WO2014185025A1 - Organic electroluminescent element - Google Patents

Organic electroluminescent element Download PDF

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Publication number
WO2014185025A1
WO2014185025A1 PCT/JP2014/002359 JP2014002359W WO2014185025A1 WO 2014185025 A1 WO2014185025 A1 WO 2014185025A1 JP 2014002359 W JP2014002359 W JP 2014002359W WO 2014185025 A1 WO2014185025 A1 WO 2014185025A1
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WIPO (PCT)
Prior art keywords
substrate
moisture
organic light
sealing wall
organic electroluminescent
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PCT/JP2014/002359
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French (fr)
Japanese (ja)
Inventor
基晋 青木
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パナソニックＩｐマネジメント株式会社
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Publication of WO2014185025A1 publication Critical patent/WO2014185025A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/874—Passivation; Containers; Encapsulations including getter material or desiccant
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to an organic electroluminescent device.
  • the light emission characteristic is easily deteriorated in the presence of water such as water vapor. Furthermore, when the organic electroluminescent element is operated for a long time, the place where it is deteriorated by the moisture does not emit light. Such non-luminescent portions are called dark spots. Dark spots grow over time. Therefore, various methods have been proposed to suppress the generation and growth of dark spots due to moisture.
  • Patent Document 1 proposes that a photocurable resin layer having moisture resistance be formed to cover an organic EL layer.
  • the present invention has been made in view of the above points, and provides an organic electroluminescent device having fastness and capable of prolonging the life by suppressing the penetration of moisture into the organic light-emitting body. To aim.
  • the organic electroluminescent device is A first substrate, An organic light emitter provided on the first substrate; A second substrate disposed opposite to the first substrate via the organic light emitter; A sealing wall provided between the first substrate and the second substrate so as to surround the organic light emitter; A hygroscopic part which is hygroscopic and covers the organic luminescent material, A moisture diffusing portion having moisture diffusibility and interposed between at least the second substrate and the hygroscopic portion; And the like.
  • the water diffusion portion is preferably formed of a porous hard resin.
  • At least one of the interface between the first substrate and the sealing wall and the interface between the sealing wall and the second substrate is formed in an uneven shape.
  • the width between the inner side surface of the sealing wall and the side surface of the hygroscopic member is narrower than the width between the side surface of the hygroscopic member and the side surface of the organic light emitter, It is preferable that the thickness of the water diffusion part is thicker than the thickness of the moisture absorption part.
  • ADVANTAGE OF THE INVENTION According to this invention, it has toughness and can suppress permeation of a water
  • FIG. 1 shows an example of the organic electroluminescent element 1 in the embodiment of the present invention.
  • the organic electroluminescent device 1 includes a first substrate 11, an organic light emitting body 20, and a second substrate 12 in layers, and further includes a sealing wall 3, a hygroscopic portion 4, and a moisture diffusion portion 5. ing.
  • the first substrate 11 preferably has optical transparency.
  • the first substrate 11 may be colorless or colored.
  • the first substrate 11 may be transparent or translucent.
  • Examples of the first substrate 11 include a glass substrate, a plastic substrate, and the like.
  • As a material of a glass substrate soda lime glass, an alkali free glass etc. can be mentioned, for example.
  • Examples of the material of the plastic substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, epoxy resin, polyamide resin, fluorine resin and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • acrylic resin epoxy resin
  • polyamide resin polyamide resin
  • fluorine resin fluorine resin and the like.
  • the shape of the first substrate 11 may be a rectangular shape in plan view, or any other shape.
  • planar view means the case where the organic electroluminescent element 1 is seen in the direction (thickness direction) in which the first substrate 11, the organic light emitting body 20, and the
  • the organic light emitting body 20 is provided on the first substrate 11. Specifically, the organic light emitting body 20 is formed by sequentially stacking, from the first substrate 11, a first electrode 21 functioning as an anode, an organic light emitting layer 23, and a second electrode 22 functioning as a cathode.
  • the first electrode 21 may function as a cathode and the second electrode 22 may function as an anode.
  • a portion where all of the first electrode 21, the organic light emitting layer 23 and the second electrode 22 overlap in a plan view is a light emitting area E (display area), and the other area is a non-light emitting area (non-display area). is there.
  • the shape of the light emitting region E may be a rectangular shape in plan view, or any other shape.
  • the organic light emitting body 20 refers to a stacked body of the first electrode 21, the organic light emitting layer 23, and the second electrode 22 in the light emitting region E.
  • the 1st electrode 21 has light transmittance.
  • the first substrate 11 is also light transmissive, it becomes a bottom emission type light extraction system, and light emitted from the organic light emitting layer 23 is transmitted through the first electrode 21 and the first substrate 11. It can be taken out outside.
  • the material of the first electrode 21 include an electrode material composed of a metal having a large work function, an alloy, an electrically conductive compound, or a mixture thereof. As such a material, for example, CuI, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), etc. can be mentioned.
  • the second electrode 22 preferably has light reflectivity.
  • the first substrate 11 and the first electrode 21 have light transmissivity, it becomes a bottom emission type light extraction system, and the light emitted from the organic light emitting layer 23 and directed to the second electrode 22 is transmitted.
  • the first electrode 21 and the first substrate 11 can be transmitted and taken out to the outside.
  • the material of the second electrode 22 include an electrode material made of a metal having a low work function, an alloy, an electrically conductive compound, or a mixture thereof. As such a material, sodium, lithium, magnesium, aluminum etc. can be mentioned, for example.
  • the first electrode 21 may have light reflectivity, and the second electrode 22 may have light transparency.
  • the moisture absorption part 4, the water diffusion part 5, and the second substrate 12 have light transmittance.
  • each of the first electrode 21 and the second electrode 22 may have light transmittance.
  • the first substrate 11, the moisture absorption unit 4, the moisture diffusion unit 5, and the second substrate 12 have light transmittance.
  • a double-sided light emission type light extraction system is realized, and light emitted from the organic light emitting layer 23 can be extracted from both the first substrate 11 and the second substrate 12 to the outside.
  • the organic light emitting layer 23 can be formed with the well-known material known as a material for organic electroluminescent elements.
  • materials include, for example, anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, quinoline metal.
  • Tri- (p-terphenyl-4-yl) amine Tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyran, quinacridone, rubrene, distyrylbenzene derivative, distyryl Arylene derivatives, and distyrylamine derivatives, various fluorescent dyes. Two or more of these materials may be used in combination.
  • the organic light emitting layer 23 may be formed by a dry process such as a vapor deposition method or a transfer method, or may be formed by a wet process such as a coating method.
  • one or more layers selected from a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer may be interposed between the first electrode 21 and the second electrode 22. It can form by a well-known method using the well-known material known as a material for organic electroluminescent elements. As described above, since at least the organic light emitting layer 23 is interposed between the first electrode 21 and the second electrode 22, the first electrode 21 and the second electrode 22 are unlikely to be in direct contact with each other, and electrical Will be isolated. As shown in FIG. 1, an insulating layer 6 is formed of a known material on a part or all of the periphery of the organic light emitting layer 23, and the insulating properties of the first electrode 21 and the second electrode 22 are further increased by this insulating layer 6. It may be enhanced.
  • the second substrate 12 is disposed to face the first substrate 11 via the organic light emitter 20.
  • the second substrate 12 is also preferably light transmissive, but if the first substrate 11 is light transmissive, the second substrate 12 has light reflectivity. It may be In this case, as described above, the bottom emission type light extraction system is used.
  • a glass substrate, a metal substrate, a resin substrate or the like can be used as the second substrate 12.
  • soda lime glass, an alkali free glass etc. can be mentioned, for example.
  • a material of a metal substrate aluminum, stainless steel, etc. can be mentioned, for example.
  • the material of the resin substrate examples include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the second substrate 12 is formed of a resin substrate, a SiON film or a SiN film may be formed on the surface of the second substrate 12 to suppress the permeation of moisture.
  • the second substrate 12 may have a rectangular shape in a plan view, or another shape.
  • the sealing wall 3 is provided between the first substrate 11 and the second substrate 12 so as to surround the organic light emitting body 20.
  • the sealing wall 3 can prevent moisture outside the organic electroluminescent element 1 from intruding into the organic light emitter 20.
  • the sealing wall 3 is preferably formed of a material having a moisture permeability of 60 g / m 2 ⁇ 24 hours or less.
  • the moisture permeability can be measured by the moisture permeability test method (cup method) of the moisture-proof packaging material defined in JIS Z0208.
  • an ultraviolet curable resin etc. can be mentioned, for example. Specific examples thereof include resin materials such as epoxy resin and acrylic resin, wax materials such as paraffin wax and microcrystalline wax, and frit materials such as glass frit.
  • the sealing wall 3 may contain an inorganic filler such as alumina, or a hygroscopic agent such as calcium oxide, strontium oxide, barium oxide or silica.
