JPH05101884A - Sealing method and patterning method of organic electroluminescent element - Google Patents

Abstract

PURPOSE:To develop a sealing method having high sealing effect for an organic electroluminescent element and patterning method with simple operation for an organic electroluminescent element. CONSTITUTION:An external surface of an organic electroluminescent element is coated with a sealing film consisting of a moisture-proofing polymer film and an adhesive layer. After the external surface of the organic electroluminescent element is coated with the sealing film, it is patterned by cutting the upper part electrode of the element.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for encapsulating an organic electroluminescence element (organic EL element) and a patterning method, and more specifically, a method for encapsulating an organic electroluminescence element having an excellent encapsulation effect and an organic electroluminescent element which is easy to operate. The present invention relates to a method for patterning a luminescence element.

[0002]

2. Description of the Related Art Generally, an EL element is self-luminous and thus highly visible, and since it is a completely solid-state device, it is excellent in impact resistance and easy to handle. For this reason, research and development and practical application are being promoted as pixels for graphic displays, pixels for television image display devices, or surface light sources. Organic EL
The device is usually a light emitting layer made of a fluorescent organic solid such as anthracene and a hole injection layer made of a triphenylamine derivative, or an electron injection layer made of a light emitting layer and a perylene derivative, or a hole injection layer and a light emitting layer. And the electron injection layer 2
A laminated structure interposed between two electrodes is formed on a substrate. Such an organic EL element utilizes light emission generated when electrons and holes injected into the light emitting layer are recombined. Therefore, the organic EL element has the advantages that it can be driven at a low voltage by reducing the thickness of the light emitting layer, has a quick response, and the luminance is high because the luminance is proportional to the injection current. Further, by changing the kind of the fluorescent organic solid used as the light emitting layer, light emission is obtained in all visible colors of blue, green, yellow and red. However, the above-mentioned fluorescent organic solid used for the light emitting layer has low mechanical strength and is weak against heat, organic solvent, moisture, oxygen, etc., and further, the organic EL is left partially exposed to the atmosphere. When the device is driven, the characteristics of the light emitting layer are deteriorated, and the device life is shortened.
Therefore, various studies have been conducted to solve the above problems.

Nakamura, Matsuura, Kusumoto et al. Seal a device by forming a Teflon AF film (manufactured by DuPont), which is a special Teflon-based polymer capable of vapor deposition, on an organic EL device by vapor deposition. No. 2-409017). However, there is a problem that the vapor deposition film thickness is 10 to 100 μm and the vapor deposition takes time. In addition, ZnS: Mn, Zn
A so-called dispersion-type inorganic EL element is known in which a thin film of fluorescent powder such as S: Cu, ZnS: Cu.Al or the like is formed with an organic resin binder to a film thickness of 30 to 100 μm, and the thin film is sandwiched between two electrodes. (JP-A-3-127487, JP-A-3-127488, JP-A-3-252)
No. 791, etc.). The moisture-proof film prevents moisture permeation. However, although a technique of press-bonding the moisture-proof film made of this thermoplastic resin onto an element is known, it cannot be applied to an organic EL element as it is. This is because the thin film of the organic layer of the organic EL element is 50 to 2
This is because the thickness is extremely thin at 00 nm, and when the organic layer is melted by thermocompression bonding, a short circuit between electrodes easily occurs, or dielectric breakdown easily occurs at the edge of the upper electrode during energization.

On the other hand, in the method of easily patterning the organic EL element, a mask is placed on the substrate when the electrodes are vapor-deposited, but there is a problem that the pattern accuracy of the counter electrode deteriorates due to the wraparound of the vapor deposition. It was Further, in an organic EL device, an electrode of magnesium and a second metal alloy or mixture is often used as a cathode formed by a binary vapor deposition method. When these electrodes are used as a counter electrode, the electrode is vapor-deposited. A non-uniform part occurs due to wraparound. Therefore, the composition of this portion deviates from that of the counter electrode, which causes a problem that the uniformity of light emission is impaired.

Recently, a highly detailed patterning method for an organic EL element has been disclosed (Japanese Patent Laid-Open No. 2-66873). This patterning method is an acid etching method using photolithography. However, this method is a wet method, and there is a limitation in that a solvent that keeps the organic material forming the organic EL element intact is selected. In addition, the organic material itself had to be selected to be resistant to the solvent. Further, the acid etching requires washing with water, which causes the organic material to permeate and absorb water, resulting in a decrease in EL function.

[0006]

Therefore, the present inventors have
As a result of intensive studies to solve the above problems, it was found that the above problems can be solved by using a moisture-proof film as a raw material of a sealing film.

The present invention has been completed based on such findings. That is, the present invention relates to a method for sealing an organic EL device and a moisture-proof polymer film, which comprises coating the outer surface of the organic EL device with a sealing film formed of a moisture-proof polymer film and an adhesive layer. A method for patterning an organic EL element, which comprises pressing a sealing film formed by an adhesive layer on the outer surface of the organic electroluminescent element and then cutting the upper electrode of the element. is there.

The sealing film used in the present invention comprises a moisture-proof polymer film and an adhesive layer (see FIG. 1). Here, the moisture-proof polymer film is a polymer film that prevents the introduction of moisture from the outside, usually composed of a small moisture-permeable film and a water-absorbing film or a film coated with a water-absorbing agent, which are laminated. It has been configured.

