JP2001313164A - Organic electroluminescent element, display device and portable terminal using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element, enabled to use under various circumstances and to keep optimum luminous facility by optimizing the material and characteristics of an antistatic macromolecular film with good antistatic property, or by adding a function to the macromolecular film, or by taking an antistatic measure at the manufacturing process of the organic electroluminescent element, and to provide a display device and a terminal using the organic electroluminescent element. SOLUTION: The organic electroluminescent element comprises at least a hole injecting anode, a luminous layer with luminous area, an electron injecting cathode on a transparent or semitransparent macromolecular film, and the macromolecular film has an antistatic layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence element used for various display devices, a light source or a backlight of the display device, a light emitting device used for an optical communication device, a display device using the same, and a display device using the same. It relates to a mobile terminal.

[0002]

2. Description of the Related Art An electroluminescent device is a light-emitting device utilizing electroluminescence of a solid fluorescent substance. Currently, an inorganic electroluminescent device using an inorganic material as a light-emitting material has been put into practical use, and a backlight of a liquid crystal display has been developed. Some applications are being developed for flat displays and flat displays. However, the voltage required for the inorganic electroluminescent element to emit light is 100 V
Since the above is high and it is difficult to emit blue light, it is difficult to achieve full color by three primary colors of RGB.

On the other hand, research on electroluminescent devices using organic materials has been attracting attention for a long time, and various studies have been made. However, since the luminous efficiency is extremely poor, no progress has been made in full-scale practical use research. Was.

However, in 1987, Kodak C.E.
W. Tang et al. Proposed an organic electroluminescent device having a function-separated type laminated structure in which an organic material was divided into two layers, a hole transport layer and a light emitting layer, and had a voltage of 1000 cd / m ² or more despite a low voltage of 10 V or less. It was found that a high emission luminance was obtained [C. W. Tan
g and S.G. A. Vanslyke: Appl. P
hys. Lett, 51 (1987) 913, etc.].
Since then, organic electroluminescent elements have begun to be noticed suddenly, and research on organic electroluminescent elements having a similar function-separated type laminated structure has been actively conducted.

Here, the configuration of a conventional general organic electroluminescent element will be described with reference to FIG.

FIG. 5 is a sectional view of a main part of a conventional organic electroluminescence element.

In FIG. 5, 1 is a glass substrate, 2 is an anode, 3 is a hole transport layer, 4 is a light emitting layer, and 5 is a cathode.

As shown in FIG. 5, an organic electroluminescent element comprises an anode 2 made of a transparent conductive film such as ITO formed on a glass substrate by a sputtering method, a resistance heating evaporation method, or the like. N, N'-diphenyl-N, N'- formed by resistance heating evaporation or the like
Bis (3-methylphenyl) -1,1'-diphenyl-
A hole transport layer 3 made of 4,4′-diamine (hereinafter abbreviated as TPD), and 8-hydroxyquinol formed on the hole transport layer 3 by a resistance heating evaporation method or the like.
a light emitting layer 4 made of, for example, ine Aluminum (hereinafter abbreviated as Alq ₃ ); and a cathode 5 made of a metal film having a thickness of 300 nm or less formed on the light emitting layer 4 by a resistance heating evaporation method or the like. I have.

When a DC voltage or a DC current is applied with the anode 2 of the organic electroluminescent device having the above structure as a positive electrode and the cathode 5 as a negative electrode, the anode 2 is applied to the light emitting layer 4 via the hole transport layer 3. Holes are injected, and electrons are injected from the cathode 5 into the light emitting layer 4. Light emitting layer 4
In such a case, recombination of holes and electrons occurs, and a light emission phenomenon occurs when the exciton generated thereby shifts from the excited state to the ground state.

[0010]

In such an organic electroluminescence device, glass is usually used as the substrate. However, when the substrate is glass, in order to prevent cracking, careful handling is required not only in the finished product but also in the manufacturing process. In addition, since it has no flexibility, it cannot be formed into a curved surface and it is difficult to process it into various shapes. Also, the weight of the glass itself has been a problem in reducing the weight.

Therefore, a flexible polymer film is used for the substrate of the organic electroluminescence element,
It has been proposed to solve the above problems.

For example, Japanese Patent Application Laid-Open No. 6-124785 discloses an invention in which the luminous efficiency and stability are improved by defining the surface shape of a polymer film or the like. Also,
JP-A-7-153571 discloses an invention in which both sides of an element portion are sandwiched between moisture-absorbing and moisture-proof films. Furthermore, a method using a film having excellent gas barrier properties and a water vapor barrier property according to JP-A-8-167475, a method of introducing a moisture-impermeable bonding improvement film described in JP-A-10-214683, and the like are used. The stability when using a molecular film has been improved. As described above, in any of the above inventions, the luminous efficiency, the stability, and the like are improved.

However, polymer films are generally more likely to generate static electricity than glass, and the static electricity may cause a failure of a display device equipped with an organic electroluminescent element, or the static electricity may cause dust to adhere. There is. In particular, the adhesion of dust to the polymer film in the manufacturing process has caused a non-light-emitting portion called a black spot (dark spot) in the organic electroluminescence device. Furthermore, not only in the manufacturing process but also in the finished product, there is a problem that the adhesion of dust to the surface of the polymer film impairs the visibility of display by light emission of the organic electroluminescence element. It was also difficult to remove dust attached to the charged polymer film. None of the above-mentioned inventions solves these problems, and none of them has sufficient characteristics.

In view of the above problems, the present invention seeks to optimize the material and properties of a polymer film having excellent antistatic properties, or to add a function to the polymer film, or to improve the properties of the organic electroluminescent device. To provide an organic electroluminescent element that can be used in various environments and maintain optimal light emitting performance by taking measures against static electricity in a manufacturing process, a display device and a mobile terminal using the same. With the goal.

