas barrier property. For example, the stopper member is preferably sealed and packaged in a nitrogen-substituted bag made of an aluminum foil film (a laminate of an aluminum foil and a polyester film). Lamination and hermetic packaging of the cover film may be performed in a nitrogen gas atmosphere or a vacuum in which moisture and oxygen are not present.

When affixing the hot-melt type member side to an organic electronic device or the like, put the packaged barrier film sealing member in the glove box replaced with nitrogen gas again, open it, peel off the cover film, and apply it. To do.
(Method for producing hot melt type member)
In the method for producing a hot melt type member of the present invention, a water scavenger, wax, and other additives may be mixed uniformly as required. As a mixing method, it is possible to add and mix an organic solvent such as heptane or triethanolamine, or to heat and melt the wax without using the organic solvent to mix. From the viewpoint of mixing, it is preferable to mix using a solvent that dissolves both the moisture scavenger and the wax.

  As a mixer, a stirrer, a kneader, etc. can be implemented using a well-known mixing apparatus or kneading apparatus, for example. After mixing each component uniformly, it can shape | mold into a desired shape as needed.

  It is desirable to remove the solvent component by heating and drying the hot melt type member of the present invention after mixing. The degree of removal is preferably set to a level at which the weight loss after drying the above member under reduced pressure at 150 ° C. for 4 hours is 0.1% or less. That is, a hot-melt type member having a weight loss of 0.1% or less after drying under reduced pressure at 150 ° C. for 4 hours under vacuum is more preferable as the hot-melt type member (solvent-free hot-melt type member) of the present invention. When the weight loss after drying under reduced pressure exceeds 0.1%, when used in an organic electronic device sealing panel, outgas is generated, and the organic electronic device may be deteriorated.

  The hot melt type member of the present invention can be suitably used particularly for an organic electronic device. More specifically, the hot melt type member is used between a barrier film of an organic electronic device sealed with a barrier film and the organic electronic device. The hot melt type member of the present invention is a mixture of a so-called moisture scavenger and wax, and can be used as a sealing material for sealing an organic electronic device with a barrier film. It can also be used as an adhesive material for fixing to an electronic device. Moreover, it functions also as a water | moisture-content trapping agent which adsorb | sucks the water | moisture content which penetrate | invaded the sealing body obtained by sealing, the water | moisture content contained in an organic electronic device, etc. The hot melt type member of the present invention is a multifunctional material having both of these functions.

2. TECHNICAL FIELD The present invention is an organic electronic device sealing panel including 1) a substrate, 2) an organic electronic device formed on the substrate, and 3) a barrier film for sealing the organic electronic device. The organic electronic device sealing panel in which the hot-melt type member of the present invention is disposed between the organic electronic device and the barrier film is included.

  In the present invention, the substrate means a substrate such as a glass plate or a transparent film for forming an organic electronic device. In the present invention, since the organic electronic device is sealed with a flexible barrier film, the entire organic electronic device sealing panel is made flexible by using a flexible transparent film as a substrate. be able to. The organic electronic device includes, for example, an organic EL element, an organic solar cell, an organic semiconductor, and the like. Specifically, in the case of an organic EL element, the organic electronic device is formed by sandwiching at least an organic light emitting layer between an anode and a cathode. A laminated body.

  As a barrier film, what is necessary is just a member which can block | close and seal an organic electronic device from external air, A metal film, a resin film, an inorganic thin film etc. are mentioned. The thickness of the barrier film is not limited, but is preferably about 30 to 150 μm. As for the thickness of the inorganic thin film part of the inorganic thin film which formed silicon nitride etc. on the PEN (polyethylene naphthalate) film etc., about 0.05-2 micrometers is preferable.

  Examples of the metal film include an aluminum foil, an aluminum foil (aluminum foil film) bonded with a PET (polyethylene terephthalate) film, a copper foil, a stainless steel foil, and an aluminum vapor deposition film.

  Examples of the resin film (transparent film) include a PET film, a PEN film, a PES (polyether sulfone) film, a nylon film, a polycarbonate film, and a cycloolefin film.