Specific examples of the film having a low moisture permeability include polyethylene trifluoride, polytrifluoroethylene chloride (PCTFE), formula

[0010]

[Chemical 1]

(In the formula, n represents the degree of polymerization.) Teflon-based polymers such as a copolymer of PVDF and PCTFE, a copolymer of PVDF and polyfluorochloroethylene, a polyimide,
Examples thereof include polycarbonate, polyethylene terephthalate, polyester, polyethylene, polystyrene and the like. The moisture permeability is preferably 1.0 g / (m ³ · day) or less at 50 ° C. and 90% (humidity), particularly preferably 0.5.
It is a film of g / (m ³ · day) or less.

Specific examples of the water-absorbing film include:
High water absorption of polyamide polymers such as nylon 6, nylon 6/6, vinyl alcohol-acrylic acid copolymers, polyethylene oxide-based polymers, acrylic acid-starch copolymers, starch-acrylonitrile copolymers, etc. Polymers of

Specific examples of the water absorbing agent include oxides of alkaline earth metals such as silica gel, molecular sieve, calcium oxide and barium oxide. The film thickness of the moisture-proof polymer film is preferably 1 to 600 μm, particularly preferably 100 to 250 μm.

Examples of the adhesive layer of the sealing film include acrylic resin such as ethylene ethyl acrylate (EEA) polymer which is a thermoplastic resin, vinyl resin such as ethylene vinyl acetate (EVA), polyamide, synthetic rubber and the like. .. Among them, the softening point is extremely low (12
0 ° C or lower) is preferable, and the softening point is particularly 70 to 50 ° C.
The following are adhesives, and the moisture-proof polymer film can be pressure-bonded at room temperature without heating. According to this, the organic EL element can be sealed without applying a heat load. In addition to the above acrylic resin, there is a pressure sensitive adhesive made of silicone resin, which can be pressure-bonded at room temperature, and specific examples thereof include Aronmelt PPET (manufactured by Toagosei Kagaku), HM600 series (manufactured by Cemedine), etc. Is mentioned. If the softening point is higher than 120 ° C, the element will be destroyed during thermocompression bonding. Further, it is preferable that the adhesive layer does not contain a solvent that deteriorates the organic EL element.

In the present invention, the above-mentioned sealing film is used for organic
This is a method of sealing the EL element. In the present invention, organic E
When sealing the L element, first, the moisture-proof polymer film
Adhesive layer is applied to rum or coated by hot melt method
To create a sealing film, and press the sealing film
Use a method of crimping from the end with a roller or hand
(See Figure 2). The one in which the organic EL element is sealed in this way
Has an extremely thin organic layer (50 to 200 nm)
Insulation at the edge of the electrode above the organic layer (see Figure 3)
Destruction may occur. This edge is oxygen and
It is a place where moisture easily enters, and the upper electrode is formed by vapor deposition.
Alloy electrodes (Mg: Ag, Mg: In, Mg: Cu,
(Yb: Ag, etc.), the composition of the alloy becomes uneven.
It is easy to cause the light emitting operation to be modulated or cause dielectric breakdown.
It is a corner. To prevent this, the edge part does not emit light
It is preferable to provide an interlayer insulating film (see FIG. 4) as a part.
Good This interlayer insulating film is formed on the device substrate.
It is formed on a partial electrode (anode or cathode). This layer
The insulating film may be a film made of an insulating material.
There are no particular restrictions, and various types can be used. Specifically
As an inorganic substance, SiO₂, Al₂O ₃ , Ta
₂O_Five, Oxides such as MgO, etc.
Examples thereof include polymers such as polyimide. These materials
In order to form a film using
Performed by a method such as a putting method or a plasma CVD method
In the case of organic substances, spin coating method, casting method,
The LB method or the like is used.

The present invention also relates to the above-mentioned sealed organic E
This is a method of patterning the L element. This patterning can be performed, for example, by cutting the upper electrode of the element using a cutter or the like for the sealing film (FIG. 5).
reference). The cutting with this cutter can be easily performed and a planned trajectory can be drawn. For example,
As shown in FIG. 6, by cutting the electrodes and passing an electric current through the arrowed portions, the fluorescent surface of the letter E is obtained (hatched portion).
The patterned element is preferably sealed again. This is because water and oxygen are more likely to penetrate from the cut site. As another patterning, there is also a method of peeling the electrode after cutting the electrode as described above.

