JP4802536B2 - Organic electroluminescent image display device - Google Patents

Description

  The present invention relates to an organic electroluminescent image display device.

Organic electroluminescence (EL) elements have advantages such as high visibility due to self-coloring, all-solid-state display unlike liquid crystal display, less influence of temperature change, and large viewing angle. In recent years, practical use as a pixel of an image display device has been advanced.
As an image display device using an organic EL element, for example, (1) display using a desired monochromatic light emitting organic EL element layer, (2) three primary color organic EL element layers are predetermined for each emission color. (3) Using a white light emitting organic EL element layer and displaying through three primary color filters, (4) Using a blue light emitting organic EL element layer and utilizing a fluorescent dye There has been proposed one that displays the three primary colors by installing the color conversion phosphor layer and converting blue light into green fluorescence or red fluorescence.

  As an example of such an organic EL image display device, as shown in FIG. 6, a color filter layer 44, a transparent smoothing layer 46, and a stripe-shaped transparent electrode layer 48 are laminated on a transparent substrate 42. On these laminates, a partition wall 55 extends in a direction orthogonal to the transparent electrode layer 48 via an insulating layer 53, and the organic EL element layer 50 is striped between the partition walls 55 (between the insulating layers 54). And the back electrode layer 51 are laminated. In this organic EL image display device, an organic EL element layer 50 and a back electrode layer 51 are formed using the partition wall 55 as a mask pattern. A dummy organic EL element layer 50 ′ and a back electrode layer 51 ′ are formed on the partition wall 55. Exists.

However, in the organic EL image display device having the above-described structure, among the external light incident from the transparent substrate 42 side, the light passes through the color filter layer 44, the transparent smoothing layer 46, and the transparent electrode layer 48, and further the insulating layer 53. The light transmitted through the partition wall 55 may be reflected by the dummy organic EL element layer 50 ′ and the back electrode layer 51 ′ existing on the partition wall 55. In this case, there is a problem that the reflected light is recognized together with the original image display light, and the contrast of the image is lowered.
In order to solve such a problem, an organic EL image display device is known in which a circularly polarizing plate is provided on the transparent substrate 42 to prevent transmission of the reflected light as described above.

However, the organic EL image display device including the circularly polarizing plate as described above has a problem in that light necessary for displaying an original image is shielded by about 60% by the circularly polarizing plate, and the luminance of the display image is lowered. .
The present invention has been made in view of such circumstances, and an object of the present invention is to provide an organic electroluminescent image display device that has high contrast and brightness and is capable of good image display.

In order to achieve such an object, the organic electroluminescent image display device of the present invention includes a pair of electrodes composed of a hole injection electrode and an electron injection electrode, and an organic electroluminescence element layer disposed between the electrodes. And at least one insulating layer arranged in a matrix in the non-light-emitting region, the insulating layer not containing an organic component and having at least one layer having an optical density OD value of 0.5 or more The structure is such that the volume resistivity is 10 ¹⁴ Ω · cm or more and the thickness is in the range of 0.2 to 1 μm .

As another aspect of the present invention, the insulating layer is formed by laminating two or more thin films made of a titanium-based black pigment that is any one of titanium nitride, titanium oxide, and titanium oxynitride , or The thin film made of the titanium black pigment and the insulating thin film were laminated .
As another aspect of the present invention, the insulating layer is composed of a three-layer thin film of silicon dioxide, titanium nitride, and silicon dioxide.

As another aspect of the present invention, a color filter layer is provided, and a color conversion phosphor layer is provided between the color filter layer and the electrode.
As another embodiment of the present invention, the organic electroluminescence element layer is one of white light emission, blue light emission, red light emission, and green light emission, or a combination of blue light emission, red light emission, and green light emission in a predetermined pattern. It was set as such a structure.
As another aspect of the present invention, the organic electroluminescence element layer emits blue light, the color conversion phosphor layer converts a blue light into green fluorescence and emits light, and converts the blue light into red fluorescence. A red conversion layer that emits light after conversion is provided.

  In the organic electroluminescent image display device of the present invention, since the insulating layer having an optical density OD value of 0.5 or more exists in the non-light-emitting region, the light that has reached the non-light-emitting region among the incident external light is Even if there is light that is mostly absorbed by the insulating layer and transmitted through the insulating layer and reflected in the organic electroluminescent image display device, such reflected light is again transmitted to the insulating layer. Since most of the light is absorbed, the reflection of external light is extremely small, and a high-quality image display with high contrast and brightness is possible.

The present invention will be described below with reference to the drawings.
FIG. 1 is a partial plan view showing an embodiment of an organic electroluminescent (EL) image display device according to the present invention, and FIG. 2 is a longitudinal section taken along line AA of the organic EL image display device shown in FIG. FIG. 3 is a longitudinal sectional view taken along line BB of the organic EL image display device shown in FIG. In FIG. 1, in order to show an auxiliary electrode 7 and a transparent electrode layer 8 which will be described later, the organic EL element layer 10 and the back electrode layer 11 are partially cut away.