[0015]

In order to solve the above-mentioned problems, an organic electroluminescence device according to the present invention has, on a transparent or translucent polymer film, an anode for injecting at least holes, and a light emitting region. An organic electroluminescence device including a light emitting layer and a cathode for injecting electrons, wherein the polymer film has a configuration having an antistatic layer.

With this configuration, a good antistatic effect can be obtained, and good emission luminance characteristics can be obtained.

[0017]

DETAILED DESCRIPTION OF THE INVENTION According to the first aspect of the present invention, an anode for injecting at least holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons are provided on a transparent or translucent polymer film. An organic electroluminescent element provided, wherein the polymer film is an organic electroluminescent element characterized by having an antistatic layer, and is excellent in antistatic properties, so that it may cause electrostatic damage. In addition, it is possible to maintain the optimum light emitting performance without any dust.

According to a second aspect of the present invention, there is provided an organic electroluminescent device comprising a transparent or translucent polymer film, comprising an anode for injecting at least holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons. A luminescent element,
The polymer film is an organic electroluminescent element characterized by containing an antistatic agent, and has excellent antistatic properties, so that it does not cause static electricity damage and further adheres to dust. Therefore, it is possible to maintain the optimum light emitting performance.

According to a third aspect of the present invention, there is provided an organic electroluminescent device comprising a transparent or translucent polymer film having at least an anode for injecting holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons. A luminescent element,
The polymer film is an organic electroluminescence element characterized by being subjected to an antistatic treatment, and has excellent antistatic properties, so that it does not cause static electricity damage and further adheres to dust. Therefore, it is possible to maintain the optimum light emitting performance.

The invention according to claim 4 of the present invention comprises an anode for injecting at least holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons on a transparent or translucent polymer film. Organic electroluminescent device, wherein the polymer film has a surface resistance of 10
¹¹ Ω / sq. It is an organic electroluminescent element characterized by the following features, and since it has excellent antistatic properties, it does not cause electrostatic damage, furthermore, there is no adhesion of dust, and the optimum light emitting performance is maintained. Can do things.

According to a fifth aspect of the present invention, there is provided an organic electroluminescent device comprising a transparent or translucent polymer film, comprising an anode for injecting at least holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons. A luminescent element,
The polymer film is an organic electroluminescent element characterized by having been subjected to an antistatic treatment, and can maintain optimal light emitting performance without adhesion of dust.

According to a sixth aspect of the present invention, there is provided an organic electroluminescent device comprising a transparent or translucent polymer film, comprising an anode for injecting at least holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons. A luminescent element,
The polymer film is an organic electroluminescent device characterized by being washed in an atmosphere having a relative humidity of 20% RH or more, and has excellent antistatic properties.
Optimum light emission performance can be maintained without adhesion of dust.

According to a seventh aspect of the present invention, there is provided a display device according to any one of the first to sixth aspects, further comprising a driving means for driving an anode and a cathode. It is possible to maintain optimal light emitting performance without causing static electricity damage and without adhesion of dust, and to perform good display.

According to an eighth aspect of the present invention, in the seventh aspect, the anode is configured to be electrically separated from each other in stripes, and the cathode is configured to be separated from each other electrically in stripes.
A display device having an image display array,
Since it is excellent in antistatic properties, it does not cause static electricity damage, does not cause dust to adhere thereto, can maintain optimal light emitting performance, and can perform good display in a simple matrix system.

According to a ninth aspect of the present invention, there is provided a voice signal converting means for converting a voice into a voice signal, an operating means for inputting a telephone number and the like, a display means for displaying an incoming call display and a telephone number and the like, A mobile terminal comprising: a communication unit that converts a signal into a transmission signal; a reception unit that converts a reception signal into an audio signal; an antenna that transmits and receives the transmission signal and the reception signal; and a control unit that controls each unit. A portable terminal characterized by comprising the display device according to any one of claims 7 and 8, which is excellent in antistatic properties, does not cause static electricity damage, and has no dust attached. Therefore, it is possible to maintain an optimal light emitting performance, to perform stable display without hindrance, and to further reduce the weight.

Hereinafter, the organic electroluminescent device of the present invention will be described in detail.

The transparent or translucent polymer film (hereinafter sometimes simply referred to as “film”) serving as a substrate of the organic electroluminescence device of the present invention includes:
Polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyether sulfone, polyvinyl fluoride, polypropylene, polyethylene, polyacrylate, amorphous polyolefin, fluorine resin, and the like are used.

In the present invention, the definition of “transparent” or “translucent” refers to a degree of transparency that does not hinder the visual recognition of light emitted by the organic electroluminescence device.

Next, the characteristics required for these polymer films are shown below.

The polymer film has a surface resistance of 10
¹¹ Ω / sq. Or less, preferably 10 ⁹ Ω / sq.
It is as follows. And more preferably, 10 ⁷ Ω / sq.
It is as follows.

Here, the polymer film is generally more likely to generate static electricity than glass, and dust adheres to the charged film surface in the process of manufacturing an organic electroluminescence element, and this dust causes the non-black spot called a black spot. A light emitting section is formed. Further, in some cases, missing dots or the like in the light emitting portion occur, and it is not possible to maintain the optimum light emitting performance.

Therefore, the surface resistance of the polymer film is 10
¹¹ Ω / sq. If it is below, adhesion of dust to the film surface is suppressed.

The surface resistance of the polymer film is 10 ⁹
Ω / sq. If it is less than the above, the charge on the film surface is reduced, so that the effect of attracting dust by static electricity is weakened, and an optimal light emitting surface can be obtained.

Further, when a minute pattern such as a dot matrix is formed, it is strongly affected by dust.
The surface resistance of the film is 10 ⁷ Ω / sq. The following is preferred.