There are various organic materials for the organic EL element used in the present invention. For example, the organic compound that can be used as the light emitting material is not particularly limited, but a brightening agent such as benzothiazole-based, benzimidazole-based, benzoxazole-based, a metal chelated oxinoid compound, a styrylbenzene-based compound, or the like can be used. Can be mentioned. If the compound name is specifically shown, for example, JP-A-59 is used.
The one described in JP-A-194393 can be mentioned. Typical examples thereof include 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) -1,3,4-thiadiazole; 4,4'-bis (5,7-t -Pentyl-2
-Benzoxazolyl) stilbene; 4,4'-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxazolyl] stilbene; 2,5-bis (5,7-
Di-t-pentyl-2-benzoxazolyl) thiophene; 2,5-bis [5-α, α-dimethylbenzyl]-
2-benzoxazolyl) thiophene; 2,5-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxazolyl] -3,4-diphenylthiophene;
2,5-bis (5-methyl-2-benzoxazolyl)
Thiophene; 4,4'-bis (2-benzoxazolyl) biphenyl; 5-methyl-2- [2- [4- (5-
Methyl-2-benzoxazolyl) phenyl] vinyl] benzoxazolyl; benzoxazoles such as 2- [2- (4-chlorophenyl) vinyl] naphtho [1,2-d] oxazole, 2,2′- Benzothiazoles such as (p-phenylenedivinylene) -bisbenzothiazole, 2- [2- [4- (2-benzimidazolyl) phenyl] vinyl] benzimidazole; 2- [2
Examples include fluorescent whitening agents such as benzimidazole-based compounds such as-(4-carboxyphenyl) vinyl] benzimidazole. Still other useful compounds are chemistry
Of Synthetic Soybean 1971, 628-63
They are listed on pages 7 and 640. Examples of the metal chelated oxinoid compound include, for example, JP-A-63-2
Those described in Japanese Patent No. 95695 can be used. Typical examples are tris (8-quinolinol) aluminum; bis (8-quinolinol) magnesium; bis (benzo [f] -8-quinolinol) zinc; bis (2-
Methyl-8-quinolinolato) aluminum oxide;
Tris (8-quinolinol) indium; Tris (5-
Methyl-8-quinolinol) aluminum; 8-quinolinol lithium; tris (5-chloro-8-quinolinol) gallium; bis (5-chloro-8-quinolinol)
Calcium; 8-hydroxyquinoline-based metal complexes such as poly [zinc (II) -bis (8-hydroxy-5-quinolinonyl) methane] and dilithium epindridione. Examples of the styrylbenzene compound include, for example, European Patent No. 0319881 and European Patent No. 0.
The thing described in 373582 can be used. Typical examples thereof include 1,4-bis (2-methylstyryl) benzene; 1,4- (3-methylstyryl) benzene; 1,4-bis- (4-methylstyryl) benzene;
Distyrylbenzene; 1,4-bis (2-ethylstyryl) benzene; 1,4-bis (3-ethylstyryl) benzene; 1,4-bis (2-methylstyryl) 2-methylbenzene; 1,4- Bis (2-methylstyryl) -2
-Ethylbenzene and the like. Furthermore, the compound represented by the following formula can also be mentioned.

[0018]

[Chemical 2]

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

[Chemical 14]

[0031]

[Chemical 15]

[0032]

[Chemical 16]

[0033]

[Chemical 17]

[0034]

[Chemical 18]

[0035]

[Chemical 19]

[0036]

[Chemical 20]

[0037]

[Chemical 21]

[0038]

[Chemical formula 22]

[0039]

[Chemical formula 23]

[0040]

[Chemical formula 24]

[0041]

[Chemical 25]

The distyrylpyrazine derivative described in JP-A-2-252793 can be used as a light emitting material. A typical example is 2,5-bis (4
-Methylstyryl) pyrazine; 2,5-bis (4-ethylstyryl) pyrazine; 2,5-bis [2- (1-naphthyl) vinyl] pyrazine; 2,5-bis (4-methoxystyryl) pyrazine; 2 , 5-bis [2- (4-biphenyl) vinyl] pyrazine; 2,5-bis [2- (1-pyrenyl) vinyl] pyrazine and the like. As other substances, for example, the polyphenyl compounds described in European Patent No. 0387715 can also be used as the light emitting material. Specific examples thereof include compounds of the following formula.

[0043]

[Chemical formula 26]

In addition to the above compounds, for example, 12-
Phthaloperinone ["Journal of Applied Physics", Vol. 27, L713 (1988)
Year)]; 1,4-diphenyl-1,3-butadiene;
1,1,4,4-Tetraphenyl-1,3-butadiene [Applied Physics Letters (Appl. Phys.
Lett.) Vol. 56, 799 (1990)], naphthalimide derivative (JP-A-2-305886), perylene derivative (JP-A-2-189890), oxadiazole derivative (JP-A-2-216791). Gazette), aldazine derivative (JP-A-2-220393), pyrazirine derivative (JP-A-2-220394), cyclopentadiene derivative (JP-A-2-289675), pyrrolopyrrole derivative (JP-A-2-296891).
), A styrylamine derivative (Applied Phys. Letter. 56, 799 (1990)), or a coumarin compound (Japanese Patent Laid-Open No. 2-19194). .. Typical examples thereof include the following compounds.

[0045]

[Chemical 27]

[0046]

[Chemical 28]

[0047]

[Chemical 29]

And the like. In addition to these, the compounds described in the aromatic dimethylidyne compounds (European Patent No. 0388768) can be used, and typical examples thereof include

[0049]

[Chemical 30]

[0050]

[Chemical 31]

[0051]

[Chemical 32]

[0052]

[Chemical 33]

[0053]

[Chemical 34]

[0054]

[Chemical 35]

[0055]

[Chemical 36]

[0056]

[Chemical 37]

[0057]

[Chemical 38]

[0058]

[Chemical Formula 39]

[0059]

[Chemical 40]

[0060]

[Chemical 41]

And the like. Further, as a light emitting material, the specifications of Japanese Patent Application Nos. 2-2448749 and 2-27.
No. 9304, the following general formula (I)

[0062]

[Chemical 42]

[X and Y represent a fluorescent compound having an electroluminescence device function and may be the same or different. Q represents a divalent group that cuts the conjugated system. ] The compound represented by these is mentioned. General formula (I)
The light emitting material represented by X and Y in the above means a visible light region (400 to 70) when excited with various energies.
It is an organic compound that emits a fluorescence of 0 nm). Among the light-emitting materials used in the present invention, near-ultraviolet (330-380n)
m) light is absorbed, and the short wavelength region (400 to 45) of the visible region is absorbed.
A fluorescent whitening agent that emits a purple to blue fluorescent light at 0 nm) may also be included. Q is a divalent group that cuts the conjugated system, and here, conjugation is due to the nonpolarity of π electrons, and also includes conjugated double bonds or unpaired electrons or lone electron pairs. Specifically, a divalent group obtained by removing one H atom from a linear alkane, for example,