  • the sealing wall 3 can be formed by, for example, a dispensing method, a printing method, an inkjet method, or the like.
  • a first electrode lead-out portion 211 is formed at an end portion of the first substrate 11 outside the sealing wall 3.
  • the first electrode lead portion 211 is formed by drawing the first electrode 21 inside the sealing wall 3 to the outside.
  • a second electrode lead-out portion 222 is formed at the other end of the first substrate 11 outside the sealing wall 3.
  • the second electrode lead-out portion 222 is formed by pulling out the second electrode 22 inside the sealing wall 3 to the outside. Electric power is supplied through the first electrode lead-out portion 211 and the second electrode lead-out portion 222 to apply a voltage between the first electrode 21 and the second electrode 22 of the organic light emitting body 20 to cause the organic light emitting layer 23 to emit light. be able to.
  • the hygroscopic part 4 has hygroscopicity, preferably further has light transparency, and covers the whole of the organic light emitting body 20.
  • the moisture absorption part 4 is solid. In this case, even if the moisture passes through the sealing wall 3 and enters inside, the moisture absorption part 4 can further suppress the moisture from entering the organic light emitting body 20.
  • the moisture absorption part 4 can be formed with the resin material containing a moisture absorption agent (drying agent).
  • the hygroscopic agent may be one that chemically adsorbs moisture or one that physically adsorbs it, and examples thereof include alkali metals such as calcium oxide, strontium oxide, barium oxide, sodium oxide, potassium oxide, sodium sulfate, calcium sulfate, etc.
  • alkali metals such as calcium oxide, strontium oxide, barium oxide, sodium oxide, potassium oxide, sodium sulfate, calcium sulfate, etc.
  • the powder particle containing an alkaline-earth metal, a zeolite, etc. can be mentioned.
  • the resin material include thermosetting resins that cure by heating at a temperature of 100 ° C. or less and ultraviolet curable resins.
  • Such a resin material is preferably one that is hard to permeate moisture, and examples thereof include epoxy resin, alkali resin, silicone resin and the like.
  • the hygroscopic agent is preferably contained in an amount of 30% by mass or more and less than 95% by mass with respect to the total amount of materials constituting the hygroscopic portion 4.
  • the moisture absorbent portion 4 can be formed, for example, by a dispensing method, a printing method, a sputtering method, a spin coating method, a dipping method, a spraying method, or the like.
  • a moisture diffusing portion 5 having moisture diffusibility, preferably further having light permeability is interposed between the second substrate 12 and the moisture absorbing portion 4. I have to. Then, the moisture which has passed through the sealing wall 3 can be diffused and moved to the inside of the light emitting area E by the water diffusing unit 5, and the moisture absorbing part 4 inside the light emitting area E can be effectively used. Can. As a result, moisture is less likely to enter the organic light emitting body 20, and the lifetime of the organic electroluminescent device 1 can be extended.
  • the moisture diffusion unit 5 may be interposed at least between the second substrate 12 and the moisture absorption unit 4, for example, as shown in FIG. 2, the inner side surface of the sealing wall 3 and the side surface of the moisture absorption unit 4 There may be a gap 7 between them.
  • the moisture that has passed through the sealing wall 3 and entered the air gap 7 is absorbed as it is by the moisture absorption part 4 outside the light emission area E or is diffused and moved to the inside of the light emission area E by the water diffusion part 5 once. After that, the moisture is absorbed by the moisture absorbing portion 4 inside the light emitting region E or the like.
  • the water diffusion portion 5 is interposed between the second substrate 12 and the moisture absorption portion 4, the second substrate 12 is less likely to be dented on the first substrate 11 side, and the fastness of the organic electroluminescent element 1 is obtained. You can also get it.
  • the robustness in this case is a concept including pressure resistance. More specifically, the water diffusion portion 5 is preferably a solid, and such a solid water diffusion portion 5 is between the second substrate 12 and the moisture absorption portion 4 in the thickness direction of the organic electroluminescent element 1. Is preferably filled without gaps. In this case, even if the pressure is applied to the organic electroluminescent element 1 from both sides in the thickness direction, the second substrate 12 contacts the organic light emitting layer 20 and the organic light emitting layer 20 is damaged.
  • the solid water diffusion unit 5 inhibits the contact between the second substrate 12 and the organic light emitting layer 20.
  • the solid water diffusion unit 5 absorbs moisture with at least the second substrate 12 in the thickness direction of the organic electroluminescent element 1. It may be filled without a gap between the part 4 and, as shown in FIG. 2, the void 7 may be present between the inner side surface of the sealing wall 3 and the side surface of the hygroscopic part 4 .
  • the second substrate 12 may be dented on the side of the first substrate 11 and may be in contact with the organic light emitting layer 20, and the organic light emitting layer 20 may be damaged.
  • the water diffusion portion 5 is preferably formed of a porous hard resin.
  • a water diffusion unit 5 coats, for example, particles having an average particle diameter of 10 to 100 ⁇ m with an ultraviolet curable resin such as an ultraviolet curable epoxy resin, and the coated particles are dispersed on the surface of the moisture absorbent 4 It can be formed.
  • the particles described above are preferably materials that do not easily adsorb moisture, such as metals and silica. In this manner, when the water diffusion portion 5 is formed, a large number of fine holes included in the hard resin serve as a passage of water, so that the water does not easily stay, and the water diffusibility can be further improved. Moreover, since the water diffusion portion 5 is hard, the fastness can be further improved.
  • an average particle diameter means the particle size in 50% of the integration value in the particle size distribution calculated
  • the moisture diffusion part 5 may be formed using a porous sheet formed by sintering polyethylene particles etc. to a thickness of 1000 ⁇ m or less .
  • the solid moisture diffusion portion 5 in the thickness direction of the organic electroluminescent element 1 It is preferable to be filled without gaps with the hygroscopic member 4.
  • the gap in this case does not mean the large number of fine holes possessed by the hard resin. These holes are secured as a water passage without being blocked.
  • the interface between the first substrate 11 and the sealing wall 3 and the interface between the sealing wall 3 and the second substrate 12 may be formed flat, but these interfaces It is preferable to form in the uneven
  • the interface between the first substrate 11 and the sealing wall 3 and the interface between the sealing wall 3 and the second substrate 12 are formed in a concavo-convex shape, moisture hardly passes through these interfaces, Infiltration of the inside of the sealing wall 3 can be suppressed. It is more preferable that both of the above interfaces be formed in a concavo-convex shape, but at least one of the interfaces may be formed in a concavo-convex shape.
  • a glass frit is previously applied to a portion where the sealing wall 3 of the first substrate 11 and the second substrate 12 is provided and then fired to have a height of 10 to 200 ⁇ m.
  • a bank-like protrusion 8 may be formed.
  • the gap between the tip of the protrusion 8 formed on the first substrate 11 and the second substrate 12 and the gap between the first substrate 11 and the tip of the protrusion 8 formed on the second substrate 12 are 20 ⁇ m or less Is preferred.
  • the gap between the first substrate 11 and the second substrate 12 is preferably 200 ⁇ m or less.
  • the first substrate 11 and the sealing wall 3 in addition to the case where the first substrate 11 and the sealing wall 3 are in direct contact, the first substrate 11 and the sealing wall 3
  • the case where the first electrode 21 is interposed is also included.
  • the width W 1 between the inner side surface of the sealing wall 3 and the side surface of the hygroscopic member 4 is the side surface of the hygroscopic member 4 and the side surface of the organic light emitting body 20 it is preferably narrower than the width W 2 between.
  • W 1 ⁇ W 2 it is possible to promote the diffusion of water to the inside of the light emitting area E by the water diffusing unit 5 while sufficiently securing the moisture absorbing part 4 outside the light emitting area E. it can.
  • the thickness T 1 of the moisture diffusion portion 5 be thicker than the thickness T 2 of the moisture absorption portion 4.
  • the thickness T 1 of the water diffusion portion 5 is preferably 20 to 200 ⁇ m, and the thickness T 2 of the moisture absorption portion 4 is preferably 10 to 100 ⁇ m.
  • a transparent conductive film such as ITO is formed on the surface of the first substrate 11 such as a glass substrate and patterned by photolithography to form the first electrode 21 and the first electrode lead-out portion 211.
  • an organic light emitting layer 23 is formed on the surface of the first electrode 21 by vapor deposition or the like using a predetermined material.
  • one or more layers selected from a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer may be appropriately formed, or the insulating layer 6 may be formed.
  • a second electrode 22 and a second electrode lead-out portion 222 are formed by depositing a metal film of aluminum or the like on the surface of the organic light emitting layer 23 by a vapor deposition method or the like.
  • the organic light emitting body 20 can be formed on the surface of the first substrate 11.
  • a resin material containing a hygroscopic agent is applied by a screen printing method or the like so as to cover the whole of the organic light emitting body 20, and then the resin material is cured by heating or ultraviolet irradiation to form the hygroscopic portion 4. .