  1 to 3, the organic EL image display device 1 is a color composed of a transparent base material 2 and strip-like red colored layers 4R, green colored layers 4G, and blue colored layers 4B provided on the transparent base material 2. The filter layer 4, the transparent smoothing layer 6 disposed so as to cover the color filter layer 4, and the transparent smoothing layer 6 are disposed in a strip shape from the peripheral terminal portion to the central pixel region. The auxiliary electrode 7 and the transparent electrode layer 8 are provided. Furthermore, in the organic EL image display device 1 of the present invention, the matrix-shaped insulating layer 13 is formed in a non-light emitting region (a region excluding a region where the transparent electrode layer 8 and the back electrode layer 11 intersect). In FIG. 1, the exposed insulating layer 13 is indicated by hatching. Further, a partition wall 15 is formed through an insulating layer 13 so as to be orthogonal to the strip-shaped transparent electrode layer 8. A strip-shaped organic EL element layer 10 and a back electrode layer 11 are formed in parallel to these portions (so as to be orthogonal to the strip-shaped transparent electrode layer 8) at portions where the partition walls 15 are not formed. A dummy organic EL element layer 10 ′ and a dummy back electrode layer 11 ′ are formed on the upper plane of the partition wall 15, and these include the organic EL element layer 10 using the partition wall 15 as patterning means and the back surface. In the formation of the electrode layer 11, it is formed as a result of removing unnecessary forming material by adhering it to the partition 15 so as not to reach the transparent electrode layer 8 in order to form a band-like pattern. The transparent electrode layer 8 and the back electrode layer 11 constitute a hole injection electrode and an electron injection electrode.

  Such an organic EL image display device 1 of the present invention is characterized in that the optical density OD value of the insulating layer 13 is 0.5 or more, preferably 1 to 3. Thereby, most of the external light incident from the transparent substrate 2 side and reaching the non-light emitting region is absorbed by the insulating layer 13. Further, the light transmitted through the insulating layer 13 and further through the partition 15 and reflected by the dummy organic EL element layer 10 'and the dummy back electrode layer 11' existing on the upper plane of the partition 15 (see FIG. 2). Most of the light (shown by a chain line arrow) is again absorbed by the insulating layer 13. Therefore, the organic EL image display device 1 has very little reflection of external light, and can display a high-quality image with high contrast and brightness. The insulating layer 13 may have a multilayer structure including at least one layer having an optical density OD value of 0.5 or more, preferably 1 to 3. If the optical density OD value of the insulating layer 13 is less than 0.5, the above effects are not achieved, which is not preferable.

The optical density OD value of the insulating layer in the present invention is obtained by measuring the spectral transmittance (wavelength: 380 to 780 nm) of the insulating layer alone with a spectrophotometer (color filter spectral characteristic inspection device manufactured by Otsuka Electronics Co., Ltd.). To calculate.
The insulating layer 13 has a volume resistivity of 10 ¹⁰ Ω · cm or more, preferably 10 ¹⁴ Ω · cm or more. If the volume resistivity of the insulating layer 13 is less than 10 ¹⁰ Ω · cm, crosstalk between adjacent picture elements tends to occur via the insulating layer 13 and the partition wall 15, which is not preferable because the image quality is deteriorated.
In the present invention, the volume resistivity of the insulating layer is measured by a double ring probe method using a high resistivity meter (Hiresta UPMCP-HT450 type manufactured by Dia Instruments Co., Ltd.).

Next, each component of the organic EL image display device 1 of the present invention will be described.
As the transparent base material 2 constituting the organic EL image display device 1, a material made of a light transmissive glass material, a resin material, or a composite material thereof can be used. 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 about 0.1 to 1.1 mm, for example.
The color filter layer 4 corrects the color of light from the organic EL element layer 10 or increases the color purity. The red colored layer 4R, the green colored layer 4G, and the blue colored layer 4B constituting the color filter layer 4 can be appropriately selected according to the light emission characteristics of the organic EL element layer 10, for example, pigments, pigment dispersants , A pigment dispersion composition containing a binder resin, a reactive compound, and a solvent. The thickness of the color filter layer 4 can be appropriately set according to the material of each colored layer, the light emission characteristics of the organic EL element layer, and the like, and can be set, for example, in the range of about 1 to 3 μm.

  When the transparent smoothing layer 6 constituting the organic EL image display device 1 has a step (surface unevenness) due to the configuration of the color filter layer 4 or less, the step is flattened by eliminating the step, and the organic EL element layer 10 is used to prevent the occurrence of thickness unevenness. Such a transparent smoothing layer 6 can be formed of a transparent (visible light transmittance of 50% or more) resin. Specifically, a photocurable resin or a thermosetting resin having an acrylate-based or methacrylate-based reactive vinyl group can be used. Moreover, as transparent resin, polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, A maleic acid resin, a polyamide resin, etc. can be used.

The thickness of such a transparent smoothing layer 6 can be set in a range where a flattening action can be expressed in consideration of a material to be used, and can be appropriately set in a range of about 1 to 5 μm, for example.
The auxiliary electrode 7 constituting the organic EL image display device 1 is generally made of a metal material such as gold, silver, copper, magnesium alloy (MgAg, etc.), aluminum alloy (AlLi, AlCa, AlMg, etc.), metallic calcium, etc. Can be mentioned. Such an auxiliary electrode 7 is disposed from the peripheral terminal portion to the central pixel region.
Moreover, as a material of the transparent electrode layer 8 constituting the organic EL image display device 1, a metal, an alloy, or a mixture thereof having a large work function (4 eV or more) can be used. For example, indium tin oxide (ITO) And conductive materials such as indium oxide, zinc oxide, and stannic oxide. The transparent electrode layer 8 is disposed in a strip shape so that a part thereof is located on the auxiliary electrode 7 from the peripheral terminal portion to the central pixel region. Such a transparent electrode layer 8 preferably has a sheet resistance of several hundred Ω / □ or less, and depending on the material, the thickness of the transparent electrode layer 8 is, for example, about 10 nm to 1 μm, preferably about 10 to 200 nm. it can.