  Examples of the inorganic thin film include silicon compounds such as silicon nitride, silicon oxide, silicon oxynitride, and silicon carbide, aluminum compounds such as aluminum oxide and aluminum nitride, aluminum silicate, zirconium oxide, tantalum oxide, titanium oxide, and titanium nitride. May be obtained by forming a film on the resin film (preferably PEN film) by using a plasma CVD (Chemical Vapor deposition) method, a Cat-CVD method, a vacuum deposition method or the like.

  In the organic electronic device sealing panel of the present invention, the hot melt type member is disposed between the substrate and the barrier film. Moreover, organic electronic devices, such as an organic EL element, can employ | adopt the structure and structure similar to a well-known organic electronic device. Therefore, basically, the hot-melt type member of the present invention can be used in organic electronic device encapsulating panels of all structures conventionally known.

  The hot melt type member of the present invention can be obtained by mixing and stirring the wax and the moisture scavenger described above. The specific structure of the organic electronic device sealing panel using this hot melt type member is organic An EL element will be described as an example with reference to FIG.

  In FIG. 2, an anode 2, an organic layer 3, and a cathode 4 are stacked as an organic EL element on a substrate 1, and a short prevention layer 8 is further stacked. Further, on the organic EL element, a hot-melt type member obtained by adding a moisture scavenger to wax is provided as an adhesive layer 9, which is solidified to bond the barrier film 10.

  In the present invention, an anti-shorting layer can be provided as necessary. The short prevention layer is formed to prevent a short circuit between the cathode and the anode, and includes an inorganic material such as silicon oxide, aluminum oxide, silicon nitride, and silicon carbide, and an organic material such as polyparaxylene. Can be used. In the present invention, a short prevention layer (polyparaxylene-based insulating layer) made of polyparaxylene is particularly preferable.

  The polyparaxylene-based insulating layer is composed of polyparaxylene and / or a derivative thereof. The derivative is not limited as long as it has para-xylene as a basic unit, and a known or commercially available derivative can be used. Preferable commercially available products include, for example, product names “diX C”, “diX D”, “diX F”, “diX N” (all are products from Daisei Kasei Co., Ltd.).

  The polyparaxylene-based insulating layer is formed on at least the cathode. In this case, the polyparaxylene derivative layer may be formed so as to cover at least the upper surface of the cathode. In particular, it is desirable to form a polyparaxylene-based insulating layer so as to cover the upper surface and side surfaces of the cathode. That is, it is desirable to form the polyparasylene-based insulating layer so as to cover all the cathode. In addition, a polyparaxylene-based insulating layer can be formed so as to cover all of the cathode and the organic light emitting layer (organic layer).

  The thickness of the polyparasylene-based insulating layer can be appropriately set according to the type of polyparasixylene or its derivative used, the type and type of the organic EL element, etc., but is usually about 20 nm to 10 μm, particularly 50 nm to 1 μm, and more preferably 50 nm to 900 nm. It is preferable to do. By setting to such a range, the occurrence of a short circuit can be prevented more effectively, and as a result, the lifetime of the element can be extended.

  The method for forming the polyparaxylene-based insulating layer is not particularly limited as long as the above configuration can be formed, and any of a gas phase method, a liquid phase method, and a solid phase method can be employed. For example, a method of forming by a vapor phase method using a raw material (for example, paraxylene (monomer) and / or paraxylene oligomer) for forming a polyparaxylene-based insulating layer is preferable. That is, in the present invention, as the polyparaxylene-based insulating layer, a polyparaxylene-based insulating layer formed by a vapor phase method using a raw material of a polyparaxylene derivative (for example, paraxylene (monomer) and / or paraxylene oligomer) is preferably used. Can be adopted. In particular, a polyparaxylene-based insulating layer formed by a vapor phase method using paraxylene oligomer (preferably paraxylene dimer) as a raw material is more preferable.

  As the vapor phase method, for example, a CVD method, a PVD method, or the like can be adopted. Among these, the CVD method, particularly the thermal CVD method can be preferably employed. The thermal decomposition temperature condition in this case is preferably about 600 to 700 ° C. The atmosphere is preferably a vacuum atmosphere of 1.0 Pa or less. The deposition rate may be about 1-2 nm / min. The thermal CVD method can be performed using a known or commercially available apparatus.

  In addition, a well-known or commercially available product can be used for the said raw material or polyparashikylene, or its derivative (s).

