TWI244874B - Organic el panel and method for manufacturing the same - Google Patents

Abstract

Making it possible to quantitatively set an amount of desiccating agent disposed within an enclosing space and its disposition state, thereby ensuring an effective use of the desiccating agent. An organic EL device 12, formed by interposing an organic layer containing at least a luminescent layer between a pair of electrodes, is mounted on a support substrate 11. A cover 13 is bonded to the support substrate 11 through an adhesive agent 15. Accordingly, the organic EL device 12 is disposed within the enclosing space 16 formed between the support substrate 11 and the cover 13. Further, a desiccating agent 14 is disposed within the enclosing space 16 on a surface facing the support substrate 11 and separated from the organic EL device 12. A ratio of an occupation volume M(=M1xM2xT) of the desiccating agent provided within the enclosing space 16 to an entire volume V of the enclosing space 16 is set at 30% or more, while a distance h between the desiccating agent 14 and the organic EL device 12 is set at 0.3 mm or less.

Description

1244874 Set in the initial moisture and moisture released or immersed in time. In particular, the organic layer on which the button element is formed is weak in heat resistance and can be removed by heat treatment before sealing, so the k-like initial waterjet cannot be completely discharged. Therefore, in a panel using an existing organic material, it is necessary to provide such a dry_8 in a concrete member. The following Patent Document 1 includes the following. Has been loaded. As a desiccant 8 ', a compound capable of chemically adsorbing moisture and maintaining a solid state even if it absorbs moisture is used, and the desiccant 8 is mounted on the inner surface of the glass sealing cover 7 (opposite to the glass substrate) using an adhesive. surface). As described above, in an organic EL panel, an organic element can be slowed down over time by arranging a desiccant in a sealed space formed by a support substrate on which the organic EI ^ # is formed and a sealing member affixed thereto. Degraded characteristics (degree of progress of non-light emitting area). However, the extent to which the desiccant is installed in the sealed space and how to set it to be effective have not been discussed in depth in the past. Therefore, conventionally, there have been problems in that the deterioration is accelerated due to insufficient amounts of the desiccant, or, although a large amount of the desiccant is installed, the progress of the deterioration cannot be sufficiently slowed due to the poor installation condition. SUMMARY OF THE INVENTION The present invention makes it a subject to deal with such problems. That is, an object of the present invention is to quantitatively set the amount and state of a desiccant disposed in a sealed space, and to dryly dispose a desiccant and the like more efficiently. In order to achieve the above object, the organic EL panel of the present invention and a method for manufacturing the same have at least the following configurations. An organic EL panel is formed on a supporting substrate between a pair of electrodes

O: \ 92 \ 92617 DOC 1244874 An organic el element having an organic layer containing at least a light-emitting layer is sandwiched, and a sealing member that isolates the organic EL element from outside air is pasted, characterized in that _ | is free from the support The ratio of the volume occupied by the desiccant in the sealed space formed between the substrate and the sealing member to the volume of the sealed space is 30% or more. An organic EL panel is formed on a supporting substrate, an organic EL element having an organic layer including at least a light-emitting layer sandwiched between a pair of electrodes, and a sealing member for blocking the organic EL element from outside air is pasted. , So that the distance between the desiccant and the organic EL element provided in the sealed space formed between the supporting board substrate and the sealing member is 0.3 mm or less. An organic EL panel manufacturing method comprising an element forming step and a sealing step, wherein the element forming step includes forming an organic EL element on a support substrate with an organic layer containing at least a light-emitting layer between a pair of electrodes, and the sealing step. A sealing member that isolates the organic EL element from outside air is affixed to the support substrate, and is characterized in that, before the sealing step, a side of the sealing member that is opposite to the supporting substrate is dried. Agent, so that the volume ratio of the volume of the desiccant to the sealed space formed between the support substrate and the sealing member is 30% or more. An organic EL panel manufacturing method comprising an element forming step and a sealing step, wherein the element forming step includes forming an organic EL element on a support substrate with an organic layer containing at least a light-emitting layer between a pair of electrodes, and the sealing step. A sealing member that isolates the organic EL element from outside air is affixed to the support substrate, and is characterized in that the sealing member is mounted on a side of the branch sealing member that is opposite to the branch substrate before the sealing step. Desiccant