[0064]

[Chemical 43]

[0065]

[Chemical 44]

Etc. are represented. The reason for using the divalent group that cuts the conjugated system in this way is that the EL emission color obtained when the light-emitting material X or Y having the EL element ability shown above is used alone as the organic EL element of the present invention. And the EL emission color obtained when the compound represented by the general formula (I) is used as the organic EL device of the present invention. In other words, this is to prevent the wavelength from becoming shorter or the wavelength from becoming longer. In addition, the glass transition temperature (Tg) when connecting with a divalent group that cuts the conjugated system
Was confirmed to be increased, and it was revealed that a uniform pinhole-free microcrystalline or amorphous thin film was obtained. Furthermore, the binding by a divalent group that cuts the conjugated system does not cause the EL light emission to have a longer wavelength, and has the advantage that synthesis or purification is easy. It is to be noted that having EL element ability means that a compound is made into a thin film by a known method such as a vapor deposition method, a spin coating method, a casting method, and an LB method, and when this is used as a light emitting layer, it is an anode or a positive electrode when an electric field is applied. Injecting function capable of injecting holes from the hole injecting and transporting layer and injecting electrons from the cathode or the electron injecting and transporting layer, and transporting function of moving the injected charges (electrons and holes) by the force of the electric field , Provides a field for recombination of electrons and holes, and has a light emitting function to connect this to light emission. Specific examples of the fluorescent compound having an EL device function represented by X and Y include organic compounds that can be used as the above-mentioned various light emitting materials.
Specific examples of the compound represented by the general formula (I) include the compounds shown below.

[0067]

[Chemical 45]

[0068]

[Chemical 46]

[0069]

[Chemical 47]

[0070]

[Chemical 48]

[0071]

[Chemical 49]

[0072]

[Chemical 50]

[0073]

[Chemical 51]

[0074]

[Chemical 52]

[0075]

[Chemical 53]

[0076]

[Chemical 54]

[0077]

[Chemical 55]

The light emitting layer can be formed by thinning it by a known method such as a vapor deposition method, a spin coating method, a casting method or an LB method, but a molecular deposition film is particularly preferable. Is more preferable. Here, the molecular deposition film is a thin film formed by depositing the compound from the gas phase state, or a film formed by solidifying from the solution state or liquid phase state of the compound, and usually this molecular deposition film. Can be distinguished from the thin film (molecular cumulative film) formed by the LB method by the difference in the aggregated structure and the higher order structure and the functional difference caused by the difference. Further, as disclosed in JP-A-57-51781, the light emitting layer is prepared by dissolving a binder such as a resin and the compound in a solvent to form a solution, which is then spin-coated. Can be formed into a thin film and formed. The thickness of the light emitting layer thus formed is not particularly limited and may be appropriately selected depending on the circumstances, but is usually preferably in the range of 5 nm to 5 μm. The light emitting layer in the EL device used in the present invention has an injection function capable of injecting holes from an anode or a hole injecting and transporting layer and electrons from a cathode or an electron injecting and transporting layer when an electric field is applied, It has a transport function of moving the injected charges (electrons and holes) by the force of an electric field, a light emitting function of providing a field for recombination of electrons and holes, and connecting this to light emission. Note that there may be a difference between the ease with which holes are injected and the ease with which electrons are injected. The transport function represented by the mobilities of holes and electrons may have different sizes, but it is preferable to move one of them.

Next, the hole injecting / transporting material of the organic EL element used in the present invention is not particularly limited as long as it has the above-mentioned preferable properties, and conventionally, in the light-transmitting material, hole charge injecting / transporting material is used. Any material can be selected and used from materials commonly used and known materials used for the hole injecting and transporting layer of EL devices. Examples of the charge transport material include triazole derivatives (see US Pat. No. 3,112,197), oxadiazole derivatives (see US Pat. No. 3,189,447), imidazole derivatives (see JP-B-37-16096). ), Polyarylalkane derivatives (US Pat. No. 3,615,
No. 402, No. 3,820,989, No. 3,542,544, No. 45-555, No. 51-1098
No. 3, Japanese Patent Laid-Open No. 51-93224, No. 55-1.
No. 7105, No. 56-4148, No. 55-1.
No. 08667, No. 55-156953, No. 5
6-36656, etc.), pyrazoline derivatives and pyrazolone derivatives (US Pat. No. 3,180,729;
4,278,746, JP-A-55-88064,
55-88065, 49-105537, 55-51086, 56-80051, 56-88141, 57-45545.
No. 54-112637, No. 55-745.
46, etc.), phenylenediamine derivatives (US Pat. No. 3,615,404, Japanese Patent Publications No. 51-10105, No. 46-3712, No. 47-25336, No. 54-53435, Ibid 54-110
No. 536, No. 54-119925, etc.),
Arylamine derivatives (US Pat. Nos. 3,567,450, 3,180,703, 3,240,597, and
3,658,520, 4,232,103, 4,175,
961 specification, 4,012,376 specification, JP-B-49-3
5702, 39-27577, and JP-A-5
No. 5,144,250, No. 56-119132, No. 56-22437, West German Patent No. 1,110,518.
, Etc.), amino-substituted chalcone derivatives (see US Pat. No. 3,526,501 etc.), oxazole derivatives (as described in US Pat. No. 3,257,203 etc.),
Styrylanthracene derivative (JP-A-56-46234)
(See Japanese Patent Laid-Open Publication No. 51-1), fluorenone derivative (Japanese Patent Laid-Open No. 54-1)
10837, etc.), hydrazone derivatives (U.S. Pat. No. 3,717,462, JP-A-54-59143, JP-A-55-52063, JP-A-55-52064, JP-A-55-46760, JP-A-55-46760). -85495
No. 57-11350, No. 57-1487.
49, JP-A-2-311591, etc.),
Stilbene derivative (Japanese Patent Laid-Open No. 61-210363)
No. 61-228451, No. 61-14642, No. 61-72255, No. 62-47646, No. 62-36674, No. 62-10652.
No. 62-30255, No. 60-9344.
5, gazette 60-94462 gazette, gazette 60-174.
No. 749, No. 60-175052, etc.). Further, as a hole injecting and transporting material, a silazane derivative (US Pat. No. 4,950,950), a polysilane type (JP-A-2-204996), an aniline type copolymer (JP-A-2-28263), and Examples thereof include conductive polymer oligomers described in Japanese Patent Application No. 1-211399, particularly thiophene oligomers.

