JP2003187962A - Manufacturing method of organic el display facing substrate and organic el display - Google Patents
Manufacturing method of organic el display facing substrate and organic el displayInfo
- Publication number
- JP2003187962A JP2003187962A JP2001381841A JP2001381841A JP2003187962A JP 2003187962 A JP2003187962 A JP 2003187962A JP 2001381841 A JP2001381841 A JP 2001381841A JP 2001381841 A JP2001381841 A JP 2001381841A JP 2003187962 A JP2003187962 A JP 2003187962A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- substrate
- counter substrate
- display
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 155
- 238000004519 manufacturing process Methods 0.000 title claims description 38
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- 239000000463 material Substances 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 239000011230 binding agent Substances 0.000 claims abstract description 46
- 239000003230 hygroscopic agent Substances 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 61
- 125000006850 spacer group Chemical group 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 17
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
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- 229920000647 polyepoxide Polymers 0.000 description 5
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- 229920000178 Acrylic resin Polymers 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
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- 229920002050 silicone resin Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- 229910007541 Zn O Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
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- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
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- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
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- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical compound C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 1
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 description 1
- CYAQYDHSEWIVLA-UHFFFAOYSA-N 1-hydroxydodecyl prop-2-enoate Chemical compound CCCCCCCCCCCC(O)OC(=O)C=C CYAQYDHSEWIVLA-UHFFFAOYSA-N 0.000 description 1
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- 239000005062 Polybutadiene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
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- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フラットディスプ
レイや平面光源などに使用される有機エレクトロルミネ
ッセンス表示装置（以下、有機ＥＬディスプレイと略
す）に用いる対向基板とその製造方法および有機ＥＬデ
ィスプレイの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a counter substrate used in an organic electroluminescence display device (hereinafter referred to as an organic EL display) used for a flat display, a flat light source, etc., a method for manufacturing the counter substrate, and a method for manufacturing the organic EL display. Regarding
【０００２】[0002]
【従来の技術】近年の情報通信分野における急速な技術
開発の進展に伴い、ＣＲＴに代わるフラットディスプレ
イに大きな期待が寄せられている。なかでも有機ＥＬデ
ィスプレイは、高速応答性、視認性、輝度などの点に優
れるため盛んに研究が行われている。2. Description of the Related Art With the rapid progress of technological development in the field of information and communication in recent years, great expectations are placed on a flat display replacing a CRT. Among them, organic EL displays have been actively researched because they are excellent in high-speed response, visibility, and brightness.
【０００３】１９８７年に米国コダック社のＴａｎｇら
によって発表された有機ＥＬ素子は、有機薄膜の２層積
層構造を有し、発光層にトリス（８−キノリノラト）ア
ルミニウム（以下「Ａｌｑ」と略称する）を使用し、１
０Ｖ以下の低電圧駆動で、１０００ｃｄ／ｍ2と高輝度
が得られた（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５１，
９１３（１９８７））。An organic EL element announced by Tang et al. Of Kodak Company in the United States in 1987 has a two-layer laminated structure of organic thin films, and tris (8-quinolinolato) aluminum (hereinafter abbreviated as "Alq") in a light emitting layer. ), 1
By driving at a low voltage of 0 V or less, a high brightness of 1000 cd / m 2 was obtained (Appl. Phys. Lett., 51,
913 (1987)).
【０００４】以降、急速に実用化に向けた研究が進めら
れ、正孔注入電極と電子注入電極に挟まれた有機層が１
層〜１０層程度の様々な積層型の有機ＥＬ素子が開発さ
れてきている。材料に関しても、多岐に渡る低分子化合
物を真空蒸着法等により薄膜形成する方法のみならず、
高分子系化合物をスピンコート法、インクジェット、ダ
イコート、フレキソ印刷といった方法で薄膜形成して有
機ＥＬ素子を作成する方法が提案されている。Since then, research for rapid practical use has progressed, and the organic layer sandwiched between the hole injection electrode and the electron injection electrode has
Various laminated organic EL devices having about 10 to 10 layers have been developed. Regarding materials, not only a method of forming thin films of various low-molecular compounds by vacuum deposition,
A method of forming an organic EL device by forming a thin film of a polymer compound by a method such as spin coating, inkjet, die coating, or flexographic printing has been proposed.
【０００５】また、ＣＲＴに代わる発光素子として、Ｒ
ＧＢの３色を発光させるため、ＲＧＢの３色の発光素子
を１つの基板上に独立に蒸着により形成する方法、白色
発光の有機ＥＬ素子をカラーフィルタ上に形成する方
法、青色発光や紫外発光の有機ＥＬ素子を色変換フィル
タ上に形成する方法等が提案されている。Further, as a light emitting element replacing the CRT, R
In order to emit three colors of GB, a method of independently forming light emitting elements of three colors of RGB on one substrate by vapor deposition, a method of forming an organic EL element of white light emission on a color filter, blue light emission and ultraviolet light emission There has been proposed a method of forming the organic EL element on the color conversion filter.
【０００６】さらに輝度向上のために、これまで一般的
とされてきた透明正孔注入電極からの光取り出しの代わ
りに、電子注入側を透明化して光を取り出す方法や、高
精細・消費電力低下を目的として、ＴＦＴ基板上に有機
ＥＬ素子を形成する方法などが提案されてきている。In order to further improve the brightness, instead of extracting light from a transparent hole injecting electrode, which has been generally used so far, a method of extracting light by making the electron injecting side transparent, and high definition / power consumption reduction For the purpose, a method of forming an organic EL element on a TFT substrate has been proposed.
【０００７】従来の有機ＥＬ素子は、効率よく電子注入
を行うためにアルカリ金属・アルカリ土類金属・希土類
金属などの仕事関数の低い金属および／またはその酸化
物・ハロゲン化物を単体あるいはアルミニウムや銀など
の金属と合金化したものを通常使用する。In the conventional organic EL device, a metal having a low work function such as an alkali metal, an alkaline earth metal or a rare earth metal and / or an oxide or a halide thereof is used alone or aluminum or silver for efficient electron injection. The one alloyed with a metal such as is usually used.
【０００８】また電極間に有機化合物を使用することか
ら、有機ＥＬ素子は大気中の酸素・水分により電極およ
び／または有機化合物層が容易に酸化したり、層間剥離
を起こすことがある。そのため、ダークスポットと呼ば
れる非発光部分が表示面内に生じる。したがって、有機
ＥＬ素子の安定性と信頼性を向上させることが必要とな
る。有機ＥＬ素子では、大気中の水分・酸素等の活性ガ
スから素子内部を保護できる封止手段が重要となる。Further, since an organic compound is used between the electrodes, in the organic EL element, the electrodes and / or the organic compound layer may be easily oxidized or delaminated due to oxygen and water in the atmosphere. Therefore, a non-light emitting portion called a dark spot occurs in the display surface. Therefore, it is necessary to improve the stability and reliability of the organic EL element. In an organic EL element, a sealing means capable of protecting the inside of the element from active gas such as moisture and oxygen in the atmosphere is important.
【０００９】その一例として、発光部の上に低透湿性の
バリヤ層を積層する封止手段が提案されている。しか
し、充分な防湿性を長期間維持できるものは得られてい
ない。As an example thereof, there has been proposed a sealing means for laminating a low moisture-permeable barrier layer on the light emitting portion. However, no one has been obtained that can maintain sufficient moisture resistance for a long period of time.
【００１０】また、防湿性を維持するために、アルカリ
金属および／またはその酸化物、水素化物、合成ゼオラ
イト、５酸化２リン等の吸湿性化合物の粉末を、有機Ｅ
Ｌディスプレイの空間内に置く方法が提案されている。
その際に、封止用キャップとして粘着剤や接着剤等を用
いて固定を行うこと、吸湿剤を真空加熱蒸着や電子線蒸
着、ＣＶＤ法やスパッタ法などで、真空下で形成する方
法などが提案されている。Further, in order to maintain moisture resistance, powder of a hygroscopic compound such as an alkali metal and / or its oxide, hydride, synthetic zeolite, diphosphorus pentaoxide or the like is mixed with organic E
A method of placing it in the space of the L display has been proposed.
At that time, fixing using a pressure-sensitive adhesive or adhesive as a sealing cap, a method of forming a hygroscopic agent under vacuum by vacuum heating vapor deposition, electron beam vapor deposition, CVD method or sputtering method, etc. Proposed.
【００１１】[0011]
【発明が解決しようとする課題】しかし、従来例では吸
湿性材料を有機ＥＬディスプレイの空間内にそのまま封
入するために以下のような問題が生じた。However, in the conventional example, since the hygroscopic material is enclosed in the space of the organic EL display as it is, the following problems occur.
【００１２】まず第１に、吸湿剤が空間内で移動し、有
機ＥＬディスプレイの内部構造と接触する可能性が生じ
る。さらに、吸湿後の膨張等によって内部構造に影響を
与える可能性もある。また、各種の有機ＥＬディスプレ
イを製造しようとする際に、多様なサイズに応じて、再
現性よく吸湿剤を封入し、配置することが難しくなり、
そのための製造装置がきわめて複雑になる。First, there is a possibility that the hygroscopic agent may move in the space and come into contact with the internal structure of the organic EL display. Furthermore, the internal structure may be affected by expansion after moisture absorption. Further, when manufacturing various organic EL displays, it becomes difficult to enclose and arrange the moisture absorbent with good reproducibility according to various sizes,
The manufacturing apparatus for that is extremely complicated.
【００１３】第２に、粘着剤・接着剤等を用いて吸湿剤
を固定化して形成した場合、高温雰囲気下で有機ＥＬデ
ィスプレイを使用すると、それらの粘着剤や接着剤から
アウトガスが発生し、有機ＥＬディスプレイの内部構造
に影響を与える可能性がある。そして、不要なアウトガ
スにより発光部が部分的に損ねられ、非発光欠点を生じ
ることになった。Secondly, when the hygroscopic agent is fixed by using a pressure sensitive adhesive or an adhesive, and the organic EL display is used in a high temperature atmosphere, outgas is generated from the pressure sensitive adhesive or the adhesive. This may affect the internal structure of the organic EL display. The unnecessary outgas partially damages the light emitting portion, resulting in a non-light emitting defect.
【００１４】第３に、有機ＥＬディスプレイの空間内に
吸湿剤を配置するに際して、必要かつ充分な量の固体、
粉末といった吸湿剤を、所定の領域に配置するには相当
の時間を要し、さらに多様なサイズに合わせて、配置位
置や量を容易に変更することが難しくなることがある。
このため、発光部を形成する工程以外で、生産性を向上
させることができず、非効率的な製造方法を強いられる
ことになった。Third, when arranging the hygroscopic agent in the space of the organic EL display, a necessary and sufficient amount of solid,
It takes a considerable amount of time to dispose a hygroscopic agent such as powder in a predetermined area, and it may be difficult to easily change the disposition position and amount in accordance with various sizes.
For this reason, the productivity cannot be improved except for the step of forming the light emitting portion, which requires an inefficient manufacturing method.
【００１５】本発明はこれらの問題を解決することを目
的とし、多様なサイズの有機ＥＬディスプレイに対応で
きる対向基板を容易に製造できるようにする。かつ長期
にわたり安定に発光できる有機ＥＬディスプレイを得よ
うとする。また、再現性がよく量産に適した有機ＥＬデ
ィスプレイの製造方法を提供し、すぐれた表示品位の有
機ＥＬディスプレイを達成するものである。The present invention aims to solve these problems, and makes it possible to easily manufacture a counter substrate which can be applied to organic EL displays of various sizes. Moreover, it is intended to obtain an organic EL display that can stably emit light for a long period of time. Further, the present invention provides a method of manufacturing an organic EL display which has good reproducibility and is suitable for mass production, and achieves an organic EL display having excellent display quality.
【００１６】[0016]
【課題を解決するための手段】すなわち、本発明の態様
１は、熱分解性の有機質バインダーと無機質吸湿剤とを
含む混合物の層を基板上に配置し、その後、前記混合物
層を有機質バインダーの熱分解温度以上に加熱して有機
質バインダーを除去して、基板上に吸湿剤層を形成す
る、有機ＥＬディスプレイ用対向基板の製造方法を提供
する。That is, in Embodiment 1 of the present invention, a layer of a mixture containing a thermally decomposable organic binder and an inorganic hygroscopic agent is arranged on a substrate, and then the mixture layer is mixed with an organic binder. Provided is a method for producing a counter substrate for an organic EL display, which comprises heating the organic binder to a temperature not lower than the thermal decomposition temperature to remove the organic binder and forming a hygroscopic agent layer on the substrate.
【００１７】また、態様２は、前記混合物層が低融点ガ
ラスをさらに含む態様１に記載の有機ＥＬディスプレイ
用対向基板の製造方法を提供する。Aspect 2 provides the method for producing a counter substrate for an organic EL display according to Aspect 1, wherein the mixture layer further contains a low melting point glass.