  • the thickness T 2 of the moisture absorption part 4 formed in this manner is preferably 10 to 100 ⁇ m as described above.
  • the uncured moisture diffusion portion 5 is formed by spraying the particles coated with the ultraviolet curable resin so as to cover the entire cured moisture absorbing portion 4. Spraying the particles is preferably carried out to a thickness T 1 shown in FIG 1 is about 100 ⁇ 1000 .mu.m.
  • the ultraviolet curable resin which is a material of the sealing wall 3 is apply
  • the first substrate 11 and the second substrate 12 having the same size as above are placed in a vacuum chamber whose pressure is reduced to about 1 Pa, and the first substrate 11 and the second substrate are separated via the organic light emitter 20. 12 is placed in close contact with each other.
  • the ultraviolet curable resin which is the material of the sealing wall 3
  • the uncured water diffusion portion 5 can be sealed.
  • the water diffusion portion 5 is crushed by both the moisture absorption portion 4 and the second substrate 12, but the thickness T 1 of the water diffusion portion 5 after being crushed is greater than the thickness T 2 of the moisture absorption portion 4. It is preferably thick, and specifically, the thickness T 1 is preferably 20 to 200 ⁇ m.
  • the entire cured moisture absorption part 4 is covered with a porous sheet.
  • a porous sheet a sheet formed by sintering polyethylene particles or the like and having a thickness of 1000 ⁇ m or less can be used.
  • the porous sheet may be adhered to the moisture absorbent portion 4 with an adhesive material so that the position of the porous sheet does not shift.
  • an ultraviolet curable resin which is a material of the sealing wall 3 is applied to the outer periphery of the porous sheet in plan view.
  • the first substrate 11 and the second substrate 12 are disposed so as to face each other via the organic light emitting body 20 so as to be in close contact with each other.
  • the ultraviolet curable resin which is the material of the sealing wall 3 is crushed by both the first substrate 11 and the second substrate 12.
  • the porous sheet which is the material of the water diffusion portion 5 is crushed in both the moisture absorption portion 4 and the second substrate 12.
  • the thickness T 1 of the water diffusion section 5 (porous sheet) thick is preferred than the thickness T 2 of the moisture absorption portion 4, the thickness T 1 is specifically is 20 ⁇ 200 [mu] m after being crushed Is preferred.
  • a glass frit is applied by screen printing or the like to a place where the sealing wall 3 of the first substrate 11 is to be provided. Thereafter, this is fired at a temperature of 800 ° C. or higher to form a bank-like protrusion 8 having a height of about 10 to 200 ⁇ m. Similarly to this, the projection 8 is formed on the second substrate 12 in advance.
  • an organic electroluminescent device 1 as shown in FIG. 3 can be obtained.

Abstract

An organic electroluminescent element equipped with: a first substrate (11); an organic light-emitting body (20) provided on the first substrate (11); a second substrate (12) positioned so as to face the first substrate (11) with the organic light-emitting body (20) interposed therebetween; a sealing wall (3) provided between the first substrate (11) and the second substrate (12) so as to surround the organic light-emitting body (20); a moisture-absorbing part (4) for covering the organic light-emitting body (20) and having moisture absorbency; and a water-content dispersion part (5) having water-dispersion properties and interposed at least between the second substrate (12) and the moisture-absorbing part (4).

Description

有機エレクトロルミネッセンス素子Organic electroluminescent device
　本発明は、有機エレクトロルミネッセンス素子に関する。 The present invention relates to an organic electroluminescent device.
　有機エレクトロルミネッセンス素子は、水蒸気などの水分の存在下で発光特性が劣化しやすくなる。さらに、有機エレクトロルミネッセンス素子が長時間動作すると、水分によって劣化した場所が発光しなくなる。このような発光しない部分は、ダークスポットと呼ばれる。ダークスポットは時間の経過とともに成長する。そこで、水分によるダークスポットの発生及び成長を抑制するため、種々の方法が提案されている。 In the organic electroluminescent element, the light emission characteristic is easily deteriorated in the presence of water such as water vapor. Furthermore, when the organic electroluminescent element is operated for a long time, the place where it is deteriorated by the moisture does not emit light. Such non-luminescent portions are called dark spots. Dark spots grow over time. Therefore, various methods have been proposed to suppress the generation and growth of dark spots due to moisture.
　例えば、特許文献１には、有機物ＥＬ層を覆うように耐湿性を有する光硬化性樹脂層を形成することが提案されている。 For example, Patent Document 1 proposes that a photocurable resin layer having moisture resistance be formed to cover an organic EL layer.
　しかし、上記の場合でも水分の浸入を抑制することは困難であり、水分が有機物ＥＬ層に到達し、有機エレクトロルミネッセンス素子の寿命が短くなるという問題がある。しかも近年においては、有機エレクトロルミネッセンス素子の堅牢性も求められている。 However, even in the above case, it is difficult to suppress the entry of moisture, and there is a problem that the moisture reaches the organic EL layer and the lifetime of the organic electroluminescent element is shortened. Moreover, in recent years, the fastness of the organic electroluminescent device is also required.
日本国特許出願公開番号特開平５－１８２７５９Japanese Patent Application Publication No. Hei 5-182759
　本発明は上記の点に鑑みてなされたものであり、堅牢性を有し、水分の有機発光体への浸入を抑制して長寿命化を図ることができる有機エレクトロルミネッセンス素子を提供することを目的とする。 The present invention has been made in view of the above points, and provides an organic electroluminescent device having fastness and capable of prolonging the life by suppressing the penetration of moisture into the organic light-emitting body. To aim.
　本発明に係る有機エレクトロルミネッセンス素子は、
　第一基板と、
　前記第一基板に設けられた有機発光体と、
　前記有機発光体を介して前記第一基板と対向して配置された第二基板と、
　前記有機発光体を取り囲むように前記第一基板と前記第二基板との間に設けられた封止壁と、
　吸湿性を有し、前記有機発光体を被覆する吸湿部と、
　水分拡散性を有し、少なくとも前記第二基板と前記吸湿部との間に介在する水分拡散部と、
　を備えることを特徴とする。 The organic electroluminescent device according to the present invention is
A first substrate,
An organic light emitter provided on the first substrate;
A second substrate disposed opposite to the first substrate via the organic light emitter;
A sealing wall provided between the first substrate and the second substrate so as to surround the organic light emitter;
A hygroscopic part which is hygroscopic and covers the organic luminescent material,
A moisture diffusing portion having moisture diffusibility and interposed between at least the second substrate and the hygroscopic portion;
And the like.
　前記有機エレクトロルミネッセンス素子において、
　前記水分拡散部が、多孔質性を有する硬質樹脂で形成されていることが好ましい。 In the organic electroluminescent device,
The water diffusion portion is preferably formed of a porous hard resin.
　前記有機エレクトロルミネッセンス素子において、
　前記第一基板と前記封止壁との界面及び前記封止壁と前記第二基板との界面の少なくともいずれかの界面が凹凸状に形成されていることが好ましい。 In the organic electroluminescent device,
It is preferable that at least one of the interface between the first substrate and the sealing wall and the interface between the sealing wall and the second substrate is formed in an uneven shape.
　前記有機エレクトロルミネッセンス素子において、
　前記封止壁の内側の側面と前記吸湿部の側面との間の幅が、前記吸湿部の側面と前記有機発光体の側面との間の幅よりも狭く、
　前記水分拡散部の厚さが、前記吸湿部の厚さよりも厚いことが好ましい。 In the organic electroluminescent device,
The width between the inner side surface of the sealing wall and the side surface of the hygroscopic member is narrower than the width between the side surface of the hygroscopic member and the side surface of the organic light emitter,
It is preferable that the thickness of the water diffusion part is thicker than the thickness of the moisture absorption part.
　本発明によれば、堅牢性を有し、水分の有機発光体への浸入を抑制して長寿命化を図ることができる。 ADVANTAGE OF THE INVENTION According to this invention, it has toughness and can suppress permeation of a water | moisture content to the organic light-emitting body, and can attain lifetime improvement.
本発明の実施の形態における有機エレクトロルミネッセンス素子の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the organic electroluminescent element in embodiment of this invention. 本発明の実施の形態における有機エレクトロルミネッセンス素子の他の一例を示す概略断面図である。It is a schematic sectional drawing which shows another example of the organic electroluminescent element in embodiment of this invention. 本発明の実施の形態における有機エレクトロルミネッセンス素子の他の一例を示す概略断面図である。It is a schematic sectional drawing which shows another example of the organic electroluminescent element in embodiment of this invention. 有機エレクトロルミネッセンス素子の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of an organic electroluminescent element.
　以下、本発明の実施の形態を説明する。 Hereinafter, embodiments of the present invention will be described.