  A UV curable sealant 6 is provided around the hot melt type member 9 to be solidified. The sealant provided around the hot melt type member is not limited to the UV curable sealant, and a known sealant such as a thermosetting epoxy sealant or a sheet-like adhesive film can also be used. The hot-melt type member is transferred to the barrier film 10 using a transfer film that is directly applied to the barrier film 10 or applied in a sheet shape (thin film shape) on the release film, and is a substrate 1 (substrate) on which organic EL elements are laminated. The thin organic EL sealing panel that can be mass-produced with high reliability can be manufactured by bonding the organic EL element forming surface) and the hot-melt member on the barrier film. Further, the hot melt type member is transferred onto the organic EL element by using a transfer film which is directly applied on the organic EL element or applied in a sheet form (thin film shape) on the release film, and on the barrier film and the organic EL element. An organic EL element sealing panel can also be manufactured by pasting together a hot melt type member. The hot melt type member may be used as a transfer film, or alternatively, a barrier film sealing member in which a hot melt type member is laminated in a layer form on a barrier film may be prepared in advance. Moreover, in order to seal an organic electronic device with a flexible barrier film in the present invention, a barrier film sealing member laminated with a hot melt type member is tangentially bonded (barrier film in the tangential direction while pressing using a rubber roll or the like) By laminating and sealing the organic electronic device by a method of sequentially sticking from the end of the sealing member), it is possible to proceed with the sealing operation while suppressing air entrapment even under an atmospheric pressure of a nitrogen atmosphere. Therefore, it is preferable.

  In addition, as shown in FIG. 2, in the case of this structure, an appropriate amount of a hot melt type member is applied on the barrier film 10 and further bonded to a substrate (organic electronic device laminated surface) to thereby form a hot melt type member. Can cover the organic EL element so that no space is created between the substrate and the barrier film 10. That is, it is desirable that the entire space between the organic EL element and the barrier film is substantially occupied by the hot melt type member. The hot-melt type member is disposed in close contact with the organic EL element without any gap between the substrate and the barrier film 10, thereby preventing contact between moisture, oxygen, outgas and the organic EL element. The strength can be increased, and at the same time, the dark spot prevention performance, the irregular reflection prevention performance, and the like can be enhanced. Furthermore, if a UV curable sealant (epoxy sealant) is provided around the hot melt type member and solidified, the sealing state of the organic EL element can be further improved.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

In the examples and comparative examples, the organic EL element sealing panel (also referred to as “organic EL display panel”) shown in FIG. 2 is used. The organic EL element sealing panel can also be used for illumination other than the display panel. .) Was produced. That is, an ITO transparent electrode 2 as an anode is formed on a substrate 1, an organic film 3 including an organic light emitting layer is formed on the transparent electrode 2, and a metal electrode 4 is formed on the organic film 3 as a cathode. ing. The organic film 3 is composed of, for example, a laminate of an organic hole transport layer and an organic light emitting layer, or is a laminate film in which an electron transport layer is further provided between the organic light emitting layer and the metal electrode 4. As the metal electrode 4, an MgAg layer, a LiF layer, and an Al layer laminated are used. The short circuit prevention layer 8, silicon oxide SiO _2, aluminum oxide _Al 2 _{O 3,} silicon carbide SiC, silicon nitride _Si 3 _{N 4} other can be used, such as para-xylene.

Specifically, an organic EL element was formed on the substrate by the following process to produce an organic EL display panel. The organic EL display panel was manufactured in a clean environment with a cleanliness level of about 1000 (1000 pieces / ft ³ ). During the manufacturing process of the organic EL display panel, all the element elements were not exposed to the air but were transported in a high vacuum or in a nitrogen atmosphere.

1) Step 1
As the substrate 1, a glass substrate on which ITO to be the anode 2 was already patterned was used. The substrate 1 was subjected to ultrasonic cleaning using an organic alkali cleaning agent “Semico Clean 56 (manufactured by Furuuchi Chemical Co., Ltd.)”, ultrapure water, acetone, and isopropyl alcohol in this order, and then dried by nitrogen blowing.

2) Step 2
Thereafter, in order to remove organic pollutants on the surface of the ITO transparent electrode 2, UV ozone treatment was performed, and it was quickly set in the preliminary exhaust chamber.