The organic EL element layer 10 constituting the organic EL image display device 1 has a structure composed of a light emitting layer alone, a structure in which a hole injection layer is provided on the transparent electrode layer 8 side of the light emitting layer, and a back electrode layer 11 side of the light emitting layer. A structure in which an electron injection layer is provided, a structure in which a hole injection layer is provided on the transparent electrode layer 8 side of the light emitting layer, and an electron injection layer is provided on the back electrode layer 11 side can be employed.
In addition, for the purpose of adjusting the emission wavelength or improving the light emission efficiency, an appropriate material can be doped in each of the above layers.

The light emitting layer of the organic EL element layer 10 is any one of monochromatic light emission such as red light emission, green light emission, and blue light emission, or a combination of red light emission, green light emission, and blue light emission in a predetermined pattern, or white light emission. May be. In the case of white light emission, a structure in which light emitting layers having different light emission wavelengths are stacked, a structure in which light emitting layers having different light emission wavelengths are divided into a plurality of regions, a structure containing materials having different light emission wavelengths, etc. Either may be sufficient.
The coloring material, the doping material, the hole transport material, the hole injection material, the electron injection material, and the like used for each layer of the organic EL element layer 10 may be any of inorganic materials and organic materials as exemplified below. Moreover, the thickness of each layer of the organic EL element layer 10 is not particularly limited, and can be, for example, about 5 nm to 5 μm.

(Coloring material)
(1) Dye-based coloring materials Cyclopentadiene derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, pyridine rings Examples thereof include compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

(2) Metal complex coloring material Aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethylzinc complex, porphyrin zinc complex, europium complex, etc., center metal such as Al, Zn, Be , Tb, Eu, Dy and the like, and a metal complex having oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure and the like as a ligand.

(3) Polymer-based coloring material Polyparaphenylene vinylene complex, polythiophene complex, polyparaphenylene complex, polysilane complex, polyacetylene complex, polyvinylcarbazole, polyfluorene complex and the like can be mentioned.

(Doping material)
Examples include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, and the like.

(Hole transport material)
Oxadiazole, oxazole, triazole, thiazole, triphenylmethane, styryl, pyrazoline, hydrazone, aromatic amine, carbazole, polyvinylcarbazole, stilbene, enamine, azine, tri Examples include phenylamine-based, butadiene-based, polycyclic aromatic compound-based, and stilbene dimer.
Further, as the π-conjugated polymer, polyacetylene, polydiacetylene, poly (P-phenylene), poly (P-phenylene sulfide), poly (P-phenylene oxide), poly (1,6-heptadiene), poly (P— Phenylene vinylene), poly (2,5-thienylene), poly (2,5-pyrrole), poly (m-phenylene sulfide), poly (4,4'-biphenylene) and the like.

As the charge transfer polymer complex, polystyrene / AgC104, polyvinylnaphthalene / TCNE, polyvinylnaphthalene / P-CA, polyvinylnaphthalene / DDQ, polyvinylmesitylene / TCNE, polynaphthaacetylene / TCNE, polyvinylanthracene / Br2, polyvinylanthracene / I2 , Polyvinyl anthracene / TNB, polydimethylaminostyrene / CA, polyvinyl imidazole / CQ, poly-P-phenylene / I2, poly-1-vinylpyridine / I2, poly-4-vinylpyridine / I2, poly-P-1- Examples include phenylene, I2, polyvinylpyridium, TCNQ, and the like. Further, TCNQ-TTF and the like are exemplified as a charge transfer low molecular complex, and polycopper phthalocyanine and the like are exemplified as a polymer metal complex.
As the hole transport material, a material having a low ionization potential is preferable, and in particular, a butadiene system, an enamine system, a hydrazone system, and a triphenylamine system are preferable.

(Hole injection material)
Phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide, etc., amorphous carbon, polyaniline, polythiophene derivative, triazole derivative, oxadiazole derivative, imidazole derivative, polyaryl Alkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilanes, aniline copolymers, And dielectric polymer oligomers such as thiophene oligomers.

  Furthermore, examples of the hole injection material include a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound. Examples of the porphyrin compound include polyfin, 1,10,15,20-tetraphenyl-21H, 23H-polyfin copper (II), aluminum phthalocyanine chloride, copper octamethylphthalocyanine, and the like. In addition, 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.

(Electron injection material)
Aluminum lithium, lithium fluoride, strontium, magnesium oxide, magnesium fluoride, strontium fluoride, calcium fluoride, barium fluoride, aluminum oxide, strontium oxide, calcium oxide, polymethyl methacrylate, sodium polystyrene sulfonate, nitro-substituted fluorene derivative , Anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, Thiazole derivatives in which the oxygen atom of the above oxadiazole ring is substituted with a sulfur atom, quinoxaline having a quinoxaline ring known as an electron withdrawing group Conductors, tris (8-quinolinol) metal complexes of 8-quinolinol derivatives, such as aluminum, phthalocyanine, metal phthalocyanine, can be mentioned distyryl pyrazine derivatives.

  The organic EL element layer 10 can be formed by vacuum evaporation or the like using the material described above with the partition wall 15 as a mask. In this method, the film is formed through a mask having an opening corresponding to the image display area (a mask for preventing film formation on the electrode terminal including the auxiliary electrode 7 and the transparent electrode layer 8 in the peripheral portion). Thus, the partition walls 15 become a mask pattern, and the light emitting layer material can pass through only between the partition walls 15 to reach the transparent electrode layer 8. Thereby, the strip | belt-shaped organic EL element layer 10 can be formed, without performing patterning, such as a photolithographic method. In the formation of the organic EL element layer 10 using such a partition wall 15, as shown in FIGS. 1 and 2, the barrier wall 15 located at the most peripheral portion of the plurality of barrier portions 15 is arranged. The end of the image display area is located on the upper plane, and the dummy organic EL element layer 10 ′ is formed only in about half of the width direction (image display area side).