　図１は本発明の実施の形態における有機エレクトロルミネッセンス素子１の一例を示す。この有機エレクトロルミネッセンス素子１は、第一基板１１と、有機発光体２０と、第二基板１２とを積層して備え、さらに封止壁３と、吸湿部４と、水分拡散部５とを備えている。 FIG. 1 shows an example of the organic electroluminescent element 1 in the embodiment of the present invention. The organic electroluminescent device 1 includes a first substrate 11, an organic light emitting body 20, and a second substrate 12 in layers, and further includes a sealing wall 3, a hygroscopic portion 4, and a moisture diffusion portion 5. ing.
　第一基板１１は、光透過性を有することが好ましい。第一基板１１は、無色であっても着色されていてもよい。第一基板１１は、透明であっても半透明であってもよい。第一基板１１としては、例えば、ガラス基板、プラスチック基板等を挙げることができる。ガラス基板の材質としては、例えば、ソーダライムガラス、無アルカリガラス等を挙げることができる。プラスチック基板の材質としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、アクリル樹脂、エポキシ樹脂、ポリアミド樹脂、フッ素樹脂等を挙げることができる。第一基板１１の形状は、平面視矩形状でも、その他の形状でもよい。なお、平面視とは、有機エレクトロルミネッセンス素子１を、第一基板１１、有機発光体２０、第二基板１２を積層する方向（厚さ方向）に見る場合をいう。 The first substrate 11 preferably has optical transparency. The first substrate 11 may be colorless or colored. The first substrate 11 may be transparent or translucent. Examples of the first substrate 11 include a glass substrate, a plastic substrate, and the like. As a material of a glass substrate, soda lime glass, an alkali free glass etc. can be mentioned, for example. Examples of the material of the plastic substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin, epoxy resin, polyamide resin, fluorine resin and the like. The shape of the first substrate 11 may be a rectangular shape in plan view, or any other shape. In addition, planar view means the case where the organic electroluminescent element 1 is seen in the direction (thickness direction) in which the first substrate 11, the organic light emitting body 20, and the second substrate 12 are stacked.
　また有機発光体２０は、第一基板１１に設けられている。具体的には有機発光体２０は、第一基板１１から順に、陽極として機能する第一電極２１、有機発光層２３、陰極として機能する第二電極２２を積層して形成されている。第一電極２１が陰極として機能し、第二電極２２が陽極として機能してもよい。なお、平面視で第一電極２１、有機発光層２３、第二電極２２が全て重なっている部分が発光領域Ｅ（表示領域）であり、これ以外の部分が非発光領域（非表示領域）である。発光領域Ｅの形状は、平面視矩形状でも、その他の形状でもよい。有機発光体２０は、発光領域Ｅにおける第一電極２１、有機発光層２３、第二電極２２の積層体を意味する。 In addition, the organic light emitting body 20 is provided on the first substrate 11. Specifically, the organic light emitting body 20 is formed by sequentially stacking, from the first substrate 11, a first electrode 21 functioning as an anode, an organic light emitting layer 23, and a second electrode 22 functioning as a cathode. The first electrode 21 may function as a cathode and the second electrode 22 may function as an anode. A portion where all of the first electrode 21, the organic light emitting layer 23 and the second electrode 22 overlap in a plan view is a light emitting area E (display area), and the other area is a non-light emitting area (non-display area). is there. The shape of the light emitting region E may be a rectangular shape in plan view, or any other shape. The organic light emitting body 20 refers to a stacked body of the first electrode 21, the organic light emitting layer 23, and the second electrode 22 in the light emitting region E.
　また第一電極２１は、光透過性を有することが好ましい。この場合、第一基板１１も光透過性を有していれば、ボトム・エミッション型の光取り出し方式となり、有機発光層２３から発せられる光を第一電極２１及び第一基板１１を透過させて外部に取り出すことができる。第一電極２１の材料としては、仕事関数の大きい金属、合金、電気伝導性化合物、あるいはこれらの混合物からなる電極材料を挙げることができる。このような材料としては、例えば、ＣｕＩ、ＩＴＯ（Indium Tin Oxide）、ＩＺＯ（Indium Zinc Oxide）等を挙げることができる。 Moreover, it is preferable that the 1st electrode 21 has light transmittance. In this case, if the first substrate 11 is also light transmissive, it becomes a bottom emission type light extraction system, and light emitted from the organic light emitting layer 23 is transmitted through the first electrode 21 and the first substrate 11. It can be taken out outside. Examples of the material of the first electrode 21 include an electrode material composed of a metal having a large work function, an alloy, an electrically conductive compound, or a mixture thereof. As such a material, for example, CuI, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), etc. can be mentioned.
　また第二電極２２は、光反射性を有することが好ましい。この場合、第一基板１１及び第一電極２１が光透過性を有していれば、ボトム・エミッション型の光取り出し方式となり、有機発光層２３から発せられて第二電極２２へ向かう光をこの第二電極２２で反射させることによって、第一電極２１及び第一基板１１を透過させて外部に取り出すことができる。第二電極２２の材料としては、仕事関数の小さい金属、合金、電気伝導性化合物、あるいはこれらの混合物からなる電極材料を挙げることができる。このような材料としては、例えば、ナトリウム、リチウム、マグネシウム、アルミニウム等を挙げることができる。 The second electrode 22 preferably has light reflectivity. In this case, if the first substrate 11 and the first electrode 21 have light transmissivity, it becomes a bottom emission type light extraction system, and the light emitted from the organic light emitting layer 23 and directed to the second electrode 22 is transmitted. By reflecting the light by the second electrode 22, the first electrode 21 and the first substrate 11 can be transmitted and taken out to the outside. Examples of the material of the second electrode 22 include an electrode material made of a metal having a low work function, an alloy, an electrically conductive compound, or a mixture thereof. As such a material, sodium, lithium, magnesium, aluminum etc. can be mentioned, for example.
　なお、第一電極２１が光反射性を有し、第二電極２２が光透過性を有していてもよい。この場合、吸湿部４、水分拡散部５、第二基板１２が光透過性を有することが好ましい。これにより、トップ・エミッション型の光取り出し方式となり、有機発光層２３から発せられて第一電極２１へ向かう光をこの第一電極２１で反射させることによって、第二電極２２、吸湿部４、水分拡散部５、第二基板１２を透過させて外部に取り出すことができる。また第一電極２１及び第二電極２２がいずれも光透過性を有していてもよい。この場合、第一基板１１、吸湿部４、水分拡散部５、第二基板１２が光透過性を有することが好ましい。これにより、両面発光型の光取り出し方式となり、有機発光層２３から発せられる光を第一基板１１及び第二基板１２の両方から外部に取り出すことができる。 The first electrode 21 may have light reflectivity, and the second electrode 22 may have light transparency. In this case, it is preferable that the moisture absorption part 4, the water diffusion part 5, and the second substrate 12 have light transmittance. This becomes a top emission type light extraction system, and the light emitted from the organic light emitting layer 23 and directed to the first electrode 21 is reflected by the first electrode 21, whereby the second electrode 22, the hygroscopic portion 4, the moisture The diffusion portion 5 and the second substrate 12 can be transmitted and taken out to the outside. Further, each of the first electrode 21 and the second electrode 22 may have light transmittance. In this case, it is preferable that the first substrate 11, the moisture absorption unit 4, the moisture diffusion unit 5, and the second substrate 12 have light transmittance. Thus, a double-sided light emission type light extraction system is realized, and light emitted from the organic light emitting layer 23 can be extracted from both the first substrate 11 and the second substrate 12 to the outside.
　また有機発光層２３は、有機エレクトロルミネッセンス素子用の材料として知られている公知の材料で形成することができる。このような材料としては、例えば、アントラセン、ナフタレン、ピレン、テトラセン、コロネン、ペリレン、フタロペリレン、ナフタロペリレン、ジフェニルブタジエン、テトラフェニルブタジエン、クマリン、オキサジアゾール、ビスベンゾキサゾリン、ビススチリル、シクロペンタジエン、キノリン金属錯体、トリス（８－ヒドロキシキノリナート）アルミニウム錯体、トリス（４－メチル－８－キノリナート）アルミニウム錯体、トリス（５－フェニル－８－キノリナート）アルミニウム錯体、アミノキノリン金属錯体、ベンゾキノリン金属錯体、トリ－（ｐ－ターフェニル－４－イル）アミン、１－アリール－２，５－ジ（２－チエニル）ピロール誘導体、ピラン、キナクリドン、ルブレン、ジスチリルベンゼン誘導体、ジスチリルアリーレン誘導体、ジスチリルアミン誘導体、各種の蛍光色素等を挙げることができる。これらのうち２種以上の材料を組み合わせて用いてもよい。また、蛍光発光を生じる材料のみならず、燐光発光等のスピン多重項発光を生じる材料、スピン多重項発光を生じる部位を分子内の一部に有する化合物等を用いてもよい。有機発光層２３は、蒸着法、転写法などの乾式プロセスによって形成しても、塗布法などの湿式プロセスによって形成してもよい。 Moreover, the organic light emitting layer 23 can be formed with the well-known material known as a material for organic electroluminescent elements. Such materials include, for example, anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, quinoline metal. Complex, tris (8-hydroxyquinolinate) aluminum complex, tris (4-methyl-8-quinolinate) aluminum complex, tris (5-phenyl-8-quinolinate) aluminum complex, aminoquinoline metal complex, benzoquinoline metal complex, Tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyran, quinacridone, rubrene, distyrylbenzene derivative, distyryl Arylene derivatives, and distyrylamine derivatives, various fluorescent dyes. Two or more of these materials may be used in combination. Further, not only a material that emits fluorescence but also a material that generates spin multiplet light emission such as phosphorescence, a compound having a site that generates spin multiplet light emission in a part of the molecule, or the like may be used. The organic light emitting layer 23 may be formed by a dry process such as a vapor deposition method or a transfer method, or may be formed by a wet process such as a coating method.