In the present invention, these compounds can be used as a hole injecting / transporting material, and the following porphyrin compounds (described in JP-A-63-295965) and aromatic tertiary compounds. Amine compounds and styrylamine compounds (U.S. Pat. No. 4,127,412, JP-A-53-27033, JP-A-54-5844)
5 gazette, the same 54-149634 gazette, the same 54-64.
299, 55-79450, 55-1
No. 44250, No. 56-119132, No. 6
No. 1-295558, No. 61-98353,
63-295695, etc.), and it is particularly preferable to use the aromatic tertiary amine compound. Typical examples of the porphyrin compound include porphine, 1,10,
15,20-Tetraphenyl-21H, 23H-porphine copper (II), 1,10,15,20-tetraphenyl 21H, 23H-porphine cuprous (II), 5,10,1
5,20-Tetrakis (pentafluorophenyl) -2
1H, 23H-porphine, silicon phthalocyanine oxide, aluminum phthalocyanine chloride, phthalocyanine (metal-free), dilithium phthalocyanine, copper tetramethylphthalocyanine, copper phthalocyanine, chromium phthalocyanine, zinc phthalocyanine, lead phthalocyanine, titanium phthalocyanine oxide, magnesium phthalocyanine, copper octaoctane Examples include methyl phthalocyanine. Further, as typical examples of the aromatic tertiary amine compound and the styrylamine compound, N, N, N ′,
N'-tetraphenyl-4,4'-diaminophenyl,
N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (TPDA),
2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-
p-tolyl-4,4'-diaminobiphenyl, 1,1-
Bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-
Methylphenyl) phenylmethane, bis (4-di-p-
Trilylaminophenyl) phenylmethane, N, N'-diphenyl-N, N'-di (4-methoxyphenyl)-
4,4'-diaminobiphenyl, N, N, N ', N'-
Tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadriphenyl, N, N, N-tri (p-tolyl) amine, 4-
(Di-p-tolylamino) -4 '-[4 (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-
Methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole and the like can be mentioned. Further, the aromatic dimethylidyne compounds shown as the hole injecting / transporting material or the light emitting material can also be used. The hole injecting and transporting layer used in the present invention can be formed by forming the above compound into a film by a known thinning method such as a vacuum vapor deposition method, a spin coating method, a casting method and an LB method. The thickness of the hole injecting and transporting layer is not particularly limited, but is usually 5 nm to 5 μm. The hole injecting and transporting layer may be composed of a single layer composed of one or more of these hole injecting and transporting materials, or a hole injecting and transporting layer composed of a compound different from the hole injecting and transporting layer. It may be a stack of layers. The electron injecting and transporting layer of the organic EL element used in the present invention is made of an electron injecting material,
It has a function of transmitting electrons injected from the cathode to the light emitting layer. There is no particular limitation on such an electron injection material, and an arbitrary material can be selected and used from conventionally known compounds. Preferred examples of the electron injection material include:

[0081]

[Chemical 56]

Nitro-substituted fluorenone derivatives such as those described above, anthraquinodimethane derivatives described in JP-A-57-149259, 58-55450, 63-104061 and the like, Polymer Preprints, Japan Vol.
37, No.3 (1988), p.681, etc.

[0083]

[Chemical 57]

A diphenylquinone derivative such as

[0085]

[Chemical 58]

Thiopyran dioxide derivatives such as

[0087]

[Chemical 59]

Examples thereof include heterocyclic tetracarboxylic acid anhydrides such as naphthalene perylene and carbodiimides.
JJ APPl. Phys., 27, L 269 (1988).

[0089]

[Chemical 60]

A compound represented by the formula: JP-A-60-696.
No. 57, No. 61-143764, No. 61-14815.
9 and the like, fluorenylidene methane derivatives, JP-A-61-225151 and 61-2337.
Anthraquinodimethane derivatives and anthrone derivatives described in Japanese Patent Publication No. 50, etc., Appl. Phys. Lett. 55 (1
5) Oxadiazole derivatives described in 1489 etc.

[0091]

[Chemical formula 61]

And the like. JP 59-1
A series of electron-transporting compounds described in Japanese Patent No. 94393. In the above publication, the substance is disclosed as a material for forming the light emitting layer, but as a result of studies, we found that it can be used as a material for forming the electron injecting and transporting layer of the present invention. The following are particularly desirable.