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, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium, Examples include lithium / aluminum mixtures and rare earth metals. Considering the electron injectability and durability against oxidation as an electrode, a mixture of an electron injectable metal and a second metal, which is a stable metal having a larger work function value than this, is preferable. For example, a magnesium / silver mixture Magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, lithium / aluminum mixture, and the like. Such a back electrode layer 11 preferably has a sheet resistance of several hundred Ω / □ or less. For this reason, the thickness of the back electrode layer 11 can be, for example, about 10 nm to 1 μm, preferably about 50 to 200 nm.

  The back electrode layer 11 can be formed by forming a film by a method such as a vacuum vapor deposition method or an ion plating vapor deposition method using the electrode material described above with the partition wall 15 as a mask. That is, the partition walls 15 serve as a mask pattern, and the electrode material can pass only between the partition walls 15 to reach the organic EL element layer 10. And since it is not necessary to perform patterning, such as a photolithographic method, the characteristic of the organic EL element layer 10 is not deteriorated.

  The insulating layer 13 constituting the organic EL image display device 1 is formed in a matrix shape in a non-light emitting region (a region excluding a region where the transparent electrode layer 8 and the back electrode layer 11 intersect). As described above, the insulating layer 13 has an optical density OD value of 0.5 or more, preferably 1 to 3. Such an insulating layer 13 is, for example, a thin film composed of one or more of titanium black pigments such as titanium nitride, titanium oxide, and titanium oxynitride, or a blue colorant, a red colorant, It may be a thin film containing at least two kinds of yellow colorants. The insulating layer 13 can be formed by forming a film by a method such as a vacuum vapor deposition method or an ion plating vapor deposition method, and then performing patterning by etching or the like. The thickness of such an insulating layer 13 can be set to, for example, about 0.2 to 1 μm.

  Moreover, the insulating layer 13 may be cured after patterning using a photosensitive resin material. In this case, it is preferable to use a positive photosensitive resin material that has a low degassing property and can prevent deterioration in image display quality and shortening of the life due to diffusion of degassing components into the organic EL element layer 10. For example, a coating liquid containing one or more of the above-described titanium-based black pigments in such a positive photosensitive resin material, or a blue colorant, a red colorant, or a yellow colorant. The insulating layer 13 can be formed by a photolithography method using a coating solution containing at least two kinds. The content of the titanium black pigment, blue colorant, red colorant, and yellow colorant can be set so that the optical density OD value of the insulating layer 13 is 0.5 or more, and the thickness of the insulating layer 13 is For example, it can be set to about 1 to 3 μm.

  In addition, the insulating layer 13 may have a multilayer structure. In this case, it is sufficient that at least one layer constituting the multilayer structure has an optical density OD value of 0.5 or more. There are no particular restrictions on the multilayer structure, for example, a laminate in which two or more thin films made of the above-mentioned titanium-based black pigment are laminated, or a laminate in which a thin film made of a titanium-based black pigment and an insulating thin film such as a silicon dioxide thin film are laminated , A blue colorant, a red colorant, a thin film containing at least two kinds of yellow colorants and an insulating thin film such as a silicon dioxide thin film, a titanium black pigment, or a blue colorant, a red colorant, A laminate in which a thin film comprising at least two kinds of yellow colorants and a cured film of a positive photosensitive resin material are laminated, and a titanium-based black pigment or a cured film of this positive photosensitive resin material, It may be one containing at least two of a blue colorant, a red colorant and a yellow colorant.

  Here, when using at least 2 or more types of a blue colorant, a red colorant, and a yellow colorant, various organic pigments or inorganic pigments can be used for each colorant. From the viewpoint of spectral characteristics and conductivity, specific examples of organic pigments include compounds classified as pigments in the color index (CI: issued by The Society of Dyers and Colorists), that is, the following compounds: Examples of color index (CI) numbers are given. Examples of suitable red colorants include C.I. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 224, C.I. I. Examples thereof include red pigments such as CI Pigment Red 254.

  Specific examples of suitable yellow colorants include C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 173, C.I. I. Pigment yellow 180, C.I. I. And yellow pigments such as CI Pigment Yellow 185.

Further, examples of suitable blue colorants include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 21, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. And a blue pigment such as CI Pigment Blue 64.
Specific examples of inorganic pigments include red iron oxide (III), cadmium red, etc. as red colorants, yellow lead, zinc yellow, etc. as yellow colorants, ultramarine blue, bitumen, etc. as blue colorants. Can do.

  The partition 15 constituting the organic EL image display device 1 is a partition for forming the organic EL element layer 10 and the back electrode layer 11 in a strip shape so as to intersect the strip-shaped transparent electrode layer 8 at right angles as described above. It is a pattern. That is, the partition wall 15 serves as a mask when the organic EL element layer 10 and the back electrode layer 11 are formed on the transparent electrode layer 8 by a vacuum deposition method or the like. Such a partition wall 15 can be formed by applying a photosensitive resin by spin coating, roll coating, cast coating, or the like, and then patterning the photosensitive resin by a photolithography method. In the example shown in FIG. 2, the partition wall 15 has an inverted trapezoidal cross section with a lower sag. In this way, to make the partition 15 have a lower sag or an upper sag shape. The positive or negative photosensitive resin layer formed with a predetermined thickness can be realized by a multiple exposure method by changing the exposure direction, a multiple exposure method from different directions by shifting the pattern, and the like. The height of the partition wall 15 can be set in the range of about 1 to 20 μm and the width in the range of about 5 to 30 μm.