3) Step 3
Next, the substrate 1 was transported into a vacuum forming film forming chamber where a shadow mask for an organic film was mounted on the substrate 1. By heating the alumina crucible, an organic hole transport material [triphenylamine derivative] (thickness 50 nm) and a light-emitting material [quinolinolamine complex (Alq)] (thickness 20 nm) are formed as the organic film 3 in this order. Each material was deposited at a deposition rate of 4 nm / min. In this case, preferably, the structure described in JP-A-2006-24432 can also be adopted.

4) Step 4
While maintaining the vacuum, the shadow mask for the organic film was replaced with a shadow mask for the cathode, the alumina crucible was resistance-heated, 1 nm of lithium fluoride was formed, and 200 nm of aluminum was formed as the cathode 4. The film formation rate was 10 to 15 nm / min, and the film formation was performed at a pressure (in vacuum) of 4 × 10 ⁻⁴ Pa or less. Further, the light emitting area of the organic EL element having the laminated structure of the anode 2, the organic film 3, and the cathode 4 was set to 20 mm × 30 mm.

Example 1 (direct application to barrier film)
(1) Preparation of transparent moisture scavenger-containing hot melt type member The following operation was performed in a nitrogen atmosphere.

Oredry (trademark) (organometallic compound) manufactured by Futaba Electronic Industry Co., Ltd. as a transparent moisture scavenger, and microcrystalline wax (product name “Hi-Mic-1070” manufactured by Nippon Seiki Co., Ltd., melting point 79 C., about 30 to 60 carbon atoms, and a molecular weight of about 500 to 800). These were mixed at a ratio of 8% by weight of microcrystalline wax and 12% by weight of heptane with respect to 80% by weight of ole dry to obtain a hot melt type member.
(2) Application to barrier film (manufacture of barrier film sealing member)
Aluminum foil: 5 μm and PET film: 70 μm bonded together (aluminum foil film: 75 μm) were prepared as a barrier film (hereinafter, “barrier film” indicates the same unless otherwise specified).

In a glove box substituted with a dew point of -70 ° C with nitrogen gas, a hot melt type member was coated with a slot die at a thickness of 20 µm (after drying) onto a barrier film that had been cleaned in advance and UV ozone cleaned. As a coating method, it is sufficient that the pattern coating can be performed on the barrier film by a single wafer method. Other examples include gravure coating and screen printing. Then, it dried for 5 minutes at 150 degreeC using the hotplate, and the solvent was volatilized. Further, a UV curable sealant (UV RESIN XNR5570-Bl manufactured by Nagase ChemteX Corporation) was applied to the outer periphery of the hot melt type member of the barrier film.
(3) Bonding of substrate and barrier film sealing member The substrate is moved to a glove box substituted with a nitrogen gas to a dew point of −70 ° C. without exposing the substrate to the atmosphere, and the organic EL element on the substrate is preliminarily 60 ° C. The barrier film sealing member that had been heated to 0 ° C. was pressed and adhered with a rubber roll in an atmosphere of atmospheric pressure so as to be bonded tangentially (tangential bonding). An organic EL barrier film sealing panel is formed by irradiating UV light from a substrate side with a 150 W UV lamp to cure the UV curable epoxy sealant, followed by heat treatment in a 100 ° C. oven for 1 hour. Got. In order to prevent the barrier film from peeling off during the heat treatment, the heat treatment was performed while holding the organic EL element sealing panel between two flat glass plates. In the organic EL element sealing panel, the hot melt type member is filled and disposed between the substrate and the barrier film without any space, and is in direct contact with the organic EL element.
(4) Light emission from the organic EL element from the substrate side was observed.

Example 2 (use of barrier film sealing member)
(1) Preparation of transparent water scavenger-containing hot melt type member The same procedure as in Example 1 was performed.
(2) Production of barrier film sealing member In a glove box substituted with a dew point of -70 ° C with nitrogen gas, a hot melt type member was coated on the barrier film with a slot die at a thickness of 20 µm (after drying). . As a coating method, it is only necessary that pattern coating can be intermittently performed on the barrier film. Examples of other coating methods include gravure coating and screen printing. Then, it was set as the barrier film with a hot-melt type member (barrier film sealing member) by drying with a hotplate. Further, a cover film was bonded to the hot melt member on the barrier film by tangential bonding. As the cover film, a polyethylene film having a slight adhesiveness (manufactured by Sekisui Chemical Co., Ltd.) was used on one side, and the adhesive surface of the cover film and the hot melt type member surface of the barrier film were bonded together.