[0093]

[Chemical formula 62]

Specific examples of the metal complex of the 8-quinolinol derivative are the following compounds, namely tris (8-quinolinol) aluminum and tris (5,7-dichloro-8-).
Quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, and complexes of magnesium, copper, gallium, tin, lead other than aluminum and indium. .. Examples of metal-free or metal phthalocyanine, or those having their ends substituted with an alkyl group, a sulfonic acid group, and the like, include the following.

[0095]

[Chemical 63]

Further, the distyrylpyrazine derivative shown as the light emitting material can also be mentioned as the electron injecting and transporting material. The electron injecting and transporting layer used in the present invention can be formed by forming the above compound into a film by a known thinning method such as a vacuum vapor deposition method, a spin coating method, a casting method and an LB method.
The thickness of the electron injecting and transporting layer is not particularly limited, but is usually 5 nm to 5 μm. The electron injecting and transporting layer may be composed of a single layer composed of one or more of these electron injecting and transporting materials, or a stack of electron injecting and transporting layers composed of a compound different from the layer. It may be. Further, a hole injecting and transporting material made of p-Si, p-SiC which is an inorganic material, n-type α-Si, n-type α-SiC
Can be used as the electron injecting and transporting material. For example, international publication WO90 / 0599
Inorganic semiconductors disclosed in No. 8 are listed. This E
The positive electrode of the L element has a large work function (4e
V or more) metals, alloys, electrically conductive compounds and mixtures thereof are preferably used as electrode materials. Specific examples of such an electrode material include metal such as Au, Cu
Dielectric transparent materials such as I, ITO, SnO ₂ and ZnO can be used. The positive electrode can be produced by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. When the emitted light is taken out from this electrode, it is desirable that the transmittance is higher than 10%, and the sheet resistance as the electrode is preferably several hundred Ω / □ or less. Furthermore, the film thickness depends on the material, but is usually 10 nm.
˜1 μm, preferably 10 to 200 nm. On the other hand, as the cathode, one having a metal, an alloy, an electrically conductive compound having a small work function (4 eV or less) and a mixture thereof as an electrode substance is used. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, Al / Al ₂ O ₃ , indium and the like.
The cathode can be produced by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. The sheet resistance as an electrode is preferably several hundred Ω / □ or less, and the film thickness is usually 10 to 500 n.
m, preferably in the range of 50 to 200 nm. In this EL element, it is convenient that either the anode or the cathode is transparent or semi-transparent to allow the emitted light to pass therethrough, so that the emission efficiency of the emitted light is good. Next, a suitable example of manufacturing the EL element used in the present invention will be described.
E consisting of the above anode / hole injecting / transporting layer / light emitting layer / cathode
Explaining the method for manufacturing the L element, first, a thin film made of a desired electrode material, for example, a material for an anode, is vapor-deposited or vapor-deposited on a suitable substrate so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm. An anode is formed by forming it by a method such as sputtering. Next, a thin film made of a hole injecting and transporting material is formed on this to provide a hole injecting and transporting layer. As a method of thinning the hole injecting and transporting material, there are spin coating method, casting method, vapor deposition method and the like as described above, but from the viewpoint that a uniform film is easily obtained and pinholes are hard to be generated. The vacuum deposition method is preferred. When this vapor deposition method is used for thinning the hole injection material, the vapor deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposited film, the association structure, etc. 50 to 450 ° C, vacuum degree 10 ^-5 to 10
^-3 Pa, evaporation rate 0.01 to 50 nm / sec, substrate temperature-
It is desirable to select appropriately in the range of 50 to 300 ° C. and the film thickness of 5 nm to 5 μm. Next, after forming the light emitting layer, a thin film made of a substance for a negative electrode is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness in the range of 10 to 500 nm, preferably 50 to 200 nm. By providing, a desired EL element can be obtained. In addition,
In manufacturing this EL element, the manufacturing order is reversed,
It is also possible to fabricate the cathode, the light emitting layer, the hole injecting and transporting layer, and the anode in this order. At least one of the light emitting layer, the hole injecting and transporting layer, etc. is irradiated with ultraviolet rays as described above. When a DC voltage is applied to the EL device thus obtained, light emission can be observed by applying a voltage of about 5 to 40 V with the positive electrode having a positive polarity and the negative electrode having a negative polarity. Further, even if a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the positive electrode is in the + state and the negative electrode is in the − state. The waveform of the alternating current applied may be arbitrary.

[0097]