Even if the partition 15 as described above has optical transparency, since the insulating layer 13 has an optical density OD value of 0.5 or more, it enters from the transparent substrate 2 side, and the transparent smoothing layer 6, transparent electrode layer Most of the external light that has passed through 8 and reaches the region where the partition wall 15 is disposed is absorbed by the insulating layer 13, passes through the insulating layer 13, and further passes through the partition wall 15. Most of the light reflected by the dummy organic EL element layer 10 ′ and the dummy back electrode layer 11 ′ present on the plane is again absorbed by the insulating layer 13. Therefore, the organic EL image display device 1 has very little reflection of external light.
The organic EL image display device of the present invention is not limited to the above-described embodiment. For example, the organic EL image display device does not include the color filter layer 4 or the color filter 4 includes a single color layer. There may be.

  In addition, the organic EL image display device of the present invention may include a color conversion phosphor layer between the color filter layer and the transparent smoothing layer. FIG. 4 is a longitudinal sectional view corresponding to FIG. 3 showing an example of an organic EL image display device provided with such a color conversion phosphor layer. 4, the organic EL image display device 21 includes a transparent base material 22 and a color filter layer 24 including a red colored layer 24R, a green colored layer 24G, and a blue colored layer 24B formed in a strip shape on the transparent base material 22. It has.

  A color conversion phosphor layer 25 is provided so as to cover the color filter layer 24. The color conversion phosphor layer 25 is provided with a red conversion phosphor layer 25R (a layer that converts blue light into red fluorescence) on the red color layer 24R, and a green conversion phosphor layer 25G (blue light on the green color layer 24G). Is converted to green fluorescence), and a blue conversion dummy layer (layer that transmits blue light emission as it is) 25B is provided on the blue colored layer 24B.

  A transparent smoothing layer 26 is provided on the transparent base material 22 so as to cover the color conversion phosphor layer 25, and the auxiliary electrode 27 and the transparent electrode layer 28 are centered on the transparent smoothing layer 26 from the peripheral terminal portion. These pixel regions are arranged and formed in a strip shape. Further, a strip-shaped organic EL element layer 30 and a back electrode layer 31 are formed on the transparent smoothing layer 26 so as to be orthogonal to the strip-shaped transparent electrode layer 28. Further, a matrix-shaped insulating layer 33 is formed in a non-light emitting region (a region excluding a region where the transparent electrode layer 28 and the back electrode layer 31 intersect), and further insulated so as to be orthogonal to the band-shaped transparent electrode layer 28. A partition wall 35 is formed via the layer 33. A dummy organic EL element layer 30 ′ and a dummy back electrode layer 31 ′ are formed on the upper plane of the partition wall 35.

  Such an organic EL image display device 21 includes the color conversion phosphor layer 25 and is the same as the organic EL image display device 1 described above except that the organic EL element layer 30 emits blue light. Therefore, the transparent base material 22, the color filter layer 24, the transparent smoothing layer 26, the auxiliary electrode 27, the transparent electrode layer 28, the back electrode layer 31, the inorganic compound film 32, the insulating layer 33, and the partition wall 35 are the above-described organic EL images. It is the same as the transparent substrate 2, the color filter layer 4, the transparent smoothing layer 6, the auxiliary electrode 7, the transparent electrode layer 8, the back electrode layer 11, the insulating layer 13, and the partition wall 15 that constitute the display device 1. Description is omitted.

  The red conversion phosphor layer 25R and the green conversion phosphor layer 25G are layers made of a single fluorescent dye or a layer containing a fluorescent dye in a resin. Examples of the fluorescent dye used for the red conversion phosphor layer 25R that converts blue light emission into red fluorescence include cyanine dyes such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran, Examples include pyridine dyes such as 1-ethyl-2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -pyridium-perchlorate, rhodamine dyes such as rhodamine B and rhodamine 6G, and oxazine dyes. It is done. Moreover, as a fluorescent dye used for the green conversion phosphor layer 25G that converts blue light emission into green fluorescence, 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolidino (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 other coumarins Examples thereof include dye-based dyes and naphthalimide dyes such as Solvent Yellow 11 and Solvent Yellow 116. Furthermore, various dyes such as direct dyes, acid dyes, basic dyes, and disperse dyes can be used as long as they have fluorescence. The above fluorescent dyes can be used alone or in combination of two or more. When the red conversion phosphor layer 25R and the green conversion phosphor layer 25G contain a fluorescent dye in the resin, the content of the fluorescent dye takes into account the fluorescent dye used, the thickness of the color conversion phosphor layer, and the like. For example, it may be about 0.1 to 1 part by weight with respect to 100 parts by weight of the resin used.

Further, the blue conversion dummy layer 25B transmits blue light emitted from the organic EL element layer 30 as it is and sends it to the color filter layer 24, which is almost the same as the red conversion phosphor layer 25R and the green conversion phosphor layer 25G. It can be set as the transparent resin layer of the same thickness.
When the red conversion phosphor layer 25R and the green conversion phosphor layer 25G contain a fluorescent dye in the resin, the resins include polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, carboxy Transparent (visible light transmittance 50% or more) resin such as methyl cellulose, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin can be used. . When the pattern of the color conversion phosphor layer 25 is formed by a photolithography method, for example, a photo-curing resist having a reactive vinyl group such as acrylic acid, methacrylic acid, polyvinyl cinnamate, or ring rubber Resin can be used. Furthermore, these resins can be used for the blue conversion dummy layer 25B described above.