Further, not only in the manufacturing process of the organic electroluminescence element but also in the finished product, dust easily adheres to the film surface due to static electricity on the film surface.
Inconveniences such as poor visibility of element display occur. Furthermore, static electricity charged on the surface of the film may flow through the organic electroluminescence element, causing an electrostatic disturbance such as damage to the element and the drive circuit.

Therefore, the surface resistance of the film is 10 ¹¹ Ω /
sq. If it is below, adhesion of dust to the film surface is suppressed.

The film has a surface resistance of 10 ⁹ Ω / s.
q. If it is below, the charge on the film surface decreases,
The effect of attracting dust due to static electricity is weakened, and an optimal light emitting surface can be obtained without causing static electricity damage due to charging.

Furthermore, when a minute pattern such as a dot matrix is formed, it is strongly affected by dust.
The surface resistance of the film is 10 ⁷ Ω / sq. The following is preferred.

Next, the antistatic layer is formed on the surface of the film or the surface of the inorganic layer on the surface of the film, and is made of a material having high transmittance and high conductivity with respect to light emission from the organic electroluminescence element. , A single-layer structure formed on the entire surface of the film, a single-layer structure formed by arranging a highly conductive material having a low transmittance with respect to light emission from the organic electroluminescent element in a non-light-emitting portion on the film surface, It can be constituted by a two-layer structure in which a moisture-proof layer is provided on the film surface and a moisture-absorbing antistatic agent is applied to the surface, or a laminated structure in which the antistatic layer and other functional layers are combined.

Examples of the antistatic agent include conductive paints, conductive plastics, inorganic oxides, and conductive antistatic agents.
Conductive carbon, metal fibers, or the like are used, and are appropriately selected and used in consideration of the transmittance with respect to light emission from the organic electroluminescence device and the conductivity. Among them,
A conductive paint containing an inorganic oxide as a filler, particularly a transparent conductive paint, is preferable because it is excellent in processability and transmittance for light emission.

Instead of using these conductive type antistatic agents as an antistatic layer on the film surface, these antistatic agents can be provided in the film to add an antistatic effect to the film itself.

Examples of the moisture-absorbing antistatic agent include surfactants such as a cationic surfactant, an anionic surfactant and a zwitterionic surfactant, a transparent glassy polymer film antistatic agent, a cyclohexane-based antistatic agent, A polymer-based antistatic agent is used, and is appropriately selected and used in consideration of the transmittance and the conductivity with respect to light emission from the organic electroluminescence element.

As the antistatic treatment method, in the manufacturing process, the film is processed while being in contact with a static elimination bar or ground, or during the manufacturing process, corona discharge, self-discharge, ultraviolet irradiation, soft X-ray irradiation, radiation A method of performing a so-called static elimination treatment such as irradiating ions generated by irradiation or the like, or a method of performing a cleaning process before depositing an organic film in an atmosphere at a relative humidity of 20% RH or more during a manufacturing process. is there. In the present invention, the antistatic treatment method includes a so-called static elimination treatment.

Next, the anode of the organic electroluminescence device will be described. The anode is an electrode for injecting holes, and it is necessary to efficiently inject holes into the light emitting layer or the hole transport layer. The anode is a light-transmitting conductive film, and is a metal oxide such as indium tin oxide (ITO), tin oxide (SnO ₂ ), zinc oxide (ZnO), or SnO: Sb (antimony), or ZnO: Al
A transparent conductive film made of a mixture such as (aluminum), a conductive polymer such as polypyrrole, or the like can be used and is formed by resistance heating evaporation, electron beam evaporation, sputtering, electrolytic polymerization, or chemical polymerization. The thickness of the anode is desirably 10 nm or more in order to have sufficient conductivity or to prevent uneven light emission due to unevenness on the surface of the polymer film as a substrate. It is desirable that the thickness be 200 nm or less in order to provide sufficient transparency.

Further, an amorphous carbon film may be provided on the anode. In this case, both have a function as a hole injection electrode. That is, holes are injected from the anode into the light emitting layer or the hole transport layer via the amorphous carbon film. The amorphous carbon film is formed between the anode and the light emitting layer or the hole transport layer by a sputtering method. As the carbon target by sputtering, there are isotropic graphite, anisotropic graphite, glassy carbon, and the like. Although not particularly limited, isotropic graphite having high purity is suitable. Specifically showing that the amorphous carbon film is excellent,
When the work function of the amorphous carbon film is measured using a surface analyzer AC-1 manufactured by Riken Keiki, the work function of the amorphous carbon film is W _c = 5.40 eV. Here, the work function of ITO generally used as the anode is W _ITO =
Since it is 5.05 eV, holes can be more efficiently injected into the light emitting layer or the hole transport layer by using the amorphous carbon film. When forming an amorphous carbon film by a sputtering method,
In order to control the electric resistance of the amorphous carbon film, reactive sputtering is performed in a mixed gas atmosphere of nitrogen or hydrogen and argon. Furthermore, in a thin film forming technique by a sputtering method or the like, if the film thickness is set to 5 nm or less, the film becomes an island structure, and a uniform film cannot be obtained. Therefore, when the thickness of the amorphous carbon film is 5 nm or less, the electric resistance becomes too high. As a result, no current flows and efficient light emission cannot be obtained.
When the thickness of the amorphous carbon film is 100 nm or more,
The color of the film becomes blackish, and the light emitted from the organic electroluminescence element does not pass sufficiently.