　また第一電極２１と第二電極２２との間には、さらにホール注入層、ホール輸送層、電子輸送層、電子注入層から選択される１種以上の層が介在していてもよい。有機エレクトロルミネッセンス素子用の材料として知られている公知の材料を用いて公知の方法により形成することができる。このように、第一電極２１と第二電極２２との間には、少なくとも有機発光層２３が介在しているので、第一電極２１と第二電極２２とは、直接接触しにくく、電気的に絶縁されることになる。図１に示すように、有機発光層２３の周囲の一部又は全部に公知の材料で絶縁層６を形成し、この絶縁層６で第一電極２１と第二電極２２との絶縁性をさらに高めるようにしてもよい。 Further, one or more layers selected from a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer may be interposed between the first electrode 21 and the second electrode 22. It can form by a well-known method using the well-known material known as a material for organic electroluminescent elements. As described above, since at least the organic light emitting layer 23 is interposed between the first electrode 21 and the second electrode 22, the first electrode 21 and the second electrode 22 are unlikely to be in direct contact with each other, and electrical Will be isolated. As shown in FIG. 1, an insulating layer 6 is formed of a known material on a part or all of the periphery of the organic light emitting layer 23, and the insulating properties of the first electrode 21 and the second electrode 22 are further increased by this insulating layer 6. It may be enhanced.
　また第二基板１２は、有機発光体２０を介して第一基板１１と対向して配置されている。第二基板１２も、第一基板１１と同様に光透過性を有することが好ましいが、第一基板１１が光透過性を有していれば、第二基板１２は、光反射性を有していてもよい。この場合、上述のようにボトム・エミッション型の光取り出し方式となる。第二基板１２としては、例えば、ガラス基板、金属基板、樹脂基板等を用いることができる。ガラス基板の材質としては、例えば、ソーダライムガラス、無アルカリガラス等を挙げることができる。金属基板の材質としては、例えば、アルミニウム、ステンレス等を挙げることができる。樹脂基板の材質としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）等を挙げることができる。第二基板１２を樹脂基板で形成する場合、第二基板１２の表面にＳｉＯＮ膜又はＳｉＮ膜を形成して、水分の透過を抑制してもよい。第二基板１２の形状も、第一基板１１と同様に平面視矩形状でも、その他の形状でもよい。 Further, the second substrate 12 is disposed to face the first substrate 11 via the organic light emitter 20. Similarly to the first substrate 11, the second substrate 12 is also preferably light transmissive, but if the first substrate 11 is light transmissive, the second substrate 12 has light reflectivity. It may be In this case, as described above, the bottom emission type light extraction system is used. For example, a glass substrate, a metal substrate, a resin substrate or the like can be used as the second substrate 12. As a material of a glass substrate, soda lime glass, an alkali free glass etc. can be mentioned, for example. As a material of a metal substrate, aluminum, stainless steel, etc. can be mentioned, for example. Examples of the material of the resin substrate include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). When the second substrate 12 is formed of a resin substrate, a SiON film or a SiN film may be formed on the surface of the second substrate 12 to suppress the permeation of moisture. Similarly to the first substrate 11, the second substrate 12 may have a rectangular shape in a plan view, or another shape.
　また封止壁３は、有機発光体２０を取り囲むように第一基板１１と第二基板１２との間に設けられている。封止壁３によって、有機エレクトロルミネッセンス素子１の外部の水分が有機発光体２０へ浸入することを抑制することができる。封止壁３は、水分の透過率が６０ｇ／ｍ２・２４ｈｏｕｒ以下の材料で形成することが好ましい。水分の透過率は、ＪＩＳ　Ｚ０２０８に規定された防湿包装材料の透湿度試験方法（カップ法）によって測定することができる。封止壁３の材料としては、例えば紫外線硬化性樹脂等を挙げることができる。具体例としては、エポキシ樹脂、アクリル樹脂等の樹脂材料、パラフィンワックス、マイクロクリスタリンワックス等のワックス材料、ガラスフリット等のフリット材料を挙げることができる。封止壁３には、アルミナ等の無機フィラー、酸化カルシウム、酸化ストロンチウム、酸化バリウム、シリカ等の吸湿剤が含有されていてもよい。封止壁３は、例えば、ディスペンス法、印刷法、インクジェット法等により形成することができる。 The sealing wall 3 is provided between the first substrate 11 and the second substrate 12 so as to surround the organic light emitting body 20. The sealing wall 3 can prevent moisture outside the organic electroluminescent element 1 from intruding into the organic light emitter 20. The sealing wall 3 is preferably formed of a material having a moisture permeability of 60 g / m 2 · 24 hours or less. The moisture permeability can be measured by the moisture permeability test method (cup method) of the moisture-proof packaging material defined in JIS Z0208. As a material of the sealing wall 3, an ultraviolet curable resin etc. can be mentioned, for example. Specific examples thereof include resin materials such as epoxy resin and acrylic resin, wax materials such as paraffin wax and microcrystalline wax, and frit materials such as glass frit. The sealing wall 3 may contain an inorganic filler such as alumina, or a hygroscopic agent such as calcium oxide, strontium oxide, barium oxide or silica. The sealing wall 3 can be formed by, for example, a dispensing method, a printing method, an inkjet method, or the like.
　また封止壁３の外側の第一基板１１の端部には、第一電極引出部２１１が形成されている。この第一電極引出部２１１は、封止壁３の内側の第一電極２１を外側に引き出して形成されている。一方、封止壁３の外側の第一基板１１の別の端部には、第二電極引出部２２２が形成されている。この第二電極引出部２２２は、封止壁３の内側の第二電極２２を外側に引き出して形成されている。第一電極引出部２１１及び第二電極引出部２２２を通じて給電して、有機発光体２０の第一電極２１と第二電極２２との間に電圧を印加することによって、有機発光層２３を発光させることができる。 Further, at an end portion of the first substrate 11 outside the sealing wall 3, a first electrode lead-out portion 211 is formed. The first electrode lead portion 211 is formed by drawing the first electrode 21 inside the sealing wall 3 to the outside. On the other hand, at the other end of the first substrate 11 outside the sealing wall 3, a second electrode lead-out portion 222 is formed. The second electrode lead-out portion 222 is formed by pulling out the second electrode 22 inside the sealing wall 3 to the outside. Electric power is supplied through the first electrode lead-out portion 211 and the second electrode lead-out portion 222 to apply a voltage between the first electrode 21 and the second electrode 22 of the organic light emitting body 20 to cause the organic light emitting layer 23 to emit light. be able to.
　また吸湿部４は、吸湿性を有し、好ましくはさらに光透過性を有し、有機発光体２０の全体を被覆している。好ましくは吸湿部４は固体である。この場合、水分が封止壁３を通過して内側に浸入しても、吸湿部４によってこの水分が有機発光体２０へ浸入することをさらに抑制することができる。吸湿部４は、吸湿剤（乾燥剤）を含有する樹脂材料で形成することができる。吸湿剤としては、水分を化学的に吸着するものでも物理的に吸着するものでもよく、例えば、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化ナトリウム、酸化カリウム、硫酸ナトリウム、硫酸カルシウム等のアルカリ金属やアルカリ土類金属を含む粉末粒子や、ゼオライト等を挙げることができる。樹脂材料としては、例えば１００℃以下の温度で加熱して硬化するような熱硬化性樹脂や、紫外線硬化性樹脂を挙げることができる。このような樹脂材料は、水分が透過しにくいものが好ましく、例えば、エポキシ樹脂、アルカリ樹脂、シリコーン樹脂等を挙げることができる。吸湿剤は、吸湿部４を構成する材料全量に対して３０質量％以上９５質量％未満含有されていることが好ましい。吸湿部４は、例えば、ディスペンス法、印刷法、スパッタ法、スピンコート法、ディップ法、スプレー法等により形成することができる。 Further, the hygroscopic part 4 has hygroscopicity, preferably further has light transparency, and covers the whole of the organic light emitting body 20. Preferably, the moisture absorption part 4 is solid. In this case, even if the moisture passes through the sealing wall 3 and enters inside, the moisture absorption part 4 can further suppress the moisture from entering the organic light emitting body 20. The moisture absorption part 4 can be formed with the resin material containing a moisture absorption agent (drying agent). The hygroscopic agent may be one that chemically adsorbs moisture or one that physically adsorbs it, and examples thereof include alkali metals such as calcium oxide, strontium oxide, barium oxide, sodium oxide, potassium oxide, sodium sulfate, calcium sulfate, etc. The powder particle containing an alkaline-earth metal, a zeolite, etc. can be mentioned. Examples of the resin material include thermosetting resins that cure by heating at a temperature of 100 ° C. or less and ultraviolet curable resins. Such a resin material is preferably one that is hard to permeate moisture, and examples thereof include epoxy resin, alkali resin, silicone resin and the like. The hygroscopic agent is preferably contained in an amount of 30% by mass or more and less than 95% by mass with respect to the total amount of materials constituting the hygroscopic portion 4. The moisture absorbent portion 4 can be formed, for example, by a dispensing method, a printing method, a sputtering method, a spin coating method, a dipping method, a spraying method, or the like.