  When the red color conversion phosphor layer 25R and the green color conversion phosphor layer 25G constituting the color conversion phosphor layer 25 are formed of a single fluorescent dye, for example, vacuum deposition or sputtering through a mask having a desired opening. It can be formed in a band shape by the method. When forming a layer containing a fluorescent dye in the resin, for example, a coating solution in which the fluorescent dye and the resin are dispersed or solubilized is applied by a method such as spin coating, roll coating, or cast coating. The red conversion phosphor layer 25R and the green conversion phosphor layer 25G can be formed by a method of forming a film and patterning it by a photolithography method, a method of pattern printing the above coating liquid by a screen printing method, or the like. The blue conversion dummy layer 25B is formed by applying a desired photosensitive resin paint by spin coating, roll coating, cast coating, or the like, and patterning this by a photolithography method, or by a desired resin coating solution. Can be formed by a method of pattern printing by a screen printing method or the like.

The thickness of the color conversion phosphor layer 25 is such that the red conversion phosphor layer 25R and the green conversion phosphor layer 25G sufficiently absorb the blue light emitted from the organic EL element layer 30 and generate fluorescence. It is necessary to be able to be set, and can be appropriately set in consideration of the fluorescent dye to be used, the concentration of the fluorescent dye, etc., for example, about 10 to 20 μm, and the red conversion phosphor layer 25R and the green conversion fluorescence The thickness of the body layer 25G may be different.
The organic EL element layer 30 that emits blue light can be formed by appropriately selecting blue light emission from the material of the organic EL element layer 10 described above. Examples of coloring materials include fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxinoid compounds, styrylbenzene compounds, distyrylpyrazine derivatives, and aromatic dimethylidin compounds. Can do.

Specifically, benzothiazoles such as 2-2 '-(p-phenylenedivinylene) -bishenzothiazole; 2- [2- [4- (2-benzimidazolyl) phenyl] vinyl] benzimidazole, 2- [ Benzimidazoles such as 2- (4-carboxyphenyl) vinyl] benzimidazole; 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) -1,3,4-thiadiazole, Benzoxazole series such as 4,4'-bis (5,7-t-pentyl-2-benzoxazolyl) stilbene, 2- [2- (4-chlorophenyl) vinyl] naphtho [1,2-d] oxazole And the like.
Examples of the metal chelated oxinoid compound include 8-hydroxyquinoline metal complexes such as tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, and bis (benzo [f] -8-quinolinol) zinc. Examples include dilithium epinetridione.

Examples of the styrylbenzene compound include 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-ethylbenzene and the like can be mentioned.
Examples of the distyrylpyrazine derivative include 2,5-bis (4-methylstyryl) pyrazine, 2,5-bis (4-ethylstyryl) pyrazine, and 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 Etc.

  Examples of the aromatic dimethylidin compounds include 1,4-phenylene dimethylidin, 4,4-phenylene dimethylidin, 2,5-xylene dimethylidin, 2,6-naphthylene dimethylidin, , 4-biphenylenedimethylidin, 1,4-p-terephenylenedimethylidin, 9,10-anthracenediyldimethylidin, 4,4'-bis (2,2-di-t-butylphenylvinyl) Biphenyl, 4,4'-bis (2,2-diphenylvinyl) biphenyl, and the like, and derivatives thereof can be mentioned.

Furthermore, as a material of the light emitting layer, a compound represented by the general formula (Rs-Q) 2-AL-OL can be exemplified (in the above formula, AL has 6 to 24 carbon atoms including a benzene ring). A hydrocarbon, OL is a phenylate ligand, Q is a substituted 8-quinolinolato ligand, Rs is a steric bond of two or more substituted 8-quinolinolato ligands to an aluminum atom. Represents an 8-quinolinolate substituent selected to interfere with. Specific examples include bis (2-methyl-8-quinolinolato) (paraphenylphenolate) aluminum (III), bis (2-methyl-8-quinolinolato) (1-naphtholato) aluminum (III), and the like.
The structure of the blue light emitting organic EL element layer 30 is a structure in which a hole injection layer is provided on the transparent electrode layer 28 side of the light emitting layer, a structure in which an electron injection layer is provided on the back electrode layer 31 side of the light emitting layer, When the hole injection layer is provided on the transparent electrode layer 28 side and the electron injection layer is provided on the back electrode layer 31 side, the hole injection layer and the electron injection layer are the above-described organic EL element layer 10. And can be similar.

  In addition, the above-mentioned embodiment is an illustration and this invention is not limited to these. For example, as shown in FIG. 5, each constituent layer such as the color filter layer 4 may be provided through a black matrix 3 having an opening 3a and a light-shielding portion 3b in a predetermined pattern. The black matrix 3 may be any of a metal thin film pattern such as chromium having a thickness of about 1000 to 2000 mm, or a resin layer pattern containing light shielding particles such as carbon fine particles.

Next, an Example is shown and this invention is demonstrated further in detail.
[Example 1]
First, soda glass (Sn surface polished product manufactured by Central Glass Co., Ltd.) having a thickness of 150 mm × 150 mm and a thickness of 0.7 mm was prepared as a transparent substrate.
(Formation of color filter layer)

  Three types of photosensitive coatings for colored layers of red, green, and blue were prepared. That is, the photosensitive paint for the red colored layer is a perylene pigment, a lake pigment, an azo pigment, a quinacridone pigment, an anthraquinone pigment, an anthracene pigment, an isoindoline pigment or the like, or a mixture of two or more. The resulting colorant was dispersed in a binder resin. The binder resin is preferably a transparent (visible light transmittance of 50% or more) resin, and examples thereof include transparent resins such as polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, and carboxymethyl cellulose. Moreover, content of the coloring material was set so that 5 to 50 weight% might be contained in the formed colored layer.