The light emitting layer is preferably made of a phosphor having a fluorescent property in the visible region and having a good film-forming property, such as Alq ₃ or Be-benzoquinolinol (BeB).
In addition to the q _2), 2,5-bis (5,7-di -t- pentyl-2-benzoxazolyl) -1,3,4-thiadiazole, 4,4'-bis (5,7 Bentyl-2-benzoxazolyl) stilbene, 4,4'-bis [5,7
-Di- (2-methyl-2-butyl) -2-benzoxazolyl] stilbene, 2,5-bis (5,7-di-t-
Ventyl-2-benzoxazolyl) thiofin, 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-benzooxazolyl) thiophene, 4,4 '-Bis (2-benzoxazolyl) biphenyl, 5-methyl-2- [2- [4- (5-methyl-
Benzoxazoles such as 2-benzoxazolyl) phenyl] vinyl] benzoxazolyl and 2- [2- (4-chlorophenyl) vinyl] naphtho [1,2-d] oxazole; 2,2 ′-(p Benzothiazoles such as -phenylenedivinylene) -bisbenzothiazole;
A fluorescent whitening agent such as a benzimidazole type such as 2- [2- [4- (2-benzimidazolyl) phenyl] vinyl] benzimidazole and 2- [2- (4-carboxyphenyl) vinyl] benzimidazole; 8-quinolinol) magnesium, bis (benzo-8-quinolinol) zinc, bis (2-methyl-8-quinolinolate)
Aluminum oxide, tris (8-quinolinol) indium, tris (5-methyl-8-quinolinol) aluminum, lithium 8-quinolinol, tris (5-
Chloro-8-quinolinol) gallium, bis (5-chloro-8-quinolinol) calcium, poly [zinc-bis (8-hydroxy-5-quinolinonyl) methane], etc.
A metal chelated oxinoid compound such as a hydroxyquinoline-based metal complex or dilithium epindridione,
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
Styrylbenzene compounds such as -bis (3-ethylstyryl) benzene, 1,4-bis (2-methylstyryl) 2-methylbenzene, and 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)
Disazine pyrazine derivatives such as pyrazine, 2,5-bis [2- (4-biphenyl) vinyl] pyrazine, 2,5-bis [2- (1-pyrenyl) vinyl] pyrazine, naphthalimide derivatives, and perylene derivatives For example, oxadiazole derivatives, aldazine derivatives, cyclopentadiene derivatives, styrylamine derivatives, coumarin derivatives, aromatic dimethylidin derivatives, and the like are used. Further, anthracene, salicylate, pyrene, coronene and the like are also used.

In addition to the single-layer structure of only the light-emitting layer, a two-layer structure of the hole-transport layer and the light-emitting layer or the light-emitting layer and the electron-transport layer,
Any of a three-layer structure of a hole transport layer, a light emitting layer, and an electron transport layer may be used. However, in the case of such a two-layer structure or a three-layer structure, they are stacked so that the hole transport layer and the anode or the electron transport layer and the cathode are in contact with each other.

As the hole transporting layer, those having high hole mobility, high transparency and good film-forming property are preferable. Porphyrin compound, 1,1-bis {4- (di-P-tolylamino) phenyl} cyclohexane, 4,4 ′, 4 ″ -trimethyltriphenylamine, N, N, N ′, N′-tetrakis ( P-tolyl)-
P-phenylenediamine, 1- (N, N-di-P-tolylamino) naphthalene, 4,4′-bis (dimethylamino) -2-2-2′-dimethyltriphenylmethane, N,
N, N ', N'-tetraphenyl-4,4'-diaminobiphenyl, N, N'-diphenyl-N, N'-di-m
-Tolyl-4, N, N-diphenyl-N, N'-bis (3-methylphenyl) -1, 1'-4, 4'-diamine, 4'-diaminobiphenyl, N-phenylcarbazole, etc. Aromatic tertiary amines, 4-di-P-tolylaminostilbene, 4- (di-P-tolylamino) -4 ′
Stilbene compounds such as-[4- (di-P-tolylamino) styryl] stilbene, triazole derivatives, oxazizazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, , Annealed amine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, silazane derivatives, polysilane aniline copolymers, high molecular oligomers, styrylamine compounds Organic materials such as aromatic dimethylidin compounds and poly-3-methylthiophene are used. Further, a polymer-dispersed hole transport layer in which a low molecular weight organic material for a hole transport layer is dispersed in a polymer such as polycarbonate is also used.

As the electron transport layer, oxadiazole derivatives such as 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7) and anthraquinodimethane derivatives And diphenylquinone derivatives.

The cathode is an electrode into which electrons are injected.
Must be efficiently injected into the light emitting layer or the electron transport layer.
It is important that the work function of Al (aluminum), I
n (indium), Mg (magnesium), Ti (titanium)
), Ag (silver), Ca (calcium), Sr (stro
Metals such as Nt) or oxides of these metals
And fluorides and their alloys and laminates are commonly used
You. Particularly, Mg, Mg-Ag alloy having a small work function,
Al-Li alloy and Sr described in JP-A-5-121172
-Mg alloy, Al-Sr alloy, Al-Ba alloy, etc.
Or LiO _Two/ Al or LiF / Al laminated structure
It is suitable. Film deposition methods include resistance heating evaporation,
Evaporation and sputtering methods are used.

Further, a sealing film for blocking the influence of oxygen or moisture in the air may be provided on the cathode by vapor deposition, sputtering, or a coating method. Examples of the material include inorganic oxides such as SiON, SiO, SiO ₂ , and Al ₂ O ₃ , thermosetting and photocurable resins, and silane-based polymer materials having a sealing effect.

Hereinafter, embodiments of the present invention will be described.

(Embodiment 1) An organic electroluminescence device according to an embodiment of the present invention will be described.

FIG. 1 is a cross-sectional view of a main part of an organic electroluminescence device according to an embodiment of the present invention.

In FIG. 1, the anode 2, the hole transport layer 3, the light emitting layer 4, and the cathode 5 are the same as those described in the prior art, and therefore, are denoted by the same reference numerals and will not be described. Reference numeral 6 denotes a polymer film.

