TWI762711B - Drying agent, sealing structure and organic el element - Google Patents

Drying agent, sealing structure and organic el element Download PDF

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TWI762711B
TWI762711B TW107130916A TW107130916A TWI762711B TW I762711 B TWI762711 B TW I762711B TW 107130916 A TW107130916 A TW 107130916A TW 107130916 A TW107130916 A TW 107130916A TW I762711 B TWI762711 B TW I762711B
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desiccant
layer
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oxide particles
substrate
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TW201918518A (en
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白神崇生
井上麻美
小川一道
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日商双葉電子工業股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09FNATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F9/00Compounds to be used as driers, i.e. siccatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
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    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/846Passivation; Containers; Encapsulations comprising getter material or desiccants
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass

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Abstract

本發明揭示了一種乾燥劑,其含有黏合劑及氧化物 顆粒,該氧化物顆粒被分散在黏合劑中並包含鹼土金屬氧化物。黏合劑包含氫矽烷改質氟樹脂。氫矽烷改質氟樹脂具有:包含氟化烴基之含氟鏈、及鍵結在該含氟鏈上且包含氫化矽烷基之矽氧烷基。 The invention discloses a desiccant containing a binder and an oxide particles, the oxide particles are dispersed in a binder and contain alkaline earth metal oxides. The adhesive contains a hydrosilane-modified fluororesin. The hydrosilane-modified fluororesin has a fluorine-containing chain including a fluorinated hydrocarbon group, and a siloxane group bound to the fluorine-containing chain and including a hydrosilyl group.

Description

乾燥劑、密封結構體及有機電致發光元件 Desiccant, sealing structure and organic electroluminescent element

本發明關於一種乾燥劑、密封結構體及有機電致發光元件。The present invention relates to a desiccant, a sealing structure and an organic electroluminescence element.

有機電致發光(Electroluminescence)元件通常具有發光部,該發光部包括有機層及夾持該有機層的一對電極。有機層是包含有機發光材料之薄膜。有機電致發光元件是一種自發光元件,其藉由向薄膜注入正電孔(電洞)和電子並使其再結合而產生激子,從而利用該激子去活化時所放射出的光(螢光或磷光)而發光。An organic electroluminescence (Electroluminescence) element generally has a light-emitting portion, and the light-emitting portion includes an organic layer and a pair of electrodes sandwiching the organic layer. The organic layer is a thin film containing an organic light-emitting material. An organic electroluminescence element is a self-luminous element that generates excitons by injecting positive holes (holes) and electrons into a thin film and recombining them, thereby utilizing the light emitted when the excitons are deactivated ( fluorescence or phosphorescence).

針對有機電致發光元件,期望可防止被稱作黑點的有機層的非發光部的產生及其生長。作為產生黑點的主要原因,已知水分和氧氣的影響較大,尤其是水分,即使存在微量的水分亦會對黑點的產生帶來很大的影響。In the organic electroluminescence element, it is desired to prevent the occurrence and growth of non-emitting portions of the organic layer called black spots. As the main cause of black spots, it is known that moisture and oxygen have a great influence, especially moisture, and even a small amount of moisture has a great influence on the generation of black spots.

因此,人們對防止水分和氧氣侵入有機電致發光元件的方法進行了各種研究。例如,專利文獻日本特開JP2003-16307A和JP2007-012372A公開了一種有機電致發光元件,其具備下述混合物作為乾燥劑,該混合物是將特定量的吸附材料混合於由氟油所構成的惰性液體或氟類凝膠中而成。並且專利文獻2公開了一種有機電致發光元件,其具備混合物作為乾燥劑,該混合物是將特定量的吸附材料混合於由矽油所構成的惰性液體中而成。Therefore, various studies have been conducted on methods for preventing the intrusion of moisture and oxygen into organic electroluminescent elements. For example, Japanese Patent Laid-Open Nos. JP2003-16307A and JP2007-012372A disclose an organic electroluminescence element having a mixture as a desiccant, which is a mixture of a specific amount of an adsorbent and an inert agent composed of fluorine oil. Liquid or fluorine gel. In addition, Patent Document 2 discloses an organic electroluminescence element including a mixture as a desiccant in which a specific amount of an adsorbent is mixed with an inert liquid composed of silicone oil.

為了使乾燥劑的捕水性能提升,認為增加作為捕水成分的吸附材料的量較為有效。然而,例如,如果增加氧化鈣這樣的鹼土金屬氧化物的顆粒來作為捕水成分,則會由於顆粒的凝聚等而使乾燥劑變稠,從而乾燥劑的塗佈會有變得困難的傾向。In order to improve the water-capturing performance of the desiccant, it is considered to be effective to increase the amount of the adsorbent as a water-capturing component. However, for example, when particles of alkaline earth metal oxides such as calcium oxide are added as a water-trapping component, the desiccant tends to become thicker due to aggregation of the particles and the like, and application of the desiccant tends to be difficult.

對此,本發明的一實施形態的目的在於,提供一種乾燥劑,其不僅能夠具有充分的捕水性能,並具有適於塗佈的較低黏度。In view of this, an object of one embodiment of the present invention is to provide a desiccant which not only has sufficient water catching performance but also has a relatively low viscosity suitable for coating.

本發明的一種實施形態提供一種乾燥劑,其含有黏合劑及氧化物顆粒,該氧化物顆粒被分散在前述黏合劑中且包含鹼土金屬氧化物。換言之,本發明的一種實施形態提供一種組成物作為乾燥劑的用途、或該組成物用於製造乾燥劑的用途,該組成物含有黏合劑及氧化物顆粒,該氧化物顆粒分散在前述黏合劑中且包含鹼土金屬氧化物。前述黏合劑包含氫矽烷改質氟樹脂。前述氫矽烷改質氟樹脂具有:包含氟化烴基之含氟鏈、及鍵結在該含氟鏈上且包含氫化矽烷基之矽氧烷基。One embodiment of the present invention provides a desiccant comprising a binder and oxide particles, wherein the oxide particles are dispersed in the aforementioned binder and include an alkaline earth metal oxide. In other words, an embodiment of the present invention provides the use of a composition as a desiccant, or the use of the composition for manufacturing a desiccant, the composition contains a binder and oxide particles, and the oxide particles are dispersed in the aforementioned binder. and contains alkaline earth metal oxides. The aforementioned adhesive includes a hydrosilane-modified fluororesin. The aforementioned hydrosilane-modified fluororesin has a fluorine-containing chain including a fluorinated hydrocarbon group, and a siloxane group bound to the fluorine-containing chain and including a hydrosilyl group.