【００１８】また、態様３は、基板をソーダガラスまた
はノンアルカリガラスを用いたガラス基板とし、前記加
熱温度をガラス基板のガラス転移点温度以下とする態様
１または２に記載の有機ＥＬディスプレイ用対向基板の
製造方法を提供する。In a third aspect, the substrate is a glass substrate using soda glass or non-alkali glass, and the heating temperature is equal to or lower than the glass transition temperature of the glass substrate. A method of manufacturing a substrate is provided.
【００１９】また、態様４は、有機質バインダーが解重
合性高分子化合物である態様１、２または３に記載の有
機ＥＬディスプレイ用対向基板の製造方法を提供する。Aspect 4 provides the method for producing a counter substrate for an organic EL display according to Aspect 1, 2 or 3, wherein the organic binder is a depolymerizable polymer compound.
【００２０】また、態様５は、前記有機質バインダーの
加熱除去を、ＣＯ２ガスを実質的に含まないガス雰囲気
で行う態様１、２、３または４に記載の有機ＥＬディス
プレイ用対向基板の製造方法を提供する。Aspect 5 is a method for producing a counter substrate for an organic EL display according to aspect 1, 2, 3 or 4 in which the organic binder is removed by heating in a gas atmosphere substantially free of CO 2 gas. I will provide a.
【００２１】また、態様６は、無機質吸湿剤として、酸
化カルシウム、酸化バリウム、酸化ストロンチウム、５
酸化リンまたは合成ゼオライトから選択した少なくとも
１つを用いる態様１、２、３、４または５に記載の有機
ＥＬディスプレイ用対向基板の製造方法を提供する。Aspect 6 also uses calcium oxide, barium oxide, strontium oxide, and 5 as inorganic hygroscopic agents.
Provided is a method for producing a counter substrate for an organic EL display according to Aspect 1, 2, 3, 4 or 5, which uses at least one selected from phosphorus oxide and synthetic zeolite.
【００２２】また、態様７は、吸湿剤層の厚みが５０〜
５００μｍである態様１〜６のいずれか１項に記載の有
機ＥＬディスプレイ用対向基板の製造方法を提供する。In the seventh aspect, the thickness of the hygroscopic agent layer is 50 to 50.
A method for manufacturing a counter substrate for an organic EL display according to any one of aspects 1 to 6, which has a thickness of 500 μm.
【００２３】また、態様８は、透明な第１の基板上に透
明な第１の電極と発光層と第２の電極とを形成し、第１
の基板と吸湿剤層を有する対向基板とを接合材によって
接合し、第１の基板と対向基板との間に吸湿剤層が配置
された有機ＥＬディスプレイの製造方法において、熱分
解性の有機質バインダーと無機質吸湿剤とを含む混合物
の層を対向基板上に配置し、この対向基板上に低融点ガ
ラスを主成分とするスペーサ材料を配置し、その後、有
機質バインダーの熱分解温度以上かつ低融点ガラスの軟
化点温度以上の温度に加熱することによって、有機質バ
インダーを分解除去し、かつスペーサを形成する有機Ｅ
Ｌディスプレイを提供する。In the eighth aspect, the transparent first electrode, the light emitting layer and the second electrode are formed on the transparent first substrate, and the first electrode is formed.
In the method for manufacturing an organic EL display in which the substrate and the counter substrate having the moisture absorbent layer are bonded by a bonding material, and the moisture absorbent layer is disposed between the first substrate and the counter substrate, a thermally decomposable organic binder And a layer of a mixture containing an inorganic hygroscopic agent are arranged on a counter substrate, a spacer material having a low melting point glass as a main component is arranged on the counter substrate, and then a glass having a thermal decomposition temperature of the organic binder or higher and a low melting point glass. Organic E that decomposes and removes the organic binder and forms spacers by heating to a temperature above the softening point temperature of
Provide an L display.
【００２４】[0024]
【発明の実施の形態】図１に本発明の有機ＥＬディスプ
レイ１０の実施の形態１を示す。ガラス、石英または樹
脂等を用いた透明な第１の基板１１の一方の表面に、Ｉ
ＴＯ等の透明な電極材料による透明な第１の電極１２が
形成されている。この第１の電極１２は、所定の形状や
所定ピッチでストライプ状に形成されている。また、従
来公知の方法でＴＦＴアレイ等のアクティブ素子が形成
された場合、第１の電極１２がアクティブ素子の上に形
成されてもよい。また、第１の基板１１上に発光素子部
に合わせてカラーフィルタが配置されていてもよい（図
示を省略）。1 shows a first embodiment of an organic EL display 10 of the present invention. On one surface of the transparent first substrate 11 made of glass, quartz or resin, I
A transparent first electrode 12 made of a transparent electrode material such as TO is formed. The first electrode 12 is formed in a stripe shape with a predetermined shape and a predetermined pitch. When an active element such as a TFT array is formed by a conventionally known method, the first electrode 12 may be formed on the active element. Further, a color filter may be arranged on the first substrate 11 in accordance with the light emitting element section (not shown).
【００２５】第１の電極１２の表面には、ホール注入材
料、ホール輸送材料、発光材料をドープしたホール輸送
材料、発光材料をドープした電子輸送材料、電子輸送材
料、電子注入材料、その他発光材料などによるＥＬ材料
からなる発光層１３が積層されている。On the surface of the first electrode 12, a hole injection material, a hole transport material, a hole transport material doped with a light emitting material, an electron transport material doped with a light emitting material, an electron transport material, an electron injection material, and other light emitting materials. A light emitting layer 13 made of an EL material is laminated.
【００２６】そして発光層１３の表面には、Ｌｉ、Ｎ
ａ、Ｃｓ、Ｃａ、Ｍｇなどの低仕事関数金属および／ま
たはこれらの酸化物、水酸化物、フッ化物、塩化物等
を、Ａｌ、Ａｇ等の低抵抗金属と積層または合金化した
ものを使用した第２の電極（背面電極）１４が適宜積層
されている。On the surface of the light emitting layer 13, Li, N
Low work function metals such as a, Cs, Ca and Mg and / or their oxides, hydroxides, fluorides, chlorides, etc. are laminated or alloyed with low resistance metals such as Al and Ag. The second electrode (back surface electrode) 14 is appropriately laminated.
【００２７】この第２の電極１４は、第１の電極１２と
対向して所定の形状や、直交するストライプ状等に形成
されている。これら第１の基板１１上に積層された第１
の電極１２から第２の電極１４までの積層構造が実質的
に発光制御層を形成する。The second electrode 14 faces the first electrode 12 and is formed in a predetermined shape or in a stripe shape orthogonal to each other. The first stacked on the first substrate 11
The laminated structure from the electrode 12 to the second electrode 14 substantially forms the emission control layer.
【００２８】ここで発光層１３は、母体材料のうちホー
ル輸送材料としては、トリフェニルアミン誘導体（ＴＰ
Ｄ）、ヒドラゾン誘導体、アリールアミン誘導体等があ
る。また、ポリスチレンスルホン酸をドープしたポリエ
チレンジオキシチオフェン、ポリアニリン誘導体等の高
分子系材料も使用できる。Here, in the light emitting layer 13, a triphenylamine derivative (TP) is used as a hole transport material in the matrix material.
D), hydrazone derivatives, arylamine derivatives and the like. Further, a polymer-based material such as polyethylenedioxythiophene doped with polystyrene sulfonic acid or a polyaniline derivative can also be used.
【００２９】一方、電子輸送材料としては、アルミキレ
ート錯体（Ａｌｑ３）、ジスチリルビフェニル誘導体
（ＤＰＶＢｉ）、オキサジアゾール誘導体、ビスチリル
アントラセン誘導体、ベンゾオキサゾールチオフェン誘
導体、ペリレン類、チアゾール類等を用いる。さらに適
宜の発光材料を混合してもよく、ホール輸送材料と電子
輸送材料を混合した発光層を形成してもよい。その場
合、ホール輸送材料と電子輸送材料の比は、１０：９０
〜９０：１０の範囲で調整できる。On the other hand, as the electron transport material, an aluminum chelate complex (Alq3), a distyrylbiphenyl derivative (DPVBi), an oxadiazole derivative, a bistyrylanthracene derivative, a benzoxazolethiophene derivative, perylenes, thiazoles and the like are used. Further, an appropriate light emitting material may be mixed, or a light emitting layer in which a hole transport material and an electron transport material are mixed may be formed. In that case, the ratio of the hole transport material to the electron transport material is 10:90.
It can be adjusted in the range of up to 90:10.
【００３０】本発明に用いる構成部材、上記の第１の基
板１１、第１の電極１２、発光層１３、第２の電極１４
には上記した例の外、従来公知の材料を用いることがで
きる。たとえば、「有機ＥＬ材料とディスプレイ」（シ
ーエムシー社発行）などに記載されている。Components used in the present invention, the first substrate 11, the first electrode 12, the light emitting layer 13, and the second electrode 14 described above.
In addition to the above-mentioned examples, a conventionally known material can be used for. For example, it is described in "Organic EL Materials and Displays" (published by CMC).
【００３１】第１の基板１１上に積層された第１の電極
１２から第２の電極１４までの発光部は、対向基板１６
により、接合材１７を用いて封止される。また、対向基
板１６上には外部から侵入してくる湿分を捕捉するため
の吸湿剤層１８が配置されている。The light emitting portion from the first electrode 12 to the second electrode 14 laminated on the first substrate 11 is the counter substrate 16.
Thus, the bonding material 17 is used for sealing. Further, on the counter substrate 16, a hygroscopic agent layer 18 for trapping moisture entering from the outside is arranged.
【００３２】本発明において空間内に設ける吸湿剤層１
８に使用される吸湿剤材料は無機質の吸湿剤であり、ア
ルカリ金属、アルカリ土類金属、アルカリ金属やアルカ
リ土類金属の酸化物、過酸化物、水素化物、フッ化物、
塩化物、硫酸塩、過塩素酸塩、炭酸塩、有機錯体、５酸
化２リン、モレキュラーシーブまたはこれらの無機質化
合物を必須成分とする複合化物等が挙げられる。また、
これらは単独で使用しても、２種以上を共存させてもよ
い。In the present invention, the hygroscopic agent layer 1 provided in the space
The moisture absorbent material used in No. 8 is an inorganic moisture absorbent, and includes alkali metals, alkaline earth metals, oxides, peroxides, hydrides, fluorides of alkali metals and alkaline earth metals,
Examples thereof include chlorides, sulfates, perchlorates, carbonates, organic complexes, phosphorus pentoxide, molecular sieves, and complex compounds containing these inorganic compounds as essential components. Also,
These may be used alone or in combination of two or more.
【００３３】なかでも酸化バリウムや、５酸化２リンは
低湿度環境下でも水分の補足力が強いので好ましい。一
方、アルカリ金属酸化物、酸化カルシウムまたは酸化ス
トロンチウムから選択した１つ、またはこれらの化合物
を６０重量％以上含有する複合酸化物は、生産工程にお
ける材料の取り扱い性または管理上の効率の観点から好
ましい。Among them, barium oxide and phosphorus pentoxide are preferable because they have a strong ability to trap water even in a low humidity environment. On the other hand, one selected from alkali metal oxides, calcium oxide or strontium oxide, or a composite oxide containing 60% by weight or more of these compounds is preferable from the viewpoint of handleability of the material in the production process or management efficiency. .
【００３４】なかでも、酸化カルシウムおよび／または
その複合酸化物は取り扱いが容易であり、また、水分を
いったん捕捉した後、再放出しにくいので特に好まし
い。また、合成ゼオライトは１００℃程度の高温状態で
も吸湿した水分を再放出する可能性が低い。また、低温
条件でも高い吸湿性を示し、上記の本発明における加熱
時に同時に活性化できるので好ましい。また、吸湿特性
の再現性がよく、量産した場合のばらつきが少なく、本
発明の有機ＥＬディスプレイに使用することが好まし
い。Of these, calcium oxide and / or its complex oxides are particularly preferable because they are easy to handle, and once water is once captured, it is difficult to release it again. Further, the synthetic zeolite is less likely to re-release the absorbed moisture even in a high temperature state of about 100 ° C. Further, it exhibits high hygroscopicity even under low temperature conditions and can be activated simultaneously with heating in the present invention, which is preferable. Further, the hygroscopic property is good in reproducibility and there is little variation in mass production, and it is preferably used for the organic EL display of the present invention.
【００３５】通常、これらの吸湿剤は粉末、粒子状、ペ
レット状の形態で使用されるが、吸湿効率の点で粉末ま
たは粒子状、または粒子と粉末の混合状態が好ましい。
特に、取り扱いやすさの点では、粉末状であって、平均
粒径を２０μｍ以下の値とするのが好ましい。より好ま
しくは、平均粒径が０．１〜１０μｍの場合である。Usually, these hygroscopic agents are used in the form of powder, particles or pellets, but from the viewpoint of hygroscopic efficiency, powder or particles, or a mixed state of particles and powder is preferable.
Particularly, from the viewpoint of ease of handling, it is preferable that it is powdery and has an average particle diameter of 20 μm or less. More preferably, the average particle size is 0.1 to 10 μm.