  The barrier film sealing member to which the cover film was bonded was wound in a roll shape, and hermetically sealed with a bag of aluminum foil film having a high gas barrier property substituted with nitrogen.

  Temporary storage was performed in an atmospheric warehouse.

  The barrier film sealing member bonded with the cover film sealed and packaged again was placed in a glove box purged with nitrogen under the above conditions, and then the following operation was performed.

A part of the barrier film sealing member to which the roll-shaped cover film was bonded was taken out, and the cover film was peeled off to obtain a barrier film sealing member. A UV curable sealant (UV RESIN XNR 5570-B1 manufactured by Nagase ChemteX Corporation) was applied to the outer periphery of the hot melt type member of the barrier film sealing member.
(3) Bonding of substrate and barrier film sealing member Same as Example 1. In the organic EL element sealing panel, the hot melt type member is filled and disposed between the substrate and the barrier film without any space, and is in direct contact with the organic EL element.
(4) Light emission from the organic EL element from the substrate side was observed.

Example 3 (formation of a short prevention layer)
(1) Production of transparent water scavenger-containing hot melt type member The same procedure as in Example 1 was performed.
(2) Production of barrier film sealing member The same procedure as in Example 2 was performed.
(3) Bonding of substrate and barrier film sealing member The substrate is set in a thermal CVD apparatus without being exposed to the atmosphere, and a paraxylene insulating layer is formed as a short-circuit preventing layer so as to cover the cathode 4 (FIG. 2). did. Subsequent bonding of the substrate and the barrier film sealing member was performed in the same manner as in Example 1. In the organic EL element sealing panel, a hot-melt member is filled and disposed between the substrate and the barrier film without any space, and is in close contact with the organic EL element covered with the paraxylene insulating layer.
(4) Light emission from the organic EL element from the substrate side was observed.

Example 4 (Hot-melt type member is solventless type)
(1) Preparation of transparent water scavenger-containing hot-melt type member Oledry (trademark) (organometallic compound) manufactured by Futaba Electronics Co., Ltd. as a transparent water scavenger, and microcrystalline manufactured by Nippon Seiki Co., Ltd. as a wax Wax (product name “Hi-Mic-1070”, melting point 79 ° C., carbon number of about 30 to 60, molecular weight of about 500 to 800) was used. These were mixed in a proportion of 3% by weight of microcrystalline wax to 97% by weight of ole dry, and the resulting mixture was dried under reduced pressure at 150 ° C. under vacuum.
(2) Manufacture of barrier film sealing member In a glove box substituted with nitrogen gas to a dew point of -70 ° C, a solvent-free hot melt type member was heated to 80 ° C on a barrier film that had been cleaned in advance and subjected to UV ozone cleaning. However, it was applied with a thickness of 30 μm using a slot die. Then, it dried for 10 minutes at 150 degreeC using the hotplate. The weight loss after drying the hot-melt member after drying under reduced pressure at 150 ° C. for 4 hours under vacuum was 0.05% or less. Any coating method may be used as long as it can be applied on the barrier film by a single wafer method. This time, intermittent pattern coating was performed with a slot die. Examples include gravure coating and screen printing. Further, a UV curable sealant (UV RESIN XNR 5570-B1 manufactured by Nagase ChemteX Corporation) was applied to the outer periphery of the hot melt type member of the barrier film.
(3) Bonding of substrate and barrier film sealing member Same as Example 1. In the organic EL element sealing panel, the hot melt type member is filled and disposed between the substrate and the barrier film without any space, and is in direct contact with the organic EL element.
(4) Light emission from the organic EL element from the substrate side was observed.

Example 5 (transparent barrier film)
(1) Preparation of transparent water scavenger-containing hot melt type member (solvent-free type)
Same as Example 4.
(2) Application to transparent barrier film (production of transparent barrier film sealing member)
A PEN film (Teonex Q65F Teijin DuPont Films Co., Ltd.) on which a silicon nitride thin film (thickness: 0.5 μm) was formed in advance was used as a transparent barrier film.