根據本發明人的見解,藉由將具有氫化矽烷基和含氟鏈之上述氫矽烷改質氟樹脂用來作為黏合劑,不僅能夠將黏度維持在能夠塗佈的較低黏度,並且能夠增加氧化物顆粒的含量而充分地提高捕水性能。獲得該效果的原因尚無定論,但是認為如下:氫矽烷改質氟樹脂所具有的氫化矽烷基的至少一部分會與氧化物顆粒發生反應而形成化學鍵,從而提高氧化物顆粒在黏合劑中的分散性,其結果,能夠將乾燥劑的黏度維持為較低。 According to the knowledge of the present inventors, by using the above-mentioned hydrosilane-modified fluororesin having a hydrosilyl group and a fluorine-containing chain as a binder, not only can the viscosity be maintained at a low viscosity for coating, but also oxidation can be increased. The content of organic particles can fully improve the water capture performance. The reason for this effect has not been determined, but it is considered as follows: At least a part of the hydrosilyl group of the hydrosilane-modified fluororesin reacts with the oxide particles to form chemical bonds, thereby improving the dispersion of the oxide particles in the binder. As a result, the viscosity of the desiccant can be kept low.

本發明的另一實施形態提供一種密封結構體,其具備:一對基板,其被配置為相對向;密封劑,其將前述一對基板的外周部進行密封;及,乾燥劑層,其被設置在前述密封劑的內側且在前述一對基板之間,並包含上述乾燥劑。 Another embodiment of the present invention provides a sealing structure comprising: a pair of substrates arranged to face each other; a sealant for sealing the outer peripheral portions of the pair of substrates; and a desiccant layer covered by It is provided inside the sealant and between the pair of substrates, and contains the desiccant.

進一步,本發明的另一實施形態提供一種有機電致發光元件,其具備:元件基板;密封基板,其被配置為與前述元件基板相對向;密封劑,其將前述元件基板和前述密封基板的外周部進行密封;發光部,其被設置在前述密封劑的內側且在前述元件基板上;及,乾燥劑層,其被設置在前述密封劑的內側且在前述元件基板與前述密封基板之間,並包含上述乾燥劑。發光部為一積層體,其具有被配置為相對向的一對電極、及被設置在該一對電極之間的有機層。 Further, another embodiment of the present invention provides an organic electroluminescence element comprising: an element substrate; a sealing substrate arranged to face the element substrate; an outer peripheral part is sealed; a light emitting part is provided inside the sealant and on the element substrate; and a desiccant layer is provided inside the sealant and between the element substrate and the sealing substrate , and contains the above-mentioned desiccant. The light-emitting portion is a laminate having a pair of electrodes arranged to face each other, and an organic layer provided between the pair of electrodes.

以下,詳細地說明本發明的若干實施形態。但是,本發明並未限定於以下實施形態。Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[乾燥劑] 一種實施形態的乾燥劑含有黏合劑及氧化物顆粒,該氧化物顆粒分散在黏合劑中且包含鹼土金屬氧化物。黏合劑包含氫矽烷改質氟樹脂。氫矽烷改質氟樹脂具有含有氟化烴基之含氟鏈、及鍵結在該含氟鏈上且包含氫化矽烷基之矽氧烷基。[Desiccant] The desiccant of one embodiment contains a binder and oxide particles, and the oxide particles are dispersed in the binder and contain an alkaline earth metal oxide. The adhesive contains a hydrosilane-modified fluororesin. The hydrosilane-modified fluororesin has a fluorine-containing chain containing a fluorinated hydrocarbon group, and a siloxane group bound to the fluorine-containing chain and containing a hydrosilyl group.

[氫矽烷改質氟樹脂] 氫矽烷改質氟樹脂的含氟鏈包含氟化烴基。該氟化烴基可以是全氟烷基或全氟亞烷基。該等可以是直鏈狀、支鏈狀、環狀或上述的組合。含氟鏈可以是由下述通式(1)表示的由氧化全氟亞烷基單元所構成的氟化聚醚鏈。在通式(1)中,n表示1以上的整數。n亦可以為2~6。

Figure 02_image001
[Hydrosilane-modified fluororesin] The fluorine-containing chain of the hydrosilane-modified fluororesin contains a fluorinated hydrocarbon group. The fluorinated hydrocarbon group may be a perfluoroalkyl group or a perfluoroalkylene group. These may be linear, branched, cyclic, or a combination of the above. The fluorine-containing chain may be a fluorinated polyether chain composed of an oxidized perfluoroalkylene unit represented by the following general formula (1). In the general formula (1), n represents an integer of 1 or more. n can also be 2~6.
Figure 02_image001

包含氫化矽烷基之矽氧烷基可以鍵結在含氟鏈的一末端或兩末端上。包含氫化矽烷基之矽氧烷基,例如包含由下述通式(2)表示的矽氧烷單元。在通式(2)中,R1 表示烷基,其碳原子數例如為1~5或1~3。當氟化聚醚鏈與矽氧烷基直接鍵結時,通常兩者以共用一個氧原子的方式鍵結。矽氧烷基可具有鍵結在矽氧烷單元的矽原子上的烷基來作為末端基。

Figure 02_image003
The siloxane group including the hydrosilyl group may be bonded to one or both ends of the fluorine-containing chain. The siloxane group including a hydrosilyl group includes, for example, a siloxane unit represented by the following general formula (2). In the general formula (2), R 1 represents an alkyl group, and the number of carbon atoms thereof is, for example, 1-5 or 1-3. When the fluorinated polyether chain is directly bonded to the siloxane group, the two are usually bonded by sharing an oxygen atom. The siloxane group may have an alkyl group bonded to a silicon atom of the siloxane unit as a terminal group.
Figure 02_image003

包含氫化矽烷基之矽氧烷基,可以進一步含有由下述通式(3)表示的矽氧烷單元。其中,R2 和R3 各自獨立地表示烷基,其碳原子數例如為1~5或1~3。同一分子中的R1 、R2 及R3 可以彼此相同或不同。

Figure 02_image005
The siloxane group containing a hydrosilyl group may further contain a siloxane unit represented by the following general formula (3). Here, R 2 and R 3 each independently represent an alkyl group, and the number of carbon atoms thereof is, for example, 1-5 or 1-3. R 1 , R 2 and R 3 in the same molecule may be the same or different from each other.
Figure 02_image005

氫矽烷改質氟樹脂可以具有1個氫化矽烷基,亦可以具有2個以上的氫化矽烷基。The hydrosilane-modified fluororesin may have one hydrosilyl group or two or more hydrosilyl groups.

從乾燥劑的塗佈性的觀點來看,氫矽烷改質氟樹脂在23℃下的黏度例如可以為0.1~100Pa·s。From the viewpoint of coatability of the desiccant, the viscosity of the hydrosilane-modified fluororesin at 23° C. may be, for example, 0.1 to 100 Pa·s.