The organic electroluminescence device according to the present embodiment has an antistatic layer 7 on the surface of a polymer film 6. Then, the value of the surface resistance is at least 10 ¹¹ Ω / sq. It is preferred that: The constituent materials and forming method of the polymer film 6 and the antistatic layer 7 can be appropriately selected from the above-described constituent materials, forming methods and conventionally known materials. Further, an antistatic agent may be contained in the polymer film 6 without providing the antistatic layer 7, or a combination of both may be used.

The anode 2, the hole transport layer 3, the light emitting layer 4,
As the constituent material and the forming method of the cathode 5, the above-described constituent material, the forming method and conventionally known materials can be used.

Further, in this embodiment, the case of the two-layer structure including the hole transport layer and the light emitting layer has been described, but the structure is not particularly limited as described above.

As for the form of sealing, an appropriate means such as forming a protective film of an inorganic oxide for sealing can be employed. There is no problem even if a combination of a protective film and a shielding material is used.

As described above, according to this embodiment, since the antistatic property of the film surface is excellent, there is no occurrence of static electricity failure, and no adhesion of dust.
Optimal light emission performance can be maintained.

(Embodiment 2) Next, a display device using the organic electroluminescence element of the present invention will be described.

FIG. 2 is a schematic perspective view of a display device using an organic electroluminescence element according to an embodiment of the present invention.

In FIG. 2, the anode 2, the hole transport layer 3, the light emitting layer 4, the cathode 5, and the polymer film 6 are denoted by the same reference numerals as in the first embodiment, and the description is omitted here.

In the present embodiment, as shown in FIG. 2, the anode 2 is linearly patterned, and the cathode 5 is similarly linearly patterned so as to be substantially perpendicular thereto.

Then, the anode 2 of the display device is set to the plus side, and the cathode 5 is set to the minus side, and connected to a drive circuit (driver) as drive means (not shown).
When a DC voltage or a DC current is applied to the cathode 5, the light emitting layers 4 in the orthogonal portions emit light, and can be used as a simple matrix type display device.

In the present embodiment, the polymer film
No. 6 contains an antistatic agent inside the film
is there. And preferably, the value of the surface resistance is at least
10 ¹¹Ω / sq. It is as follows. This
A small pattern like a dot matrix
In the case of
Surface resistance is 10⁷Ω / sq. Less preferred
New Composition of polymer film 6 and antistatic agent to be contained
The materials and forming methods are the same as those described above for the constituent materials, forming methods and
It can be appropriately selected from known materials and used. Change
Without containing an antistatic agent in the polymer film 6,
An antistatic layer may be provided.
Is also good. If the surface resistance is lowered too much,
The anode 2 patterned on the film 6 is substantially conductive.
Insulation between the patterned anodes 2
Needless to say, the surface resistance is such that the surface resistance can be maintained.

The anode 2, the hole transport layer 3, the light emitting layer 4,
As the constituent material and the forming method of the cathode 5, the above-described constituent material, the forming method and conventionally known materials can be used.

As described above, also in the display device of the present embodiment, the antistatic property of the film surface is excellent, so that it does not cause static electricity damage, furthermore, there is no adhesion of dust, and the optimum light emitting performance. Can be maintained.

In this embodiment, a display device of a simple matrix system has been described. However, a display device of an active matrix system may be used, and a TFT may be formed on the polymer film 6. In this case, it is needless to say that the polymer film 6 is prevented from being charged.

(Embodiment 3) Next, a portable terminal using the organic electroluminescence device of the present invention will be described. 3 and 4 are a perspective view and a block diagram, respectively, showing a portable terminal provided with a display device using an organic electroluminescence element according to an embodiment of the present invention. 3 and 4, reference numeral 8 denotes a microphone for converting an audio signal to an audio signal, 9 denotes a speaker for converting an audio signal to an audio signal, 10 denotes an operation unit including dial buttons and the like, 1
Reference numeral 1 denotes a display unit for displaying an incoming call and the like, which is constituted by a display device using the organic electroluminescence of the present invention, 12 is an antenna, and 13 is a transmission unit for converting a voice signal from the microphone 8 into a transmission signal. The transmission signal produced by the transmission unit 13 is emitted outside through the antenna 12.
A receiving unit 14 converts a received signal received by the antenna 12 into an audio signal. The audio signal created by the receiving unit 14 is converted into audio by the speaker 9. 15 is a transmitting unit 13,
The control unit controls the reception unit 14, the operation unit 10, and the display unit 11.

The microphone 8 receives a voice or the like of a user (caller) during a call, and the speaker 9 outputs a voice or a notification sound of the other party and transmits it to the user (receiver). When a pager is used as the mobile terminal, the microphone 8 need not be particularly provided.

Further, the operation unit 10 is provided with ten keys as dial buttons and various function keys. Also,
Not only numeric keys and various function keys but also character keys may be provided. From this operation unit 10, telephone number, name, time, setting of various functions, e-mail address, URL
And other predetermined data. Further, the operation unit 10 may use not only such a keyboard operation but also a pen input device, a voice input device, a magnetic or optical input device.

The display section 11 displays predetermined data input from the operation section 10, data such as telephone numbers, e-mail addresses, URLs, and the like stored in the memory, character icons, and the like.

The antenna 12 performs at least one of transmission and reception of radio waves. In this embodiment, an antenna (helical antenna, planar antenna, or the like) is provided because signal transmission and reception are performed by radio waves. However, when performing optical communication or the like, a light emitting element or a light receiving element is connected to the antenna. It may be provided instead. In this case, the light emitting element transmits a signal to another communication device or the like, and the light receiving element receives an external signal.

The transmitting unit 13 and the receiving unit 14 convert an audio signal into a transmission signal, and convert the received signal into an audio signal.