A transparent barrier film is placed in a glove box substituted with a dew point of -70 ° C with nitrogen gas, and a solvent-free hot melt type member is heated to 80 ° C on a silicon nitride thin film of the transparent barrier film to a thickness of 40 µm with a slot die. Coated with. Any coating method may be used as long as it can be applied on a transparent barrier film by a single wafer method. Intermittent pattern coating with a slot die may be used. Other examples include gravure coating and screen printing. Further, a UV curable sealant (UV RESIN XNR 5570-B1 manufactured by Nagase ChemteX Corporation) was applied to the outer periphery of the hot melt type member of the barrier film.
(3) Bonding of substrate and transparent barrier film sealing member The same procedure as in Example 1 was conducted, except that a 20 nm thick aluminum film was used as the cathode 4 of the organic EL element. In the organic EL element sealing panel, the hot melt type member is filled and disposed between the substrate and the barrier film without any space, and is in direct contact with the organic EL element.
(4) The light emission by the organic EL element from the transparent barrier film side was observed.

Example 6 (substrate is a transparent film)
(1) Preparation of transparent water scavenger-containing hot melt type member (solvent-free type)
Same as Example 4.
(2) Production of barrier film sealing member The same procedure as in Example 4 was performed.
(3) Bonding of transparent film substrate and barrier film sealing member Example except that PEN film (Teonex Q65F Teijin DuPont Film Co., Ltd.) on which a silicon nitride thin film was formed in advance was used as the substrate instead of the glass substrate Same as 1. In the organic EL element sealing panel, the hot melt type member is filled and disposed between the substrate and the barrier film without any space, and is in direct contact with the organic EL element.
(4) The light emission by the organic EL element from the transparent film substrate side was observed.

Example 7 (using transfer film)
(1) Preparation of transparent water scavenger-containing hot melt type member The same procedure as in Example 1 was performed.
(2) Production of barrier film sealing member (using transfer film)
In a glove box substituted with a dew point of -70 ° C with nitrogen gas, a hot melt type member was coated with a slot die at a thickness of 10 µm (after drying) on a release film (PET100FD Lintec Co., Ltd.). As a coating method, it is sufficient that the pattern coating can be intermittently performed on the release film. Examples of other coating methods include gravure coating and screen printing. Then, it was set as the release film (transfer film) with a hot-melt type member by drying a solvent with a hotplate. Further, a cover film was bonded to the hot melt type member on the release film by tangential bonding. As the cover film, a cover film of a polyethylene film (manufactured by Sekisui Chemical Co., Ltd.) having slight adhesiveness on one side was used, and the adhesive side of the cover film and the hot melt type member side were bonded together.

  The transfer film on which the cover film was bonded was wound into a roll and hermetically packaged with a bag of aluminum foil film having a high gas barrier property that was purged with nitrogen.

  Temporary storage was performed in an atmospheric warehouse.

  The transfer film bonded with the cover film was again placed in a glove box purged with nitrogen under the above conditions, and the following transfer operation was performed.

A part of the roll-shaped transfer film was taken out, the cover film was peeled off, and a release film with a hot melt type member was obtained. While the release film is further heated to 60 ° C., the hot-melt type member on the release film is transferred by tangential bonding to the barrier film that has been cleaned in advance and subjected to UV ozone cleaning. The film was peeled off. Further, a UV curable sealant (UV RESIN XNR 5570-B1 manufactured by Nagase ChemteX Corporation) was applied to the outer periphery of the hot melt type member on the barrier film.
(3) Bonding of substrate and barrier film sealing member Same as Example 1. In the organic EL element sealing panel, the hot melt type member is filled and disposed between the substrate and the barrier film without any space, and is in direct contact with the organic EL element.
(4) Light emission from the organic EL element from the substrate side was observed.

Comparative Example 1 (Hot melt type member not used)
(1) Preparation of barrier film The barrier film used in Example 1 was prepared. A UV curable sealant (UV RESIN XNR5570-Bl Nagase ChemteX Co., Ltd.) was applied to the outer periphery of the barrier film, that is, in Comparative Example 1, no hot melt type member was used.
(2) Bonding of substrate and barrier film Same as Example 1.