【００３６】また、粉末の最大粒径は５００μｍ以下、
好ましくは１００μｍ以下、さらに好ましくは、５０μ
ｍ以下とする。本発明において、吸湿剤を有機ＥＬディ
スプレイの内部に配置した際に、膜厚ばらつきや異常突
起などによる素子との接触・破壊を生じにくくなるから
である。さらに、目標とする吸湿剤層の平均厚みよりも
最大粒径が小さいことが好ましい。吸湿剤層の厚みより
７０％以下、さらには５０％以下にすることで均一な吸
湿材層を形成しやすいので特に好ましい。The maximum particle size of the powder is 500 μm or less,
Preferably 100 μm or less, more preferably 50 μm
m or less. This is because, in the present invention, when the hygroscopic agent is placed inside the organic EL display, it is less likely to cause contact with or damage to the element due to variations in film thickness or abnormal protrusions. Furthermore, it is preferable that the maximum particle size is smaller than the target average thickness of the moisture absorbent layer. It is particularly preferable that the thickness of the moisture absorbent layer is 70% or less, more preferably 50% or less, because a uniform moisture absorbent layer can be easily formed.
【００３７】本発明において、吸湿剤層１８は熱分解性
の有機質バインダーと上記の無機質吸湿剤とを含む混合
物の層を対向基板１６上に配置した後に、所定の熱処理
工程を経て形成される。配置の方法としては、吸湿剤の
粉末やペレットを有機質の低分子化合物や高分子化合物
などの有機質バインダーを用いて、混合してペースト状
にしたものを、スクリーン印刷、ディスペンサーを用い
たディスペンス、ダイコート、ブレードコート、プレス
成形等の方法で対向基板１６の上にシート状に塗布を行
って混合物層を形成する。In the present invention, the hygroscopic agent layer 18 is formed by arranging a layer of a mixture containing a thermally decomposable organic binder and the above inorganic hygroscopic agent on the counter substrate 16 and then performing a predetermined heat treatment process. As a placement method, a powder or pellet of a hygroscopic agent is mixed with an organic binder such as an organic low molecular compound or a high molecular compound to form a paste, which is screen-printed, dispensed using a dispenser, or die-coated. Sheet-shaped application is performed on the counter substrate 16 by a method such as blade coating or press molding to form a mixture layer.
【００３８】または、あらかじめシート状等の所望の形
状に成形した上記混合物を対向基板上に載置して混合物
層とする方法を用いることもできる。なお、混合物層を
あらかじめ基板上に形成する方法はこれらに限られるも
のではない。Alternatively, a method may be used in which the above-mentioned mixture, which has been molded into a desired shape such as a sheet, is placed on the counter substrate to form a mixture layer. The method of forming the mixture layer on the substrate in advance is not limited to these.
【００３９】具体的な好ましい方法としては、たとえば
吸湿剤と高分子化合物、硬化性のオリゴマー、モノマー
などの硬化性低分子化合物などの、高分子化合物になり
える低分子化合物、界面活性剤、脂肪酸アミドのような
高粘度低分子化合物とを混合した流動性のある混合物を
対向基板上にシート状に配置する方法が挙げられる。ま
た、必要に応じて、後述する補助的なバインダーを混合
物にさらに添加して用いてもよい。さらに、必要に応じ
て水および／または有機溶剤を上記混合物に添加するこ
ともできる。このような成分を含む流動性のある混合物
を、対向基板上にシート状に配置し、必要により乾燥し
て、混合物層を形成する。Specific preferred methods include low molecular weight compounds capable of becoming high molecular weight compounds, such as hygroscopic agents and high molecular weight compounds, curable oligomers, curable low molecular weight compounds such as monomers, surfactants and fatty acids. A method of arranging a fluid mixture containing a high-viscosity low-molecular compound such as amide as a sheet on a counter substrate can be mentioned. In addition, an auxiliary binder described below may be further added to the mixture and used, if necessary. Furthermore, water and / or an organic solvent may be added to the above mixture, if necessary. A fluid mixture containing such components is placed in a sheet on the counter substrate and dried if necessary to form a mixture layer.
【００４０】また、接着性や粘着性を有する有機質バイ
ンダーの層をまず対向基板上に形成し、次いで乾燥剤を
散布し、必要によりプレス等により密着させる方法を用
いてもよい。また、これらの有機質バインダーの層と吸
湿剤の層を積層する方法も採用できる。生産工程の効率
や一定量を均一に固定化する、また、多様な形状に容易
に対応できるという点では、吸湿剤を前記有機質バイン
ダーに均一に分散したものを対向基板に塗布する方法が
好ましい。また、複数の吸湿剤を混合して使用してもよ
く、また、異なる種類の吸湿剤を含む混合物層を積層し
てもよい。Further, a method may be used in which a layer of an organic binder having adhesiveness or tackiness is first formed on a counter substrate, then a desiccant is sprinkled on, and if necessary, pressed by a press or the like. Further, a method of laminating a layer of these organic binders and a layer of a hygroscopic agent can also be adopted. From the viewpoint that the efficiency of the production process and a fixed amount can be fixed uniformly, and various shapes can be easily accommodated, it is preferable to apply a solution in which the moisture absorbent is uniformly dispersed in the organic binder to the counter substrate. Further, a plurality of hygroscopic agents may be mixed and used, or a mixture layer containing different types of hygroscopic agents may be laminated.
【００４１】このようにして、対向基板上に配置した混
合物層は、その含有する材料成分に応じて、混合物層の
表層のみが固体状態で内部が流動状態であってもよく、
また、内部まで完全に固体状態で固定化されていてもよ
い。本発明においては、所定の温度以上に設定した熱処
理後に、性能的に安定した吸湿剤層が形成され、配置さ
れるようにする。Thus, in the mixture layer arranged on the counter substrate, only the surface layer of the mixture layer may be in a solid state and the inside may be in a fluid state, depending on the material components contained therein,
Further, the inside may be completely fixed in a solid state. In the present invention, after the heat treatment set to a predetermined temperature or higher, a performance-stable hygroscopic agent layer is formed and arranged.
【００４２】本発明で用いることのできる有機質バイン
ダーとして、高分子化合物が挙げられる。たとえば、塩
化ビニル系樹脂、フェノール系樹脂、シリコーン系樹
脂、エポキシ系樹脂、ポリエステル系樹脂、ウレタン系
樹脂、アクリル系樹脂、オレフィン系樹脂、フッ素樹
脂、シリコーン系樹脂・セルロース系樹脂等の一種単独
または二種以上の組合わせを使用できる。なお、これら
の樹脂には、ゴム弾性を有する柔軟なエラストマーや、
硬化性および常温で流動性を有するオリゴマー状化合物
等も含まれる。As the organic binder that can be used in the present invention, a polymer compound can be mentioned. For example, vinyl chloride resin, phenol resin, silicone resin, epoxy resin, polyester resin, urethane resin, acrylic resin, olefin resin, fluororesin, silicone resin, cellulose resin, etc. alone or Combinations of two or more can be used. In addition, these resins include a flexible elastomer having rubber elasticity,
An oligomeric compound having curability and fluidity at room temperature is also included.
【００４３】また、高分子化合物として、硬化性樹脂、
特に、熱硬化性および／または光硬化性樹脂を含有する
ことも好ましい。なかでも、常温で液状の低粘度樹脂を
バインダーとして使用して、硬化させることにより、乾
燥剤含有層を対向基板内面に極めて短時間で設けること
ができる。この場合、有機ＥＬディスプレイの製造時間
を短縮できる。As the polymer compound, a curable resin,
In particular, it is also preferable to contain a thermosetting and / or photocurable resin. In particular, by using a low-viscosity resin that is liquid at room temperature as a binder and curing it, the desiccant-containing layer can be provided on the inner surface of the counter substrate in an extremely short time. In this case, the manufacturing time of the organic EL display can be shortened.
【００４４】このような硬化性樹脂としては、硬化性シ
リコーン系樹脂、エポキシ系樹脂、硬化性アクリル系樹
脂、硬化性ポリブタジエン系樹脂、硬化性ポリウレタン
等の一種単独または二種以上の組合わせが挙げられる。Examples of such a curable resin include a curable silicone resin, an epoxy resin, a curable acrylic resin, a curable polybutadiene resin, a curable polyurethane and the like, which may be used alone or in combination of two or more. To be
【００４５】光硬化性樹脂を用いる場合、熱硬化型に比
較して、低温プロセスで硬化可能であり、好ましい。し
かし、吸湿剤含量が多い場合には光が透過しないため、
硬化が表層部の近傍で止まり、内部まで完全に硬化しな
いという問題が生ずる。したがって、光硬化性樹脂の場
合、生産工程上の問題で内部まで完全に固定化した状態
が必要になる場合には、ＵＶおよび／または可視光の硬
化に必要な波長域の光が、形成しようとする吸湿剤層の
内部まで充分到達するような厚みに設定することが重要
である。または、吸湿剤の含有量を適切に選択すること
が重要である。光が透過しにくい組成になる場合には、
熱硬化性樹脂を選択することが好ましい。When a photocurable resin is used, it can be cured by a low temperature process as compared with a thermosetting type resin, which is preferable. However, when the moisture absorbent content is high, light does not penetrate, so
Curing stops in the vicinity of the surface layer, and there is a problem that the interior is not completely cured. Therefore, in the case of a photo-curable resin, if the state of being completely fixed is required due to a problem in the production process, light in the wavelength range necessary for curing UV and / or visible light will be formed. It is important to set the thickness so as to sufficiently reach the inside of the moisture absorbent layer. Alternatively, it is important to properly select the content of the hygroscopic agent. If the composition does not allow light to easily pass,
It is preferable to select a thermosetting resin.
【００４６】本発明において、これらの熱分解性の有機
質バインダーと無機質吸湿剤を含む混合物の層を対向基
板上に配置した後、その有機質バインダーの熱分解温度
以上の温度に加熱して、実質的に有機材料を熱分解して
除去する。これにより、二つの基板を封止後、有機ＥＬ
ディスプレイの内部でのアウトガスの発生を抑制でき
る。In the present invention, after a layer of a mixture containing these thermally decomposable organic binder and inorganic hygroscopic agent is placed on a counter substrate, it is heated to a temperature not lower than the thermal decomposition temperature of the organic binder to substantially The organic material is thermally decomposed and removed. As a result, after sealing the two substrates, the organic EL
Generation of outgas inside the display can be suppressed.
【００４７】また、本発明において、吸湿剤として特に
アルカリ金属やアルカリ土類金属系の化合物のように、
塩基性部位を有する化合物を使用する場合、熱処理工程
において、空気中に存在する炭酸ガスや、熱分解により
発生する炭酸ガス・一酸化炭素などのガスを吸収するこ
とがある。Further, in the present invention, as a hygroscopic agent, particularly, an alkali metal or alkaline earth metal compound,
When a compound having a basic site is used, carbon dioxide gas existing in the air or carbon dioxide gas or carbon monoxide gas generated by thermal decomposition may be absorbed in the heat treatment step.
【００４８】この炭酸ガス吸収により、吸湿性能の低下
が引き起こされる可能性がある。これを抑制するため
に、有機質バインダーを熱分解する際に、実質的にＣＯ
２ガスが無い状態で行うことが好ましい。ＣＯ２ガスの
無い状態を作る具体的な方法としては、高純度窒素ガス
・高純度アルゴンガスなどの不活性ガス、窒素および酸
素の混合ガスなどの炭酸ガスを含有しないガス雰囲気下
で有機質バインダーを熱分解する方法が挙げられる。The absorption of carbon dioxide gas may cause a decrease in moisture absorption performance. In order to suppress this, when the organic binder is thermally decomposed, CO
It is preferable to carry out in the absence of 2 gases. As a specific method for producing a state without CO 2 gas, an organic binder is used under a gas atmosphere containing no inert gas such as high-purity nitrogen gas and high-purity argon gas, and carbon dioxide gas such as a mixed gas of nitrogen and oxygen. A method of thermal decomposition can be mentioned.
【００４９】また、有機質バインダーとして解重合性高
分子を使用することも有利である。なぜなら、有機質バ
インダーの熱分解が生じる際に、解重合による熱分解ガ
スが主成分となり、炭酸ガスや一酸化炭素の発生を抑制
できるために好ましい。It is also advantageous to use a depolymerizable polymer as the organic binder. This is preferable because when the organic binder is thermally decomposed, the thermally decomposed gas due to depolymerization becomes the main component and the generation of carbon dioxide gas or carbon monoxide can be suppressed.
【００５０】具体的な解重合性高分子としては、たとえ
ば、テトラフルオロエチレン、アクリル酸誘導体、メタ
クリル酸誘導体、α−メチルスチレンなどのモノマー単
位を主成分とする単独もしくは共重合体が挙げられる。
入手のしやすさや熱分解物の揮発性、安全性の観点でポ
リメチルメタクリレート、ポリメチルアクリレート、ポ
リα−メチルスチレンなどが特に好ましい。Specific examples of the depolymerizable polymer include a homopolymer or a copolymer containing a monomer unit such as tetrafluoroethylene, an acrylic acid derivative, a methacrylic acid derivative, and α-methylstyrene as a main component.