[氧化物顆粒] 氧化物顆粒包含能夠對氧化物顆粒賦予捕水性能的鹼土金屬氧化物。以氧化物顆粒的質量作為基準計,氧化物顆粒通常包含80質量%以上或90質量%以上的鹼土金屬氧化物。氧化物顆粒能夠包含1種或2種以上的成分不同的鹼土金屬氧化物。[Oxide Particles] The oxide particles contain an alkaline earth metal oxide capable of imparting water-capturing properties to the oxide particles. The oxide particles usually contain 80% by mass or more or 90% by mass or more of alkaline earth metal oxides based on the mass of the oxide particles. The oxide particles can contain one or two or more kinds of alkaline earth metal oxides with different components.

作為鹼土金屬氧化物,例如可列舉:氧化鎂(MgO)、氧化鈣(CaO)、氧化鍶(SrO)及氧化鋇(BaO)。鹼土金屬氧化物亦可以是氧化鎂、氧化鈣或其組合。Examples of alkaline earth metal oxides include magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), and barium oxide (BaO). The alkaline earth metal oxide can also be magnesium oxide, calcium oxide, or a combination thereof.

氧化物顆粒的平均粒徑並未特別限定,例如可以是0.01~30μm。若氧化物顆粒的平均粒徑在該範圍內,則會有獲得更加充分的捕水性能的傾向。從相同的觀點來看,氧化物顆粒的平均粒徑可以是0.1μm以上、0.5μm以上或1μm以上,亦可以是20μm以下、10μm以下或5μm以下。The average particle diameter of the oxide particles is not particularly limited, and may be, for example, 0.01 to 30 μm. When the average particle diameter of the oxide particles is within this range, there is a tendency that more sufficient water trapping performance is obtained. From the same viewpoint, the average particle diameter of the oxide particles may be 0.1 μm or more, 0.5 μm or more, or 1 μm or more, and may be 20 μm or less, 10 μm or less, or 5 μm or less.

在本說明書中,氧化物顆粒的平均粒徑意指:利用動態光散射式粒度分布裝置所測定出的體積分布的中間值。該平均粒徑為使用將氧化物顆粒分散於特定的分散介質中而製備出的分散液所測定出的值。In this specification, the average particle diameter of oxide particles means the median value of the volume distribution measured by a dynamic light scattering particle size distribution apparatus. The average particle diameter is a value measured using a dispersion liquid prepared by dispersing oxide particles in a specific dispersion medium.

氧化物顆粒在乾燥劑中的含量例如,以乾燥劑總量作為基準計,可以是5~70質量%,從獲得更高的捕水性能的觀點來看,可以是10%質量以上或20%質量以上。氧化物顆粒的含量亦可以是60%質量以下或50%質量以下。從相同的觀點來看,每1mL乾燥劑中的氧化物顆粒的含量可以是0.1g以上或0.2g以上,亦可以是1.5g以下或1.1g以下。The content of the oxide particles in the desiccant may be, for example, 5 to 70% by mass based on the total amount of the desiccant, and may be 10% by mass or more or 20% by mass from the viewpoint of obtaining higher water capture performance above quality. The content of oxide particles may be 60% by mass or less or 50% by mass or less. From the same viewpoint, the content of oxide particles per 1 mL of desiccant may be 0.1 g or more or 0.2 g or more, and may be 1.5 g or less or 1.1 g or less.

包含氧化鈣之氧化物顆粒例如可以通過如下方法獲得,該方法依序包括:將生石灰(CaO)進行氫氧化處理而獲得消石灰(Ca(OH)2 )的步驟;將消石灰煅燒而獲得生石灰的步驟;及,將生石灰粉碎的步驟。消石灰的煅燒溫度可以是300~600℃。煅燒時間可以是1~20小時。The oxide particles containing calcium oxide can be obtained, for example, by a method including, in this order: a step of subjecting quicklime (CaO) to a hydrogenation treatment to obtain slaked lime (Ca(OH) 2 ); a step of calcining the slaked lime to obtain quicklime and, the step of pulverizing the quicklime. The calcination temperature of slaked lime can be 300~600℃. The calcination time may be 1 to 20 hours.

乾燥劑除了含有黏合劑及氧化物顆粒以外,例如亦可以含有AEROSIL(註冊商標)等的二氧化矽顆粒。The desiccant may contain silica particles such as AEROSIL (registered trademark), for example, in addition to the binder and oxide particles.

乾燥劑在25°C時可以是糊狀。若乾燥劑為糊狀,則能夠更加易於藉由塗佈在有機電致發光元件的微小的氣密空間內形成乾燥劑層。乾燥劑在25℃時的黏度可以是1~500Pa·s。若乾燥劑在25℃時的黏度在該範圍內,則能夠更加易於藉由塗佈來形成乾燥劑層。從相同的觀點來看,乾燥劑的黏度可以為10Pa·s以上或30Pa·s以上,亦可以是400Pa·s以下或200Pa·s以下。塗佈操作可以使用點膠機等來實行。乾燥劑的黏度能夠依據氟改質矽樹脂的黏度和氧化物顆粒的含量來進行調整。此處的黏度是使用B型黏度計、流變儀等的旋轉黏度計所測定出的值。The desiccant can be pasty at 25°C. When the desiccant is in the form of a paste, the desiccant layer can be more easily formed by coating in the fine airtight space of the organic electroluminescence element. The viscosity of the desiccant at 25°C can be 1~500Pa·s. When the viscosity of the desiccant at 25° C. is within this range, the desiccant layer can be more easily formed by coating. From the same viewpoint, the viscosity of the desiccant may be 10 Pa·s or more or 30 Pa·s or more, and may be 400 Pa·s or less or 200 Pa·s or less. The coating operation can be carried out using a dispenser or the like. The viscosity of the desiccant can be adjusted according to the viscosity of the fluorine-modified silicone resin and the content of oxide particles. The viscosity here is a value measured using a rotational viscometer such as a Brookfield viscometer and a rheometer.

乾燥劑可以利用包括將氧化物顆粒與氟改質矽樹脂進行混合的步驟之方法來製造。上述混合可以藉由離心攪拌等來實行。離心攪拌的轉速,例如可以為100~3000轉/分鐘。離心攪拌的時間可以為1~60分鐘。The desiccant can be produced by a method including the step of mixing oxide particles and fluorine-modified silicone resin. The above-mentioned mixing can be carried out by centrifugal stirring or the like. The rotational speed of the centrifugal stirring can be, for example, 100 to 3000 rpm. The time of centrifugal stirring can be 1 to 60 minutes.