　ところで、図４に示すように、第一基板１１、有機発光体２０、第二基板１２、封止壁３によって囲まれる空間全体を吸湿部４で充填することが考えられる。しかし、この場合、封止壁３を通過して浸入した水分は、主として発光領域Ｅの外側の吸湿部４で吸湿されてしまい、発光領域Ｅの内側の吸湿部４が有効に利用されにくいという問題がある。 By the way, as shown in FIG. 4, it is conceivable to fill the entire space surrounded by the first substrate 11, the organic light emitting body 20, the second substrate 12, and the sealing wall 3 with the hygroscopic portion 4. However, in this case, the moisture that has permeated through the sealing wall 3 is absorbed mainly by the moisture absorbing portion 4 outside the light emitting region E, and the moisture absorbing portion 4 inside the light emitting region E is difficult to be effectively used. There's a problem.
　そこで、本実施形態においては、図１に示すように、水分拡散性を有し、好ましくはさらに光透過性を有する水分拡散部５を第二基板１２と吸湿部４との間に介在させるようにしている。そうすると、封止壁３を通過して浸入した水分を、水分拡散部５によって発光領域Ｅの内側まで拡散させて移動させることができ、発光領域Ｅの内側の吸湿部４を有効に利用することができる。その結果、水分が有機発光体２０へ浸入しにくくなり、有機エレクトロルミネッセンス素子１の長寿命化を図ることができる。 Therefore, in the present embodiment, as shown in FIG. 1, a moisture diffusing portion 5 having moisture diffusibility, preferably further having light permeability is interposed between the second substrate 12 and the moisture absorbing portion 4. I have to. Then, the moisture which has passed through the sealing wall 3 can be diffused and moved to the inside of the light emitting area E by the water diffusing unit 5, and the moisture absorbing part 4 inside the light emitting area E can be effectively used. Can. As a result, moisture is less likely to enter the organic light emitting body 20, and the lifetime of the organic electroluminescent device 1 can be extended.
　また水分拡散部５は、少なくとも第二基板１２と吸湿部４との間に介在していればよいので、例えば図２に示すように、封止壁３の内側の側面と吸湿部４の側面との間に空隙部７が存在していてもよい。封止壁３を通過して空隙部７に浸入した水分は、そのまま発光領域Ｅの外側の吸湿部４で吸湿されたり、あるいは一旦水分拡散部５によって発光領域Ｅの内側まで拡散して移動した後、発光領域Ｅの内側の吸湿部４で吸湿されたりする。 Further, since the moisture diffusion unit 5 may be interposed at least between the second substrate 12 and the moisture absorption unit 4, for example, as shown in FIG. 2, the inner side surface of the sealing wall 3 and the side surface of the moisture absorption unit 4 There may be a gap 7 between them. The moisture that has passed through the sealing wall 3 and entered the air gap 7 is absorbed as it is by the moisture absorption part 4 outside the light emission area E or is diffused and moved to the inside of the light emission area E by the water diffusion part 5 once. After that, the moisture is absorbed by the moisture absorbing portion 4 inside the light emitting region E or the like.
　また、水分拡散部５が第二基板１２と吸湿部４との間に介在していることによって、第二基板１２が第一基板１１の側にへこみにくくなり、有機エレクトロルミネッセンス素子１の堅牢性も得ることができる。この場合の堅牢性は、耐押圧性を含む概念である。より詳細には、水分拡散部５は固体であることが好ましく、このような固体の水分拡散部５が、有機エレクトロルミネッセンス素子１の厚さ方向において、第二基板１２と吸湿部４との間に隙間なく充填されていることが好ましい。この場合、有機エレクトロルミネッセンス素子１に厚さ方向に両側から圧力が加わったとしても、第二基板１２が有機発光層２０に接触して有機発光層２０に傷が付くことを、固体の水分拡散部５によって抑制することができる。つまり、固体の水分拡散部５が、第二基板１２と有機発光層２０との接触を阻害している。このように、第二基板１２と有機発光層２０との接触が阻害されればよいので、固体の水分拡散部５は、有機エレクトロルミネッセンス素子１の厚さ方向において、少なくとも第二基板１２と吸湿部４との間に隙間なく充填されていればよく、図２に示すように封止壁３の内側の側面と吸湿部４の側面との間に空隙部７が存在していても構わない。しかし、もし第二基板１２と吸湿部４との間に隙間があって中空であったり、あるいは水分拡散部５が液体であったりすると、有機エレクトロルミネッセンス素子１に厚さ方向に両側から圧力が加わった場合に、第二基板１２が第一基板１１の側にへこみ、有機発光層２０に接触して、有機発光層２０に傷が付くおそれがある。 In addition, since the water diffusion portion 5 is interposed between the second substrate 12 and the moisture absorption portion 4, the second substrate 12 is less likely to be dented on the first substrate 11 side, and the fastness of the organic electroluminescent element 1 is obtained. You can also get it. The robustness in this case is a concept including pressure resistance. More specifically, the water diffusion portion 5 is preferably a solid, and such a solid water diffusion portion 5 is between the second substrate 12 and the moisture absorption portion 4 in the thickness direction of the organic electroluminescent element 1. Is preferably filled without gaps. In this case, even if the pressure is applied to the organic electroluminescent element 1 from both sides in the thickness direction, the second substrate 12 contacts the organic light emitting layer 20 and the organic light emitting layer 20 is damaged. It can be suppressed by the part 5. That is, the solid water diffusion unit 5 inhibits the contact between the second substrate 12 and the organic light emitting layer 20. As described above, since the contact between the second substrate 12 and the organic light emitting layer 20 may be inhibited, the solid water diffusion unit 5 absorbs moisture with at least the second substrate 12 in the thickness direction of the organic electroluminescent element 1. It may be filled without a gap between the part 4 and, as shown in FIG. 2, the void 7 may be present between the inner side surface of the sealing wall 3 and the side surface of the hygroscopic part 4 . However, if there is a gap between the second substrate 12 and the hygroscopic member 4 and it is hollow or the moisture diffusion part 5 is liquid, pressure is applied to the organic electroluminescent element 1 from both sides in the thickness direction When it is added, the second substrate 12 may be dented on the side of the first substrate 11 and may be in contact with the organic light emitting layer 20, and the organic light emitting layer 20 may be damaged.
　また水分拡散部５は、多孔質性を有する硬質樹脂で形成することが好ましい。このような水分拡散部５は、例えば平均粒子径１０～１００μｍの粒子を紫外線硬化性エポキシ樹脂等の紫外線硬化性樹脂でコーティングし、このコーティングされた粒子を吸湿部４の表面に散布することによって形成することができる。上記の粒子は、金属やシリカのような水分を吸着しにくい材料であることが好ましい。このようにして水分拡散部５が形成されていると、硬質樹脂が有する多数の微細な孔が水分の通り道となって、水分が滞留しにくくなり、水分拡散性をさらに向上させることができる。しかも水分拡散部５は硬質であるため、堅牢性もさらに向上させることができる。なお、本明細書において、平均粒子径は、レーザー回折・散乱法によって求めた粒度分布における積算値５０％での粒径を意味する。また上記のように紫外線硬化性樹脂でコーティングされた粒子の代わりに、ポリエチレン粒子等を焼結して厚さ１０００μｍ以下に成形された多孔質シートを用いて水分拡散部５を形成してもよい。 Further, the water diffusion portion 5 is preferably formed of a porous hard resin. Such a water diffusion unit 5 coats, for example, particles having an average particle diameter of 10 to 100 μm with an ultraviolet curable resin such as an ultraviolet curable epoxy resin, and the coated particles are dispersed on the surface of the moisture absorbent 4 It can be formed. The particles described above are preferably materials that do not easily adsorb moisture, such as metals and silica. In this manner, when the water diffusion portion 5 is formed, a large number of fine holes included in the hard resin serve as a passage of water, so that the water does not easily stay, and the water diffusibility can be further improved. Moreover, since the water diffusion portion 5 is hard, the fastness can be further improved. In addition, in this specification, an average particle diameter means the particle size in 50% of the integration value in the particle size distribution calculated | required by the laser diffraction and the scattering method. Also, instead of the particles coated with the ultraviolet curable resin as described above, the moisture diffusion part 5 may be formed using a porous sheet formed by sintering polyethylene particles etc. to a thickness of 1000 μm or less .