The organic EL display panel obtained in Comparative Example 1 has no hot-melt type member between the organic EL element and the barrier film, so the barrier film and the organic EL element are in direct contact with each other, and the Al electrode of the organic EL element is damaged. did.
(3) Light emission from the organic EL element from the substrate side could not be observed. The organic EL element only allowed leakage current due to a short circuit.

Test example 1
The shelf life characteristics of the organic EL display panels produced in each example and comparative example were examined. Specifically, each organic EL display panel (Examples 1 to 7 and Comparative Example 1) was placed in a high-temperature and high-humidity environment of 60 ° C./90% Rh, and an accelerated standing test was performed. In a high-temperature and high-humidity environment of 60 ° C./90% Rh, the light emission state after 10 hours of Examples 1 to 7 is almost the same as that before the test, and the generation and growth of non-light-emitting parts are suppressed. It was confirmed that the hot melt type member of the example functions sufficiently. On the other hand, in Comparative Example 1, since there is no hot melt type member, the organic EL element, in particular, the cathode aluminum electrode was damaged when the barrier film (aluminum foil film) was bonded and short-circuited. Light emission from the device could not be confirmed.

  From the above results, by using the hot melt type member of the present invention, a hot melt type member having an arbitrary thickness and pattern can be formed on a barrier film (aluminum foil film or the like). It can be seen that an organic EL element that can maintain stable light emission characteristics without the influence of the above can be configured as a thin organic EL display panel that can be mass-produced with high reliability. Further, by forming only a hot melt type member on the barrier film, the organic EL display panel can be continuously produced, and improvement in productivity can be expected. In addition, it is possible to design freely including use of the hot melt type member by the user such as easy transportation to the user and relatively easy size change.

  Further, by using the transparent barrier film as in Example 5, light emission from the cathode side could be observed through the hot melt type member and the transparent barrier film. This indicates that it can be applied to a top emission type display.

  Furthermore, in Example 6, a transparent film is used for the substrate, and the substrate and the barrier film are flexible by bonding and sealing with the barrier film, so that a substantially flexible organic EL display panel is produced. I was able to.

It is the schematic which shows the cross-section of the conventional organic electronic device (organic EL display panel). It is the schematic which shows an example of the cross-section of the organic electronic device (organic EL display panel) of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode or ITO transparent electrode 3 Organic layer or organic film 4 Cathode or metal electrode 5 Sealing cap 6 UV curable sealant 7 Moisture trap 8 Short-circuit prevention layer 9 Adhesive layer (hot melt type member)
10 Barrier film (enclosure for conventional technology)

Claims (10)

Including a moisture scavenger and wax,
In sealed organic electronic device with a barrier film, the barrier film and are found using between the organic electronic device,
The moisture scavenger includes an organometallic compound,
The wax content is 1 to 8% by weight,
Hot-melt type member for organic electronic devices. The hot-melt member according to claim 1, wherein the moisture scavenger further contains a powdered inorganic oxide having an average particle size of 90 µm or less.   The hot melt type member according to claim 1 or 2, wherein a moisture scavenger is contained in the hot melt type member in an amount of 50 to 99% by weight. The hot melt type member according to any one of claims 1 to 3 , wherein the weight loss after drying under reduced pressure at 150 ° C for 4 hours under vacuum is 0.1% or less. The hot melt member according to any one of claims 1 to 4 , wherein the hot melt member has a thin film shape with a thickness of 100 µm or less. The organic electronic device is an organic EL device, an organic solar cell or organic semiconductor, a hot melt-type member according to any one of claims 1-5. The barrier film sealing member which laminated | stacked the hot-melt type member in any one of Claims 1-6 on the barrier film. 1) a substrate, 2) an organic electronic device formed on the substrate, and 3) an organic electronic device sealing panel comprising a barrier film for sealing the organic electronic device,
The organic electronic device sealing panel by which the hot-melt type member in any one of Claims 1-6 is arrange | positioned between the said organic electronic device and the said barrier film. The organic electronic device sealing panel according to claim 8 , wherein all of the space between the organic electronic device and the barrier film is occupied by the hot melt type member. The organic electronic device sealing panel according to claim 8 or 9 , wherein the substrate is a transparent film.

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