[密封結構體] 一種實施形態中的密封結構體具備:一對基板,其被配置為相對向;密封劑,其將一對基板的外周部進行密封;及,乾燥劑層,其被設置在密封劑的內側且在一對基板之間,並包含上述實施形態中的乾燥劑或其硬化物。藉由一對基板的外周部被密封劑密封,可在基板之間形成有氣密空間。乾燥劑層可以填充在一對基板之間且在密封劑內側的氣密空間,亦可以僅形成在氣密空間的一部分上,例如可以僅形成在基板上的特定部位。[Sealing Structure] A sealing structure in one embodiment includes: a pair of substrates arranged to face each other; a sealant that seals the outer peripheral portions of the pair of substrates; and a desiccant layer provided on The inner side of the sealant is between the pair of substrates, and contains the desiccant in the above-described embodiment or a cured product thereof. By sealing the outer peripheral portions of the pair of substrates with the sealant, an airtight space can be formed between the substrates. The desiccant layer may be filled in the airtight space inside the sealant between the pair of substrates, or may be formed only in a part of the airtight space, for example, may be formed only in a specific portion of the substrate.

一種實施形態中的密封結構體,尤其適合使用在將容易受水分影響的設備進行封入的情況。作為這種設備,例如可列舉:有機電致發光元件、有機半導體、有機太陽能電池等的有機電子設備。The sealing structure in one embodiment is particularly suitable for use when enclosing a device that is easily affected by moisture. Examples of such devices include organic electronic devices such as organic electroluminescence elements, organic semiconductors, and organic solar cells.

[有機電致發光元件] 第1圖是表示有機電致發光元件的一種實施形態的示意剖面圖。第1圖所示的有機電致發光元件1A由下述結構所構成:元件基板2;密封基板3,其被配置為與元件基板2相對向;發光部10,其為被設置在元件基板2上的積層體,該積層體具有被配置為相對向的陽極5和陰極6、及被設置在陽極5與陰極6之間的有機層4;密封劑8,其將元件基板2和密封基板3的外周部進行密封;及,乾燥劑層7,其被設置在密封劑8的內側且在發光部10的周圍,並且該乾燥劑層7包含上述實施形態中的乾燥劑或其硬化物。藉由密封劑8將元件基板2和密封基板3的外周部進行密封,便可以在元件基板2和密封基板3之間且在發光部10的周圍形成有氣密空間。[Organic Electroluminescence Element] FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic electroluminescence element. The organic electroluminescence element 1A shown in FIG. 1 is composed of the following structures: an element substrate 2 ; a sealing substrate 3 arranged to face the element substrate 2 ; and a light-emitting portion 10 provided on the element substrate 2 A laminate having an anode 5 and a cathode 6 arranged to face each other, and an organic layer 4 provided between the anode 5 and the cathode 6; a sealant 8 that seals the element substrate 2 and the sealing substrate 3 and the desiccant layer 7 is provided inside the sealant 8 and around the light-emitting portion 10, and the desiccant layer 7 contains the desiccant in the above-mentioned embodiment or a cured product thereof. By sealing the outer peripheral portions of the element substrate 2 and the sealing substrate 3 with the sealant 8 , an airtight space can be formed between the element substrate 2 and the sealing substrate 3 and around the light-emitting portion 10 .

乾燥劑層7填充在密封劑8的內側且在發光部10周圍的氣密空間。亦即,有機電致發光元件1A是所謂的填充密封結構的有機電致發光元件。然而,乾燥劑層不必填充在設置有發光部10的整個氣密空間中,例如,可以在密封基板3上形成乾燥劑層7,從而在密封劑的內側殘留有中空空間。此時,乾燥劑層7的膜厚例如可以是1~300μm。The desiccant layer 7 fills the airtight space inside the sealant 8 and around the light-emitting portion 10 . That is, the organic electroluminescence element 1A is a so-called fill and seal structure organic electroluminescence element. However, the desiccant layer need not be filled in the entire airtight space where the light-emitting portion 10 is provided, and for example, the desiccant layer 7 may be formed on the sealing substrate 3 so that a hollow space remains inside the sealant. At this time, the film thickness of the desiccant layer 7 may be, for example, 1 to 300 μm.

有機電致發光元件1A中,除了乾燥劑層7以外的元件能夠應用以往公知的元件。下面,簡單地說明其中一例。In the organic electroluminescence element 1A, conventionally known elements can be applied to elements other than the desiccant layer 7 . Hereinafter, one example will be briefly described.

元件基板2由具有絕緣性和透光性之矩形玻璃基板所構成,在此元件基板2上,利用透明導電材料ITO(Indum Tin Oxide/銦錫氧化物)形成有陽極5(電極)。該陽極5例如可由以下方式來形成:藉由真空蒸鍍法、濺鍍法等的PVD(Physical Vapor Deposition/物理氣相沉積)法在元件基板2上形成ITO膜,並且利用光刻法的蝕刻將該ITO膜進行圖案化為特定圖案形狀。作為電極的陽極5的一部分,被引出至元件基板2的端部並與驅動電路(未圖示)連接。The element substrate 2 is composed of a rectangular glass substrate having insulating properties and translucency, and an anode 5 (electrode) is formed on the element substrate 2 using a transparent conductive material ITO (Indum Tin Oxide). The anode 5 can be formed by, for example, forming an ITO film on the element substrate 2 by a PVD (Physical Vapor Deposition) method such as a vacuum evaporation method or a sputtering method, and etching by a photolithography method. The ITO film is patterned into a specific pattern shape. Part of the anode 5 serving as an electrode is drawn out to the end of the element substrate 2 and connected to a drive circuit (not shown).

例如,藉由真空蒸鍍法、電阻加熱法等的PVD法,在陽極5的上表面積層薄膜也就是有機層4,該有機層4包含有機發光材料。有機層4可以由單一的層來形成,亦可以由功能不同的複數層來形成。本實施形態中的有機層4為四層結構,其從陽極5側依序積層有:電洞注入層4a、電洞傳輸層4b、發光層4c及電子傳輸層4d。電洞注入層4a例如由膜厚為數十nm的酞菁銅(CuPc)所形成。電洞傳輸層4b例如由膜厚為數十nm的雙[N-(1-萘基)-N-苯基]聯苯胺(bis[N-(1-naphthyl)-N-phenyl]benzidine)(α-NPD)所形成。發光層4c例如由膜厚為數十nm的三(8-羥基喹啉)鋁(Alq3 )所形成。電子傳輸層4d例如由膜厚為數nm膜厚的氟化鋰(LiF)所形成。For example, by a PVD method such as a vacuum evaporation method or a resistance heating method, a thin film, ie, an organic layer 4, is formed on the upper surface of the anode 5, and the organic layer 4 contains an organic light-emitting material. The organic layer 4 may be formed of a single layer, or may be formed of a plurality of layers with different functions. The organic layer 4 in this embodiment has a four-layer structure, and the hole injection layer 4a, the hole transport layer 4b, the light emitting layer 4c, and the electron transport layer 4d are laminated in this order from the anode 5 side. The hole injection layer 4a is formed of, for example, copper phthalocyanine (CuPc) with a thickness of several tens of nm. The hole transport layer 4b is made of, for example, bis[N-(1-naphthyl)-N-phenyl]benzidine (bis[N-(1-naphthyl)-N-phenyl]benzidine) ( α-NPD). The light-emitting layer 4c is formed of, for example, tris(8-quinolinolato) aluminum (Alq 3 ) with a film thickness of several tens of nm. The electron transport layer 4d is formed of, for example, lithium fluoride (LiF) having a thickness of several nm.