　上記のように水分拡散部５を、多孔質性を有する硬質樹脂で形成する場合も、このような固体の水分拡散部５は、有機エレクトロルミネッセンス素子１の厚さ方向において、第二基板１２と吸湿部４との間に隙間なく充填されていることが好ましい。もちろんこの場合の隙間は、硬質樹脂が有している多数の微細な孔を意味するのではない。これらの孔は、閉塞されずに水分の通り道として確保される。 As described above, also in the case where the moisture diffusion portion 5 is formed of a porous hard resin, the solid moisture diffusion portion 5 in the thickness direction of the organic electroluminescent element 1 It is preferable to be filled without gaps with the hygroscopic member 4. Of course, the gap in this case does not mean the large number of fine holes possessed by the hard resin. These holes are secured as a water passage without being blocked.
　また図１に示すように、第一基板１１と封止壁３との界面及び封止壁３と第二基板１２との界面は平坦に形成されていてもよいが、これらの界面は図３に示すように凹凸状に形成されていることが好ましい。このように、第一基板１１と封止壁３との界面及び封止壁３と第二基板１２との界面が凹凸状に形成されていると、水分はこれらの界面を通過しにくくなり、封止壁３の内側に浸入することを抑制することができる。上記の両方の界面が凹凸状に形成されていることがより好ましいが、少なくともいずれかの界面が凹凸状に形成されていればよい。上記の界面を凹凸状に形成するにあたっては、例えば、第一基板１１及び第二基板１２の封止壁３を設ける箇所にあらかじめガラスフリットを塗布した後に焼成することによって、高さ１０～２００μｍの土手状などの突起部８を形成しておけばよい。第一基板１１に形成した突起部８の先端と、第二基板１２との間の隙間、及び第一基板１１と、第二基板１２に形成した突起部８の先端との隙間は２０μｍ以下であることが好ましい。第一基板１１と第二基板１２との間の隙間は２００μｍ以下であることが好ましい。なお、第一基板１１と封止壁３との界面という場合には、第一基板１１と封止壁３とが直接接触している場合のほか、第一基板１１と封止壁３との間に第一電極２１が介在している場合も含まれる。 Further, as shown in FIG. 1, the interface between the first substrate 11 and the sealing wall 3 and the interface between the sealing wall 3 and the second substrate 12 may be formed flat, but these interfaces It is preferable to form in the uneven | corrugated shape as shown to. As described above, when the interface between the first substrate 11 and the sealing wall 3 and the interface between the sealing wall 3 and the second substrate 12 are formed in a concavo-convex shape, moisture hardly passes through these interfaces, Infiltration of the inside of the sealing wall 3 can be suppressed. It is more preferable that both of the above interfaces be formed in a concavo-convex shape, but at least one of the interfaces may be formed in a concavo-convex shape. In order to form the above-described interface in a concavo-convex shape, for example, a glass frit is previously applied to a portion where the sealing wall 3 of the first substrate 11 and the second substrate 12 is provided and then fired to have a height of 10 to 200 μm. A bank-like protrusion 8 may be formed. The gap between the tip of the protrusion 8 formed on the first substrate 11 and the second substrate 12 and the gap between the first substrate 11 and the tip of the protrusion 8 formed on the second substrate 12 are 20 μm or less Is preferred. The gap between the first substrate 11 and the second substrate 12 is preferably 200 μm or less. In addition, in the case of the interface between the first substrate 11 and the sealing wall 3, in addition to the case where the first substrate 11 and the sealing wall 3 are in direct contact, the first substrate 11 and the sealing wall 3 The case where the first electrode 21 is interposed is also included.
　また本実施形態においては、図１に示すように、封止壁３の内側の側面と吸湿部４の側面との間の幅Ｗ１は、吸湿部４の側面と有機発光体２０の側面との間の幅Ｗ２よりも狭いことが好ましい。このようにＷ１＜Ｗ２である場合には、発光領域Ｅの外側における吸湿部４を十分に確保しつつ、水分拡散部５による水分の発光領域Ｅの内側への拡散を促進させることができる。また図１に示すように、水分拡散部５の厚さＴ１は、吸湿部４の厚さＴ２よりも厚いことが好ましい。このようにＴ１＞Ｔ２である場合には、水分拡散部５による水分拡散性をさらに向上させることができるほか、堅牢性もさらに向上させることができる。水分拡散部５の厚さＴ１は２０～２００μｍであることが好ましく、吸湿部４の厚さＴ２は１０～１００μｍであることが好ましい。 Further, in the present embodiment, as shown in FIG. 1, the width W 1 between the inner side surface of the sealing wall 3 and the side surface of the hygroscopic member 4 is the side surface of the hygroscopic member 4 and the side surface of the organic light emitting body 20 it is preferably narrower than the width W 2 between. As described above, in the case of W 1 <W 2, it is possible to promote the diffusion of water to the inside of the light emitting area E by the water diffusing unit 5 while sufficiently securing the moisture absorbing part 4 outside the light emitting area E. it can. Further, as shown in FIG. 1, it is preferable that the thickness T 1 of the moisture diffusion portion 5 be thicker than the thickness T 2 of the moisture absorption portion 4. As described above, in the case of T 1 > T 2, it is possible to further improve the water diffusibility by the water diffusion portion 5 and to further improve the fastness. The thickness T 1 of the water diffusion portion 5 is preferably 20 to 200 μm, and the thickness T 2 of the moisture absorption portion 4 is preferably 10 to 100 μm.
　次に本発明の実施の形態における有機エレクトロルミネッセンス素子１の製造方法について説明する。 Next, the manufacturing method of the organic electroluminescent element 1 in embodiment of this invention is demonstrated.
　まずガラス基板等の第一基板１１の表面にＩＴＯ等の透明導電膜を成膜し、フォトリソグラフィー法によりパターニングすることによって、第一電極２１及び第一電極引出部２１１を形成する。 First, a transparent conductive film such as ITO is formed on the surface of the first substrate 11 such as a glass substrate and patterned by photolithography to form the first electrode 21 and the first electrode lead-out portion 211.
　次に第一電極２１の表面に所定の材料を用いて蒸着法等により有機発光層２３を形成する。このとき適宜、ホール注入層、ホール輸送層、電子輸送層、電子注入層から選択される１種以上の層を形成したり、絶縁層６を形成したりしてもよい。 Next, an organic light emitting layer 23 is formed on the surface of the first electrode 21 by vapor deposition or the like using a predetermined material. At this time, one or more layers selected from a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer may be appropriately formed, or the insulating layer 6 may be formed.
　次に有機発光層２３の表面にアルミニウム等の金属膜を蒸着法等により成膜することによって、第二電極２２及び第二電極引出部２２２を形成する。このようにして第一基板１１の表面に有機発光体２０を形成することができる。 Next, a second electrode 22 and a second electrode lead-out portion 222 are formed by depositing a metal film of aluminum or the like on the surface of the organic light emitting layer 23 by a vapor deposition method or the like. Thus, the organic light emitting body 20 can be formed on the surface of the first substrate 11.
　次に有機発光体２０の全体を被覆するように、吸湿剤を含有する樹脂材料をスクリーン印刷法等により塗布した後、加熱又は紫外線照射して樹脂材料を硬化させることによって吸湿部４を形成する。このようにして形成された吸湿部４の厚さＴ２は、上述のように１０～１００μｍであることが好ましい。 Next, a resin material containing a hygroscopic agent is applied by a screen printing method or the like so as to cover the whole of the organic light emitting body 20, and then the resin material is cured by heating or ultraviolet irradiation to form the hygroscopic portion 4. . The thickness T 2 of the moisture absorption part 4 formed in this manner is preferably 10 to 100 μm as described above.
　次に硬化した吸湿部４の全体を被覆するように、紫外線硬化性樹脂でコーティングされた粒子を散布することによって、未硬化の水分拡散部５を形成する。上記の粒子の散布は、図１に示す厚さＴ１が１００～１０００μｍ程度となるように行うことが好ましい。 Next, the uncured moisture diffusion portion 5 is formed by spraying the particles coated with the ultraviolet curable resin so as to cover the entire cured moisture absorbing portion 4. Spraying the particles is preferably carried out to a thickness T 1 shown in FIG 1 is about 100 ~ 1000 .mu.m.
　次に平面視において未硬化の水分拡散部５の外周に、封止壁３の材料である紫外線硬化性樹脂を塗布する。 Next, the ultraviolet curable resin which is a material of the sealing wall 3 is apply | coated to the outer periphery of the moisture diffusion part 5 which is not hardened in planar view.