Polymethyl methacrylate, polymethyl acrylate, poly α-methylstyrene and the like are particularly preferable from the viewpoints of availability, volatility of the pyrolyzed product, and safety.
【００５１】本発明において、吸湿剤は熱処理後に対向
基板上に固定化されることが好ましい。吸湿剤が熱処理
工程で基板に固着する場合、特に基板への密着、膜質を
改良するための骨材のようなものを添加する必要はな
い。しかし、熱処理後の対向基板上への固定化がしにく
い、または膜質が脆いといった特性を有する吸湿剤を用
いる場合、それを補償するために、必要に応じて補助的
なバインダーを含有させることもできる。その際、有機
成分を全て熱分解除去できるように、補助的なバインダ
ーとして無機系バインダーを用いることが好ましい。In the present invention, the hygroscopic agent is preferably immobilized on the counter substrate after heat treatment. When the hygroscopic agent adheres to the substrate in the heat treatment process, it is not necessary to add an aggregate for improving the film quality and the adhesion to the substrate. However, in the case of using a hygroscopic agent having a property that it is difficult to fix on the counter substrate after heat treatment or the film quality is brittle, in order to compensate for it, an auxiliary binder may be added if necessary. it can. At that time, it is preferable to use an inorganic binder as an auxiliary binder so that all the organic components can be thermally decomposed and removed.
【００５２】たとえば、アルコキシシラン、アルコキシ
チタン、シランカップリング剤・チタネート系カップリ
ング剤等の有機金属化合物および低融点ガラス粉末等が
挙げられる。Examples thereof include alkoxysilanes, alkoxytitaniums, organometallic compounds such as silane coupling agents and titanate coupling agents, and low-melting glass powders.
【００５３】また、テトラアルコキシシラン、テトラア
ルコキシシランオリゴマー、シラザン等のシラン化合
物、テトラアルコキシチタン等に代表される金属元素の
アルコキサイド、有機酸塩、アセチルアセトナート塩
等、加熱や加湿により無機酸化物・窒化物、金属酸化
物、窒化物を形成しうる化合物などが挙げられる。Further, tetraalkoxysilanes, tetraalkoxysilane oligomers, silane compounds such as silazanes, alkoxides of metal elements typified by tetraalkoxytitanium, organic acid salts, acetylacetonate salts, etc., inorganic oxides by heating or humidification. -Nitride, a metal oxide, a compound which can form a nitride, etc. are mentioned.
【００５４】また、低融点ガラスとしては、公知のもの
を使用できるが、具体的な材料としては、Ｂ２Ｏ３・Ｐ
ｂＯ、Ｂ２Ｏ３・ＰｂＯ・ＺｎＯ、Ｂ２Ｏ３・ＳｉＯ２
・ＰｂＯ、Ｂ２Ｏ３・ＳｉＯ２・ＺｎＯ、ＰｂＯ・Ｚｎ
Ｏ、ＰｂＯ・ＳｎＯ、Ｐｂ２Ｏ５・ＳｎＯ、Ｐ２Ｏ５・
ＺｎＯ・ＳｎＯ、Ｂ２Ｏ３・Ｂｉ２Ｏ３等の各主成分か
らなるガラスを使用できる。これら低融点ガラスを使用
する際には、その軟化点温度以上で焼成を行うことが好
ましい。Known glass can be used as the low-melting glass, but specific materials include B 2 O 3 .P
bO, B 2 O 3 · PbO · ZnO, B 2 O 3 · SiO 2
・ PbO, B 2 O 3・ SiO 2・ ZnO, PbO ・ Zn
O, PbO · SnO, Pb 2 O 5 · SnO, P 2 O 5 ·
ZnO · SnO, the glass consisting of the main components such as B 2 O 3 · Bi 2 O 3 may be used. When using these low-melting-point glasses, it is preferable to perform firing at a softening point temperature or higher.
【００５５】また、これらの化合物に形状保持や結晶化
促進のためにアルミナやジルコニア系酸化物を混合して
もよい。また、アルカリ土類金属酸化物のような吸湿剤
を用いた場合で、熱処理温度を９００℃以下にすると、
前記低融点ガラスと吸湿剤とが複合酸化物層を形成せず
に、低融点ガラスのみが溶融して多孔質状のバインダー
を形成できる。そのため、吸湿剤層の構造上、吸湿剤の
吸湿性能が高まるので好ましい。特に７００℃以下が好
ましく、プロセス効率を考慮すると６００℃以下、より
好ましくは５００℃以下である。Alumina or zirconia-based oxide may be mixed with these compounds in order to maintain the shape and promote crystallization. In addition, when a hygroscopic agent such as an alkaline earth metal oxide is used and the heat treatment temperature is set to 900 ° C. or lower,
The low melting glass and the hygroscopic agent do not form a complex oxide layer, but only the low melting glass can be melted to form a porous binder. Therefore, the structure of the hygroscopic agent layer is preferable because the hygroscopic property of the hygroscopic agent is enhanced. In particular, it is preferably 700 ° C. or lower, 600 ° C. or lower, more preferably 500 ° C. or lower in consideration of process efficiency.
【００５６】このように、安定した吸湿剤層の膜質が得
られる点で低融点ガラスが特に好ましい。上記した補助
的なバインダーには有機材料との化合物も含まれている
が、これらを使用する場合には、熱処理工程によりバイ
ンダー中の有機成分が熱分解によって、消失するような
条件で熱分解を行えばよい。As described above, the low-melting glass is particularly preferable in that stable film quality of the hygroscopic agent layer can be obtained. The above-mentioned auxiliary binder also contains a compound with an organic material, but when using these, the thermal decomposition is carried out under the condition that the organic component in the binder disappears due to the thermal decomposition in the heat treatment step. Just go.
【００５７】また、例示したバインダーと吸湿剤とを含
む混合物を対向基板上に形成する前に、対向基板をテト
ラアルコキシシランやシランカップリング剤等の密着性
付与剤で処理しておくことも熱処理後の混合物層の固定
化のための好ましい方法である。It is also possible to heat the counter substrate with an adhesion-imparting agent such as tetraalkoxysilane or a silane coupling agent before forming the mixture containing the exemplified binder and hygroscopic agent on the counter substrate. It is the preferred method for the subsequent immobilization of the mixture layer.
【００５８】混合物層を対向基板に配置し、加熱処理す
る前において、混合物層中の吸湿剤の含有量としては、
１０〜９９重量％であることが好ましい。１０重量％未
満の場合、対向基板上に充分な量の吸湿剤を配置するこ
とが困難となる。９９重量％を越えると吸湿剤層の形成
が困難となる。好ましくは４０〜９５重量％、さらに好
ましくは６０〜９０重量％である。また、熱処理後の吸
湿剤層における、吸湿剤の含有量は３０％以上であるこ
とが好ましい。さらには、５０％以上が好ましく、特に
８０％以上が好ましい。高い吸湿性能を維持できるから
である。Before the mixture layer is placed on the counter substrate and heat-treated, the content of the hygroscopic agent in the mixture layer is as follows.
It is preferably 10 to 99% by weight. If it is less than 10% by weight, it becomes difficult to dispose a sufficient amount of the moisture absorbent on the counter substrate. If it exceeds 99% by weight, it becomes difficult to form the hygroscopic agent layer. It is preferably 40 to 95% by weight, more preferably 60 to 90% by weight. Further, the content of the hygroscopic agent in the hygroscopic agent layer after the heat treatment is preferably 30% or more. Furthermore, 50% or more is preferable, and 80% or more is particularly preferable. This is because high moisture absorption performance can be maintained.
【００５９】本発明の有機ＥＬディスプレイの製造方法
の１態様においては、対向基板上に混合物層を配置した
後、有機成分の熱分解温度以上に加熱して有機成分の除
去をして吸湿剤層１８を形成する。このような温度処理
を行うことにより、有機質バインダーの分解除去によっ
て、封止後のアウトガス発生を抑制し、加熱処理による
吸湿剤層の多孔化をうながし、さらには、無機材料系バ
インダーと吸湿剤との複合化によって、吸湿性能の向上
および吸湿剤層の膜質の向上といった効果が得られる。In one embodiment of the method for producing an organic EL display of the present invention, after the mixture layer is arranged on the counter substrate, the mixture is heated to a temperature not lower than the thermal decomposition temperature of the organic component to remove the organic component and the hygroscopic agent layer. 18 is formed. By performing such a temperature treatment, by decomposition and removal of the organic binder, the outgassing after sealing is suppressed, and it promotes the porosity of the hygroscopic agent layer by the heat treatment, and further, the inorganic material-based binder and the hygroscopic agent. By combining the above, it is possible to obtain the effects of improving the moisture absorption performance and the film quality of the hygroscopic agent layer.
【００６０】本発明で必須とする熱処理の際の温度は、
有機質バインダーが熱分解でほとんど消失する温度条件
であれば特に制限されない。好ましくは、２５０℃以
上、特に３００℃以上、さらには３５０℃以上の温度で
熱処理することが好ましい。The temperature during the heat treatment which is essential in the present invention is
There is no particular limitation as long as the temperature condition is such that the organic binder almost disappears due to thermal decomposition. It is preferable to perform heat treatment at a temperature of 250 ° C. or higher, particularly 300 ° C. or higher, and further 350 ° C. or higher.
【００６１】熱処理後に形成される吸湿剤層の厚みに制
限はない。有機ＥＬディスプレイの封止に使用する接着
剤の透湿性や、接着剤の幅、要求される素子寿命によっ
て、吸湿剤の必要量を変更する。しかし、充分な吸湿性
を発揮させるために、１０μｍ以上の厚みに形成するこ
とが好ましい。特に５０μｍ以上、さらに好ましくは１
００μｍ以上とする。また、吸湿剤層の厚みが０．５ｍ
ｍを越えると、形成した吸湿剤層が吸湿後の体積膨張等
により素子破壊を起こしたり、対向基板から剥離したり
する可能性がある。したがって、所望の厚みに形成でき
るように製造時の管理が必要となる。There is no limitation on the thickness of the hygroscopic agent layer formed after the heat treatment. The required amount of the hygroscopic agent is changed according to the moisture permeability of the adhesive used for sealing the organic EL display, the width of the adhesive, and the required device life. However, in order to exhibit sufficient hygroscopicity, it is preferable to form it with a thickness of 10 μm or more. Especially 50 μm or more, more preferably 1
It is set to 00 μm or more. Also, the thickness of the moisture absorbent layer is 0.5 m.
If it exceeds m, the formed hygroscopic agent layer may break down the element due to volume expansion after moisture absorption or may be peeled from the counter substrate. Therefore, management at the time of manufacturing is required so that the film can be formed to a desired thickness.
【００６２】本発明における対向基板としてはガス透過
性、湿気透過性が低い基板であれば特に制限はない。具
体的な基板としては、ソーダライムガラスや、ノンアル
カリガラス、ホウケイ酸ガラス、プラズマディスプレイ
用ガラス（旭硝子社製ＰＤ２００）等の耐熱性ガラス基
板が挙げられる。The counter substrate in the present invention is not particularly limited as long as it is a substrate having low gas permeability and moisture permeability. Specific substrates include heat resistant glass substrates such as soda lime glass, non-alkali glass, borosilicate glass, and plasma display glass (PD200 manufactured by Asahi Glass Co., Ltd.).
【００６３】また、アルミニウムやステンレススチール
のような金属性基板またはフィルム基板またはセラミッ
ク基板も使用できる。なかでも、有機ＥＬディスプレイ
の発光素子基板と同じ材料を用いて対向基板として使用
する場合、発光素子基板と対向基板との線膨張係数が等
しくなり、接合部の信頼性が高まるので好ましい。ま
た、対向基板として、ソーダガラス基板やノンアルカリ
ガラス基板を使用する場合、これらの基板のガラス転移
温度以下の温度で熱処理をすることが、基板の平坦性を
確保できるので好ましい。Further, a metal substrate such as aluminum or stainless steel, a film substrate or a ceramic substrate can be used. Above all, it is preferable to use the same material as the light emitting element substrate of the organic EL display as the counter substrate because the light emitting element substrate and the counter substrate have the same linear expansion coefficient and the reliability of the bonding portion is improved. When a soda glass substrate or a non-alkali glass substrate is used as the counter substrate, it is preferable to perform heat treatment at a temperature not higher than the glass transition temperature of these substrates because the flatness of the substrates can be secured.
【００６４】本発明において、接合材１７としては従来
公知の接着剤を使用することができる。アウトガスの問
題や、耐熱接着性の観点から、無溶剤もしくは溶剤含量
が１０％以下の接着剤、好ましくは熱および／または光
硬化型接着剤、さらに好ましくは常温で０．１〜１００
００ＰａＳ、特に好ましくは１〜５０００ＰａＳの粘度
の液状接着剤が好適である。In the present invention, as the bonding material 17, a conventionally known adhesive can be used. From the viewpoint of outgassing problems and heat-resistant adhesiveness, a solvent-free or solvent-containing adhesive having a solvent content of 10% or less, preferably a heat- and / or photo-curable adhesive, and more preferably 0.1-100 at room temperature.