藉由真空蒸鍍法等的PVD法,在有機層4(電子傳輸層4d)的上表面積層金屬薄膜也就是陰極6(電極)。作為金屬薄膜的材料,例如可列舉:Al、Li、Mg、In等的功函數小的金屬單體;及,Al-Li、Mg-Ag等的功函數小的合金等。陰極6例如可形成為數十nm~數百nm(較佳為50nm~200nm)的膜厚。陰極6的一部分,被引出至元件基板2的端部並與驅動電路(未圖示)連接。A metal thin film, that is, the cathode 6 (electrode), is layered on the upper surface area of the organic layer 4 (the electron transport layer 4 d ) by a PVD method such as a vacuum deposition method. Examples of the material of the metal thin film include simple metals such as Al, Li, Mg, and In, which have a small work function; and alloys such as Al-Li, Mg-Ag, and the like, which have a small work function. The cathode 6 can be formed to have a film thickness of, for example, several tens of nm to several hundreds of nm (preferably, 50 nm to 200 nm). A part of the cathode 6 is drawn out to the end of the element substrate 2 and connected to a drive circuit (not shown).

密封基板3以隔著有機層4且與元件基板2相對向的方式來配置。元件基板2和密封基板3的外周部被密封劑8所密封。作為密封劑,例如能夠使用紫外線硬化樹脂。The sealing substrate 3 is arranged so as to face the element substrate 2 with the organic layer 4 interposed therebetween. The outer peripheral portions of the element substrate 2 and the sealing substrate 3 are sealed with the sealant 8 . As the sealant, for example, an ultraviolet curable resin can be used.

第2圖是表示有機電致發光元件的另一實施形態的示意剖面圖。如第2圖所示的有機電致發光元件1B由下述結構所構成:元件基板2;密封基板3,其被配置為與元件基板2相對向;發光部10,其被設置在元件基板2上;密封劑8,其將元件基板2和密封基板3的外周部進行密封;乾燥劑層7,其被設置在密封劑8的內側表面上;及,填充劑層9,其填充在乾燥劑層7的內側且在發光部10的周圍。元件基板2和密封基板3之間的氣密空間被乾燥劑層7和填充劑層9所填充。第2圖的有機電致發光元件1B,除了設置有填充劑層9之外,其他結構與第1圖的有機電致發光元件1A的結構相同。填充劑9例如能夠由選自環氧樹脂、丙烯酸樹脂、矽酮樹脂及全氟化碳油等的填充劑來形成。FIG. 2 is a schematic cross-sectional view showing another embodiment of the organic electroluminescence element. The organic electroluminescence element 1B shown in FIG. 2 is composed of the following structures: an element substrate 2 ; a sealing substrate 3 arranged to face the element substrate 2 ; and a light-emitting portion 10 provided on the element substrate 2 the sealant 8, which seals the outer peripheral portions of the element substrate 2 and the sealing substrate 3; the desiccant layer 7, which is provided on the inner surface of the sealant 8; and the filler layer 9, which is filled with the desiccant Inside the layer 7 and around the light-emitting portion 10 . The airtight space between the element substrate 2 and the sealing substrate 3 is filled with the desiccant layer 7 and the filler layer 9 . The organic electroluminescence element 1B of FIG. 2 has the same structure as the organic electroluminescence element 1A of FIG. 1 except that the filler layer 9 is provided. The filler 9 can be formed of a filler selected from epoxy resin, acrylic resin, silicone resin, perfluorocarbon oil, and the like, for example.

[有機電致發光元件的製造方法] 有機電致發光元件例如可以藉由包括對元件基板2或密封基板3塗佈乾燥劑的步驟之方法來製造。[Manufacturing Method of Organic Electroluminescence Element] The organic electroluminescence element can be manufactured, for example, by a method including a step of applying a desiccant to the element substrate 2 or the sealing substrate 3 .

在一種實施形態中的製造方法中,準備一積層體,其在元件基板2上形成有具有有機層4等之發光部。此時,藉由使用點膠機等的方法,將上述實施形態中的乾燥劑塗佈在另外準備的密封基板3上,便可形成乾燥劑層7。之後,以包圍塗佈在密封基板3上的乾燥劑的方式,使用點膠機來塗佈密封劑8。這些操作較佳是在露點為-76℃以下的經氮氣置換後的手套箱(Glove box)中來實行。In the manufacturing method in one embodiment, a laminate in which a light-emitting portion having an organic layer 4 and the like is formed on the element substrate 2 is prepared. At this time, the desiccant layer 7 can be formed by applying the desiccant in the above-described embodiment on the sealing substrate 3 prepared separately by using a dispenser or the like. Then, the sealant 8 is applied using a dispenser so as to surround the desiccant applied on the sealing substrate 3 . These operations are preferably performed in a nitrogen-substituted glove box with a dew point of -76°C or lower.

接著,以使乾燥劑層7和密封劑8被夾持在裝配有發光部的元件基板2與密封基板3之間的方式,來貼合元件基板2與密封基板3。並且,依據需要,藉由對所獲得的結構體照射紫外線及/或進行加熱,而使乾燥劑及/或密封劑硬化,從而便可得到本實施形態中的有機電致發光元件1A。有機電致發光元件1B,除了使用填充劑形成填充劑層的步驟之外,亦能夠利用與上述製造方法相同的方法來製造。Next, the element substrate 2 and the sealing substrate 3 are bonded together so that the desiccant layer 7 and the sealing agent 8 are sandwiched between the element substrate 2 and the sealing substrate 3 on which the light-emitting portion is mounted. Furthermore, the organic electroluminescent element 1A in this embodiment can be obtained by irradiating an ultraviolet-ray and/or heating the obtained structure as needed, and hardening a desiccant and/or a sealing agent. The organic electroluminescence element 1B can also be produced by the same method as the above-mentioned production method, except for the step of forming the filler layer using the filler.