O: \ 92 \ 926l7 DOC 1244874 The distance from the organic EL element is 0.3 or less. [Embodiment] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Fig. 2 is an explanatory diagram showing an outline of an organic panel according to an embodiment of the present invention (details such as lead electrodes are omitted in the drawings). In the organic iris panel 10, an organic EL element 12 is formed on a branch substrate 11, and the organic iris element 12 sandwiches an organic layer including at least a light emitting layer between a pair of electrodes. In addition, the sealing member 13 is adhered to the supporting substrate 丨 丨 through the adhesive 15, so that the organic ELtg member 12 is disposed in the sealed space 16 formed between the supporting substrate 丨 丨 and the sealing member 13 to isolate it from the outside. gas. Inside the sealed space 6 is separated from the organic EL element 12, and a desiccant 14 is provided on the side opposite to the support substrate u. Here, in the embodiment of the present invention, the volume ratio of the occupied volume M (= M × M2 × T) of the desiccant 14 provided in the sealed space 16 to the volume V (= VlXV2XH) of the sealed space 16 is set to 30% or more. The distance h between the desiccant 14 and the organic EL element 12 is 0.3 mm or less. In this way, the initial moisture existing in the sealed space 16 and the moisture released or immersed in the sealed space 16 with time can be effectively absorbed and removed by the desiccant 14, the progress of deterioration of the organic EL element 12 over time can be slowed, and it can be ensured The life of a practical organic EL panel. In the embodiment of the present invention, the desiccant 14 is specified in the sealed space 16 by focusing on the occupied volume M of the desiccant 4 in the sealed space i 6 or the distance h ′ between the surface of the desiccant 14 and the organic el element 12. Effective configuration. In this way, the amount and distribution of the desiccant 4 arranged in the sealed space 16 can be set quantitatively.

0 \ 92 \ 926I7.DOC 1244874 Setting state ’can configure the desiccant more effectively. In addition, in the present method, the occupation volume M of the desiccant 14 in the sealed space 1 16 or the distance h between the surface of the desiccant 14 and the organic du element 12 is used to mount the desiccant 14 to the sealing member. The value at 3 or the value after driving the organic el element 12 is the object. At any time point, the volume ratio of the desiccant_sealed space 16 is greater than or equal to; ^ 3 、 芬 / 十 # π + 丨 Look at Chuan Jiu, And / or the distance h between the desiccant 14 and the organic EL element 12 is smaller than 箄 mm ##. In the case of two or three millimeters, it can be found as the embodiment of the present invention. Hereinafter, the structure of each part of the organic EL panel 10 will be described more specifically. [Desiccant 14] As the desiccant 14, a physical desiccant such as vermiculite, Shi Guifan, carbon, carbon nanotubes, etc.), a chemical hygroscopic agent described later, and an organic metal complex dissolved in a petroleum solvent (曱As the monomer such as a desiccant such as benzene, xylene, and an aliphatic organic solvent, a hygroscopic molded body as shown below may be used. The so-called hygroscopic molded body is a core plastic body in which a hygroscopic agent is dispersed in a resin component (adhesion d). As the hygroscopic agent, any substance may be used as long as it has a function of at least adsorbing moisture, but a compound capable of adsorbing moisture chemically and maintaining a solid state even if it absorbs moisture is particularly preferable. Examples of such a compound include metal oxides, inorganic acid salts and organic acid salts of metals, but it is particularly preferable to use at least one of the metal-oxide-type metal oxides and sulfates. Examples of the soil test metal oxide include emulsified calcium (CaO), barium oxide (Ba0), and magnesium oxide (Mg0). Examples of the sulfate include lithium sulfate (U2S04), sodium sulfate, and calcium sulfate.

O: \ 92 \ 92617.DOC 1244874 (4); IL 驮 magnesium (MgS04), cobalt sulfate (cos), gallium sulfate (2 (4) 3) I titanium acid (buti (s〇4) 2), nickel sulfate (so4), and the like. In addition to h: use organic materials with hygroscopicity as hygroscopic agents. At first glance, the known ingredients (adhesives) are not particularly limited as long as they do not hinder the moisture-removing effect of the hygroscopic agent, and it is preferable to use a material having high air permeability (that is, a material with low barrier properties, especially a breathable resin). ). Examples of such materials include polyolefins, polyacrylics, and polyacrylonitrile. Polymer materials such as ⑮ · ⑮, polyester, epoxy, and polycarbonate. R ^ Polyolefin is preferred in this wool. Specific examples include polyethyleneimide, polypropylene, polybutadiene, polyisoprene, etc., and their copolymers and the like. • he