A liquid adhesive having a viscosity of 00 PaS, particularly preferably 1 to 5000 PaS, is suitable.
【００６５】具体的には、たとえばアクリレート、ウレ
タンアクリレート、エポキシアクリレート、メラミンア
クリレート、イソシアヌレート変性アクリレート、アク
リル樹脂変性アクリレートおよび／または前記アクリレ
ートがメタクリレートに変換されたメタクリレート化合
物、等のラジカル重合性樹脂、エポキシ樹脂、オキセタ
ン樹脂、ビニルエーテル樹脂等の樹脂を用いたカチオン
重合性樹脂、チオール・エン付加型樹脂、ビニル・ハイ
ドロシラン付加型樹脂などの接着剤が挙げられる。Specifically, for example, a radical polymerizable resin such as acrylate, urethane acrylate, epoxy acrylate, melamine acrylate, isocyanurate modified acrylate, acrylic resin modified acrylate and / or a methacrylate compound in which the acrylate is converted to methacrylate, Examples of the adhesive include a cationically polymerizable resin using a resin such as an epoxy resin, an oxetane resin, and a vinyl ether resin, a thiol / ene addition type resin, a vinyl / hydrosilane addition type resin, and the like.
【００６６】これらのうち、硬化時の副成物の発生が少
ないカチオン重合性樹脂が好ましい。また、前記樹脂の
硬化タイプとしては、有機ＥＬディスプレイの耐熱性を
考慮すると光硬化型が素子への熱の影響がなく、低温で
の硬化が可能となるなので好ましい。なかでも、光カチ
オン硬化型エポキシ樹脂および／またはオキセタン樹脂
が好ましい。これらの接着剤には、接着性・透湿性等の
改良の観点で、シリカ、タルク、炭酸カルシウム等の従
来公知のフィラーやシランカップリング剤等の接着付与
剤、また、光硬化性のものを使用する場合には、光増感
剤が添加されていてもよい。特に接着性の点でシランカ
ップリング剤が添加されていると好ましい。Of these, a cationically polymerizable resin that produces less by-products during curing is preferred. Further, as the curing type of the resin, a photo-curing type is preferable in consideration of the heat resistance of the organic EL display because the element is not affected by heat and curing at a low temperature is possible. Of these, photocationic curing type epoxy resins and / or oxetane resins are preferable. From the viewpoint of improving adhesiveness, moisture permeability and the like, these adhesives include adhesion promoters such as conventionally known fillers such as silica, talc and calcium carbonate, and silane coupling agents, and photocurable adhesives. When used, a photosensitizer may be added. It is particularly preferable to add a silane coupling agent from the viewpoint of adhesiveness.
【００６７】また、接着剤が接触する基板表面にあらか
じめシランカップリング剤等の接着性付与剤を塗布処理
しておくことも長期接着信頼性の点から好ましい。ま
た、本発明の実施の形態２を図２に示す。その構成は実
施の形態１（図１）の構成とほぼ同様であるが、枠状の
スペーサ１５がさらに設けられている。枠状のスペーサ
１５を基板間の構成部材として設けた。このことによ
り、吸湿剤層の厚みが２０μｍ程度を越える場合に、接
合材１７の厚みだけで空間を作成することが難しい場合
があるが、その封止の際に、吸湿剤層と発光部とが相互
に接触しないように空間を設けることが可能となる。Further, it is also preferable from the viewpoint of long-term adhesion reliability that an adhesiveness-imparting agent such as a silane coupling agent is previously applied to the surface of the substrate with which the adhesive comes into contact. A second embodiment of the present invention is shown in FIG. The structure is almost the same as that of the first embodiment (FIG. 1), but a frame-shaped spacer 15 is further provided. The frame-shaped spacer 15 was provided as a constituent member between the substrates. This may make it difficult to create a space only by the thickness of the bonding material 17 when the thickness of the hygroscopic agent layer exceeds about 20 μm. It is possible to provide a space so that they do not contact each other.
【００６８】また、吸湿剤層がアルカリ土類金属酸化物
のように、吸湿後体積変化を起こすようなもので構成さ
れている場合、吸湿剤層の体積膨張も考慮する必要があ
る。その空間を図１における接合材１７の硬化後の厚み
で制御する場合、接着剤として熱硬化型接着剤を用いれ
ば、接着剤厚みによらず均一な硬化が期待できる。しか
し、上述したような光硬化系接着剤を使用する場合、接
着剤厚みが５０μｍを越えると、光が樹脂材料の内部ま
で到達しにくくなり、均一な硬化と充分な接着性を発現
できない場合がある。When the hygroscopic agent layer is composed of an alkaline earth metal oxide that causes a volume change after moisture absorption, it is necessary to consider the volume expansion of the hygroscopic agent layer. When the space is controlled by the thickness of the bonding material 17 after curing in FIG. 1, if a thermosetting adhesive is used as the adhesive, uniform curing can be expected regardless of the adhesive thickness. However, in the case of using the photo-curable adhesive as described above, if the adhesive thickness exceeds 50 μm, it becomes difficult for light to reach the inside of the resin material, and uniform curing and sufficient adhesiveness may not be exhibited. is there.
【００６９】また、接着剤の厚み制御は再現性の点で難
しくなる問題がある。そこで、上述したような空間を設
けるために、金属基板やガラス基板、プラスチック基板
をプレス、エッチング、サンドブラストのような研削等
の方法で凹状に空間を設ける方法が考えられる。しか
し、これらの手法は有機ＥＬディスプレイの多用な素子
サイズに容易に対応することが難しくなることがある。
図２の実施の形態２における枠状のスペーサ１５は低融
点ガラスなどのスペーサ材料を焼成することにより形成
できる。Further, there is a problem that control of the thickness of the adhesive becomes difficult in terms of reproducibility. Therefore, in order to provide the above-described space, a method of providing a concave space by a method such as pressing, etching, or grinding such as sandblasting a metal substrate, a glass substrate, or a plastic substrate can be considered. However, it may be difficult for these methods to easily cope with various element sizes of the organic EL display.
The frame-shaped spacer 15 in the second embodiment shown in FIG. 2 can be formed by firing a spacer material such as low melting glass.
【００７０】本発明に用いる低融点ガラスとしては、従
来公知のものを使用できる。具体的な例として、たとえ
ばＢ２Ｏ３・ＰｂＯ、Ｂ２Ｏ３・ＰｂＯ・ＺｎＯ、Ｂ２
Ｏ３・ＳｉＯ２・ＰｂＯ、Ｂ２Ｏ３・ＳｉＯ２・Ｚｎ
Ｏ、ＰｂＯ・ＺｎＯ、Ｐ２Ｏ５・ＳｎＯ、Ｐ２Ｏ５・Ｚ
ｎＯ・ＳｎＯ、Ｂ２Ｏ３・Ｂｉ２Ｏ３等の各主成分から
なるガラスや、これらにアルカリ金属、アルカリ土類金
属等を添加したものが挙げられる。As the low melting point glass used in the present invention, conventionally known ones can be used. As a specific example, for example, B 2 O 3 .PbO, B 2 O 3 .PbO.ZnO, B 2
O 3 · SiO 2 · PbO, B 2 O 3 · SiO 2 · Zn
O, PbO · ZnO, P 2 O 5 · SnO, P 2 O 5 · Z
nO · SnO, glass and consisting of the main components such as B 2 O 3 · Bi 2 O 3, these alkali metals include those obtained by adding an alkaline earth metal.
【００７１】これらの中でも軟化温度が６００℃以下、
好ましくは５５０℃以下、さらに好ましくは５００℃以
下であるものが、生産効率や、基板にガラスを使用する
場合に、ガラスの耐熱性を超えて加熱する必要がないの
で好ましい。また、上記の低融点ガラスは焼成中に結晶
化するものや、結晶化しないガラスについては、アルミ
ナやジルコニア系酸化物のような、焼成時に形状保持性
を向上できるフィラー、または基材との線膨張係数を合
わせるように調整できるフィラーを添加することも好ま
しい。成形性、つまり焼成時に所望の形状を再現性良く
形成できるからである。これは、１００μｍ以上の厚み
でスペーサを形成する場合が特に好ましい。Among these, the softening temperature is 600 ° C. or lower,
It is preferably 550 ° C. or lower, and more preferably 500 ° C. or lower, because it is not necessary to heat the glass in excess of the production efficiency and the heat resistance of glass when using glass for the substrate. Further, the above low-melting glass is one that crystallizes during firing, and for glass that does not crystallize, such as alumina or zirconia-based oxide, a filler that can improve shape retention during firing, or a line with a base material. It is also preferable to add a filler that can be adjusted to match the expansion coefficient. This is because moldability, that is, a desired shape can be formed with good reproducibility during firing. This is particularly preferable when the spacer is formed with a thickness of 100 μm or more.
【００７２】このような低融点ガラスを用いた枠状スペ
ーサを形成する場合に、使用できる対向基板の材料とし
ては、ソーダライムガラスや、ノンアルカリガラス、ホ
ウケイ酸ガラスのような一般のガラス基板を使用でき
る。しかし、焼成条件が５００℃を越える場合や、焼成
時間が長くなる場合には、前記基板を熱処理温度で前処
理しておく方法や、基板としてプラズマディスプレイ用
ガラス（旭硝子社製ＰＤ２００）のような耐熱性ガラス
を使用することも好ましい。また金属基板を使用した場
合、板厚みが薄くても前記の焼成工程における高温変形
等の問題が少ないので好ましい。When forming a frame-like spacer using such a low melting point glass, as a material for the counter substrate that can be used, a general glass substrate such as soda lime glass, non-alkali glass, or borosilicate glass is used. Can be used. However, when the firing condition exceeds 500 ° C. or the firing time becomes long, a method of pretreating the substrate at a heat treatment temperature, or a glass for plasma display (PD200 manufactured by Asahi Glass Co., Ltd.) as the substrate is used. It is also preferable to use heat resistant glass. Further, when a metal substrate is used, even if the plate thickness is thin, there are few problems such as high temperature deformation in the firing step, which is preferable.
【００７３】これらの低融点ガラスを用いてスペーサを
形成するための方法としては、低融点ガラスの粉末状の
ものを、ペースト状にして対向基板上に所望の形状で成
形し、焼成する方法、あらかじめ低融点ガラスペースト
を所望のスペーサ形状に仮焼成して成形したものを対向
基板上に搭載し、焼成する方法などが挙げられる。As a method for forming spacers using these low-melting-point glasses, a low-melting-point glass powdered material is formed into a paste and molded into a desired shape on a counter substrate, followed by firing. Examples thereof include a method in which a low-melting-point glass paste is preliminarily fired into a desired spacer shape and formed, and then mounted on an opposing substrate and fired.
【００７４】これらの方法によれば、成形が容易であ
り、必要な空間厚みが厚い場合でも多様な素子サイズに
あわせて種々の形状に容易に対応させることができる。According to these methods, molding is easy, and even when the required space thickness is large, it is possible to easily adapt to various shapes in accordance with various element sizes.
【００７５】前記の低融点ガラスペーストは、従来公知
の方法で調整でき、または市販のものをそのまま使用し
てもよい。具体的には、たとえば、上述した低融点ガラ
ス粉末に、水、有機溶剤等の希釈剤、オリゴマー状のオ
イル、エポキシ樹脂、アクリル樹脂、ポリスチレン、セ
ルロース系高分子、酢酸ビニル系樹脂、ポリスチレン、
キシレン樹脂、フェノール樹脂、フッ素樹脂等の高分子
またはオリゴマー、脂肪酸アミド、ＳｉＯ２超微粒子
（エアロジル）のような揺変性付与剤、等を加えてペー
スト組成物とし、コーティング、乾燥後焼成すること
で、本発明に使用できるスペーサを形成できる。The low melting point glass paste can be prepared by a conventionally known method, or a commercially available one may be used as it is. Specifically, for example, in the above-mentioned low melting point glass powder, water, a diluent such as an organic solvent, an oligomeric oil, an epoxy resin, an acrylic resin, polystyrene, a cellulosic polymer, a vinyl acetate resin, polystyrene,
By adding a polymer or oligomer such as xylene resin, phenol resin, or fluororesin, fatty acid amide, thixotropic agent such as SiO 2 ultrafine particles (aerosil), etc. to form a paste composition, coating, drying and baking The spacer that can be used in the present invention can be formed.
【００７６】これらの低融点ガラスなどのスペーサ材料
を用いた一般的なスペーサの形成方法としては、スクリ
ーン印刷、ダイコート、ディスペンサーを用いてシリン
ジより押し出す方法、金型・鋳型等を用いてプレス成形
あるいは転写する方法、あらかじめ所定の膜厚で全面コ
ートしてから、サンドブラスト等の方法を用いて研削成
形する方法、前述した方法であらかじめ枠状に成形し、
仮乾燥および／または仮焼成して固体状に成形したもの
を対向基板上に配置する方法等が挙げられる。As a general method for forming a spacer using such a spacer material such as low-melting glass, screen printing, die coating, a method of extruding from a syringe using a dispenser, press molding using a die or mold, or the like A method of transferring, a method of coating the entire surface with a predetermined film thickness in advance, and a method of grinding using a method such as sandblasting, a method of forming in a frame shape in advance by the method described above,
Examples include a method of disposing on a counter substrate what is formed into a solid state by provisionally drying and / or preliminarily firing.