[實施例] 以下,列舉實施例並進一步具體地說明本發明。但是,本發明並未限定於該等實施例。[Examples] Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these Examples.

1.乾燥劑的製備 (實施例1~3) 準備具有聚(氧全氟丙烯)鏈、與包含氫化矽烷基之矽氧烷基之氫矽烷改質氟樹脂(信越化學工業股份有限公司製造,產品名「SIFEL 8370」)。 將平均粒徑調整為2μm的氧化鈣顆粒與作為黏合劑的氫矽烷改質氟樹脂進行混合,並以1000轉/分鐘的轉速離心攪拌5分鐘,從而得到了表1所示實施例的糊狀乾燥劑。表1中示出了質量%和每1ml乾燥劑中的氧化鈣顆粒的克數,來作為以乾燥劑總量作為基準計的氧化鈣顆粒的含量。表1中亦合併示出了自氧化鈣顆粒的含量求出的乾燥劑的捕水容量的理論值。1. Preparation of desiccant (Examples 1 to 3) A hydrosilane-modified fluororesin having a poly(oxyperfluoropropylene) chain and a siloxane group containing a hydrosilyl group (manufactured by Shin-Etsu Chemical Co., Ltd., product name) was prepared. "SIFEL 8370"). Calcium oxide particles adjusted to an average particle size of 2 μm were mixed with a hydrosilane-modified fluororesin as a binder, and centrifuged at 1,000 rpm for 5 minutes to obtain a paste of the examples shown in Table 1. desiccant. The mass % and the grams of calcium oxide particles per 1 ml of the desiccant are shown in Table 1 as the content of the calcium oxide particles based on the total amount of the desiccant. Table 1 also shows the theoretical value of the water-capturing capacity of the desiccant obtained from the content of calcium oxide particles.

(比較例1~4) 除了使用了二甲基矽樹脂(產品名:Element 14PDMS 10K-JC,Momentive Performance Materials公司製造)來替代氟樹脂作為黏合劑以外,與實施例同樣地操作,來獲得表1所示比較例的糊狀乾燥劑。但是,在比較例4中,混合物變成粉末狀,所以未能得到能夠進行塗佈的糊狀乾燥劑。(Comparative Examples 1 to 4) Tables were obtained in the same manner as in the Examples, except that dimethyl silicone resin (product name: Element 14PDMS 10K-JC, manufactured by Momentive Performance Materials) was used as the binder instead of the fluororesin. The paste desiccant of the comparative example shown in 1. However, in Comparative Example 4, the mixture was in powder form, so that a paste-like desiccant that could be applied could not be obtained.

(捕水容量) 藉由以下方法來計算出乾燥劑的捕水容量的理論值。 (1)氧化鈣的捕水容量 氧化鈣藉由下述反應與1當量的水進行反應。 CaO + H2 O→Ca(OH)2 因此,以氧化鈣的質量作為基準計的捕水容量的理論值,利用下述公式並以氧化鈣的分子量56g/mol和水的分子量18g/mol來計算,為32質量%。 氧化鈣的捕水容量= 18/56×100 = 32 [質量%] (2)乾燥劑的捕水容量 藉由下述公式並以氧化鈣的捕水容量和乾燥劑中的氧化鈣濃度,來計算以乾燥劑的質量作為基準計的捕水容量的理論值。 乾燥劑的捕水容量[質量%] =氧化鈣的捕水容量×乾燥劑中的氧化鈣濃度 接著,藉由下述公式並使用乾燥劑的密度,來計算以乾燥劑的體積作為基準計的捕水容量。 乾燥劑的捕水容量[體積%] =乾燥劑的捕水容量[質量%]×乾燥劑的密度[g/cm3 ] 此處,將使用了氫矽烷改質氟樹脂之實施例的乾燥劑的密度設為2.32g/cm3 ,將使用了二甲基矽樹脂之比較例的乾燥劑的密度設為1.47g/cm3 ,來求出以乾燥劑的體積作為基準計的捕水量。由於設置在有機電致發光元件等的各種設備中的乾燥劑層被限制為微小體積,因此通常期待以乾燥劑的體積作為基準計的捕水能力較高。(Water-capturing capacity) The theoretical value of the water-capturing capacity of the desiccant was calculated by the following method. (1) Water Capture Capacity of Calcium Oxide Calcium oxide reacts with 1 equivalent of water by the following reaction. CaO + H 2 O → Ca(OH) 2 Therefore, the theoretical value of the water-capturing capacity based on the mass of calcium oxide is calculated using the following formula and with the molecular weight of calcium oxide 56 g/mol and the molecular weight of water 18 g/mol Calculated, it is 32 mass %. Water-capturing capacity of calcium oxide = 18/56×100 = 32 [mass %] (2) The water-capturing capacity of desiccant is calculated by the following formula using the water-capturing capacity of calcium oxide and the concentration of calcium oxide in the desiccant Calculate the theoretical value of the water capture capacity based on the mass of the desiccant. Water-capturing capacity [mass %] of desiccant = water-capturing capacity of calcium oxide × calcium oxide concentration in desiccant Catch capacity. Water-capturing capacity of desiccant [volume %] = water-capturing capacity of desiccant [mass %]×density of desiccant [g/cm 3 ] Here, the desiccant of the example using the hydrosilane-modified fluororesin is used The density of the desiccant was set to 2.32 g/cm 3 , and the density of the desiccant of the comparative example using dimethyl silicone resin was set to 1.47 g/cm 3 , and the water capture amount based on the volume of the desiccant was determined. Since the desiccant layer provided in various devices such as organic electroluminescence elements is limited to a small volume, it is generally expected that the water-trapping ability based on the volume of the desiccant is high.

[表1]

Figure 107130916-A0304-0001
[Table 1]
Figure 107130916-A0304-0001

2.乾燥劑的黏度 使用旋轉式流變儀作為測量裝置,在剪切速度5s-1 的條件下測量了實施例2、3以及比較例1~3的乾燥劑在25℃時的黏度。 第3圖是表示各乾燥劑的黏度與以乾燥劑的體積作為基準的捕水容量的關係的圖表。由該圖可確認到包含氫矽烷改質氟樹脂之實施例的乾燥劑不僅能夠維持較低黏度且具有更高的捕水容量。2. Viscosity of Desiccant Using a rotational rheometer as a measuring device, the viscosity of the desiccants of Examples 2, 3 and Comparative Examples 1 to 3 at 25° C. was measured under the condition of a shear rate of 5 s −1 . FIG. 3 is a graph showing the relationship between the viscosity of each desiccant and the water-capturing capacity based on the volume of the desiccant. From this figure, it can be confirmed that the desiccant of the Example containing the hydrosilane-modified fluororesin not only maintains a lower viscosity but also has a higher water-capturing capacity.