And the content of the resin component can be set according to their type, etc. However, the system A is set to _% by weight s ± ^ \ Bar total amount of hygroscopic agent and resin component, the resin component is about 7〇 40% by weight to 80% in the heavy chamber, 15 to 15%. It is preferable that the moisture absorbent is about%, and the best-Moisturizer So: 50% to 30% by weight; the amount ^ reset% to 70% by weight, and the resin component is about hygroscopic molding body can be mixed by homogeneous Need :: such as: status and so on. In this case, it is preferable to fully dry the u emulsion sorbent, etc .: When mixing with the _ component, it can also be heated as needed: In addition, the Hit molded body is preferably made of a hygroscopic agent. And resin composition

O: \ 92 \ 926I7.DOC • 11-1244874 2: Substances that are formed by the mouthpieces. That is, using a three-component material that does not contain a solvent, etc., to produce a hygroscopic molded body, it is possible to avoid the disadvantages caused by the third component remaining in the molded body (for example, the remaining solvent is hygroscopic Adhesive adsorption, (I prepare it as ω such as μ α & reduce the performance of the adsorbent, or the disadvantage caused by the residual solvent volatilization in the sealing member over time). [Seal member] The seal member 13 is made of metal or glass It is preferably formed by a substrate made of glass (sodium glass or non-inspection glass). Pressing molding, engraving, sandblasting, etc. are used to form a sealing recess on the substrate to form a part of the sealed space 16 Or use an adhesive containing spacers with a diameter of 300 // m or more to form a sealed space 丨 6. [Adhesive] Adhesive 15 uses thermal curing, chemical curing (dual solvent mixing), light ( Ultraviolet) curing type adhesives can use acrylic resin,% oxygen resin, polyester, polyolefin, etc. It is particularly preferred to use ultraviolet curing epoxy resin. An appropriate amount (about 〇. (% By weight to 0.5% by weight in summer)) spacers (preferably glass or plastic spacers) having a particle size of 1 to 500 # m, and coated with a dispenser, etc. [Organic EL element] On the substrate of the supporting building Examples of specific structures and materials of the organic El element 12 formed on 11 with an organic layer containing at least a light-emitting layer between a pair of electrodes are as follows. (A) Support substrate As the support substrate 11, a transparent flat plate is preferred. The substrate can be made of glass or plastic, etc. (b) The electrodes are front-mounted in a way that emits light from the support substrate 11 side (bottom emission method). O: \ 92 \ 92617.DOC -12- 1244874 : Barrier / Brother T 'Set the electrode on the u side of the substrate as an anode made of a transparent electrode'. Another side electrode is a cathode made of a metal electrode. Applicable anode materials can be ίτο, Zn〇, etc. It is formed by film forming methods such as steaming bells and base shots. As the cathode, metals, metal oxides, metal fluorides, alloys, etc., having a small work function are used. Specifically, Ab can be used.

In, Mg, etc. | Layered structure, L102 / A1 and other laminated structures are formed by vapor deposition and low-temperature special film formation methods. (C) When the organic layer uses the electrode on the support substrate 11 side as the anode and the other electrode as the cathode, the organic layer is generally a d, ,, and σ structure of the hole transport layer / light emitting layer / electron transport layer. However, it is also possible to provide more than one light emitting layer, hole transporting layer, and electron transporting layer, and it is also possible to omit any one of the hole transporting layer and the electron transporting layer. . As the organic layer, an organic functional layer such as a hole injection layer, an electron injection layer, a hole blocking layer, and an electron blocking layer can be inserted depending on the application. The material of the organic layer can be appropriately selected according to the application of the organic EL element 12. Examples are given below, but are not limited thereto. The hole transporting layer may be any material as long as it has a function of high hole mobility, and any material can be selected from known compounds. As a specific example, a hematoporphyrin compound such as copper phthalocyanine blue, 4,4, a bis [N— (l — {yl) _; ^ —benzylamino] — biphenyl (NPB), an aromatic tertiary amine, 4 Mono (di-p-phenylamino), 4 '-[4 (di-p-phenylamino) styryl] dibenzyl ethylene, dibenzyl compounds such as dibenzyl ethylene, triazole derivatives or vinylvinylamine compounds material. In addition, it is also possible to use a polymer dispersed material such as polycarbonate, which is divided into polymers: O: \ 92W2617.DOC -13-1244874, which is a low-knife organic material for transmission. The light-emitting layer may use a known light-emitting material. As a specific example, 4,4, —bis (2,2, —biphenylvinylbiphenyl (DPV is called an aromatic secondary f-based compound such as i, i, 4-Bis (2-methylphenethyl) benzene and other styrene compounds, 3- (4-biphenyl) -4_phenyl-5_tert-butylphenyl— 丨, 2, 4-di .Disaloids such as TAZ, fluorescent organic materials such as anthracene derivatives, Gadolinium derivatives, fluorescent organometallic compounds such as (8-hydroxyquinoline) aluminum complex (Alq3), poly-p-phenylacetylene Polymer materials such as (ppv), Jugo (shown as "" 7 小 才 k >), polyethylene (VK), etc., platinum complexes or iridium complexes, etc. Organic materials that emit luminescent light (Special Table 2001 — 520450). The light-emitting layer may be composed of only the above-mentioned light-emitting materials, or may contain a hole-transporting material, an electron-transporting material, an additive (donor 'acceptor 4), or light-emitting Dopants, etc. In addition, they can be dispersed in polymer materials or inorganic materials. As long as the electron-transporting layer has electricity injected from the cathode It is sufficient to transfer the function to the light-emitting layer. As the material, any one of conventionally known compounds can be selected. As a specific example, organic materials such as a nitro-substituted Gou-type j derivative and anthraquinocridane derivative can be used. , Metal complex of 8-hydroxyquinoline derivative, metal phthalocyanine blue, etc. The above hole transport layer, light emitting layer, and electron transport layer can be applied by spin coating method, dip coating method, spray method, etc. It can be formed by a wet process such as a printing method such as a screen printing method or a dry process such as a vapor deposition method or a laser transfer method. [Various methods of an organic EL panel] The organic EL element 12 may be a single-structure organic EL The element may have a desired pattern structure and constitute a plurality of O: \ 92 \ 92617 DOC -14-12244874. The volume ratio of the volume V of the sealed space 16 is equal to or greater than 30%. In addition, a dry arrangement is set. Or thickness τ so that the distance h between the desiccant 14 and the organic el element ⑽ is 0.3 mm or less. Specifically, the volume V of the sealed space 16 may be defined in advance as the area of the sealing recess formed on the sealing member 13 and the seal. Part 13 The distance Η between the surface and the support substrate 11 is obtained by multiplying the distance Η. Here, the distance Η can be obtained as the sum of the depth of the sealing recessed portion and the thickness (spacer diameter) of the dead contact layer. It is possible to set the volume M of the desiccant 14 by multiplying the obtained volume V and the occupation ratio (30% or more). In addition, since the thickness of the organic EL element 12 can be ignored, the desiccant can be considered as an organic EL element. The distance h of 12 is h = H (the distance)-τ (dry thickness). Therefore, T = H-h (less than or equal to 03) can be used to set the thickness D of the desiccant 14. Install the desiccant 14 to The sealing member 13 is not particularly limited as long as it can be reliably fixed to the sealing member. For example, the following method can be used: a known adhesive, an adhesive (preferably a solventless adhesive) Adhesive) and other methods to bond the desiccant 14 and the sealing member 13 and the method of thermally fusing the desiccant 14 to the sealing member 3; fixing the molded body of the desiccant 14 to the sealing member with a fixing member such as a screw 13 on the method then, as the secret Step S2, a support substrate Shushu peripheral member or the adhesive coated surface of the seal portion 3 Shu adhesive 15, attaching the sealing member mound 13, the sealing member 12 organic £ 1 ^ on the support substrate u. Then, the organic EL panel 10 according to the embodiment is obtained through an appropriate inspection step S3 as necessary. ,

O: \ 92 \ 926l7DOC -16- 1244874 [Implementing Example 2] The volume ratio (occupancy rate) of the dry soil to the sealed space volume was 40%, except for + ^ plate β. Same as in Example 1, organic L was obtained [[:: Example 1] The desiccant was molded so that the volume ratio (area =) of the sealed space volume was 2G%, except that it was the same as that of Shiqing, and organic was obtained. EL panel C. [= Example 3] The desiccant was molded to have a volume ratio of 40 相对 relative to the volume of the sealed space, and the distance between the desiccant and the organic EL element was set to 职: the same as in Example 1 except that an organic EL panel was obtained. D. Comparative Example 2] Molding the desiccant to a volume ratio relative to the volume of the sealed space) was 40%, and the distance between the desiccant and the organic EL element was set to 0.4. Other than that, the same as Example 1 was performed to obtain an organic EL panel E. . [Measurement of panel degradation characteristics] The organic rainbow panels A to E were driven under the conditions of a temperature of 6 generations and a degree of clarity of 9 ° C to measure the degree of progress of the non-progressive regions that changed with time. The degree of progress of the non-light-emitting area is as follows: The degree of non-light-emitting area around the organic rainbow element is measured every predetermined time, and the ratio to the initial value is obtained. [Measurement results] The measurement results are shown below, and they are plotted in FIG. 4 (This figure is a graph obtained by comparing panels with different occupancy ratios when the distance between the desiccant and the organic EL element is constant. ⑻ is a graph obtained when a panel having a constant distance between the desiccant and the organic EL element is used.)