【００７７】スペーサ厚みを厚くする場合、たとえばペ
ーストを２５０ｋＰａ以下の減圧状態、好ましくは１２
５ｋＰａ以下の減圧下で上記印刷あるいはコーティング
を行うことも、焼成後の内部気泡やクラックを抑制する
ために好ましい。この場合は、ペーストを構成する成分
が前記減圧条件下で揮発しないものを選択することが好
ましい。When the spacer thickness is increased, for example, the paste is depressurized to 250 kPa or less, preferably 12
It is also preferable to perform the printing or coating under a reduced pressure of 5 kPa or less in order to suppress internal bubbles and cracks after firing. In this case, it is preferable to select a component that does not volatilize under the reduced pressure conditions.
【００７８】また、スペーサの形状としては、有機ＥＬ
ディスプレイの形状に合わせて図３のように枠状スペー
サに形成したり、図４のように枠状の中に１〜数カ所空
白がある形状にしたり、図５のように点状に形成する方
法が挙げられる。この際、接着剤として光硬化型接着剤
を使用し、たとえばスペーサが５０μｍ以上といった厚
みがある場合には、図３に示す枠状の態様のものが接着
剤層を薄くすることができるので好ましい。The shape of the spacer is an organic EL.
A method of forming a frame-shaped spacer according to the shape of the display as shown in FIG. 3, forming a frame having one to several blanks in the frame as shown in FIG. 4, or forming a dot-like shape as shown in FIG. Is mentioned. At this time, when a photo-curable adhesive is used as the adhesive and the spacer has a thickness of 50 μm or more, for example, the frame-shaped embodiment shown in FIG. 3 is preferable because the adhesive layer can be thinned. .
【００７９】本発明で用いる吸湿剤層は、スペーサを対
向基板上に焼成により形成した後、吸湿剤層を形成して
も、スペーサを焼成する前に吸湿材層を形成した後、ス
ペーサ焼成と同時に有機質バインダーの熱分解温度以上
かつスペーサ材料の軟化点温度以上で熱処理を行って同
時に形成してもよい。スペーサの同時形成を、同じ熱処
理工程で行う場合、熱処理温度が一般的には３５０℃以
上になる。この場合は、吸湿剤が製造前に多少吸湿して
いても、製造時に再活性化できるので、好ましい。The hygroscopic agent layer used in the present invention is formed by firing the spacer on the counter substrate, and then forming the hygroscopic material layer before firing the spacer, even after forming the hygroscopic agent layer. At the same time, heat treatment may be performed at a temperature equal to or higher than the thermal decomposition temperature of the organic binder and equal to or higher than the softening point temperature of the spacer material to form them at the same time. When the spacers are simultaneously formed in the same heat treatment step, the heat treatment temperature is generally 350 ° C. or higher. In this case, even if the hygroscopic agent absorbs some moisture before production, it can be reactivated during production, which is preferable.
【００８０】また、熱処理工程のなかで、スペーサの形
成と同時に吸湿剤層を形成する場合、上述したように、
吸湿剤として、アルカリ金属やアルカリ土類金属を含む
化合物のように、塩基性部位を有するものを使用する場
合、焼成および有機質バインダーの熱分解の熱処理工程
において、空気中に存在する炭酸ガスや、熱分解により
発生する炭酸ガス・一酸化炭素などのガスを吸収する。
このために、吸湿性能の低下を引き起こす可能性があ
る。Further, in the heat treatment step, when the hygroscopic agent layer is formed simultaneously with the formation of the spacer, as described above,
As the hygroscopic agent, when using a compound having a basic site, such as a compound containing an alkali metal or an alkaline earth metal, carbon dioxide gas existing in the air in the heat treatment step of firing and thermal decomposition of the organic binder, or Absorbs gases such as carbon dioxide and carbon monoxide generated by thermal decomposition.
For this reason, there is a possibility that the moisture absorption performance may be deteriorated.
【００８１】これを抑制するために、熱処理工程を実質
的に炭酸ガスが無い状態で行うことが好ましい。具体的
に炭酸ガスの無い状態を作る方法としては、高純度窒素
ガス・高純度アルゴンガスなどの不活性ガス、窒素およ
び酸素の混合ガスなどの炭酸ガスを含有しないガス雰囲
気下で熱処理を行う方法が挙げられる。In order to suppress this, it is preferable to carry out the heat treatment step in a state where carbon dioxide gas is substantially absent. Specifically, a method of producing a state without carbon dioxide is a method of performing heat treatment in a gas atmosphere containing no inert gas such as high-purity nitrogen gas and high-purity argon gas, or a carbon dioxide gas such as a mixed gas of nitrogen and oxygen. Is mentioned.
【００８２】また、スペーサを形成するために、低融点
ガラスおよび高分子化合物を含むペーストを使用する場
合、解重合性高分子を使用すると、有機物の熱分解にお
いて、熱分解ガスは解重合により生成する分解ガスが主
成分となり、炭酸ガスや一酸化炭素の発生を抑制できる
ので好ましい。具体的な解重合性高分子としては、たと
えば、テトラフルオロエチレン、アクリル酸誘導体、メ
タクリル酸誘導体、α−メチルスチレンなどのモノマー
単位を主成分とする単独もしくは共重合体が挙げられ
る。入手のしやすさや分解物の揮発性、安全性の観点で
ポリメチルメタクリレート、ポリメチルアクリレート、
ポリα−メチルスチレンなどが特に好ましい。以下、例
Ａ１〜Ａ２の基板作成例、例１〜５の実施例および比較
例１〜３の説明を行う。When a paste containing a low-melting glass and a polymer compound is used to form the spacer, if a depolymerizable polymer is used, the thermal decomposition gas is generated by the depolymerization in the thermal decomposition of the organic substance. It is preferable that the decomposition gas to be generated becomes the main component and the generation of carbon dioxide gas and carbon monoxide can be suppressed. Specific examples of the depolymerizable polymer include a homopolymer or a copolymer containing a monomer unit such as tetrafluoroethylene, an acrylic acid derivative, a methacrylic acid derivative, and α-methylstyrene as a main component. Polymethyl methacrylate, polymethyl acrylate, from the viewpoint of availability and volatility of decomposition products, and safety
Poly α-methylstyrene and the like are particularly preferable. Hereinafter, examples of forming substrates of Examples A1 and A2, Examples of Examples 1 to 5 and Comparative Examples 1 to 3 will be described.
【００８３】（例Ａ１）第１の基板とするソーダガラス
基板上にＳｉＯ２を２０ｎｍ、次にＩＴＯを膜厚２００
ｎｍで蒸着して陽極を形成した。シート抵抗は７Ω／□
であった。その後、真空蒸着法により正孔注入層として
銅フタロシアニンを２０ｎｍ蒸着し、次に下記化１のα
−ＮＰＤを膜厚４０ｎｍに蒸着して正孔輸送層を形成し
た。そして、Ａｌｑを膜厚６０ｎｍに蒸着して発光層を
形成した。最後に、ＭｇとＡｇを共蒸着して膜厚２００
ｎｍのＭｇＡｇ（１０：１）陰極合金を形成して有機Ｅ
Ｌディスプレイの発光側基板を形成した。(Example A1) SiO 2 having a thickness of 20 nm and ITO having a thickness of 200 are formed on a soda glass substrate as a first substrate.
to form an anode. Sheet resistance is 7Ω / □
Met. Then, 20 nm of copper phthalocyanine is vapor-deposited as a hole injection layer by a vacuum vapor deposition method, and then α of the following chemical formula 1 is used.
-NPD was vapor-deposited to a film thickness of 40 nm to form a hole transport layer. Then, Alq was vapor-deposited to a film thickness of 60 nm to form a light emitting layer. Finally, Mg and Ag are co-deposited to a film thickness of 200
nm MgAg (10: 1) cathode alloy to form organic E
The light emitting side substrate of the L display was formed.
【００８４】[0084]
【化１】 [Chemical 1]
【００８５】（例Ａ２）第１の基板とするソーダガラス
基板上にＳｉＯ２を２０ｎｍ、次にＩＴＯを膜厚２００
ｎｍで蒸着して陽極２を形成した。シート抵抗は７Ω／
□であった。この陽極２上に、真空蒸着法により前記の
銅フタロシアニンを２０ｎｍ、次に、下記化２のＴＰＴ
Ｅを膜厚４０ｎｍに蒸着して正孔輸送層５を形成した。(Example A2) SiO 2 having a thickness of 20 nm and then ITO having a thickness of 200 are formed on a soda glass substrate which is a first substrate.
The anode 2 was formed by vapor deposition at a thickness of nm. Sheet resistance is 7Ω /
It was □. 20 nm of the above copper phthalocyanine was deposited on the anode 2 by a vacuum deposition method, and then TPT of the following chemical formula 2 was used.
E was evaporated to a film thickness of 40 nm to form the hole transport layer 5.
【００８６】[0086]
【化２】 [Chemical 2]
【００８７】次に、前記のＡｌｑとルブレンを、異なる
ボートを用いて膜厚６０ｎｍに共蒸着して発光層３を形
成した。次に、ＬｉＦを０．５ｎｍ、最後に、Ａｌを膜
厚１００ｎｍの厚さで蒸着して陰極を形成し、有機ＥＬ
ディスプレイの発光側基板を形成した。Next, the above-mentioned Alq and rubrene were co-evaporated to a film thickness of 60 nm using different boats to form the light emitting layer 3. Next, LiF is vapor-deposited to a thickness of 100 nm to form a cathode by forming LiF with a thickness of 0.5 nm and finally Al to form an organic EL.
The light emitting side substrate of the display was formed.
【００８８】（例Ａ３）ノンアルカリガラス基板をソー
ダガラス基板の代わりに使用した以外は、例Ａ２と同様
にして有機ＥＬディスプレイを形成した。(Example A3) An organic EL display was formed in the same manner as in Example A2 except that a non-alkali glass substrate was used instead of the soda glass substrate.
【００８９】（例１）酸化カルシウム粉末（最大粒径５
０μｍ）３５gをポリメチルメタクリレート樹脂（以
下、ＰＭＭＡという）の２５％エチレングリコールブト
キシアセテート溶液７０g、リン酸錫系低融点ガラス粉
末（最大粒径５０μｍ）７ｇとを混合し、ソーダガラス
基板表面にＳｉＯ２層を形成した基板上にメタルスクリ
ーンを用いて塗布した。Example 1 Calcium oxide powder (maximum particle size 5
(0 μm) 35 g was mixed with a 25% ethylene glycol butoxyacetate solution 70 g of polymethylmethacrylate resin (hereinafter referred to as PMMA) and 7 g of tin phosphate low melting glass powder (maximum particle size 50 μm) to form SiO on the surface of the soda glass substrate. It applied using the metal screen on the board | substrate which formed two layers.
【００９０】これとは別に、リン酸錫系低融点ガラス粉
末５０ｇとＰＭＭＡの２５％エチレングリコールブトキ
シアセテート溶液７０ｇで調製したペーストをディスペ
ンサーにて、上記の吸湿剤含有混合物の配置部分の外側
に四角形状に印刷した。Separately, a paste prepared from 50 g of tin phosphate-based low melting point glass powder and 70 g of 25% ethylene glycol butoxyacetate solution of PMMA was squared outside the portion where the mixture containing the hygroscopic agent was placed with a dispenser. Printed in shape.
【００９１】この基板を、窒素雰囲気下、「１２０℃・
３０分＋３５０℃・３０分＋４００℃・１０分」の条件
で加熱処理を行い対向基板を作成した。形成した対向基
板は平均１５０μｍ厚みの吸湿剤層が形成され、また、
平均４００μｍ厚みの低融点ガラスからなるスペーサが
形成された。This substrate was placed in a nitrogen atmosphere at 120 ° C.
Heat treatment was performed under the condition of “30 minutes + 350 ° C./30 minutes + 400 ° C./10 minutes” to form a counter substrate. On the counter substrate thus formed, a hygroscopic agent layer having an average thickness of 150 μm is formed.
Spacers made of low melting point glass having an average thickness of 400 μm were formed.
【００９２】Ｓｉ（ＮＣＯ）４を主成分とするシランカ
ップリング剤を希釈した溶液をスペーサ表面に塗布した
後、さらに、空気雰囲気下で「１５０℃・１時間」乾燥
した。さらに、この上のスペーサ部に接着剤としてナガ
セスペシャリティーケミカルズ社製ＸＮＲ５５１６をデ
ィスペンサーにて塗布し、上記の例Ａ−１で形成した発
光基板と貼り合わせた。A solution obtained by diluting a silane coupling agent containing Si (NCO) 4 as a main component was applied to the surface of the spacer, and then dried at 150 ° C. for 1 hour in an air atmosphere. Further, XNR5516 manufactured by Nagase Specialty Chemicals Co., Ltd. was applied as an adhesive to the spacer portion on this by a dispenser, and was bonded to the light emitting substrate formed in Example A-1.