　次に１Ｐａ程度まで減圧した真空チャンバーの中に、上記の第一基板１１と、これと同じ大きさの第二基板１２とを入れ、有機発光体２０を介して第一基板１１と第二基板１２とを対向配置して密着させる。このとき封止壁３の材料である紫外線硬化性樹脂が第一基板１１及び第二基板１２の両方で押し潰されて、未硬化の水分拡散部５を密封することができる。このとき水分拡散部５は、吸湿部４及び第二基板１２の両方で押し潰されるが、押し潰された後の水分拡散部５の厚さＴ１は吸湿部４の厚さＴ２よりも厚いことが好ましく、具体的には厚さＴ１は２０～２００μｍであることが好ましい。この状態で紫外線を照射して、水分拡散部５の材料である紫外線硬化性樹脂及び封止壁３の材料である紫外線硬化性樹脂の両方を硬化させた後、大気圧下に戻すと図１に示すような有機エレクトロルミネッセンス素子１を得ることができる。 Next, the first substrate 11 and the second substrate 12 having the same size as above are placed in a vacuum chamber whose pressure is reduced to about 1 Pa, and the first substrate 11 and the second substrate are separated via the organic light emitter 20. 12 is placed in close contact with each other. At this time, the ultraviolet curable resin, which is the material of the sealing wall 3, is crushed by both the first substrate 11 and the second substrate 12, and the uncured water diffusion portion 5 can be sealed. At this time, the water diffusion portion 5 is crushed by both the moisture absorption portion 4 and the second substrate 12, but the thickness T 1 of the water diffusion portion 5 after being crushed is greater than the thickness T 2 of the moisture absorption portion 4. It is preferably thick, and specifically, the thickness T 1 is preferably 20 to 200 μm. In this state, ultraviolet rays are irradiated to cure both the ultraviolet curable resin which is the material of the water diffusion portion 5 and the ultraviolet curable resin which is the material of the sealing wall 3 and then return to atmospheric pressure. The organic electroluminescent element 1 as shown in can be obtained.
　図２に示す有機エレクトロルミネッセンス素子１を製造するにあたっては、上記と同様にして吸湿部４まで形成した後、この硬化した吸湿部４の全体を多孔質シートで被覆する。多孔質シートとしては、ポリエチレン粒子等を焼結して厚さ１０００μｍ以下に成形されたものを用いることができる。多孔質シートの位置がずれないように、粘着性のある材料で吸湿部４に多孔質シートを接着してもよい。 In manufacturing the organic electroluminescent element 1 shown in FIG. 2, after forming up to the moisture absorption part 4 in the same manner as described above, the entire cured moisture absorption part 4 is covered with a porous sheet. As the porous sheet, a sheet formed by sintering polyethylene particles or the like and having a thickness of 1000 μm or less can be used. The porous sheet may be adhered to the moisture absorbent portion 4 with an adhesive material so that the position of the porous sheet does not shift.
　その後は平面視において多孔質シートの外周に、封止壁３の材料である紫外線硬化性樹脂を塗布する。 Thereafter, an ultraviolet curable resin which is a material of the sealing wall 3 is applied to the outer periphery of the porous sheet in plan view.
　そして、上記と同様に真空チャンバーの中において、有機発光体２０を介して第一基板１１と第二基板１２とを対向配置して密着させる。このとき封止壁３の材料である紫外線硬化性樹脂が第一基板１１及び第二基板１２の両方で押し潰される。また水分拡散部５の材料である多孔質シートは、吸湿部４及び第二基板１２の両方で押し潰される。押し潰された後の水分拡散部５（多孔質シート）の厚さＴ１は吸湿部４の厚さＴ２よりも厚いことが好ましく、具体的には厚さＴ１は２０～２００μｍであることが好ましい。この状態で紫外線を照射して封止壁３の材料である紫外線硬化性樹脂を硬化させた後、大気圧下に戻すと図２に示すような有機エレクトロルミネッセンス素子１を得ることができる。 Then, similarly to the above, in the vacuum chamber, the first substrate 11 and the second substrate 12 are disposed so as to face each other via the organic light emitting body 20 so as to be in close contact with each other. At this time, the ultraviolet curable resin which is the material of the sealing wall 3 is crushed by both the first substrate 11 and the second substrate 12. Further, the porous sheet which is the material of the water diffusion portion 5 is crushed in both the moisture absorption portion 4 and the second substrate 12. The thickness T 1 of the water diffusion section 5 (porous sheet) thick is preferred than the thickness T 2 of the moisture absorption portion 4, the thickness T 1 is specifically is 20 ~ 200 [mu] m after being crushed Is preferred. After ultraviolet light is irradiated in this state to cure the ultraviolet curable resin which is the material of the sealing wall 3, when the pressure is returned to atmospheric pressure, the organic electroluminescent device 1 as shown in FIG. 2 can be obtained.
　図３に示す有機エレクトロルミネッセンス素子１を製造するにあたっては、まず第一基板１１の封止壁３を設ける予定の箇所にガラスフリットをスクリーン印刷法等により塗布する。その後、これを８００℃以上の温度で焼成することによって、高さ１０～２００μｍ程度の土手状などの突起部８を形成する。これと同様にして第二基板１２にもあらかじめ突起部８を形成しておく。このような第一基板１１及び第二基板１２を用いると、図３に示すような有機エレクトロルミネッセンス素子１を得ることができる。 In order to manufacture the organic electroluminescent element 1 shown in FIG. 3, first, a glass frit is applied by screen printing or the like to a place where the sealing wall 3 of the first substrate 11 is to be provided. Thereafter, this is fired at a temperature of 800 ° C. or higher to form a bank-like protrusion 8 having a height of about 10 to 200 μm. Similarly to this, the projection 8 is formed on the second substrate 12 in advance. When such a first substrate 11 and a second substrate 12 are used, an organic electroluminescent device 1 as shown in FIG. 3 can be obtained.
　１　有機エレクトロルミネッセンス素子
　３　封止壁
　４　吸湿部
　５　水分拡散部
　１１　第一基板
　１２　第二基板
　２０　有機発光体 DESCRIPTION OF SYMBOLS 1 organic electroluminescent element 3 sealing wall 4 moisture absorption part 5 water-diffusion part 11 1st board | substrate 12 2nd board | substrate 20 organic light-emitting body

Claims (4)

  1. 　第一基板と、
    　前記第一基板に設けられた有機発光体と、
    　前記有機発光体を介して前記第一基板と対向して配置された第二基板と、
    　前記有機発光体を取り囲むように前記第一基板と前記第二基板との間に設けられた封止壁と、
    　吸湿性を有し、前記有機発光体を被覆する吸湿部と、
    　水分拡散性を有し、少なくとも前記第二基板と前記吸湿部との間に介在する水分拡散部と、
    を備えることを特徴とする
    　有機エレクトロルミネッセンス素子。     A first substrate,
    An organic light emitter provided on the first substrate;
    A second substrate disposed opposite to the first substrate via the organic light emitter;
    A sealing wall provided between the first substrate and the second substrate so as to surround the organic light emitter;
    A hygroscopic part which is hygroscopic and covers the organic luminescent material,
    A moisture diffusing portion having moisture diffusibility and interposed between at least the second substrate and the hygroscopic portion;
    An organic electroluminescent device comprising:
  2. 　前記水分拡散部が、多孔質性を有する硬質樹脂で形成されていることを特徴とする
    　請求項１に記載の有機エレクトロルミネッセンス素子。     The organic electroluminescent element according to claim 1, wherein the water diffusion portion is formed of a porous hard resin.
  3. 　前記第一基板と前記封止壁との界面及び前記封止壁と前記第二基板との界面の少なくともいずれかの界面が凹凸状に形成されていることを特徴とする
    　請求項１又は２に記載の有機エレクトロルミネッセンス素子。     The interface between the first substrate and the sealing wall and / or the interface between the sealing wall and the second substrate are formed in a concavo-convex shape. The organic electroluminescent element of description.
  4. 　前記封止壁の内側の側面と前記吸湿部の側面との間の幅が、前記吸湿部の側面と前記有機発光体の側面との間の幅よりも狭く、
    　前記水分拡散部の厚さが、前記吸湿部の厚さよりも厚いことを特徴とする
    　請求項１乃至３のいずれか一項に記載の有機エレクトロルミネッセンス素子。     The width between the inner side surface of the sealing wall and the side surface of the hygroscopic member is narrower than the width between the side surface of the hygroscopic member and the side surface of the organic light emitter,
    The organic electroluminescent element according to any one of claims 1 to 3, wherein a thickness of the water diffusion portion is thicker than a thickness of the moisture absorption portion.
PCT/JP2014/002359 2013-05-13 2014-04-28 Organic electroluminescent element WO2014185025A1 (en)

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