O: \ 92 \ 92617 DOC -18- 1244874

Table 1_ Panel Classification / Time (hr) Panel A (Example 1) Panel B (Example 2) Panel C (Comparative Example 1) Panel D (Example 3) Panel E (Comparative Example 2) The evaluation is: Panel c and panel D, whose occupancy (%) or the progress degree from the non-light-emitting region changed drastically, were determined to be unacceptable (X). π From Tables 1 and 4, it can be seen that the percentage of desiccant (the volume ratio of the volume of the desiccant to the volume of the sealed space) is greater than or equal to %%, or the distance between the desiccant and the organic EL element is less than or equal to . In three surfaces, the deterioration characteristics are not generally stable. However, if the percentage of the desiccant is less than %%, or the distance between the desiccant and the organic EL element is more than 0.3, the deterioration tends to be noticeable. 〇 From this, it can be confirmed that by setting the occupant ratio of the desiccant to be greater than or equal to 30 /, or the distance between the desiccant and the organic EL element to be less than or equal to ο] fiber, the degradation characteristics of the organic EL element can be reduced, and practical use can be obtained Life of the organic hole panel. [Brief Description of the Drawings] FIG. 1 is an explanatory diagram of the prior art. FIG. 2A shows an outline of an organic panel according to an embodiment of the present invention.

〇 \ 92 \ 926l7D〇C -19-1244874. FIG. 3 is an explanatory diagram showing an outline of a method of manufacturing an organic el panel according to the embodiment of the present invention. Fig. 4 is an explanatory diagram showing degradation characteristics of an organic el panel according to an embodiment of the present invention. [Illustration of Symbols in Drawings] 10 Organic EL Panel 11 Supporting Substrate 12 Organic EL Element 13 Sealing Part 14 Drying Part 15 Adhesive 16 Sealing Space O: \ 92 \ 92617.DOC -20-

Claims (1)

1244874 Patent application park: A kind of organic electroluminescence panel, on the supporting substrate, an organic electroluminescence element with an organic layer containing at least a light-emitting layer sandwiched between a pair of 瀵 electrodes is formed, and is affixed with This organic electroluminescence element is sealed from outside air, and is characterized in that the volume occupied by the desiccant in the two seals formed between the supporting substrate and the seal member is equal to the seal. The volume ratio of space is 30% or more. 2. The organic electroluminescence panel according to item 1 of the scope of patent application, wherein the distance between the desiccant and the organic electroluminescence element is 0.3 mm or less. 3. An organic electroluminescence panel in which an organic electroluminescence element having an organic layer containing at least a light-emitting layer is formed between a pair of electrodes on a supporting substrate, and the organic electroluminescence element is pasted to isolate the organic electroluminescence element from the outside. A gas sealing member, characterized in that the distance between the desiccant and the organic electroluminescence element provided in a sealed space formed between the support substrate and the sealing member is 0.3 mm or less 〇4. A kind of A method for manufacturing an electroluminescence panel includes an element forming step of forming an organic electroluminescence element on a support substrate and an organic layer including at least an organic layer containing a light emitting layer between a pair of electrodes, and a sealing step. The sealing step is to paste a sealing member that isolates the organic electroluminescence element from outside air on the support substrate, and is characterized in that before the sealing step, the sealing member is connected with the branch O: \ 92 \ 926l7 DOC 1244874 A desiccant is installed on the opposite side of the substrate, so that the volume of the desiccant is formed between the support substrate and the sealing member. Stimulated sealed space volume ratio 30% or more. 5. The method for manufacturing an organic electroluminescence panel according to item 4 of the scope of patent application, wherein the desiccant is installed so that the distance between the desiccant and the electroluminescence element is 0.3 mm or less. 6. A method of manufacturing an organic electroluminescence panel, comprising an element forming step and a sealing step, wherein the element forming step forms an organic electroluminescence on a support substrate with an organic layer containing at least a light emitting layer sandwiched between a pair of electrodes. Element, the sealing step will seal the organic electroluminescence element from outside ^ a sealing member that is outside air is pasted on the support substrate, and is characterized in that: before the sealing step, the sealing member and the support A desiccant is installed on the opposite side of the substrate, so that the distance between the desiccant and the organic electroluminescent element is less than or equal to 0.33 mm. O: \ 92 \ 926l7 DOC