3.有機電致發光設備的製備及其評價 3. Preparation and Evaluation of Organic Electroluminescent Devices

藉由濺鍍法在元件基板上形成ITO膜(膜厚140nm),並且利用光刻法的蝕刻將該ITO膜進行圖案化為特定圖案形狀,從而形成陽極。藉由電阻加熱法在陽極的上表面依序形成:作為電洞注入層的酞菁銅(CuPc)膜(膜厚70nm)、作為電洞傳輸層的雙[N-(1-萘基)-N-苯基]聯苯胺(Bis[N-(1-naphthyl)-N-phenyl]benzidine)(α-NPD)膜(膜厚30nm)、作為發光層的參(8-羥基喹啉)鋁(Alq3)膜(膜厚50nm)。進一步,藉由物理蒸鍍法在發光層的上表面以7nm的膜厚形成作為電子傳輸層的氟化鋰(LiF)膜(膜厚7nm)及作為陰極的鋁膜(膜厚150nm)。 An ITO film (film thickness: 140 nm) was formed on the element substrate by sputtering, and the ITO film was patterned into a specific pattern shape by etching by photolithography to form an anode. A copper phthalocyanine (CuPc) film (film thickness 70 nm) as a hole injection layer, bis[N-(1-naphthyl)- bis[N-(1-naphthyl)- N-phenyl]benzidine (Bis[N-(1-naphthyl)-N-phenyl]benzidine) (α-NPD) film (film thickness 30 nm), paras(8-hydroxyquinoline)aluminum ( Alq 3 ) film (film thickness 50 nm). Furthermore, a lithium fluoride (LiF) film (film thickness 7 nm) as an electron transport layer and an aluminum film (film thickness 150 nm) as a cathode were formed on the upper surface of the light emitting layer by a physical vapor deposition method with a film thickness of 7 nm.

接著,在露點為-76℃以下的經氮氣置換後的手套箱中,使用點膠機將實施例1或比較例3的乾燥劑塗佈於密封基板上。接著,以包圍已塗佈的乾燥劑的方式,使用點膠機來塗佈由紫外線硬化樹脂所構成的密封劑。 Next, the desiccant of Example 1 or Comparative Example 3 was applied on the sealing substrate using a glue dispenser in a nitrogen-substituted glove box with a dew point of -76°C or lower. Next, a sealant made of an ultraviolet curable resin is applied using a dispenser so as to surround the applied desiccant.

將積層有陽極、有機層及陰極的元件基板與密封基板貼合之後,藉由照射紫外線及加熱至80℃使密封劑硬化,來獲得在氣密容器內填充有乾燥劑之填充密封結構的有機電致發光元件。 After bonding the element substrate on which the anode, the organic layer, and the cathode are stacked, and the sealing substrate, the sealing agent is cured by irradiating ultraviolet rays and heating to 80° C. to obtain a filling and sealing structure filled with a desiccant in an airtight container. Electroluminescent element.

將所獲得的有機電致發光元件放置於85℃、85%RH的高溫高濕環境中,追蹤並觀察發光面積率的變化。第4圖是表示高溫高濕環境中的有機電致發光元件的發光面積率與經過時間的關係的圖表。包含實施例之乾燥劑的有機電致發光元件在經過1000小時為止時維持了超過96%的較高的發光面積率。The obtained organic electroluminescence element was placed in a high temperature and high humidity environment of 85° C. and 85% RH, and the change in the luminous area ratio was tracked and observed. FIG. 4 is a graph showing the relationship between the emission area ratio and the elapsed time of the organic electroluminescence element in a high temperature and high humidity environment. The organic electroluminescent element containing the desiccant of the Example maintained a high luminous area ratio of more than 96% after 1000 hours.

4.實施例4及比較例5 (實施例4) 除了將氧化鈣顆粒的含量改變為50質量%(35體積%)以外,藉由與實施例1同樣地操作,來獲得糊狀乾燥劑。乾燥劑在25℃時的黏度為160Pa·s。使用所獲得的乾燥劑,依照與「3.有機電致發光設備的製備及其評價」相同的步驟,來製造有機電致發光設備。但是,將乾燥劑塗佈在密封劑的內側,並進一步在其內側將填充劑(環氧樹脂)進行填充,從而製備出與第2圖的有機電致發光元件1B具有相同結構之有機電致發光設備。4. Example 4 and Comparative Example 5 (Example 4) A paste-like desiccant was obtained in the same manner as in Example 1, except that the content of the calcium oxide particles was changed to 50% by mass (35% by volume). The viscosity of the desiccant at 25°C is 160 Pa·s. Using the obtained desiccant, an organic electroluminescent device was produced according to the same procedure as "3. Preparation and evaluation of organic electroluminescent device". However, an organic electroluminescence device having the same structure as the organic electroluminescence element 1B in FIG. 2 was prepared by applying a desiccant to the inner side of the sealant and filling the inner side with a filler (epoxy resin). Lighting equipment.

(比較例5) 除了使用了二甲基矽樹脂(產品名:Element 14PDMS 10K-JC,Momentive Performance Materials公司製造)來替代氟樹脂作為黏合劑以外,藉由與實施例4同樣地操作,來獲得乾燥劑。氧化鈣顆粒的含量為50質量%(22體積%)。乾燥劑在25℃時的黏度為180Pa·s。使用所獲得的乾燥劑,製備出與實施例4相同的有機電致發光設備。(Comparative Example 5) The same procedure as in Example 4 was carried out, except that dimethyl silicone resin (product name: Element 14PDMS 10K-JC, manufactured by Momentive Performance Materials Co., Ltd.) was used as the binder instead of the fluororesin. desiccant. The content of calcium oxide particles was 50% by mass (22% by volume). The viscosity of the desiccant at 25°C is 180 Pa·s. Using the obtained desiccant, the same organic electroluminescence device as in Example 4 was prepared.

(評價) 將實施例4和比較例5的有機電致發光元件放置於85℃、85%RH的高溫高濕環境中,並且每經過一定時間,通過Ca法測量水分侵入有機電致發光設備的水分侵入距離。第5圖是表示水分侵入距離與經過時間的關係的圖表。從第5圖所示的結果可確認到,針對抑制水分侵入,包含氫矽烷改質氟樹脂之乾燥劑可發揮更加優異的效果。(Evaluation) The organic electroluminescent elements of Example 4 and Comparative Example 5 were placed in a high-temperature and high-humidity environment of 85° C. and 85% RH, and the rate of moisture intrusion into the organic electroluminescent device was measured by the Ca method every time a certain period of time passed. Moisture intrusion distance. FIG. 5 is a graph showing the relationship between the moisture intrusion distance and the elapsed time. From the results shown in FIG. 5 , it was confirmed that the desiccant containing the hydrosilane-modified fluororesin has a more excellent effect of suppressing the intrusion of water.

根據本發明,可提供一種乾燥劑,其不僅具有充分的捕水性能,並具有適於塗佈的較低黏度。雖然藉由對氧化物顆粒進行表面處理也能夠期待提高氧化物顆粒的分散性,但是本發明的乾燥劑在製造時無需進行上述表面處理,因此在製造簡便性方面,本發明的乾燥劑亦具有優勢。並且,用於表面處理的處理劑可能會影響有機層等的穩定性,但是本發明的乾燥劑則能夠避免這種顧慮。According to the present invention, it is possible to provide a desiccant which not only has sufficient water catching performance, but also has a lower viscosity suitable for coating. Although the dispersibility of the oxide particles can be expected to be improved by surface treatment of the oxide particles, the desiccant of the present invention does not require the above-mentioned surface treatment during production, so the desiccant of the present invention also has the advantages of simplicity in production. Advantage. Also, the treatment agent used for surface treatment may affect the stability of the organic layer and the like, but the desiccant of the present invention can avoid such a concern.

1A、1B‧‧‧有機電致發光元件2‧‧‧元件基板3‧‧‧密封基板4‧‧‧有機層4a‧‧‧電洞注入層4b‧‧‧電洞傳輸層4c‧‧‧發光層4d‧‧‧電子傳輸層5‧‧‧陽極6‧‧‧陰極7‧‧‧乾燥劑層1A, 1B‧‧‧Organic electroluminescent device 2‧‧‧Element substrate 3‧‧‧Sealing substrate 4‧‧‧Organic layer 4a‧‧‧hole injection layer 4b‧‧‧hole transport layer 4c‧‧‧luminescence Layer 4d‧‧‧Electron transport layer 5‧‧‧Anode 6‧‧‧Cathode 7‧‧‧Desiccant layer

8:密封劑 8: Sealant

9:填充劑層 9: Filler layer

10:發光部 10: Light-emitting part

第1圖是表示一種實施形態中的有機電致發光元件的示意剖面圖。 第2圖是表示一種實施形態中的有機電致發光元件的示意剖面圖。 第3圖是表示乾燥劑的黏度與捕水容量的關係的圖表。 第4圖是表示高溫高濕環境中的有機電致發光元件的發光面積率與經過時間的關係的圖表。 第5圖是表示高溫高濕環境中水分侵入有機電致發光元件的水分侵入距離與經過時間的關係的圖表。FIG. 1 is a schematic cross-sectional view showing an organic electroluminescence element in one embodiment. FIG. 2 is a schematic cross-sectional view showing an organic electroluminescence element in one embodiment. Fig. 3 is a graph showing the relationship between the viscosity of the desiccant and the water-capturing capacity. FIG. 4 is a graph showing the relationship between the emission area ratio and the elapsed time of the organic electroluminescence element in a high temperature and high humidity environment. FIG. 5 is a graph showing the relationship between the moisture intrusion distance and the elapsed time for moisture intrusion into the organic electroluminescent element in a high-temperature and high-humidity environment.

國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無Domestic storage information (please note in the order of storage institution, date and number) None

國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記) 無Foreign deposit information (please note in the order of deposit country, institution, date and number) None

1A:有機電致發光元件 1A: Organic electroluminescent element

2:元件基板 2: Component substrate

3:密封基板 3: Seal the substrate

4:有機層 4: organic layer

4a:電洞注入層 4a: hole injection layer

4b:電洞傳輸層 4b: hole transport layer

4c:發光層 4c: light-emitting layer

4d:電子傳輸層 4d: electron transport layer

5:陽極 5: Anode

6:陰極 6: Cathode

7:乾燥劑層 7: Desiccant layer

8:密封劑 8: Sealant

10:發光部 10: Light-emitting part

Claims (4)

一種乾燥劑,其含有黏合劑及氧化物顆粒,該氧化物顆粒被分散在前述黏合劑中且包含鹼土金屬氧化物,前述黏合劑包含氫矽烷改質氟樹脂,前述氫矽烷改質氟樹脂具有:包含氟化烴基之含氟鏈、及鍵結在該含氟鏈上且包含氫化矽烷基之矽氧烷基,每1毫升乾燥劑中的前述氧化物顆粒的含量為0.1~1.5g,並且,前述乾燥劑在25℃時的黏度為1~500Pa.s。 A desiccant comprising a binder and oxide particles, the oxide particles being dispersed in the binder and containing an alkaline earth metal oxide, the binder comprising a hydrosilane-modified fluororesin, the hydrosilane-modified fluororesin having : a fluorine-containing chain containing a fluorinated hydrocarbon group, and a siloxane group bound to the fluorine-containing chain and containing a hydrosilyl group, the content of the aforementioned oxide particles per 1 ml of the desiccant is 0.1-1.5 g, and , the viscosity of the aforementioned desiccant at 25 ℃ is 1 ~ 500Pa. s. 一種密封結構體,其具備:一對基板,其被配置為相對向;密封劑,其將前述一對基板的外周部進行密封;及,乾燥劑層,其被設置在前述密封劑的內側且在前述一對基板之間,前述乾燥劑層包含請求項1所述之乾燥劑。 A sealing structure comprising: a pair of substrates arranged to face each other; a sealant for sealing outer peripheral portions of the pair of substrates; and a desiccant layer provided inside the sealant and Between the pair of substrates, the desiccant layer contains the desiccant according to claim 1. 一種有機電致發光元件,其具備:元件基板;密封基板,其被配置為與前述元件基板相對向;密封劑,其將前述元件基板和前述密封基板的外周部進行密封;發光部,其被設置在前述密封劑的內側且在前述元件基板上,並具有被配置為相對向的一對電極、及被設置在 該一對電極之間的有機層;及,乾燥劑層,其被設置在前述密封劑的內側且在前述元件基板與前述密封基板之間,前述乾燥劑層包含請求項1所述之乾燥劑。 An organic electroluminescence element comprising: an element substrate; a sealing substrate arranged to face the element substrate; a sealant for sealing the element substrate and the outer peripheral portion of the sealing substrate; and a light-emitting portion provided on the inside of the encapsulant and on the element substrate, having a pair of electrodes arranged to face each other, and provided on an organic layer between the pair of electrodes; and a desiccant layer provided inside the sealant and between the element substrate and the seal substrate, the desiccant layer containing the desiccant described in claim 1 . 如請求項3所述之有機電致發光元件,其中,前述乾燥劑層填充在前述密封劑的內側且在前述發光部周圍的氣密空間。 The organic electroluminescence element according to claim 3, wherein the desiccant layer is filled in an airtight space inside the sealant and around the light-emitting portion.
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