【００９３】その後、紫外線照射器による照射を行い、
窒素雰囲気下「８０℃・１時間」加熱を行い封止を行っ
た。このようにして形成した有機ＥＬディスプレイを６
０℃・９０％ＲＨ湿度下で保管し、初期状態と比較し
て、非発光面積が１０％増加するまでの時間を測定し
た。Then, irradiation with an ultraviolet irradiator is performed,
Sealing was performed by heating at 80 ° C. for 1 hour in a nitrogen atmosphere. The organic EL display formed in this way is
It was stored at 0 ° C. and 90% RH humidity, and the time until the non-luminous area increased by 10% was measured as compared with the initial state.
【００９４】すると、５００時間経過後でも、１０％ま
で増加しなかった。また、大気雰囲気下「１００℃・２
４時間」にて保管したが、素子の非発光部は初期と比較
し全く変化がなかった。Then, after 500 hours, it did not increase to 10%. Also, in an air atmosphere, "100 ° C / 2
However, the non-light-emitting portion of the device did not change at all compared to the initial stage.
【００９５】（比較例１）例１の製造法を用いて、対向
基板上にスペーサのみを形成し、吸湿剤含有混合物層を
有しない対向基板を作成した。これに、例１と同じ量の
酸化カルシウム粉末を散布した後、上記の例Ａ−１で形
成した発光基板と、例１と同様の方法で封止を行った。
そして、例１と同様の試験を行ったところ、２００時間
経過後に、酸化カルシウム粉末が素子と部分的に接触
し、素子破壊が発生した。Comparative Example 1 Using the manufacturing method of Example 1, only the spacer was formed on the counter substrate to prepare a counter substrate having no hygroscopic agent-containing mixture layer. The same amount of calcium oxide powder as in Example 1 was sprayed on this, and then the light emitting substrate formed in Example A-1 above was sealed in the same manner as in Example 1.
Then, when the same test as in Example 1 was conducted, after 200 hours, the calcium oxide powder partially contacted the element, and element destruction occurred.
【００９６】（例２）まず、ソーダガラス基板上にＳｉ
Ｏ２層を形成した対向基板を準備した。次に、酸化カル
シウム粉末４５ｇ、最大粒径が５０μｍである燐酸錫系
の低融点ガラス粉末９ｇ、ドデカンジオールアクリレー
ト６０ｇ、アゾ系ラジカル重合開始剤である和光純薬社
製Ｖ−６５の０．３ｇとを良く混錬した後、スクリーン
印刷によって対向基板上に塗布した。Example 2 First, Si is placed on a soda glass substrate.
A counter substrate having an O2 layer was prepared. Next, 45 g of calcium oxide powder, 9 g of tin phosphate-based low melting point glass powder having a maximum particle size of 50 μm, 60 g of dodecanediol acrylate, and 0.3 g of Wako Pure Chemical Industries V-65, which is an azo radical polymerization initiator. After kneading well, and was applied on the counter substrate by screen printing.
【００９７】さらに、例１と同様の方法で、スペーサ材
料を基板の周辺に塗布した。そして、「大気下・１２０
℃・３０分＋３５０℃・３０分＋４００℃・１０分」の
条件で、加熱処理を行った。Further, a spacer material was applied to the periphery of the substrate in the same manner as in Example 1. And "atmosphere, 120
The heat treatment was performed under the conditions of "° C, 30 minutes + 350 ° C, 30 minutes + 400 ° C, 10 minutes".
【００９８】すると、基板の周辺部には平均厚みが約４
００μｍであるスペーサが形成され、基板の中央部には
１５０μｍ厚みの吸湿剤層が形成された。Then, the average thickness is about 4 at the periphery of the substrate.
A spacer having a thickness of 00 μm was formed, and a hygroscopic agent layer having a thickness of 150 μm was formed in the central portion of the substrate.
【００９９】Ｓｉ（ＮＣＯ）４を主成分とするシランカ
ップリング剤を希釈した溶液をスペーサの表面に塗布し
た後、さらに大気下で「１５０℃・１時間」乾燥した。
さらに、スペーサの端部に接着剤として、ナガセスペシ
ャリティーケミカルズ社製ＸＮＲ５５１６をディスペン
サーにて塗布し、上記の例Ａ−１で形成した発光基板と
貼り合せた。A solution obtained by diluting a silane coupling agent containing Si (NCO) 4 as a main component was applied to the surface of the spacer, and then dried at 150 ° C. for 1 hour in the atmosphere.
Further, XNR5516 manufactured by Nagase Specialty Chemicals Co., Ltd. was applied as an adhesive to the end portion of the spacer by a dispenser and bonded to the light emitting substrate formed in Example A-1.
【０１００】その後、紫外線照射器による照射を行い、
窒素雰囲気下８０℃・１時間の加熱処理を行い、封止を
行った。このようにして形成した有機ＥＬ素子を６０℃
・９０％ＲＨ湿度下で保管し、初期状態と比較して、非
発光面積が１０％増加するまでの時間を測定したとこ
ろ、５００時間であった。また、大気下１００℃・２４
時間で保管したところ、有機ＥＬ素子の非発光部は初期
と比較して変化がなかった。Then, irradiation with an ultraviolet irradiator is performed,
Heat treatment was performed at 80 ° C. for 1 hour in a nitrogen atmosphere to perform sealing. The organic EL device formed in this way is treated at 60 ° C.
When stored under 90% RH humidity, the time until the non-luminous area increased by 10% was measured as compared with the initial state, and it was 500 hours. Also, in the atmosphere at 100 ° C / 24
When stored for a period of time, the non-light emitting portion of the organic EL element was unchanged compared to the initial stage.
【０１０１】（比較例２）対向基板を準備し、例２と同
様の方法でスペーサ材料を配置した。この対向基板を大
気下で、「１２０℃・３０分＋３５０℃・３０分＋４０
０℃・１０分」の条件で加熱処理を行った。その後、例
２と同様にして酸化カルシウムを含有するペーストをス
クリーン印刷によって対向基板上に印刷した。さらに、
例２と同様にして有機ＥＬ素子を形成した。Comparative Example 2 A counter substrate was prepared, and a spacer material was arranged in the same manner as in Example 2. This counter substrate was exposed to the air at "120 ° C for 30 minutes + 350 ° C for 30 minutes + 40 ° C.
The heat treatment was performed under the condition of “0 ° C. and 10 minutes”. Then, in the same manner as in Example 2, a paste containing calcium oxide was printed on the counter substrate by screen printing. further,
An organic EL device was formed in the same manner as in Example 2.
【０１０２】６０℃・９０％ＲＨ湿度下で保管し、初期
状態と比較して非発光面積が１０％増加するまでの時間
を測定した。その結果、４００時間となった。また、大
気下１００℃・２４時間で保管したところ、有機ＥＬ素
子の非発光部は初期と比べて２０％増大した。It was stored at 60 ° C. and 90% RH humidity, and the time until the non-luminous area increased by 10% compared to the initial state was measured. As a result, it was 400 hours. Further, when it was stored at 100 ° C. for 24 hours in the air, the non-light emitting portion of the organic EL device increased by 20% compared to the initial stage.
【０１０３】（例３）ＢａＯ粉末（最大粒径２０μｍ）
８５ｇとポリα−メチルスチレンの５０％キシレン溶液
３０ｇを混錬したものをソーダガラス基板の表面に塗布
した。その後、窒素雰囲気下「１２０℃・３０分＋３５
０℃・３０分＋３８０℃・３０分」の条件で、熱処理を
行い、対向基板を作成した。Example 3 BaO powder (maximum particle size 20 μm)
A mixture obtained by kneading 85 g and 30 g of a 50% xylene solution of poly α-methylstyrene was applied to the surface of a soda glass substrate. Then, in a nitrogen atmosphere, "120 ° C, 30 minutes +35
A heat treatment was performed under the conditions of 0 ° C./30 minutes + 380 ° C./30 minutes to prepare a counter substrate.
【０１０４】本例で形成した吸湿剤層の厚みは平均３０
μｍであった。この基板の吸湿剤が配置されている部位
の外側に枠状に接着剤としてナガセスペシャリティーケ
ミカルズ社製ＸＮＲ５５１６をディスペンサーにて塗布
し、例Ａ−２で形成した発光基板と貼り合わせた後、紫
外線照射器による照射および８０℃・１時間、窒素雰囲
気下で加熱を行い封止を行った。接着剤の硬化後の厚み
は約７０μｍであった。The average thickness of the hygroscopic agent layer formed in this example is 30.
was μm. XNR5516 manufactured by Nagase Specialty Chemicals Co., Ltd. is applied as a frame-like adhesive to the outside of the portion where the hygroscopic agent is arranged on this substrate with a dispenser, and after bonding with the light-emitting substrate formed in Example A-2, ultraviolet rays are applied. Irradiation with an irradiator and heating at 80 ° C. for 1 hour in a nitrogen atmosphere were performed for sealing. The thickness of the adhesive after curing was about 70 μm.
【０１０５】このようにして形成した有機ＥＬディスプ
レイを６０℃・９０％ＲＨ湿度下で保管し、初期状態と
比較した。そして、非発光面積が１０％増加するまでの
時間を測定したところ５００時間経過後も、１０％まで
増加していなかった。また、１００℃・２４時間大気オ
ーブンにて保管したが、有機ＥＬディスプレイの非発光
部は初期と比較し全く変化がなかった。The organic EL display thus formed was stored at 60 ° C. and 90% RH humidity and compared with the initial state. Then, when the time until the non-light emitting area increased by 10% was measured, it did not increase up to 10% even after 500 hours had elapsed. Further, when stored in an atmospheric oven at 100 ° C. for 24 hours, the non-light-emitting part of the organic EL display did not change at all compared to the initial stage.
【０１０６】（比較例３）例３の対向基板を作成する際
に、例３における「１５０℃・１０分＋３５０℃・３０
分＋３８０℃・３０分」の加熱処理工程の代わりに、１
５０℃・１０分の窒素下加熱＋１５０℃・１時間の減圧
加熱」をすることで揮発成分を除去した。このようにし
て、高温熱処理工程を行わない基板を作成した。この基
板を用いて例３と同様の方法で有機ＥＬディスプレイの
封止を行った。形成した有機ＥＬディスプレイは６０℃
・９０％ＲＨで湿度下保管し、初期状態と比較した。(Comparative Example 3) When the counter substrate of Example 3 was prepared, "150 ° C for 10 minutes + 350 ° C for 30 minutes in Example 3"
1 min instead of the heat treatment process of “min + 380 ° C · 30 min”
The volatile components were removed by "heating at 50 ° C for 10 minutes under nitrogen + heating at 150 ° C for 1 hour under reduced pressure". In this way, a substrate without the high temperature heat treatment process was prepared. Using this substrate, the organic EL display was sealed in the same manner as in Example 3. The formed organic EL display is 60 ℃
-It was stored under humidity at 90% RH and compared with the initial state.
【０１０７】非発光面積が１０％増加するまでの時間を
測定したところ３００時間であった。また、１００℃・
２４時間大気オーブンにて保管したが１５％程度の非発
光部の増大が確認された。When the time until the non-light emitting area increased by 10% was measured, it was 300 hours. Also, 100 ° C
After being stored in an air oven for 24 hours, it was confirmed that the non-light emitting area increased by about 15%.
【０１０８】（例４）スペーサ材料として、５０ｇのＡ
ＳＦ１３０４ＭをＰＭＭＡの３５％エチレングリコール
ブトキシアセテート溶液５０ｇと混練してペースト化し
たものを準備し、表面にＳｉＯ２層を形成したソーダガ
ラス基板上にスクリーン印刷により枠状に形成した。(Example 4) As a spacer material, 50 g of A was used.
SF1304M was kneaded with 50 g of a 35% ethylene glycol butoxyacetate solution of PMMA to prepare a paste, which was formed into a frame shape by screen printing on a soda glass substrate having a SiO 2 layer formed on the surface.
【０１０９】その後、１２０℃・３０分乾燥した。次
に、酸化ストロンチウム粉末（最大粒径５０μｍ）６０
ｇおよびＰＭＭＡの３５％エチレングリコールブトキシ
アセテート溶液１２０ｇ、６ｇの旭硝子社製ＡＳＦ１３
０４Ｍ（最大粒径を５０μｍ以下に選別したもの）を混
練してペーストを調製しディスペンサーにより上記の枠
状に印刷したスペーサ材料の内側の基板表面に塗布し
た。Then, it was dried at 120 ° C. for 30 minutes. Next, strontium oxide powder (maximum particle size 50 μm) 60
g and PMMA 35% ethylene glycol butoxyacetate solution 120 g, 6 g Asahi Glass Co. ASF13
A paste was prepared by kneading 04M (screened with a maximum particle size of 50 μm or less), and was applied by a dispenser to the substrate surface inside the spacer material printed in the frame shape.