The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. Reference Example 1 ITO on a glass substrate of 25 mm x 75 mm x 1.1 mm
A film formed by vapor deposition to a thickness of 100 nm (HOY
A product) was used as a transparent support substrate. Next, this transparent supporting substrate was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then cleaned with pure water for 5 minutes, and further ultrasonically cleaned with isopropyl alcohol for 5 minutes. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N′-diphenyl-N, N ′ was used as a material for the hole injection layer in a resistance heating boat made of molybdenum. -Bis- (3-methylphenyl)-(1,1'-biphenyl)
Put 200 mg of -4,4'-diamine (TPDA),
In another molybdenum boat, tris (8-quinolinol) aluminum (Alq) was used as a material for the light emitting layer.
0 mg was put, and another molybdenum boat was charged with 200 mg of the hole injection material (H2: BCzVBi), and the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa. Then, the boat containing TPDA is heated to 215 to 220 ° C., TPDA is deposited on the ITO film constituting the transparent supporting substrate at a vapor deposition rate of 0.1 to 0.3 nm / sec, and a hole having a thickness of 60 nm is formed. The injection layer was formed. The substrate temperature at this time was room temperature. Then, without taking this out from the vacuum chamber, Alq was used as a light emitting layer from another boat on the hole injecting layer by 60 n.
m vapor deposition was performed. The boat temperature at this time is 265-27.
The temperature was 3 ° C., the vapor deposition rate was 0.1 to 0.2 nm / sec, and the substrate temperature was room temperature. Next, 1 g of a magnesium ribbon was put in a resistance heating boat made of molybden, and 500 mg of indium was attached to another resistance heating filament made of tungsten. Then, the vacuum tank was decompressed to 2 × 10 ⁻⁴ Pa, the boat was heated to about 500 ° C., and the magnesium deposition rate was increased.
1.7 to 2.8 nm / sec, at the same time the other boat is 800
Deposition rate of indium by heating to about ℃ 0.03 ～ 0.08n
Deposition was performed at m / sec. In this way, a mixed metal electrode of magnesium and indium was laminated and vapor-deposited on the light emitting layer in a thickness of 150 nm to form a counter electrode. This mixed metal electrode is used as a cathode and ITO
As a result of applying DC 7V with the electrode as the anode, the current was 20
Flowing at about mA / cm ² , uniform green light was obtained. As a result of the spectroscopic measurement, the emission luminance was 950 cd / m ² .

Reference Example 2 A glass substrate having a size of 75 mm × 25 mm × 1 mm, on which ITO was deposited by a vapor deposition method to a thickness of 1000 Å, was used as a substrate having a lower electrode (manufactured by HOYA Co., Ltd.). A photosensitive polyimide coating agent (made by TORAY Co., U
R3140) by spin coating, spinner rotation speed 4
It was applied at 000 rpm for 30 seconds. Then, dry (prebaking) at 80 ° C for 60 minutes in an oven,
Through the photomask of the light emission pattern, the ultra high pressure mercury lamp (1
Contact exposure was carried out by bringing the pre-baked polyimide coating surface into close contact with the photomask for 8 seconds at 0 mW / cm ² ). After this, a developing solution (manufactured by TORAY, DV-
140) for 35 to 40 seconds, further immersed in an isopropanol solution, and then subjected to ultrasonic treatment for 15 seconds. The exposed portion of the polyimide coating agent was removed from the substrate, and the patterning of the polyimide as the interlayer insulating film was obtained. Then, 180 in an oven under a nitrogen gas atmosphere
Cure for 30 minutes at ℃, 30 minutes at 300 ℃,
A glass substrate / ITO / interlayer insulating film was formed. The film thickness of the interlayer insulating film is measured by a stylus film thickness meter (DEKTAK manufactured by Sloon Co., Ltd.).
3030), it was 1.2 μm.

Example 1 A sealing film (Scotch tape: Sumitomo 3M, film thickness 1) was formed on the mixed metal electrode of the organic EL device obtained in Reference Example 1.
30 μm) was pressed by hand. However, one end of the mixed metal electrode was left open. The electrodes of this sealed element were cut from the sealing film into strips by hand with a cutter using a ruler (see FIG. 7). Then, the mixed metal electrode was used as a cathode and the ITO electrode was used as an anode, and electricity was applied. As a result, it was found that the strip-shaped portion emitted light (hatched portion in FIG. 7) and was patterned. When the cut portion was observed with an optical microscope, the cut portion of the electrode was confirmed by contrast. as a result,
It was found that the Mg: In electrodes were separated within 50 μm. The deviation of the straight line from the straight line of 100 μm was ± 5 μm.

Example 2 Chuko Flow Tape, AGF-10 was used as a sealing film.
0 (manufactured by Chukoh Chemical Industry Co., Ltd., film thickness 130 μm) was used, and the organic EL device was sealed in the same manner as in Example 1.
Patterned. Then, as a result of energizing in the same manner as in Example 1, it was found that the portion cut into strips emitted light and was patterned.

Example 3 An element was prepared in the same manner as in Example 1 except that the light emitting surface was 5 mm × 8 mm. As the sealing film, a commercially available trifluoride polyethylene film (thickness 200 μm) was used as the moisture-proof polymer film, and HM-645 was used as the adhesive layer.
The adhesive layer was hot-melted and uniformly applied to this moisture-proof polymer film by using (Cemedine Co., softening point 106 ° C.). Then, the sealing film was thermocompression bonded onto the element using a heating roller. The heating roller was set at 115 ° C. so as not to exceed the melting point of TPD which is a hole injection material. When the sealed device was maintained at a current of ² mA / cm ² in air, the initial brightness was 10
It was 0 cd / m ² . The luminance half-life of the unsealed device was 80 hours, while the luminance half-life of the sealed device was 440 hours.

Example 4 As a sealing film, a moisture-proof polymer film coated with commercially available polyethylene trifluoride (thickness: 200 μm), a super absorbent polymer made of vinyl acrylate copolymer, and dried (coating film) The device was sealed in the same manner as in Example 3 except that the thickness of 20 μm) was used. When this sealed device was maintained at a current of ² mA / cm ² in air, the initial luminance was 105 cd / m ² . The luminance half-life of the unsealed element was 80 hours, while the luminance half-life of the sealed element was 600 hours.

Example 5 An element was sealed in the same manner as in Example 4 except that the interlayer insulating film obtained in Reference Example 2 was used. When this sealed device was maintained at a current of ² mA / cm ² in air, the initial luminance was 110 cd / m ² . The brightness half-life of the unsealed device was 100 hours, but the sealed device maintained the brightness of 35% after 1500 hours. In addition, this device uniformly emitted light on the light emitting surface defined by the interlayer insulating film without producing dark spots and dark lines (that is, non-light emitting portions).