Further, the control unit 15 has a C (not shown)
The transmission unit 13, the reception unit 14, and the operation unit 10 are configured by a conventionally known method using a PU, a memory, and the like.
The display unit 11 is controlled. More specifically, an instruction is given to each control circuit, drive circuit, and the like (not shown) provided in these units. For example, the display control circuit that has received the display command from the control unit 15 drives the display drive circuit, and the display is performed on the display unit 11.

Hereinafter, an example of the operation will be described.

First, when there is an incoming call, the receiving unit 14
Sends an incoming signal to the control unit 15, the control unit 15 displays a predetermined character or the like on the display unit 11 based on the incoming signal, and further presses a button or the like for receiving an incoming call from the operation unit 10. And a signal is sent to the control unit 15,
The control unit 15 sets each unit to the incoming call mode. That is, the signal received by the antenna 12 is converted into an audio signal by the receiving unit 14, the audio signal is output as audio from the speaker 9, and the audio input from the microphone 8 is converted into an audio signal, Through the antenna 12 to the outside.

Next, the case of making a call will be described.

First, when transmitting a signal, a signal to the effect that the signal is transmitted from the operation unit 10 is input to the control unit 15. Subsequently, when a signal corresponding to the telephone number is transmitted from the operation unit 10 to the control unit 15, the control unit 15 transmits a signal corresponding to the telephone number from the antenna 12 via the transmission unit 13. When the transmission signal establishes communication with the other party,
When a signal to that effect is sent to the control unit 15 via the reception unit 14 via the antenna 12, the control unit 15 sets each unit to the transmission mode. That is, the signal received by the antenna 12 is converted into an audio signal by the receiving unit 14, the audio signal is output as audio from the speaker 9, and the audio input from the microphone 8 is converted into an audio signal, Through the antenna 12 to the outside.

In this embodiment, an example in which voice is transmitted and received has been described. However, the present invention is not limited to voice, and the same applies to a portable terminal that transmits and / or receives data other than voice such as character data. The effect can be obtained.

The portable terminal according to the present embodiment also has an excellent antistatic property on the film surface, so that it does not cause an electrostatic disturbance, adheres no dust, and maintains an optimum light emitting performance. You can do it.

In particular, in recent years, portable terminals have been required to be lighter, and the use of a polymer film instead of the glass substrate of the conventional organic electroluminescence device can bring about a drastic reduction in weight. Becomes And when the display area is relatively small like a mobile terminal,
In the display area, stable display without hindrance is required. Therefore, by using the organic electroluminescence device of the present invention, it is extremely effective to maintain the optimum light emitting performance, and it is also extremely effective to suppress the inhibition due to dust adhesion.

[0084]

(Example 1) After forming an ITO film having a thickness of 160 nm on polyethylene terephthalate (PET), a resist material (OFPR, manufactured by Tokyo Ohka Co., Ltd.) was formed on the ITO film.
-800) by spin coating to a thickness of 10 μm.
After forming a resist film of m, the resist film was patterned into a predetermined shape by masking, exposing and developing. Next, the film substrate is immersed in 50% hydrochloric acid at 60 ° C. to etch a portion of the ITO film where the resist film is not formed, and then the resist film is also removed.
A polyethylene terephthalate film substrate on which a membrane anode was formed was obtained.

Next, a transparent conductive paint containing a conductive inorganic oxide as a filler was applied to the surface of the film substrate opposite to the surface on which the anode was formed, to form an antistatic film.

Next, this film substrate was subjected to ultrasonic cleaning with a detergent (Semico Clean, manufactured by Furuuchi Chemical Co., Ltd.) for 5 minutes, ultrasonic cleaning with pure water for 10 minutes, ammonia water 1
(Volume ratio), ultrasonic cleaning with a mixed solution of hydrogen peroxide water 1 and water 5 for 5 minutes, ultrasonic cleaning with pure water at 70 ° C. for 5 minutes, and then a substrate with a nitrogen blower. The water adhering to the was removed, and further heated and dried.

Next, the surface of the film substrate on the anode side
TPD was formed to a thickness of about 50 nm as a hole transport layer in a resistance heating evaporation apparatus in which the pressure was reduced to a degree of vacuum of × 10 ⁻⁶ Torr or less.

Next, similarly, in a resistance heating vapor deposition apparatus, Alq ₃ was formed to a thickness of about 60 nm as a light emitting layer on the hole transport layer. The deposition rates of TPD and Alq ₃ were both 0.2 nm / s.

Next, similarly, in a resistance heating vapor deposition apparatus, a cathode was formed to a thickness of 150 nm on the light emitting layer using an Al—Li alloy containing 15 at% of Li as a vapor deposition source.

The surface resistance of the polymer film of the organic electroluminescent device of Example 1 thus obtained was measured to be 2.5 × 10 ⁷ Ω / sq. Met.

(Example 2) A polyethylene terephthalate film substrate on which an anode made of an ITO film having a predetermined pattern was formed was obtained using the same material and the same method as in Example 1.

Next, the amount of the inorganic oxide having conductivity used in Example 1 was reduced, and the surface of the film substrate opposite to the surface on which the anode was formed was coated with the inorganic oxide having conductivity. A transparent conductive paint containing the material as a filler was applied to form an antistatic film.

Next, this film substrate was subjected to ultrasonic cleaning with a detergent (Semico Clean, manufactured by Furuuchi Chemical Co., Ltd.) for 5 minutes, ultrasonic cleaning with pure water for 10 minutes, ammonia water 1
(Volume ratio), ultrasonic cleaning with a mixed solution of hydrogen peroxide water 1 and water 5 for 5 minutes, ultrasonic cleaning with pure water at 70 ° C. for 5 minutes, and then a substrate with a nitrogen blower. The water adhering to the was removed, and further heated and dried.

Next, the surface on the anode side of the film substrate is
TPD was formed to a thickness of about 50 nm as a hole transport layer in a resistance heating evaporation apparatus in which the pressure was reduced to a degree of vacuum of × 10 ⁻⁶ Torr or less.

Next, similarly, in a resistance heating vapor deposition apparatus, Alq ₃ was formed to a thickness of about 60 nm as a light emitting layer on the hole transport layer. The deposition rates of TPD and Alq ₃ were both 0.2 nm / s.

Next, in the same manner, a cathode was formed in a thickness of 150 nm on the light emitting layer using an Al—Li alloy containing 15 at% Li as an evaporation source in a resistance heating evaporation apparatus.

The surface resistance of the polymer film of the organic electroluminescence device of Example 2 thus obtained was 10 ⁹ Ω / sq. It was an order.

(Example 3) A polyethylene terephthalate film substrate on which an anode made of an ITO film having a predetermined pattern was formed was obtained by using the same material and the same method as in Example 1.

Next, the amount of the inorganic oxide having conductivity used in Example 2 was reduced, and the surface of the film substrate opposite to the surface on which the anode was formed was coated with the inorganic oxide having conductivity. A transparent conductive paint containing the material as a filler was applied to form an antistatic film.

Next, the film substrate was subjected to ultrasonic cleaning for 5 minutes with a detergent (Semico Clean, manufactured by Furuuchi Chemical Co., Ltd.), ultrasonic cleaning for 10 minutes with pure water, and ammonia water for 1 minute.
(Volume ratio), ultrasonic cleaning with a mixed solution of hydrogen peroxide water 1 and water 5 for 5 minutes, ultrasonic cleaning with pure water at 70 ° C. for 5 minutes, and then a substrate with a nitrogen blower. The water adhering to the was removed, and further heated and dried.

Next, the surface of the film substrate on the anode side
TPD was formed to a thickness of about 50 nm as a hole transport layer in a resistance heating evaporation apparatus in which the pressure was reduced to a degree of vacuum of × 10 ⁻⁶ Torr or less.

Next, similarly, in a resistance heating vapor deposition apparatus, Alq ₃ was formed to a thickness of about 60 nm as a light emitting layer on the hole transport layer. The deposition rates of TPD and Alq ₃ were both 0.2 nm / s.

Next, in the same manner, a cathode was formed in a thickness of 150 nm on the light emitting layer using an Al—Li alloy containing 15 at% Li as an evaporation source in a resistance heating evaporation apparatus.

The surface resistance of the polymer film of the organic electroluminescence device of Example 3 thus obtained was 10 ¹¹ Ω / sq. It was an order.

(Example 4) The same materials as in Example 1 above,
In a similar manner, a polyethylene terephthalate film substrate on which an anode made of an ITO film having a predetermined pattern was formed was obtained.

Next, the film substrate was set to a relative humidity of 32.
% RH, and ultrasonic cleaning with a detergent, ultrasonic cleaning with pure water,
Ultrasonic cleaning with a solution of a mixture of hydrogen peroxide and water, 7
After cleaning treatment was performed in the order of ultrasonic cleaning with pure water at 0 ° C., moisture attached to the substrate was removed with a nitrogen blower.

Next, it was heated and dried using an oven in a room having a relative humidity of 20% RH.

Next, the surface of the film substrate on the anode side is
TPD was formed to a thickness of about 50 nm as a hole transport layer in a resistance heating evaporation apparatus in which the pressure was reduced to a degree of vacuum of × 10 ⁻⁶ Torr or less.

Next, similarly, in a resistance heating vapor deposition apparatus, Alq ₃ was formed in a thickness of about 60 nm as a light emitting layer on the hole transport layer. The deposition rates of TPD and Alq ₃ were both 0.2 nm / s.

Next, in the same manner, a cathode was formed in a thickness of 150 nm on the light-emitting layer in a resistance heating vapor deposition apparatus using an Al—Li alloy containing 15 at% Li as a vapor deposition source.
Was obtained.

(Comparative Example 1) As in Example 1, a 160 nm-thick I-film was formed on polyethylene terephthalate (PET).
After forming the TO film, a resist material (OFPR-800, manufactured by Tokyo Ohka Co., Ltd.) is applied on the ITO film by spin coating to form a resist film having a thickness of 10 μm, and the resist film is formed by masking, exposing and developing. Was patterned into a predetermined shape. Next, the film substrate was immersed in 50% hydrochloric acid at 60 ° C.
After etching the O film, the resist film was also removed to obtain a polyethylene terephthalate film substrate on which an anode made of an ITO film having a predetermined pattern was formed.

Next, the film substrate was set at a relative humidity of 20%.
% RH, 5 minutes of ultrasonic cleaning with a detergent (Semico Clean, manufactured by Furuuchi Chemical Co., Ltd.), 10 minutes of ultrasonic cleaning with pure water, and 1% aqueous ammonia to 1% aqueous ammonia (volume ratio) After performing a cleaning process in the order of 5 minutes of ultrasonic cleaning with a solution in which water 5 is mixed, and 5 minutes of ultrasonic cleaning with pure water at 70 ° C., moisture attached to the substrate is removed with a nitrogen blower, and further heated and dried. did.

Next, the surface of the film substrate on the anode side
TPD was formed to a thickness of about 50 nm as a hole transport layer in a resistance heating evaporation apparatus in which the pressure was reduced to a degree of vacuum of × 10 ⁻⁶ Torr or less.

Next, similarly, in a resistance heating vapor deposition apparatus, Alq ₃ was formed as a light emitting layer with a thickness of about 60 nm on the hole transport layer. The deposition rates of TPD and Alq ₃ were both 0.2 nm / s.

Next, a cathode was formed in a thickness of 150 nm on the light emitting layer in the same manner as above using a Al-Li alloy containing 15 at% Li as an evaporation source in a resistance heating evaporation apparatus.

The surface resistance of the polymer film of the organic electroluminescence device of Comparative Example 1 thus obtained was 10 ¹⁶ Ω / sq. It was an order.

The thus obtained organic electroluminescent devices of Examples 1 to 3 and Comparative Example 1 were driven to emit light, and an evaluation test was performed.

The test results are shown in (Table 1).

[0119]

[Table 1]

Here, the evaluation methods and evaluation criteria for the evaluation items in (Table 1) will be described.

The visibility of the light-emitting surface was evaluated by visually observing the degree of visibility of the light-emitting surface due to adhesion of dust after each element was left under the same atmosphere for a certain period of time. The evaluation is a three-level evaluation of △, Δ, ×, and the evaluation criteria are ○: good, Δ: acceptable, ×: inhibition.

The easiness of removing dust was determined by spraying a fixed amount of dust on the light emitting surface, blowing air to the light emitting surface for a certain time, and visually evaluating the dust remaining on the light emitting surface. The evaluation is a three-level evaluation of △, Δ, ×, and the evaluation criteria are ○: good, Δ: acceptable, ×: inhibition.

The inhibition by the non-light emitting portion was evaluated by visually observing the presence or absence of visibility inhibition by the non-light emitting portion (black spot). The evaluation is a two-stage evaluation of ○ and ×, and the evaluation criteria are ○:
Inhibited, ×: no inhibition.

Table 2 shows the results of the evaluation in the processing of Example 4 and Comparative Example 1, and the results of the evaluation test in which the obtained organic electroluminescent elements of Example 4 and Comparative Example 1 were driven to emit light. Show.

[0125]

[Table 2]

Here, the evaluation methods and evaluation criteria in the evaluation items of (Table 2) will be described.

The processing suitability was evaluated for the presence or absence of handling inhibition due to sticking of the polymer film in the processing of the organic electroluminescence device. The evaluation was a two-step evaluation of ， and ×, and the evaluation criteria were ：: inhibition, ×:
No inhibition.

The inhibition by the non-light-emitting portion was evaluated by visually observing the presence or absence of visibility inhibition by the non-light-emitting portion (black spot). The evaluation is a two-stage evaluation of ○ and ×, and the evaluation criteria are ○:
Inhibited, ×: no inhibition.

[0129]

As described above, according to the present invention, the material and the characteristics of the polymer film used as the substrate of the organic electroluminescence element are optimized or the function is added to the polymer film. Alternatively, by devising a manufacturing process of an organic electroluminescence element, it is possible to provide an organic electroluminescence element having excellent antistatic properties and capable of maintaining optimum light emitting performance, a display device and a portable terminal using the same. it can.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a main part of an organic electroluminescence element according to an embodiment of the present invention.

FIG. 2 is a schematic perspective view of a display device using an organic electroluminescence element according to an embodiment of the present invention.

FIG. 3 is a perspective view showing a mobile terminal provided with a display device using an organic electroluminescence element according to an embodiment of the present invention.

FIG. 4 is a block diagram showing a mobile terminal provided with a display device using an organic electroluminescence element according to an embodiment of the present invention.

FIG. 5 is a cross-sectional view of a main part of a conventional organic electroluminescence element.

[Explanation of symbols]

 Reference Signs List 1 glass substrate 2 anode 3 hole transport layer 4 light emitting layer 5 cathode 6 polymer film 7 antistatic layer 8 microphone 9 speaker 10 operation unit 11 display unit 12 antenna 13 transmission unit 14 reception unit 15 control unit

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Akira Akitoku 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Koji Yoshida 1006 Kadoma Kadoma Kadoma City, Osaka Matsushita Electric Industrial Co. F Terms (reference) 3K007 AB18 BA06 BA07 CA06 CB01 DA01 DB03 EB00 FA01 5C080 AA06 BB05 DD28 FF03 FF09 JJ02 JJ06 5K023 AA07 BB28 HH06 QQ00 RR00

Claims (9)

[Claims] 1. A transparent or translucent polymer film,
An organic electroluminescent device comprising at least an anode for injecting holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons, wherein the polymer film has an antistatic layer. Luminescent element. 2. On a transparent or translucent polymer film,
An organic electroluminescence device including at least an anode for injecting holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons, wherein the polymer film contains an antistatic agent. Organic electroluminescent element. 3. On a transparent or translucent polymer film,
An organic electroluminescence device including at least an anode for injecting holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons, wherein the polymer film is subjected to an antistatic treatment. Organic electroluminescent element. 4. On a transparent or translucent polymer film,
An organic electroluminescence device comprising at least an anode for injecting holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons, wherein the polymer film has a surface resistance of 10 ¹¹ Ω / sq. An organic electroluminescence device characterized by the following. 5. On a transparent or translucent polymer film,
An organic electroluminescent device comprising at least an anode for injecting holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons, wherein the polymer film is subjected to an antistatic treatment. Electroluminescence element. 6. On a transparent or translucent polymer film,
An organic electroluminescence device comprising at least an anode for injecting holes, a light emitting layer having a light emitting region, and a cathode for injecting electrons, wherein the polymer film is washed in an atmosphere having a relative humidity of 20% RH or more. An organic electroluminescent device characterized by being processed. 7. A display device, comprising: the organic electroluminescence device according to claim 1; and driving means for driving the anode and the cathode. 8. The image display device according to claim 7, wherein said anode is electrically separated in stripes and said cathode is electrically separated in stripes, and has an image display arrangement. Display device. 9. A voice signal converting means for converting voice into a voice signal, an operating means for inputting a telephone number, a display means for displaying an incoming call display, a telephone number, etc., and a communication for converting a voice signal into a transmission signal. 8. A portable terminal comprising: means, a receiving means for converting a received signal into an audio signal, an antenna for transmitting and receiving the transmission signal and the received signal, and a control means for controlling each unit, wherein the display means is provided. 9. A portable terminal comprising the display device according to any one of claims 8 and 9.