【０１１０】この基板を、「１２０℃・３０分＋３６０
℃・１０分＋３９０℃・２０分」の条件で、窒素雰囲気
下で加熱処理した。形成した対向基板は１００μｍの吸
湿剤層と３００μｍ厚みのスペーサが形成された。この
スペーサ上にシランカップリング剤（信越化学工業社製
ＫＢＭ４０３）の０．５％メタノール溶液を塗布し、１
５０℃・１０分乾燥した。その後、例１と同様にして有
機ＥＬディスプレイを形成し、保管試験を行ったが、６
０℃・９０％ＲＨ湿度下で５００時間保管しても非発光
欠点は増加しなかった。また、１００℃・２４時間大気
下で保管しても変化は生じなかった。This substrate was placed at “120 ° C., 30 minutes + 360
The heat treatment was performed in a nitrogen atmosphere under the conditions of "° C, 10 minutes + 390 ° C, 20 minutes". The counter substrate thus formed was provided with a hygroscopic agent layer having a thickness of 100 μm and a spacer having a thickness of 300 μm. A 0.5% methanol solution of a silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied onto this spacer, and 1
It was dried at 50 ° C for 10 minutes. Then, an organic EL display was formed in the same manner as in Example 1 and a storage test was conducted.
Even when stored at 0 ° C. and 90% RH for 500 hours, the non-luminous defects did not increase. In addition, no change occurred when stored in the atmosphere at 100 ° C for 24 hours.
【０１１１】（例５）モレキュラーシーブス１３Ｘの粉
末（最大粒径１０μｍ）５０ｇをエチルセルロースの２
０％エチレングリコールブトキシアセテート溶液５０ｇ
と混練し、さらに多摩化学工業社製エチルシリケート４
０の６ｇを添加し、無アルカリガラス基板上にスクリー
ン印刷にて塗布した。(Example 5) 50 g of a powder of molecular sieves 13X (maximum particle size: 10 μm) was mixed with 2 parts of ethyl cellulose.
50 g of 0% ethylene glycol butoxyacetate solution
Ethyl silicate 4 made by Tama Chemical Industry Co., Ltd.
6 g of No. 0 was added and applied by screen printing on a non-alkali glass substrate.
【０１１２】そして、「１２０℃・３０分＋室温・１時
間＋４００℃・１時間」の条件で、空気雰囲気下で加熱
処理を行った。吸湿剤層は平均５０μｍ厚みであった。
形成した対向基板に接着剤としてナガセスペシャリティ
ーケミカルズ社製ＸＮＲ５５１６をディスペンサーにて
塗布した。例Ａ−３で形成した発光基板と貼り合わせた
後、紫外線照射器による照射および「８０℃・１時間」
窒素雰囲気下で加熱を行い封止を行った。接着剤の厚み
は８５μｍとした。Then, the heat treatment was carried out in an air atmosphere under the condition of "120 ° C./30 minutes + room temperature / 1 hour + 400 ° C./1 hour". The moisture absorbent layer had an average thickness of 50 μm.
XNR5516 manufactured by Nagase Specialty Chemicals Co., Ltd. was applied as an adhesive to the formed counter substrate with a dispenser. After bonding with the light emitting substrate formed in Example A-3, irradiation with an ultraviolet irradiator and “80 ° C. for 1 hour”
Sealing was performed by heating in a nitrogen atmosphere. The thickness of the adhesive was 85 μm.
【０１１３】形成した素子を「６０℃・９０％」の条件
でＲＨ湿度下で保管し、初期状態と比較した。そして、
非発光面積が１０％増加するまでの時間を測定したとこ
ろ５００時間経過後も１０％まで増加は見られなかっ
た。また、１００℃・２４時間大気オーブンにて保管し
たが、素子の非発光部は初期と比較し全く変化がなかっ
た。The formed element was stored under RH humidity under the condition of “60 ° C./90%” and compared with the initial state. And
When the time until the non-emission area increased by 10% was measured, no increase was observed up to 10% even after 500 hours had elapsed. Moreover, when the device was stored in an air oven at 100 ° C. for 24 hours, the non-light emitting part of the device did not change at all compared to the initial stage.
【０１１４】（比較例４）モレキュラーシーブス１３Ｘ
の粉末（最大粒径１０μｍ）５０ｇをエチルセルロース
の２０％エチレングリコールブトキシアセテート溶液５
０ｇと混練し、無アルカリガラス基板上にスクリーン印
刷にて塗布した。(Comparative Example 4) Molecular sieves 13X
50 g of powder (maximum particle size 10 μm) of 20% ethyl cellulose in ethylene glycol butoxyacetate 5
It was kneaded with 0 g and applied by screen printing on a non-alkali glass substrate.
【０１１５】そして、「窒素下で１５０℃・１０分＋１
５０℃・１時間」の条件で減圧乾燥を行った。吸湿剤層
は平均５０μｍ厚みであった。このようにして形成した
対向基板を用いて例５と同様にして有機ＥＬ素子を製造
した。この有機ＥＬ素子を６０℃・９０％ＲＨ条件で保
管したところ、３５０時間で１０％の非発光部の増加が
見られた。また、１００℃・２４時間の大気オーブンに
て保管したところ１０％の非発光部の増大が観察され
た。Then, "under nitrogen, at 150 ° C for 10 minutes + 1
Drying under reduced pressure was carried out under the condition of "50 ° C for 1 hour". The moisture absorbent layer had an average thickness of 50 μm. An organic EL element was manufactured in the same manner as in Example 5 using the counter substrate thus formed. When this organic EL device was stored under the conditions of 60 ° C. and 90% RH, a 10% increase in the non-light emitting portion was observed in 350 hours. Further, when stored in an atmospheric oven at 100 ° C. for 24 hours, an increase of 10% in non-light emitting part was observed.
【０１１６】図６に本発明の例１〜５の有機ＥＬディス
プレイの対向基板上での吸湿剤層および枠状スペーサの
配置の状態を示す。発光部側の図示を省略しているが、
枠状スペーサ１５の内側に入る大きさで吸湿剤層１８が
形成されている。なお、陽極および陰極からは、外部取
り出し電極が枠状スペーサ１５よりも外側に出るように
延長されている。FIG. 6 shows the arrangement of the hygroscopic agent layer and the frame-shaped spacer on the counter substrate of the organic EL displays of Examples 1 to 5 of the present invention. Although illustration of the light emitting portion side is omitted,
The hygroscopic agent layer 18 is formed so as to fit inside the frame-shaped spacer 15. An external extraction electrode is extended from the anode and the cathode so as to extend outside the frame-shaped spacer 15.
【０１１７】[0117]
【発明の効果】本発明によれば、有機ＥＬディスプレイ
の封止後の発光安定性を保持できる吸湿剤層を安定して
形成できる。吸湿剤材料を均一に有機ＥＬディスプレイ
の空間に対応した位置に導入し固定化できる。そして、
有機ＥＬディスプレイの薄型化を達成できる。According to the present invention, it is possible to stably form a hygroscopic agent layer capable of maintaining the emission stability of an organic EL display after sealing. The hygroscopic material can be uniformly introduced and fixed at a position corresponding to the space of the organic EL display. And
A thin organic EL display can be achieved.
【０１１８】また、有機質バインダーの熱分解温度以上
の温度で熱処理を行うことで、封止後の有機ＥＬディス
プレイの内部でアウトガスが生じることがなく、安定し
た発光を長期にわたり持続することができるようにな
る。Further, by performing the heat treatment at a temperature equal to or higher than the thermal decomposition temperature of the organic binder, outgas is not generated inside the organic EL display after sealing, and stable light emission can be maintained for a long time. become.
【図１】本発明の有機ＥＬディスプレイの模式的断面
図。FIG. 1 is a schematic sectional view of an organic EL display of the present invention.
【図２】本発明の有機ＥＬディスプレイの模式的断面
図。FIG. 2 is a schematic sectional view of an organic EL display of the present invention.
【図３】本発明の有機ＥＬディスプレイの模式的平面
図。FIG. 3 is a schematic plan view of an organic EL display of the present invention.
【図４】本発明の有機ＥＬディスプレイの模式的平面
図。FIG. 4 is a schematic plan view of an organic EL display of the present invention.
【図５】本発明のスペーサを有する有機ＥＬディスプレ
イの模式的平面図。FIG. 5 is a schematic plan view of an organic EL display having a spacer of the present invention.
【図６】本発明のスペーサを有する有機ＥＬディスプレ
イの模式的平面図。FIG. 6 is a schematic plan view of an organic EL display having a spacer of the present invention.
１０：有機ＥＬディスプレイ １１：第１の透明基板 １２：第１の電極 １３：発光層 １４：第２の電極（背面電極） １５：枠状スペーサ １６：対向基板 １７：接合材 １８：吸湿剤層 10: Organic EL display 11: First transparent substrate 12: first electrode 13: Light emitting layer 14: Second electrode (back electrode) 15: Frame-shaped spacer 16: Counter substrate 17: Bonding material 18: Moisture absorbent layer
Claims (8)
剤とを含む混合物の層を基板上に配置し、その後、前記
混合物層を有機質バインダーの熱分解温度以上に加熱し
て有機質バインダーを除去して、基板上に吸湿剤層を形
成する、有機ＥＬディスプレイ用対向基板の製造方法。1. A layer of a mixture containing a thermally decomposable organic binder and an inorganic hygroscopic agent is disposed on a substrate, and then the mixture layer is heated to a temperature above the thermal decomposition temperature of the organic binder to remove the organic binder. And forming a hygroscopic agent layer on the substrate, a method for manufacturing a counter substrate for an organic EL display.
請求項１に記載の有機ＥＬディスプレイ用対向基板の製
造方法。2. The method for manufacturing a counter substrate for an organic EL display according to claim 1, wherein the mixture layer further contains a low melting point glass.
ラスを用いたガラス基板とし、前記加熱温度をガラス基
板のガラス転移点温度以下とする請求項１または２に記
載の有機ＥＬディスプレイ用対向基板の製造方法。3. The production of a counter substrate for an organic EL display according to claim 1, wherein the substrate is a glass substrate using soda glass or non-alkali glass, and the heating temperature is not higher than the glass transition temperature of the glass substrate. Method.
である請求項１、２または３に記載の有機ＥＬディスプ
レイ用対向基板の製造方法。4. The method for producing a counter substrate for an organic EL display according to claim 1, 2 or 3, wherein the organic binder is a depolymerizable polymer compound.
２ガスを実質的に含まないガス雰囲気で行う請求項１、
２、３または４に記載の有機ＥＬディスプレイ用対向基
板の製造方法。5. The organic binder is removed by heating with CO
2. The process is performed in a gas atmosphere that does not substantially contain 2 gases.
5. The method for manufacturing a counter substrate for an organic EL display according to 2, 3 or 4.
化バリウム、酸化ストロンチウム、５酸化リンまたは合
成ゼオライトから選択した少なくとも１つを用いる請求
項１、２、３、４または５に記載の有機ＥＬディスプレ
イ用対向基板の製造方法。6. The organic EL display according to claim 1, wherein at least one selected from calcium oxide, barium oxide, strontium oxide, phosphorus pentoxide or synthetic zeolite is used as the inorganic hygroscopic agent. Method for manufacturing counter substrate.
請求項１〜６のいずれか１項に記載の有機ＥＬディスプ
レイ用対向基板の製造方法。7. The method for manufacturing a counter substrate for an organic EL display according to claim 1, wherein the hygroscopic agent layer has a thickness of 50 to 500 μm.
発光層と第２の電極とを形成し、第１の基板と吸湿剤層
を有する対向基板とを接合材によって接合し、第１の基
板と対向基板との間に吸湿剤層が配置された有機ＥＬデ
ィスプレイの製造方法において、 熱分解性の有機質バインダーと無機質吸湿剤とを含む混
合物の層を対向基板上に配置し、この対向基板上に低融
点ガラスを主成分とするスペーサ材料を配置し、その
後、有機質バインダーの熱分解温度以上かつ低融点ガラ
スの軟化点温度以上の温度に加熱することによって、有
機質バインダーを分解除去し、かつスペーサを形成する
有機ＥＬディスプレイの製造方法。8. A transparent first electrode, a light emitting layer and a second electrode are formed on a transparent first substrate, and the first substrate and a counter substrate having a hygroscopic agent layer are bonded by a bonding material. Then, in the method for manufacturing an organic EL display in which the hygroscopic agent layer is disposed between the first substrate and the counter substrate, a layer of a mixture containing a thermally decomposable organic binder and an inorganic hygroscopic agent is disposed on the counter substrate. Then, a spacer material having a low melting point glass as a main component is arranged on this counter substrate, and then the organic binder is heated by heating to a temperature not lower than the thermal decomposition temperature of the organic binder and not lower than the softening temperature of the low melting point glass. A method for manufacturing an organic EL display which is decomposed and removed, and a spacer is formed.
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|---|---|---|---|
| JP2001381841A JP3975739B2 (en) | 2001-12-14 | 2001-12-14 | Method for manufacturing counter substrate for organic EL display and method for manufacturing organic EL display |
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