Example 6 HM-408 (manufactured by Cemedine, softening point 76) was used for the adhesive layer.
The device was sealed in the same manner as in Example 5 except that (° C.) Was used. This sealed element is supplied with a current of 2 mA in air.
/ Initial luminance was then maintained at cm ² is, 95cd / m
^{Was 2} . The luminance half-life of the unsealed element was 100 hours, but the luminance half-life of the sealed element was 400 hours.
It was time.

Example 7 Chuuko Flow Tape, AUE-11 was used as a sealing film.
The device was sealed in the same manner as in Example 5 except that 2 (manufactured by Chukoh Chemical Industry Co., Ltd., film thickness 250 μm) was used. When this sealed device was maintained at a current of ² mA / cm ² in air, the initial luminance was 110 cd / m ² .
The luminance half-life of the unsealed element was 100 hours,
The luminance half-life of the sealed device was 210 hours.

Example 8 After patterning in the same manner as in Example 1, the sealing film and the electrode other than the strip-shaped light emitting surface were peeled off. Then, the mixed metal electrode was used as a cathode and the ITO electrode was used as an anode, and electricity was applied. As a result, it was found that the portion cut into strips emitted light and was patterned.

Comparative Example 1 As a sealing film, a moisture-proof polymer film was overlaid with a water-absorbent resin made of nylon 6 film (thickness: 50 μm) on a commercially available polyethylene trifluoride (thickness: 200 μm) and thermocompression-bonded with a heating roller. The device was sealed in the same manner as in Example 3. The heating roller was 170 ° C. When this sealed element was energized in air, it was found that a current flowed more ( ² mA / cm ² ) and a short circuit occurred. After that, the element was destroyed by melting at the short-circuited portion.

Comparative Example 2 An element was prepared in the same manner as in Example 3 except that the organic EL element was not sealed. When this unsealed element was maintained at a current of ² mA / cm ² in air, the initial luminance was
It was 110 cd / m ² . The luminance half-life of the unsealed element was 30 hours, but after that, it rapidly deteriorated and the non-light emitting portion increased, and it was destroyed 100 hours later.

[0109]

As described above, according to the present invention, it is possible to produce an organic EL device having high mechanical strength, resistance to heat, organic solvent, moisture, oxygen, etc., and having a long device life. .. Further, the light emitting surface of the organic EL element can be easily patterned. Therefore, the present invention can be used in various industrial fields as an efficient manufacturing method of a light emitting material and a display element.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of a sealing film used in the present invention.

FIG. 2 is an explanatory diagram showing an example of a sealing method of the present invention.

FIG. 3 is a diagram showing an edge portion of an organic EL element used in the method of the present invention.

FIG. 4 is a diagram showing an interlayer insulating film of an organic EL element used in the method of the present invention.

FIG. 5 is an explanatory diagram showing an example of a patterning method of the present invention.

FIG. 6 is a diagram showing a specific example of the patterning method of the present invention.

FIG. 7 is a diagram showing patterning according to the first embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Adhesive layer 2 Moisture-proof polymer film 3 Sealing film 4 Pressure bonding roller 5 Organic EL layer 6 Substrate 7 Upper electrode 8 Edge 9 Interlayer insulating film 10 Lower electrode 11 Cutter 12 Light emitting part 13 Light emitting surface (light emitting layer forming part) 14 Cutting Locus 15 Unsealed upper electrode 16 Arrow 17 Unsealed lower electrode

Claims (10)

[Claims] 1. A method for encapsulating an organic electroluminescence device, which comprises coating an outer surface of the organic electroluminescence device with a encapsulation film formed of a moisture-proof polymer film and an adhesive layer. 2. The adhesive layer is a thermoplastic resin.
A method for encapsulating an organic electroluminescence device according to the description. 3. The method for encapsulating an organic electroluminescence device according to claim 1, wherein the adhesive layer has a softening point of 120 ° C. or lower. 4. The method for encapsulating an organic electroluminescent element according to claim 1, wherein the moisture-proof polymer film contains a fluorine-containing film. 5. The method for encapsulating an organic electroluminescence device according to claim 1, wherein the moisture-proof polymer film is a laminate composed of a film having low moisture permeability and a water-absorbing polymer film. 6. The method for encapsulating an organic electroluminescence device according to claim 1, wherein an interlayer insulating film is provided and encapsulated in the organic electroluminescence device. 7. An organic electro-luminescent device, which comprises pressing a sealing film formed of a moisture-proof polymer film and an adhesive layer onto the outer surface of an organic electroluminescence device and then cutting the upper electrode of the device. Luminescence element patterning method. 8. A sealing film formed of a moisture-proof polymer film and an adhesive layer is pressure-bonded to the outer surface of the organic electroluminescence device, the upper electrode of the device is cut, and then peeled off. A method for patterning an organic electroluminescence device. 9. An outer surface of the organic electroluminescence device patterned by the patterning method according to claim 7, is covered with a sealing film formed of a moisture-proof polymer film and an adhesive layer. A method for encapsulating an organic electroluminescence device, comprising: 10. An organic electroluminescence device patterned by the patterning method according to claim 8 is coated with a sealing film formed of a moisture-proof polymer film and an adhesive layer on the outer surface of the organic electroluminescence device. A method for encapsulating an organic electroluminescence device, comprising: