JP2003249365A - Organic electroluminescent image display device and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent image display device with a transparent electrode layer free from breaking and an organic electroluminescence cell layer for developing stable luminescence leading to high quality image display, and its manufacturing method enabling simple manufacturing of the device. <P>SOLUTION: The organic electroluminescent image display device comprises a color filter layer, a color change fluorescent material layer, a transparent protecting layer, the transparent electrode layer, the organic electroluminescence cell layer, and a back electrode layer provided in sequence on a transparent substrate. The color change fluorescent material layer has a plurality of band patterns arranged in parallel and each band pattern has an end formed as an inclined portion having a thickness gradually decreasing as tending to the outside in the longitudinal direction of the pattern. The transparent protecting layer is provided on the transparent substrate to cover the inclined portions and the color change fluorescent material layer. The transparent electrode layer is arranged on the transparent protecting layer in such a band form that it rides over a range from the transparent substrate to the color change fluorescent material layer where the inclined portions are formed. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic electroluminescent image display device and a method for manufacturing the same.

[0002]

2. Description of the Related Art Organic electroluminescence (E
The L) element has advantages such as high visibility due to self-coloring, being an all-solid-state display unlike a liquid crystal display, being hardly affected by temperature changes, and having a wide viewing angle. Practical application is progressing as a pixel of a device. As an image display device using an organic EL element, (1) an organic EL element layer of three primary colors is formed in a predetermined pattern for each emission color, (2) an organic EL element layer of white emission is used, and three primary colors are used. To be displayed through the color filter of (3) Blue-emitting organic EL
It has been proposed that an element layer is used and a color conversion phosphor layer using a fluorescent dye is provided to convert blue light into green fluorescence or red fluorescence to display three primary colors.

However, in the organic EL image display device of the above (1), although the extraction efficiency of each colored light is high, it is difficult to make the characteristics of the organic EL elements of each color uniform, and further, the three primary colors are formed in a fine pattern. The process of forming the organic EL element layer is complicated, which makes mass production difficult.
Further, in the organic EL image display device of the above (2), when white light is separated by the color filters of the three primary colors, the emission efficiency of one of the three primary colors is reduced to one third of the white light, and the extraction efficiency is poor. Therefore, a high-efficiency white organic EL element is required, but a white organic EL element with sufficient brightness can be obtained stably.
The element has not been obtained yet. On the other hand, in the organic EL image display device of the above (3), since the conversion efficiency of the color conversion phosphor layer is determined by the product of the light absorption efficiency and the fluorescence efficiency, the fluorescence having the high light absorption efficiency and the fluorescence efficiency is obtained. By using a dye, three primary color light emission with extremely high conversion efficiency is possible.

Since the organic EL element is deteriorated by gases such as water vapor, oxygen, organic monomers, and low molecular components generated from the color conversion phosphor layer, etc., the organic EL element layer is directly formed on the color conversion phosphor layer. Therefore, it is necessary to cover the above-mentioned gas by covering the color conversion phosphor layer with a transparent protective layer. Then, a transparent electrode is formed in a predetermined pattern on the transparent protective layer, and an organic EL element layer is formed on the transparent electrode.
The back electrode layer will be formed. Further, there is a difference in the conversion performance of the phosphors corresponding to each color, and when it is necessary to make the thickness of the color conversion phosphor layer different for each color in order to obtain a desired color tone, there is a step between the color conversion phosphor layers. Occurs. When such a step exists, the thickness of the organic EL element layer becomes uneven, and stable light emission cannot be obtained. However, by forming the above transparent protective layer, it is necessary to eliminate such a step. You can Therefore, in the organic EL image display device, the transparent protective layer formed so as to cover the color conversion phosphor layer has an essential structure.

[0005]

However, in order to obtain a color conversion phosphor layer having high light absorption efficiency and fluorescence efficiency, it is necessary to make the color conversion phosphor layer thicker. The thicker the color conversion phosphor layer is, the thicker the color conversion phosphor layer becomes. , The step at the end becomes large. Then, the size of this step difference is reflected in the transparent protective layer formed so as to cover the color conversion phosphor layer. On the other hand, the strip-shaped transparent electrode layer formed on the transparent protective layer from the peripheral terminal portion to the pixel region is generally formed by forming a transparent electrode film by a vacuum film forming method and pattern etching this. For this reason, at the stepped portion of the transparent protective layer generated at the end portion of the color conversion phosphor layer described above, film formation failure or disconnection due to stress during the etching process is likely to occur, causing a disconnection in the transparent electrode layer. There is a problem that it is easy.

The present invention has been made in view of such circumstances, and there is no breakage of the transparent electrode layer, stable light emission of the organic electroluminescence element layer is obtained, and high quality image display is possible. It is an object of the present invention to provide an electroluminescent image display device and a manufacturing method capable of easily manufacturing such a device.

[0007]

In order to achieve such an object, an organic electroluminescent image display device of the present invention comprises a transparent base material and a color filter layer sequentially provided on the transparent base material. A color conversion phosphor layer, a transparent protective layer, a transparent electrode layer, an organic electroluminescence element layer, and a back electrode layer, wherein the color conversion phosphor layer has a plurality of strip-shaped patterns arranged in parallel, each strip-shaped The end portion of the pattern has an inclined portion whose thickness decreases toward the outside in the pattern length direction, and the transparent protective layer is provided on the transparent base material so as to cover the color conversion phosphor layer and the inclined portion. The transparent electrode layer is arranged in a strip shape on the transparent protective layer so as to ride on the color conversion phosphor layer from the transparent base material at the portion where the inclined portion is provided.

As another aspect of the present invention, a straight line connecting the end of the surface of the color conversion phosphor layer and the end of the inclined portion is
The transparent substrate was formed so as to form an angle of 60 ° or less. According to another aspect of the present invention, a black matrix having a predetermined opening pattern is provided between the transparent substrate and the color filter. Further, as another aspect of the present invention, the organic electroluminescence element layer emits blue light, the color conversion phosphor layer converts the blue light into green fluorescence and emits light, and the blue light emits red fluorescence. And a red conversion layer that emits light after being converted into.

The method of manufacturing an organic electroluminescent image display device according to the present invention comprises a step of forming a plurality of colored layers of different colors in a band shape on a transparent substrate to provide a color filter layer, and the step of forming the color filter layer. Forming the color conversion phosphor layer in a strip shape at the same time, and forming an inclined portion whose thickness decreases toward the outer side in the pattern length direction at the end of each strip pattern of the color conversion phosphor layer, the color conversion phosphor A step of forming a transparent protective layer on the transparent base material so as to cover the layer and the inclined portion, and a strip shape so as to ride on the color conversion phosphor layer from the transparent base material at the portion where the inclined portion is arranged. A step of forming a transparent electrode layer on, a step of forming an organic electroluminescent element layer in a strip shape so as to intersect with the transparent electrode layer, and a step of forming a back electrode layer on the organic electroluminescent element layer. It was configured such that. As another aspect of the present invention, a material for forming a color conversion phosphor layer using a photocurable resist resin is applied on the color filter layer to form a photosensitive film, and a strip for the color conversion phosphor layer is formed. By exposing and developing the photosensitive film through a photomask having an opening and a half-exposure portion adjacent to the strip-shaped opening, the inclined portion is integrally formed with the strip-shaped color conversion phosphor layer. It was configured to be formed.

In the present invention as described above, the step at the end of the color conversion phosphor layer is alleviated by the inclined portion, and this occurs in the transparent protective layer formed so as to cover the inclined portion and the color conversion phosphor layer. The step difference becomes small and the occurrence of disconnection of the transparent electrode layer is prevented.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described below with reference to the drawings. Organic Electroluminescent Image Display Device FIG. 1 shows an organic electroluminescent (E) device of the present invention.
L) FIG. 2 is a partial plan view showing an embodiment of the image display device, and FIG.
FIG. 3 is a vertical sectional view taken along line II, and FIG. 3 is a vertical sectional view taken along line III-III of the organic EL image display device shown in FIG. Incidentally, in FIG. 1, an auxiliary electrode 8 and a transparent electrode layer 9 which will be described later are provided.
In order to show, the blue organic EL element layer 10 and the back electrode layer 1
A part of 1 is shown in a cutout state. 1 to 3, the organic EL image display device 1 includes a transparent base material 2 and a strip-shaped red colored layer 4R and a green color through a black matrix 3 having a predetermined opening pattern on the transparent base material 2. A color filter layer 4 in which a layer 4G and a blue coloring layer 4B are arranged in parallel is provided.

On the color filter layer 4, a color conversion phosphor layer 5 composed of a red conversion phosphor layer 5R, a green conversion phosphor layer 5G and a blue conversion dummy layer 5B is formed. The layers forming the color conversion phosphor layer 5 are the red conversion phosphor layer 5R on the red coloring layer 4R, the green conversion phosphor layer 5G on the green coloring layer 4G, and the blue conversion dummy layer on the blue coloring layer 4B. 5B are arranged in parallel in a strip shape. Such a thickness of the color conversion phosphor layer 5 sufficiently absorbs blue light emitted from the blue organic EL element layer 10 described later by the red conversion phosphor layer 5R and the green conversion phosphor layer 5G to generate fluorescence. It is necessary that the function can be expressed, and it can be appropriately set in consideration of the fluorescent dye to be used, the concentration of the fluorescent dye, and the like, and for example, can be about 2 to 15 μm.
Further, the thickness of the blue conversion dummy layer 5B can be made substantially the same as that of the red conversion phosphor layer 5R and the green conversion phosphor layer 5G. The red conversion phosphor layer 5R and the green conversion phosphor layer 5G may have different thicknesses.

The end portion 5a of each strip-shaped pattern 5R, 5G, 5B of the color conversion phosphor layer 5 is an inclined portion whose thickness decreases toward the outer side in the pattern length direction (direction indicated by arrow a in FIG. 2). It is supposed to be 6. The positional relationship between the inclined portion 6 and the color conversion phosphor layer 5 is shown in FIG. 4, and in the illustrated example,
The slanted portion 6 is shown with diagonal lines. However, in FIG.
In order to show the states of the black matrix 3 and the color filter layer 4, a part of the color conversion phosphor layer 5 is cut away. A straight line L (a straight line shown by a chain line in FIG. 2) connecting the tip 6a of the inclined portion 6 and the surface end 5'a of the color conversion phosphor layer 5 to the surface of the transparent substrate 2 is 60
The angle can be set to be less than or equal to 0 °, preferably in the range of 5 to 30 °. If the angle formed by the straight line L with respect to the surface of the transparent substrate 2 does not satisfy the above range, the effect of reducing the step at the end of the color conversion phosphor layer 5 by the inclined portion 6 becomes insufficient, which will be described later. The transparent electrode layer 9 formed on the transparent protective layer 7 is likely to be broken, which is not preferable. In the example shown in FIGS. 2 and 4, the inclined portion 6 formed on the end 5a of the color conversion phosphor layer 5 has a flat inclined surface with a constant inclination angle, but the invention is not limited to this. Not something. For example, as an inclined surface shape, a convex surface shape,
It may be a concave shape, one having small irregularities, one in which planes having different inclination angles are continuous, etc. In any case, the thickness of each band-shaped pattern of the color conversion phosphor layer 5 increases toward the outer side in the length direction. Any sloping portion that decreases can be used.

A transparent protective layer 7 is provided on the transparent substrate 2 so as to cover the inclined portion 6 and the color conversion phosphor layer 5 as described above,
An auxiliary electrode 8 and a transparent electrode layer 9 are formed on this transparent protective layer 7. FIG. 5 is a partial plan view showing a state in which the auxiliary electrode 8 and the transparent electrode layer 9 are thus formed on the transparent protective layer 7. As shown in FIG. 5, the auxiliary electrode 8
The transparent electrode layer 9 and the transparent electrode layer 9 are arranged in a band shape on the transparent protective layer 7 from the peripheral terminal portion to the central pixel area, and the transparent base material 2 is provided at the portion where the inclined portion 6 (the portion shaded with a chain line) exists.
The color conversion phosphor layer 5 (pixel region) runs over the (peripheral terminal portion).

In the organic EL image display device 1 of the present invention, the strip-shaped blue organic material is formed so as to intersect the strip-shaped transparent electrode layer 9 arranged as described above at a right angle and to be located on the opening of the black matrix 3. The EL element layer 10 and the back electrode layer 11 are formed on the transparent protective layer 7. In addition, the partition wall portion 15 is interposed via the insulating layer 13 so as to intersect the strip-shaped transparent electrode layer 9 at a right angle and to be located on the light shielding portion of the black matrix 3.
Are formed on the transparent protective layer 7. A dummy organic EL element layer 10 ′ and a back electrode layer 11 ′ are formed on the upper plane of the partition wall portion 15. These are the blue organic EL element layer 1 using the partition wall portion 15 as a patterning means.
0 and the back electrode layer 11 are formed as a result of removing the forming material by adhering it to the partition 15 so as not to reach the transparent electrode layer 9 in order to form a strip-shaped pattern. In the illustrated example, the insulating layer 13 is provided in a stripe shape only in the portion where the partition 15 is formed, but the present invention is not limited to this, and the transparent electrode layer 9 and the back electrode layer 11 are blue organic EL. The insulating layer 13 may be a lattice-shaped pattern having openings at respective portions (picture elements) intersecting with each other through the element layer 10.

In the organic EL image display device 1 of the present invention as described above, the blue light emitted from the blue organic EL element layer 10 is converted into red fluorescence by the red conversion phosphor layer 5R and the green conversion phosphor layer. The light is made green in 5G, and the blue light is transmitted through the blue conversion dummy layer 5B as it is. After that, the light of each color is color-corrected by the color filter layer 4 to display the three primary colors. Then, the stepped portion at the end portion of the color conversion phosphor layer 5 is alleviated by the inclined portion 6, and the step formed on the transparent protective layer 7 formed so as to cover the inclined portion 6 and the color conversion phosphor layer 5 is small. Has become. Therefore, the transparent protective layer 7
The strip-shaped transparent electrode layer 9 formed on the transparent base material 2 is
Since there is no disconnection at the step portion that rides on the color conversion phosphor layer 5, it is possible to display a high-quality image with high reliability.

Although the constituent layers such as the color filter 4 are provided through the black matrix 3 in the above-described embodiment, the black matrix 3 may not be provided. The color conversion phosphor layer 5 includes a red conversion phosphor layer 5R and a green conversion phosphor layer 5G that convert blue light emitted from the blue organic EL element layer 10 into red fluorescence and green fluorescence.
However, the present invention is not limited to this, as long as it includes a color conversion phosphor layer capable of converting into fluorescence having a wavelength longer than the emission (blue) wavelength. Then, by setting the combination with the color filter layer 4 that enhances the color purity by color-correcting the light of each color from the color conversion phosphor layer 5, it is possible to display the three primary colors.

Next, each component of the organic EL image display device 1 of the present invention will be described. Organic EL image display device 1
As the transparent base material 2 constituting the above, it is possible to use a material made of a glass material having a light transmitting property, a resin material, or a composite material thereof. The thickness of the transparent substrate 2 can be set in consideration of the material, the usage status of the image display device, and the like, and can be set to, for example, about 0.2 to 2.0 mm. Further, the color filter layer 4 corrects the light of each color from the color conversion phosphor layer 5 to enhance the color purity. Blue colored layer 4B and red colored layer 4 which compose the color filter layer 4.
The R and green colored layers 4G are made of appropriate materials according to the characteristics of blue light emission from the blue organic EL element layer 10, red fluorescence from the red conversion phosphor layer 5R, and green fluorescence from the green conversion phosphor layer 5G. It can be formed selectively, and for example, it can be formed using a resin composition prepared by dispersing one or more kinds of pigments such as azo, phthalocyanine and anthraquinone pigments in a photosensitive resin.

Among the color conversion phosphor layers 5 constituting the organic EL image display device 1, the red conversion phosphor layer 5R and the green conversion phosphor layer 5G are layers containing a fluorescent dye in the resin. Red conversion phosphor layer 5 for converting blue light emission into red fluorescence
The fluorescent dye used for R is 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl)-
Cyanine dye such as 4H-pyran, 1-ethyl-2-
Examples include pyridine dyes such as [4- (p-dimethylaminophenyl) -1,3-butadienyl] -pyridinium-perchlorate, rhodamine dyes such as rhodamine B and rhodamine 6G, and oxazine dyes. Further, as the fluorescent dye used for the green conversion phosphor layer 5G for converting blue light emission into green fluorescence, 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolizino (9,
9a, 1-gh) coumarin, 3- (2'-benzothiazolyl) -7-diethylaminocoumarin, 3- (2'-benzimidazolyl) -7-N, N-diethylaminocoumarin and other coumarin dyes, Basic Yellow 51 and the like. Examples thereof include coumarin dye-based dyes and naphthalimide dyes such as Solvent Yellow 11 and Solvent Yellow 116. Further, various dyes such as direct dyes, acid dyes, basic dyes and disperse dyes can also be used if they have fluorescence. The above-mentioned fluorescent dyes can be used alone or in combination of two or more. The content of the fluorescent dye in the red conversion phosphor layer 5R and the green conversion phosphor layer 5G can be appropriately set in consideration of the fluorescent dye to be used, the resin, the thickness of the color conversion phosphor layer, and the like. It can be about 0.1 to 10% by weight with respect to the resin used.

The blue conversion dummy layer 5B transmits the blue light emitted from the blue organic EL element layer 10 as it is and sends it to the color filter layer 4, and the red conversion phosphor layer 5R and the green conversion phosphor. It can be a transparent resin layer having almost the same thickness as the layer 5G. Resins used for forming the red conversion phosphor layer 5R, the green conversion phosphor layer 5G, and the blue conversion dummy layer 5B include polymethylmethacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethylcellulose, carboxymethylcellulose. Transparent resins (visible light transmittance of 50% or more) such as polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin and polyamide resin can be used. In particular, by using a photocurable resist resin having a reactive vinyl group such as an acrylic acid type, a methacrylic acid type, a polyvinyl cinnamate type, or a ring rubber type, the color conversion phosphor layer 5
It is possible to collectively form the pattern and the inclined portion by the photolithography method.

The inclined portion 6 constituting the organic EL image display device 1 is formed at the end portion 5a of each band-shaped pattern of the color conversion phosphor layer 5, and is formed integrally with the color conversion phosphor layer 5 described above. Has been done. Therefore, the inclined portion 6G is formed of the same material as the green conversion phosphor layer 5G at the end of the green conversion phosphor layer 5G, and the same material as the red conversion phosphor layer 5R is formed at the end of the red conversion phosphor layer 5R. Thus, the inclined portion 6R is formed, and the inclined portion 6B is formed at the end portion of the blue conversion dummy layer 5B with the same material as that of the blue conversion dummy layer 5B. In the illustrated example, the inclined portion 6
Is provided on the color filter layer 4, but is not limited to this. For example, a black color filter layer 4 does not exist depending on the pattern of the color filter layer 4, the formation region of the black matrix 3, and the like. It may be provided on the matrix 3, or a part of the inclined portion 6 may be provided on the transparent base material 2, or the entire inclined portion 6 may be provided on the transparent base material 2. Good.

The transparent protective layer 7 which constitutes the organic EL image display device 1 is a blue organic EL element layer by blocking gases such as water vapor, oxygen, organic monomers and low molecular components generated from the color conversion phosphor layer 5 and the like. When the step (surface irregularities) is present due to the protective function of preventing 10 from being deteriorated and the structure of the color conversion phosphor layer 5 and below, the step is eliminated to achieve flatness, and the blue organic EL element layer 10 It has a flattening action to prevent the occurrence of uneven thickness. Such a transparent protective layer 7
Can be formed of a transparent (visible light transmittance of 50% or more) resin. Specifically, an acrylate-based or methacrylate-based photocurable resin or thermosetting resin having a reactive vinyl group can be used. Further, as the transparent resin, polymethylmethacrylate, polyacrylate,
Polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin,
Polyamide resin or the like can be used. The transparent protective layer 7 has a smaller film thickness within a range where the above protective action and flattening action can be exhibited, in order to prevent light leakage due to a gap between the blue organic EL element layer 10 and the color conversion phosphor layer 5. Preferably, it can be in the range of 0.5 to 10 μm, for example.

In the present invention, it is preferable to provide an inorganic oxide film as an insulating transparent barrier layer on the transparent protective layer 7. This inorganic oxide film is composed of silicon oxide, aluminum oxide, titanium oxide, yttrium oxide, germanium oxide, zinc oxide, magnesium oxide, calcium oxide,
It can be formed by using one or more oxides such as boron oxide, strontium oxide, barium oxide, lead oxide, zirconium oxide, sodium oxide, lithium oxide and potassium oxide, and particularly silicon oxide, aluminum oxide, Titanium oxide can be preferably used. The thickness of the inorganic oxide film is 0.01 to 0.01 in consideration of the barrier property and the transparency.
It can be appropriately set within the range of 200 μm. Such an inorganic oxide film may have a multilayer structure of two or more layers, or may contain a nitride such as silicon nitride as an accessory component.

A metal material is generally used for the auxiliary electrode 8 constituting the organic EL image display device 1, and gold, silver, copper,
Examples thereof include magnesium alloys (MgAg and the like), aluminum alloys (AlLi, AlCa, AlMg and the like), metallic calcium and the like. Such an auxiliary electrode 8 is arranged so as to be located on the light shielding portion of the black matrix 3 from the peripheral terminal portion to the central pixel area.

As a material of the transparent electrode layer 9 constituting the organic EL image display device 1, a metal, an alloy, or a mixture thereof having a high work function (4 eV or more) can be used. For example, indium tin oxide (ITO). ), Indium oxide, zinc oxide, stannic oxide, and the like. The transparent electrode layer 9 is arranged in a strip shape so as to be located on the opening portion of the black matrix 3 and on the auxiliary electrode 8 from the peripheral terminal portion to the central pixel area. The sheet resistance of such a transparent electrode layer 9 is preferably several hundreds Ω / □ or less, and the thickness of the transparent electrode layer 9 is, for example, 10 nm to 1 μm, preferably 1 although it depends on the material.
It can be about 0 to 200 nm.

The blue organic EL element layer 10 constituting the organic EL image display device 1 has a structure consisting of a light emitting layer alone, a structure in which a hole injection layer is provided on the transparent electrode layer 9 side of the light emitting layer, and a back electrode of the light emitting layer. For example, an electron injection layer may be provided on the layer 11 side, a hole injection layer may be provided on the transparent electrode layer 9 side of the light emitting layer, and an electron injection layer may be provided on the back electrode layer 11 side. The light emitting layer forming the blue organic EL element layer 10 also has the following functions. -Injection function: A function that can inject holes from the anode or the hole injection layer when an electric field is applied, and can inject electrons from the cathode or the electron injection layer-Transport function: Injected charges (electrons and holes) Function of moving electrons by the force of an electric field, light emitting function: a function of providing a field for recombination of electrons and holes and connecting this to light emission

Examples of the material of the light emitting layer having such a function include fluorescent brightening agents such as benzothiazole type, benzimidazole type and benzoxazole type disclosed in JP-A-8-279394, and metal chelates. Oxynoid compounds, styrylbenzene compounds, distyrylpyrazine derivatives, aromatic dimethylidene compounds, and the like.

Specifically, a benzothiazole system such as 2-2 '-(p-phenylenedivinylene) -bishenzothiazole; 2- [2- [4- (2-benzimidazolyl) phenyl] vinyl] benzimidazole, 2- [2
-(4-Carboxyphenyl) vinyl] benzimidazole-based compounds such as benzimidazole;
7-di-t-pentyl-2-benzoxazolyl)-
1,3,4-thiadiazole, 4,4'-bis (5,7
Examples of optical brighteners such as benzoxazole-based compounds such as -t-pentyl-2-benzoxazolyl) stilbene and 2- [2- (4-chlorophenyl) vinyl] naphtho [1,2-d] oxazole. it can. Further, as the above-mentioned metal chelated oxinoid compound, tris (8
Examples thereof include 8-hydroxyquinoline-based metal complexes such as -quinolinol) aluminum, bis (8-quinolinol) magnesium, and bis (benzo [f] -8-quinolinol) zinc, and dilithium epinetridione.

As the styrylbenzene compound, 1,4-bis (2-methylstyryl) benzene, 1,4-bis (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-
Examples thereof include ethylbenzene. Further, as the above-mentioned distyrylpyrazine derivative, 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.

The aromatic dimethylidyne compounds mentioned above include 1,4-phenylenedimethylidin, 4,
4-phenylene dimethylidene, 2,5-xylylene dimechilidene, 2,6-naphthylene dimechilidene, 1,
4-biphenylene dimethylidene, 1,4-p-terephenylene dimethylidene, 9,10-anthracenediylzilmethylidyne, 4,4'-bis (2,2-di-t
-Butylphenylvinyl) biphenyl, 4,4'-bis (2,2-diphenylvinyl) biphenyl and the like, and derivatives thereof.

Further, as a material for the light emitting layer, there is disclosed in
The general formula (Rs-
Q) The compound represented by 2-AL-OL can also be mentioned (wherein AL is a carbon atom 6 containing a benzene ring).
~ 24 hydrocarbons, OL is a phenylate ligand, Q is a substituted 8-quinolinolate ligand,
Rs represents an 8-quinolinolate substituent selected to sterically hinder the attachment of two or more substituted 8-quinolinolate ligands to the aluminum atom). In particular,
Bis (2-methyl-8-quinolinolato) (para-phenylphenolato) aluminum (III), bis (2-
Methyl-8-quinolinolate) (1-naphtholato) aluminum (III) and the like. The thickness of the light emitting layer is not particularly limited and may be, for example, about 5 nm to 5 μm.

The material of the hole injecting layer is any of those conventionally used as a hole injecting material of a photoconductive material and known materials used for a hole injecting layer of an organic EL element. Can be selected and used. The material of the hole injection layer has either hole injection or electron barrier properties, and may be either an organic substance or an inorganic substance. Specifically, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives,
Styrylanthracene derivative, fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative,
Examples thereof include polysilane-based and aniline-based copolymers and dielectric polymer oligomers such as thiophene oligomers.

Further, as the material of the hole injection layer, a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound can be mentioned. Examples of the porphyrin compound include polyfin, 1,10,15,20-
Tetraphenyl-21H, 23H-polyfin copper (I
I), aluminum phthalocyanine chloride, copper octamethylphthalocyanine and the like. Also,
Examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,
4'-diaminophenyl, N, N'-diphenyl-N,
N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine, 4- (di-p-tolylamino) -4 '-[4 (di-p-tolylamino) styryl ] Stilbene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, 4,4′-bis [N- (1
-Naphthyl) -N-phenylamino] biphenyl, 4,
4 ', 4 "-tris [N- (3-methylphenyl) -N
-Phenylamino] triphenylamine and the like can be mentioned. The thickness of the hole injection layer is not particularly limited and may be, for example, about 5 nm to 5 μm.

The material for the electron injecting layer may be any one having a function of transmitting the electrons injected from the cathode to the light emitting layer, and any material can be selected from conventionally known compounds. Can be used. Specifically, a nitro-substituted fluorene derivative, an anthraquinodimethane derivative, a diphenylquinone derivative, a thiopyran dioxide derivative, a heterocyclic tetracarboxylic acid anhydride such as naphthalene perylene, a carbodiimide, a fluorenylidene methane derivative, an anthraquinodimethane. And anthrone derivative, oxadiazole derivative, thiazole derivative in which oxygen atom of the above oxadiazole ring is substituted with sulfur atom, quinoxaline derivative having quinoxaline ring known as electron withdrawing group, tris (8-quinolinol)
A metal complex of an 8-quinolinol derivative such as aluminum,
Examples thereof include phthalocyanine, metal phthalocyanine, and distyrylpyrazine derivatives. The thickness of the electron injection layer is not particularly limited and may be, for example, about 5 nm to 5 μm.

The material of the back electrode layer 11 constituting the organic EL image display device 1 is formed of a metal, an alloy or a mixture thereof having a low work function (4 eV or less). Specifically, sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture,
Examples thereof include a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium, a lithium / aluminum mixture, a rare earth metal and the like.
Considering the electron injecting property and the durability against oxidation etc. as an electrode, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value is preferable, for example, a magnesium / silver mixture. ,magnesium/
Examples thereof include an aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture and the like. The sheet resistance of the back electrode layer 11 is preferably several hundreds Ω / □ or less, and therefore, the thickness of the back electrode layer 11 can be set to, for example, 10 nm to 1 μm, preferably about 50 to 200 nm.

The insulating layer 13 constituting the organic EL image display device 1 is formed so as to be located on the light shielding portion of the black matrix 3. The insulating layer 13 can be formed using, for example, the same photosensitive resin as the above-mentioned transparent protective layer 7 and a photosensitive resin such as a polyimide resin, and has a thickness of about 0.3 to 2.0 μm. be able to.

In the manufacturing method of the present invention to be described later, the partition wall portion 15 which constitutes the organic EL image display device 1 has a blue organic EL element layer 10 and a back electrode layer 11 which intersect the strip-shaped transparent electrode layer 9 at a right angle. It is a partition pattern for forming and in a strip shape. The partition 15 is formed by a photolithography method using a photosensitive resin similar to that of the transparent protective layer 7 described above or a photosensitive resin obtained by adding a dye, a pigment, carbon black or the like to the photosensitive resin. The height of the partition wall portion 15 can be set to about 2.0 to 10.0 μm, and the width can be set according to the width of the light shielding portion of the black matrix 3, etc., and is usually set to about 10 to 100 μm. You can

Organic electroluminescent image display device
Next, the organic electroluminescent (EL) of the present invention is manufactured.
An embodiment of a method for manufacturing an image display device is the above-mentioned organic E
The L image display device 1 will be described as an example with reference to the drawings. (1) In the first step of the manufacturing method of the present invention, as shown in FIG. 6, the color filter layer 4 is formed on the transparent substrate 2 via the black matrix 3. In addition, in FIG. 6, in order to show the state of the black matrix 3, a part of the red colored layer 4R is cut away. The black matrix 3 has a predetermined pattern and has openings 3a and light-shielding portions 3.
b. Such a black matrix 3
Has a thickness of 100 by a sputtering method, a vacuum deposition method, or the like.
A thin metal film of chromium or the like having a thickness of 0 to 2000 Å or a thin metal oxide film of chromium oxide or the like, which is formed by patterning this thin film, a polyimide resin containing light shielding particles such as carbon fine particles, and acrylic. A resin layer such as a resin or an epoxy resin is formed, and the resin layer is patterned to form a photosensitive resin layer containing light shielding particles such as carbon fine particles and metal oxides. It may be any one such as one formed by patterning a layer.

In the color filter layer 4, the red coloring layer 4R, the green coloring layer 4G, and the blue coloring layer 4B are arranged in a strip shape so as to cover the openings 3a of the black matrix 3, respectively. It can be formed by a pigment dispersion method using the contained photosensitive resin, and further can be formed by a known method such as a printing method, an electrodeposition method or a transfer method. The thickness of such a color filter layer 4 can be appropriately set according to the material of each colored layer, the fluorescence emitted from the color conversion phosphor layer 5, and the like.
It can be set in the range of about 1.0 to 2.0 μm.

(2) In the next step of the manufacturing method of the present invention, the band-shaped red conversion phosphor layer 5 is formed on the color filter layer 4.
In addition to forming the color conversion phosphor layer 5 including the R, green conversion phosphor layer 5G and the blue conversion dummy layer 5B, as shown in FIG.
As shown in FIG. 5, the end portion 5a of each strip-shaped pattern of the color conversion phosphor layer 5 is formed by forming an inclined portion whose thickness decreases toward the outside in the pattern length direction (direction of arrow a in FIG. 4). The part 6 is integrally formed. In the formation of the color conversion phosphor layer 5, the red conversion phosphor layer 5R is arranged on the red coloring layer 4R, the green conversion phosphor layer 5G is arranged on the green coloring layer 4G, and the blue conversion dummy layer 5B is formed. It is arranged on the blue colored layer 4B. The red conversion phosphor layer 5R and the green conversion phosphor layer 5G constituting the color conversion phosphor layer 5 are spin-coated, roll-coated, cast with a coating liquid in which a fluorescent dye and a photocurable resin are dispersed or solubilized. A red conversion phosphor layer 5R or a green conversion phosphor layer is formed by coating by a method such as coating to form a film, patterning the same by a photolithography method, pattern printing the above coating solution by a screen printing method, or the like. 5G can be formed. Also,
The blue conversion dummy layer 5B is formed by applying a desired photosensitive resin coating material by a method such as spin coating, roll coating, or cast coating to form a film, and patterning it by a photolithography method. It can be formed by a pattern printing method such as a printing method.

Simultaneously with the formation of the color conversion phosphor layer 5 as described above, an inclined portion whose thickness decreases toward the outer side in the pattern length direction is integrally formed at the end of each strip-shaped pattern of the color conversion phosphor layer 5. Form. That is, first, a photocurable resist resin is coated with a coating solution for a color conversion phosphor layer containing a fluorescent dye by a method such as spin coating, roll coating, or cast coating to form a photosensitive film. Next, the above-mentioned photosensitive film is exposed using a photomask having a band-shaped opening for the color conversion phosphor layer and a half-exposed region adjacent to the band-shaped opening. As a result, the portion exposed through the half-exposed portion of the photomask is in a semi-cured state, and by the subsequent development, the inclined portion is formed integrally with the band-shaped color conversion phosphor layer. The half-exposure part of the above photomask has a plurality of fine holes each having an opening diameter equal to or smaller than the resolving power, a semi-transmissive film capable of obtaining a desired amount of transmitted light, and the exposure light by roughening the surface of the photomask. Can be used for diffusing.

Further, by using a screen printing plate provided with a screen pattern adjacent to the band-shaped screen pattern for the color conversion phosphor layer so that the ink amount is small, the band-shaped color conversion is performed by the screen printing method. It is also possible to form the inclined portion integrally with the phosphor layer. As described above, the sloped portion 6G is integrally formed at the end of the green conversion phosphor layer 5G, and the sloped portion 6R is integrally formed at the end of the red conversion phosphor layer 5R, and the blue conversion dummy layer is formed. The inclined portion 6B can be integrally formed at the end of 5B.

(3) In the next step of the manufacturing method of the present invention, the transparent protective layer 7 is formed on the transparent substrate 2 so as to cover the color conversion phosphor layer 5 and the inclined portion 6. This transparent protective layer 7 is formed by spin coating, roll coating,
The film is applied by a method such as cast coating to form a film, and the photocurable resin is thermally cured after being irradiated with ultraviolet light as needed, and the thermosetting resin is cured as it is after the film is formed. As described above, since the step at the end of each band-shaped pattern of the color conversion phosphor layer 5 is mitigated by the inclined portion 6, the step at the transparent protective layer 7 at the portion where the inclined portion 6 is formed is small. Will be things.

(4) In the next step of the manufacturing method of the present invention, the transparent protective layer 7 is assisted so that the transparent base material 2 rides on the color conversion phosphor layer 5 at the portion where the inclined portion 6 is formed. The electrode 8 and the transparent electrode layer 9 are formed (see FIG. 5 above). The auxiliary electrode 8 and the transparent electrode layer 9 can be formed into a desired shape by forming a thin film using the above materials by a vacuum deposition method or a sputtering method and performing pattern etching using the photolithography method. As described above, since the stepped portion of the transparent protective layer 7 is small due to the inclined portion 6, film formation failure (material adhesion failure at the stepped portion) during formation of the auxiliary electrode 8 and the transparent electrode layer 9, and It is possible to prevent the occurrence of disconnection due to stress or the like during pattern etching. Therefore, the organic EL image display device having high reliability and capable of displaying high-quality images can be manufactured with a good manufacturing yield.

(5) In the next step of the manufacturing method of the present invention, first, the striped insulating layer 13 is formed so as to intersect the strip-shaped transparent electrode layer 9 at a right angle and to be located on the light-shielding portion of the black matrix 3. Then, the barrier section 15 is formed on the insulating layer 13. Then, the blue organic EL element layer 10 is formed in a band shape so as to intersect with the transparent electrode layer 9, and the back electrode layer 11 is formed on the blue organic EL element layer 10. The insulating layer 13 is formed by vacuum vapor deposition using the insulating material described above.
A thin film can be formed by a sputtering method or the like, and this can be formed into a desired shape by pattern etching using a photolithography method. The barrier portion 15 is a partition pattern for forming the blue organic EL element layer 10 and the back electrode layer 11 in a strip shape, and the photosensitive resin material is spin-coated, roll-coated, cast-coated, or the like. It can be formed by applying and forming a film, and patterning this by a photolithography method. The barrier portion 15 thus formed is located on the light shielding portion of the black matrix 3. Therefore, the transparent electrode layer 9 located in the opening 3a of the black matrix 3 is exposed without the barrier 15 being formed.

The formation of the blue organic EL element layer 10 is
A film can be formed using the above-described light emitting layer material by a vacuum deposition method, a printing method such as an inkjet method, or the like.
In this method, the film is formed through a photomask (a mask for preventing film formation on the electrode terminals formed of the auxiliary electrode 8 and the transparent electrode layer 9 in the peripheral portion) having an opening corresponding to the image display region. As a result, the partition portions 15 serve as a mask pattern, and the light emitting layer material can pass through only between the partition portions 15 and reach the transparent electrode layer 9. As a result, without performing patterning such as photolithography,
The belt-shaped blue organic EL element layer 10 can be formed. In the formation of the blue organic EL element layer 10 using the partition wall portion 15 as described above, as shown in FIG. 1 and FIG.
Of the plurality of barrier portions 15 arranged, the end portion of the image display area is located on the upper plane of the partition wall portion 15 located at the most peripheral portion, and approximately half the width direction (image display area The dummy organic EL element layer 10 'is formed only on the side).

The structure in which the blue organic EL element layer 10 is not composed of the light emitting layer alone, but has a structure in which a hole injection layer is provided on the transparent electrode layer 9 side of the light emitting layer, and electrons are injected on the back electrode layer 11 side of the light emitting layer In the case of a structure including a layer, a structure including a hole injection layer on the transparent electrode layer 9 side of the light emitting layer and an electron injection layer on the back electrode layer 11 side, the above-described hole injection layer material and electron injection layer, respectively. By using the material to form a film by a vacuum deposition method, a printing method such as an inkjet method, or the like, it is possible to form a strip-shaped pattern, similarly to the above light emitting layer. Further, the back electrode layer 11 is formed by the vacuum evaporation method using the above-mentioned electrode material,
It can be formed by forming a film by a method such as a sputtering method. Also here, the partition portions 15 serve as a mask pattern, and the electrode material can pass through only between the partition portions 15 and reach the blue organic EL element layer 10. Since it is not necessary to perform patterning such as photolithography, the characteristics of the blue organic EL element layer 10 are not deteriorated.

[0048]

EXAMPLES Next, the present invention will be described in more detail by showing examples. [Example]

Formation of Black Matrix As a transparent substrate, 550 mm × 650 mm, thickness 0.7
mm soda glass (Soda glass with SiO ₂ manufactured by Asahi Glass Co., Ltd.) was prepared. After cleaning this transparent substrate according to a standard method, a chromium thin film (thickness: 0.2 μm) is formed on one entire surface of the transparent substrate by a sputtering method, a photosensitive resist is applied on the chromium thin film, mask exposure,
Develop and etch chrome thin film, 70μm × 2
A black matrix having 70 μm rectangular openings at a 100 μm pitch in a matrix was formed.

Formation of Color Filter Layer Next, three types of photosensitive coatings for colored layers having the following compositions were used to form colored layers of respective colors. That is, a photosensitive coating material for the green colored layer was applied to the entire surface of the transparent substrate on which the black matrix had been formed by spin coating, and prebaking (100 ° C., 5 minutes) was performed. Then, it exposed using the photomask for predetermined coloring layers. Next, development is performed with a developing solution (0.05% KOH aqueous solution), and then,
Post-baking (200 ° C., 60 minutes) was performed to form a strip-shaped (width 80 μm) green colored layer (thickness 2.0 μm) at a predetermined position with respect to the black matrix pattern.

Similarly, a strip-shaped (width 80 μm) red color layer (thickness 2.0 μm) was formed at a predetermined position with respect to the black matrix pattern using the photosensitive coating material for the red color layer.
Was formed. Further, using a photosensitive coating material for the blue colored layer, a band-shaped (width 80 μm) blue colored layer (thickness 2.0 μm) was formed at a predetermined position with respect to the black matrix pattern.
Was formed. (Red colored layer photosensitive coating) Dianthraquinonyl red (Red-177) 1 part by weight Methyl methacrylate-methacrylic acid copolymer 8 parts by weight (methyl methacrylate: methacrylic acid = 2: 1) agent ... 1 part by weight (manufactured by Ciba Specialty Chemicals Co., Ltd. Irgacure 907) diglyme [Bis (2-methoxyethyl) Ether ] ... 90 parts by weight _{(CH 3 OCH 2 CH 2)} 2 O

(Photosensitive coating for green colored layer) Phthalocyanine green (Green-7) 1 part by weight Methyl methacrylate-methacrylic acid copolymer 8 parts by weight (methyl methacrylate: methacrylic acid = 2: 1) Photopolymerization initiator ... 1 part by weight (manufactured by Ciba Specialty Chemicals Co., Ltd. Irgacure 907) diglyme [Bis (2-methoxyethyl) Ether ] ... 90 parts by weight _{(CH 3 OCH 2 CH 2)} 2 O

(Photosensitive coating for blue colored layer) Phthalocyanine blue (α) (Blue-15: 1) 1 part by weight Methyl methacrylate-methacrylic acid copolymer 8 parts by weight (methyl methacrylate: methacrylic acid = 2: 1) photopolymerization initiator ... 1 part by weight (manufactured by Ciba Specialty Chemicals Corp. Irgacure 907) diglyme [Bis (2-methoxyethyl) Ether ] ... 90 parts by weight _{(CH 3 OCH 2 CH 2)} 2 O

Formation of Color Converting Phosphor Layer and Inclined Part Next, a photosensitive blue converting dummy layer coating liquid having the following composition,
A coating liquid for a green conversion phosphor layer and a coating liquid for a red conversion phosphor layer were prepared. Then, the blue conversion dummy layer coating liquid is applied to the entire surface of the transparent base material on which the color filter layer is formed by a spin coating method to perform prebaking (100
(° C, 5 minutes). Then, exposure was performed using a predetermined color conversion phosphor layer photomask. As the photomask for the color conversion phosphor layer, a band-shaped opening (width 80 μm) for the color conversion phosphor layer and a half-exposed region (a fine hole having an opening diameter of 5 μm with a density of 30,000) is adjacent to the tip of the band-shaped opening. / Mm ² and a plurality of 80 μm × 100 μm rectangular portions) were provided. Next, development was performed with a developing solution (0.05% KOH aqueous solution), and post baking (200 ° C., 60 minutes) was performed. As a result, a band-shaped (width 80 μm) blue conversion dummy layer (thickness 15 μm) is formed on the blue colored layer, and an inclined portion whose thickness decreases outward in the pattern length direction is formed at the end of this blue conversion dummy layer. did. This inclined portion has an angle of about 9 with respect to the transparent substrate.
It was provided with an inclined surface having a substantially flat shape of °.

Then, the green conversion phosphor layer coating solution was applied by spin coating and prebaked (100 ° C., 5 minutes). It exposed using the said photomask for color conversion fluorescent substance layers, developed with a developing solution (0.05% KOH aqueous solution), and post-baked (200 degreeC, 60 minutes). As a result, a strip (width 80 μm) is formed on the green colored layer.
Of the green conversion phosphor layer (thickness: 15 μm) was formed, and an inclined portion whose thickness was reduced outward in the pattern length direction was formed at the end of this green conversion phosphor layer. The inclined portion was provided with a substantially plane-shaped inclined surface having an angle of about 9 ° with respect to the transparent substrate.

Similarly, a band-shaped (width 80 μm) red conversion phosphor layer (thickness 15 μm) was formed on the red colored layer using the coating liquid for red conversion phosphor layer, and the edge of this red conversion phosphor layer was formed. In the portion, an inclined portion having a reduced thickness is formed outside in the pattern length direction. The inclined portion was provided with a substantially plane-shaped inclined surface having an angle of about 9 ° with respect to the transparent substrate. As described above, the color conversion phosphor layer including the blue conversion dummy layer, the green conversion phosphor layer, and the red conversion phosphor layer, each of which has the end portion having the inclined shape, was formed. (Coating liquid for blue conversion dummy layer) -Methyl methacrylate-methacrylic acid copolymer: 19 parts by weight (methyl methacrylate: methacrylic acid = 2: 1) -Photopolymerization initiator: 1 part by weight (Ciba Specialty Chemicals Co., Ltd. ) Irgacure 907) diglyme [Bis (2-methoxyethyl) Ether ] ... 80 parts by weight _{(CH 3 OCH 2 CH 2)} 2 O

(Coating Liquid for Green Conversion Phosphor Layer) Basic Yellow 51 1 Part by Weight Methyl Methacrylate-Methacrylic Acid Copolymer 18 Parts by Weight (Methyl Methacrylate: Methacrylic Acid = 2: 1) Photoinitiator 1 part by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.)-Diglyme [Bis (2-methoxyethyl) Ether] 80 parts by weight (CH ₃ OCH ₂ CH ₂ ) ₂ O

(Red-Conversion Phosphor Layer Coating Solution) Rhodamine B 1 part by weight Methyl methacrylate-methacrylic acid copolymer 18 parts by weight (methyl methacrylate: methacrylic acid = 2: 1) Photoinitiator ... 1 part by weight (manufactured by Ciba Specialty Chemicals Co., Ltd. Irgacure 907) diglyme [Bis (2-methoxyethyl) Ether ] ... 80 parts by weight _{(CH 3 OCH 2 CH 2)} 2 O

Formation of Transparent Protective Layer Next, a transparent protective layer coating solution having the following composition was used and applied on a transparent substrate by spin coating, followed by baking (2).
Was carried out at 00 ° C. for 60 minutes). Thereby, the transparent protective layer (thickness 10) is formed so as to cover the color conversion phosphor layer and the inclined portion.
μm) was formed. Next, a silicon oxide film (thickness 0.2 μm) was formed on the transparent protective layer by a sputtering method. (Coating liquid for transparent protective layer) Methyl methacrylate-methacrylic acid copolymer 18 parts by weight (methyl methacrylate: methacrylic acid = 2: 1) Photoinitiator 2 parts by weight (Ciba Specialty Chemicals Co., Ltd.) Irgacure 907) ・ Diglyme [Bis (2-methoxyethyl) Ether] ... 80 parts by weight (CH ₃ OCH ₂ CH ₂ ) ₂ O

Formation of Auxiliary Electrode Next, an aluminum thin film (thickness: 0.2 μm) is formed on the entire surface of the transparent protective layer by a sputtering method, a photosensitive resist is applied on the aluminum thin film, mask exposure and development are performed. The aluminum thin film was etched to form an auxiliary electrode. This auxiliary electrode has a striped pattern in which the above-mentioned inclined portion is present, and it rides from the transparent base material onto the color conversion phosphor layer. On the color conversion phosphor layer, the width is 15 μm and the black matrix is formed. The width of the terminal portion at the peripheral portion of the transparent substrate located on the light shielding portion was 80 μm.

Formation of transparent electrode layer Next, an indium tin oxide (ITO) electrode film having a film thickness of 200 nm is formed on the transparent protective layer by a sputtering method so as to cover the above-mentioned auxiliary electrode, and a photosensitive film is formed on the ITO electrode film. A resist was applied, mask exposure, development, and etching of the ITO electrode film were performed to form a transparent electrode layer. This transparent electrode layer is a strip-shaped pattern having a width of 80 μm that rides from the transparent base material onto the color conversion phosphor layer at the location where the above-mentioned inclined portion is present. It was located on each colored layer and overlapped with the auxiliary electrode. In the above-mentioned formation of the auxiliary electrode and the transparent electrode layer, since the step existing at the end of the color conversion phosphor layer is mitigated by the inclined portion, it is possible to prevent the auxiliary electrode and the transparent electrode layer from being formed on the transparent protective layer. Defects in film formation and disconnection due to stress during pattern etching did not occur.

Formation of Insulating Layer and Partition Section Next, an insulating layer coating material having the following composition was applied to the entire surface by a spin coating method so as to cover the transparent electrode layer and prebaked (100 ° C., 5 minutes). After that, exposure is performed by using a predetermined insulating layer photomask, and a developing solution (0.05
% KOH aqueous solution) and then post-baked (200 ° C., 60 minutes) to form an insulating layer (thickness 2 μm) on the transparent protective layer. This insulating layer has the same pattern as the black matrix, and is located on the light-shielding portion of the black matrix. (Insulating layer coating) -Methyl methacrylate-methacrylic acid copolymer ... 9 parts by weight (methyl methacrylate: methacrylic acid = 2: 1) -Photopolymerization initiator ... 1 part by weight (Ciba Specialty Chemicals Co., Ltd. Irgacure) 907) Diglyme [Bis (2-methoxyethyl) Ether] ... 90 parts by weight (CH ₃ OCH ₂ CH ₂ ) ₂ O

Next, a partition wall coating material having the following composition was applied on the entire surface by spin coating so as to cover the insulating layer, and prebaked (100 ° C., 5 minutes). After that, exposure is performed using a predetermined photomask for partition walls, and a developing solution (0.05
% KOH aqueous solution) and then post-baked (200 ° C., 60 minutes) to form partition walls on the insulating layer. The partition wall had a shape having a height of 5 μm, a lower (insulating layer side) width of 15 μm, and an upper width of 20 μm. (Paint for partition wall) ・ Carbon black 0.1 part by weight Methyl methacrylate-methacrylic acid copolymer 17.9 parts by weight (methyl methacrylate: methacrylic acid = 2: 1) Photoinitiator 2 parts by weight (manufactured by Ciba Specialty Chemicals Corp. Irgacure 907) diglyme [Bis (2-methoxyethyl) Ether ] ... 80 parts by weight _{(CH 3 OCH 2 CH 2)} 2 O

Formation of Blue Organic EL Element Layer Next, using the above partition wall as a mask, a blue organic E consisting of a hole injection layer, a light emitting layer and an electron injection layer is formed by a vacuum deposition method.
The L element layer was formed. That is, first, 4, 4 ', 4 "
-Tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine was evaporated to a thickness of 200 nm to form a film, and then 4,4'-bis [N- (1-naphthyl) -N- Phenylamino] biphenyl was vapor-deposited to a thickness of 20 nm to form a film, thereby forming a hole injection layer. Then, 4,4'-bis (2,2-diphenylvinyl) biphenyl was vapor-deposited to a thickness of 50 nm to form a film, thereby forming a light emitting layer. Then, tris (8-quinolinol) aluminum was vapor-deposited to a thickness of 20 nm to form an electron injection layer. Blue organic E formed in this way
The L element layer exists as a strip-shaped pattern having a width of 280 μm between the partition portions, and a dummy blue organic EL element layer was formed on the upper surface of the partition portion with the same layer configuration.

Formation of Back Electrode Layer Next, magnesium and silver are simultaneously vapor-deposited by a vacuum vapor deposition method using the above partition walls as a mask (magnesium vapor deposition rate = 1.3 to 1.4 nm / sec, silver vapor deposition rate = 0.1n
m / sec) to form a back electrode layer (thickness: 200 nm) made of a magnesium / silver mixture. The back electrode layer thus formed was present on the blue organic EL element layer as a belt-shaped pattern having a width of 280 μm, and a dummy back electrode layer was also formed on the upper surface of the partition.

The organic EL image display device was obtained as described above. By applying a voltage of 5 V DC to the transparent electrode layer and the back electrode layer of this organic EL image display device, the blue organic EL element layer at a desired portion where the transparent electrode layer and the back electrode layer intersect each other was caused to emit light. And color conversion with the color conversion phosphor layer,
Alternatively, the CIE chromaticity coordinates (JIS Z 8701) were measured for the luminescence of each color observed on the opposite surface side of the transparent substrate after being transmitted as it is and color-corrected by the color filter layer. As a result, x = 0.64 in CIE chromaticity coordinates,
Red light emission of y = 0.33, x = 0.3 in CIE chromaticity coordinates
0, green emission of y = 0.60, x = in CIE chromaticity coordinates
Blue emission of 0.15 and y = 0.06 was confirmed, and three-primary color image display was possible.

[Comparative Example] Similar to the example except that when the color conversion phosphor layer was formed, the inclined portion was not formed using the photomask having only the band-shaped opening for the color conversion phosphor layer. Then, formation of the transparent electrode layer was performed. However, at the stepped portion of the transparent protective layer caused by the end portion of the color conversion phosphor layer, film formation failure during the formation of the auxiliary electrode or the transparent electrode layer, and disconnection due to stress during pattern etching, etc. The rate of wire breakage was 204/5520. Then, a blue organic EL element layer and a back electrode layer were formed in the same manner as in the example to obtain an organic EL image display device. A voltage was applied to this organic EL image display device in the same manner as in the example, and the image display quality was observed. However, a defective light emission due to the occurrence of the above disconnection was observed, and a good three-primary-color image display was not obtained.

[0068]

As described above in detail, according to the present invention, the end portion of each band-shaped pattern of the color conversion phosphor layer has the inclined portion whose thickness decreases toward the outer side in the pattern length direction. The portion reduces the step at the end of the color conversion phosphor layer, and the step formed in the transparent protective layer formed so as to cover the inclined portion and the color conversion phosphor layer becomes small,
The strip-shaped transparent electrode layer formed on this transparent protective layer prevents the occurrence of disconnection due to film formation failure during formation or stress during etching processing, thereby providing a highly reliable and high-quality image. It is possible to manufacture an organic electroluminescent image display device capable of displaying with a good manufacturing yield.

[Brief description of drawings]

FIG. 1 is a partial plan view showing an embodiment of an organic electroluminescent image display device of the present invention.

FIG. 2 is a vertical sectional view taken along line II-II of the organic electroluminescent image display device shown in FIG.

FIG. 3 is a vertical sectional view taken along line III-III of the organic electroluminescent image display device shown in FIG.

FIG. 4 is a partial plan view showing the positional relationship between the inclined portion and the color conversion phosphor layer in the organic electroluminescent image display device of the present invention.

FIG. 5 is a partial plan view showing a positional relationship between an inclined portion and a transparent electrode layer in the organic electroluminescent image display device of the present invention.

FIG. 6 is a diagram illustrating the method of manufacturing the organic electroluminescent image display device of the present invention, and is a partial plan view showing the positional relationship between the black matrix and the color filter layer.

[Explanation of symbols]

1. Organic electroluminescent image display device 2 ... Transparent base material 3 ... Black matrix 4 ... Color filter layer 4R, 4G, 4B ... Colored layer 5 ... Color conversion phosphor layer 5R ... Red conversion phosphor layer 5G ... Green conversion phosphor layer 5B ... Blue conversion dummy layer 5'a ... Surface end of color conversion phosphor layer 6 (6R, 6G, 6B) ... Inclined part 6a ... Tip of inclined portion 7 ... Transparent protective layer 8 ... Auxiliary electrode 9 ... Transparent electrode layer 10 ... Organic electroluminescence element layer 11 ... Back electrode layer 13 ... Insulating layer 15 ... Partition wall

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Koji Arai             1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo             Dai Nippon Printing Co., Ltd. F term (reference) 3K007 AB04 AB08 AB11 AB18 BB06                       DB03 FA01

Claims (6)

[Claims] 1. A transparent substrate, a color filter layer, a color conversion phosphor layer, a transparent protective layer, which are sequentially provided on the transparent substrate,
At least a transparent electrode layer, an organic electroluminescence element layer, and a back electrode layer, the color conversion phosphor layer is a plurality of strip-shaped patterns are arranged in parallel, the end of each strip-shaped pattern outward in the pattern length direction. The transparent protective layer is provided on the transparent base material so as to cover the color conversion phosphor layer and the inclined portion, and the transparent electrode layer has the inclined portion. An organic electroluminescent image display device, characterized in that it is arranged on the transparent protective layer in a strip shape so as to ride on the color conversion phosphor layer from the transparent base material at the provided portion. 2. The straight line connecting the end of the surface of the color conversion phosphor layer and the end of the inclined portion forms an angle of 60 ° or less with respect to the surface of the transparent substrate. Item 1
The organic electroluminescent image display device described in 1. 3. The organic electroluminescent image display according to claim 1, further comprising a black matrix having a predetermined opening pattern between the transparent substrate and the color filter. apparatus. 4. The organic electroluminescence element layer emits blue light, and the color conversion phosphor layer converts a blue light into a green fluorescence to emit light, and a blue conversion light into a red fluorescence to emit light. The organic electroluminescent image display device according to any one of claims 1 to 3, further comprising: 5. A step of forming colored layers of a plurality of colors in a band shape for each color on a transparent substrate to provide a color filter layer, wherein the color conversion phosphor layer is formed in a band shape on the color filter layer and at the same time, A step of forming an inclined portion whose thickness decreases toward the outer side in the pattern length direction at the end of each band-shaped pattern of the conversion phosphor layer, on the transparent substrate so as to cover the color conversion phosphor layer and the inclined portion A step of forming a transparent protective layer on the transparent electrode layer, a step of forming a transparent electrode layer in a strip shape so as to ride on the color conversion phosphor layer from the transparent base material at a portion where the inclined portion is provided, A step of forming an organic electroluminescent element layer in a strip shape so as to intersect with each other, and forming a back electrode layer on the organic electroluminescent element layer, and an organic electroluminescent image display, Method of manufacturing location. 6. A color conversion phosphor layer forming material using a photocurable resist resin is applied on the color filter layer to form a photosensitive film, and a band-shaped opening for the color conversion phosphor layer is formed. Forming the inclined portion integrally with the strip-shaped color conversion phosphor layer by exposing and developing the photosensitive film through a photomask having a half-exposed portion adjacent to the strip-shaped opening. The method of manufacturing an organic electroluminescent image display device according to claim 5.