The photosensitive coating for the green colored layer is a single product such as a halogen multi-substituted phthalocyanine pigment, a halogen multi-substituted copper phthalocyanine pigment, a triphenylmethane basic dye, an isoindoline pigment, an isoindolinone pigment, or two types. The coloring material comprising the above mixture was dispersed in a binder resin. Examples of the binder resin include the above-described transparent resin, and the content of the coloring material was set to be contained in the formed colored layer in an amount of 5 to 50% by weight.
The photosensitive coating for the blue colored layer is composed of a single material such as a copper phthalocyanine pigment, an indanthrene pigment, an indophenol pigment, a cyanine pigment, a dioxazine pigment, or a colorant composed of a mixture of two or more binder resins. It was assumed that they were dispersed. Examples of the binder resin include the above-described transparent resin, and the content of the coloring material was set to be contained in the formed colored layer in an amount of 5 to 50% by weight.

Next, a colored layer of each color was formed using the above-described three types of photosensitive paints for colored layers. That is, a photosensitive paint for a green colored layer was applied to the entire surface of the transparent substrate by a spin coating method, and prebaked (80 ° C., 30 minutes). Then, it exposed using the predetermined photomask for colored layers. Next, development is performed with a developer (0.05% aqueous KOH solution), followed by post-baking (100 ° C., 30 minutes), and a strip-like (width 85 μm) green colored layer (thickness 1.5 μm) is 300 μm. Formed with pitch.
Similarly, a strip-like (width 85 μm) red colored layer (thickness 1.5 μm) was formed at a pitch of 300 μm in parallel with the extending direction of the green colored layer, using a photosensitive paint of a red colored layer. . The pitch between the adjacent green colored layer and red colored layer was 100 μm. Further, by using the photosensitive paint of the blue colored layer, a belt-like (width 85 μm) blue colored layer (thickness 1.5 μm) is formed between the green colored layer and the red colored layer in parallel with the extending direction of the green colored layer. Each of the intermediate regions was formed at a pitch of 300 μm. As a result, a strip-like (85 μm wide) green colored layer, a red colored layer, and a blue colored layer are arranged at a pitch of 100 μm within a width of 300 μm perpendicular to the extending direction of the colored layer, and this 300 μm unit can be repeated. A colored layer was formed.

(Formation of transparent smoothing layer)
A transparent smoothing layer coating solution obtained by diluting norbornene resin (ARTON manufactured by JSR Co., Ltd.) with toluene is applied onto the color filter layer by spin coating, and is cured (230 ° C., 60 minutes) to be transparent. A smoothing layer (thickness 1.5 μm) was formed.

(Formation of auxiliary electrode)
Next, a chromium thin film (thickness 0.2 μm) is formed on the entire surface of the transparent smoothing layer by sputtering, and a photosensitive resist is applied on the chromium thin film, and mask exposure, development, and etching of the chromium thin film are performed. And an auxiliary electrode was formed. This auxiliary electrode is a striped pattern formed at a pitch of 100 μm parallel to each colored layer of the color filter layer, 5 μm of the width of 15 μm is located on each colored layer, and the remaining portion in the width direction is transparent It is located on the smoothing layer, and the width of the terminal part at the peripheral part of the transparent substrate is 60 μm.

(Formation of transparent electrode layer)
Next, an indium tin oxide (ITO) electrode film having a thickness of 150 nm is formed on the transparent smoothing layer so as to cover the auxiliary electrode by an ion plating method, and a photosensitive resist is applied on the ITO electrode film, 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 with a width of 80 μm formed in parallel with each colored layer of the color filter layer, and is located on each colored layer and overlaps with the auxiliary electrode (overlap width 2.5 μm) Met.

(Formation of insulating layer and partition)
A three-layer thin film of silicon dioxide, titanium nitride, and silicon dioxide is formed by sputtering to cover the transparent electrode layer, and the thickness is 0.3 μm (each silicon dioxide thin film = 0.1 μm, titanium nitride = 0.1 μm). An insulating film was formed. Next, a photosensitive resist was applied on the insulating film, mask exposure and development were performed to form a resist pattern. Using this resist pattern as a mask, the exposed insulating film is removed by spray etching using an etching solution (9H ₂ O · 1HF solution or 7H ₂ O · 2HNO ₃ · 1HF solution) at 30 ° C. Formed. The insulating layer has rectangular openings of 90 μm × 290 μm at a pitch of 300 μm in the side direction of 290 μm and a pitch of 100 μm in the side direction of 90 μm, and the side of 290 μm of the opening is a colored layer or a transparent electrode layer. The matrix shape was the same as the extending direction, and the openings were located on each colored layer.

The optical density OD value and volume resistivity of the insulating layer were measured by the following method. As a result, the optical density OD value was 2.0 and the volume resistivity was 10 ¹⁴ Ω · cm.
(Measurement method of optical density OD value)
The spectral transmittance (wavelength: 380 to 780 nm) of the insulating layer was calculated by measuring with a spectrophotometer (color filter spectral characteristic inspection device manufactured by Otsuka Electronics Co., Ltd.).
(Measurement method of volume resistivity)
High resistance resistivity meter (Dia Instruments Co., Ltd. Hiresta UPMCP
-HT450 type) was measured by a double ring probe method.

  Next, a partition wall coating material (photograph ZPN1100 manufactured by Nippon Zeon Co., Ltd.) was applied to the entire surface by a spin coating method so as to cover the insulating layer, and prebaked (70 ° C., 30 minutes). Then, it exposed using the photomask for predetermined | prescribed partition, developed with the developing solution (Nippon ZEON Co., Ltd. product ZTMA-100), and then post-baked (100 degreeC, 30 minutes). Thereby, a partition was formed on the matrix-shaped insulating layer (direction parallel to the 90 μm side of the opening). The partition wall had a shape with a height of 10 μm, a lower portion (insulating layer side) width of 15 μm, and an upper portion width of 26 μm.

(Formation of organic EL element layer)
Next, an organic EL element layer composed of a hole injection layer, a light emitting layer, and an electron injection layer was formed by a vacuum deposition method using the partition walls as a mask. That is, first, 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine is 200 nm thick through a mask having an opening corresponding to the image display region. By vapor-depositing to 4 nm, and then depositing 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl to a thickness of 20 nm, the partition wall becomes a mask pattern, The hole injection layer material passed only between the partition walls, and a hole injection layer was formed on the transparent electrode layer.

Next, in the same manner as described above, a light emitting layer was formed by depositing an organic coloring material up to 300 nm using the partition walls as a mask.
Further, tris (8-quinolinol) aluminum was vapor-deposited to a thickness of 20 nm to form an electron injection layer.
The thus formed organic EL element layer (thickness 500 nm) is present between each partition as a strip pattern having a width of about 280 μm, and a dummy organic EL element layer having a similar layer structure on the upper surface of the partition. Formed.

(Formation of back electrode layer)
Next, magnesium and silver are simultaneously vapor-deposited in a region where the partition walls are formed through a mask having a predetermined opening wider than the image display region by a vacuum vapor deposition method (magnesium vapor deposition rate = 1.3 to The film was formed at 1.4 nm / second, silver deposition rate = 0.1 nm / second).
Thereby, the partition wall was used as a mask, and a back electrode layer (thickness 200 nm) made of a magnesium / silver mixture was formed on the organic EL element layer. This back electrode layer exists on the organic EL element layer as a band-like pattern having a width of 280 μm, and a dummy back electrode layer was also formed on the upper surface of the partition wall.
Thus, the organic EL image display device of the present invention was obtained.

[ Reference Example 1 ]
An organic EL image display device of the present invention was produced in the same manner as in Example 1 except that the insulating layer was formed as follows.
That is, a positive photosensitive insulating layer coating solution having the following composition is applied by a spin coating method so as to cover the transparent electrode layer, and then baked (230 ° C., 30 minutes), followed by mask exposure and development. Thus, an insulating layer (thickness 1.2 μm) was formed.
(Coating solution for insulating layer)
・ Ester of 1,2-naphthoquinone- (2) -diazide-5-sulfonic acid and 2,3,4-trihydroxybenzophenone 30 parts by weight ・ Co-methacrylic acid / methyl methacrylate / 2-hydroxyethyl methacrylate / cyclohexyl methacrylate Polymer (composition ratio 22: 26: 30: 22,
Molecular weight 15000) ... 100 parts by weight Black dispersion liquid: 60 parts by weight

In addition, said black dispersion liquid was prepared as follows. That is, titanium black (Mitsubishi Materials Co., Ltd. 13M-C) 200g, MBA (methoxy butyl acetate) 300g, colloidal silica (Nissan Chemical Co., Ltd. Snowtex NPC-ST, average particle size 10-20nm) 50g 300 cc of zirconia beads (manufactured by Showa Shell Sekiyu Co., Ltd., Microhaika Z Z300, diameter 0.3 mm) was added, and the mixture was dispersed in a sand mill at a rotor rotational speed of 1500 rpm for 2 hours. Thereafter, 20 g of a dispersant (Solsperse 24000 manufactured by Avicia Co., Ltd.) was added to the above dispersion, and further dispersed for 3 hours at a rotor rotation speed of 1500 rpm with a sand mill, and then the zirconia beads were removed to disperse black. A liquid was obtained.
As a result of measuring the optical density OD value and the volume resistivity of the obtained insulating layer in the same manner as in Example 1, the optical density OD value was 1.0 and the volume resistivity was 10 ¹⁵ Ω · cm.

[ Reference Example 2 ]
A red pigment dispersion, a yellow pigment dispersion, and a blue pigment dispersion are weighed and mixed according to the following blending amounts, and zirconia beads (Microhaika Z Z300, Showa Shell Sekiyu KK's diameter 0.3 mm) are used for each mixture. Then, the mixture was dispersed for 3 hours using a paint shaker (PAINT SHAKER manufactured by Asada Tekko Co., Ltd.) to obtain red, blue and yellow pigment dispersions.
(Red pigment dispersion)
・ CIPigment Red254: 22 parts by weight (Ciba Specialty Chemicals)
・ High molecular weight pigment dispersant: 9 parts by weight (Solsparse 24000GR manufactured by Avicia Co., Ltd.)
・ Methoxypropyl acetate (Daicel Chemical Industries, Ltd.) ... 69 parts by weight

(Contains yellow pigment dispersion)
・ CIPigment Yellow139 (manufactured by BASF) ... 30 parts by weight ・ High molecular weight pigment dispersant: 9 parts by weight (Arvasia Co., Ltd. Solsperse 24000GR)
・ Methoxypropyl acetate: 61 parts by weight (manufactured by Daicel Chemical Industries, Ltd.)

(Blue pigment dispersion)
・ CIPigment Blue (manufactured by Toyo Ink Co., Ltd.): 24 parts by weight ・ High molecular weight pigment dispersant: 10 parts by weight (Solsparse 24000GR, manufactured by Avicia Co., Ltd.)
・ Methoxypropyl acetate: 66 parts by weight (manufactured by Daicel Chemical Industries, Ltd.)

Next, the red, blue and yellow pigment dispersions were mixed in the following ratio to obtain a black dispersant.
(Ratio to each pigment dispersion of black dispersant)
・ Red pigment dispersion: 40% by weight
・ Blue pigment dispersion: 40% by weight
・ Yellow pigment dispersion: 20% by weight

Next, a positive photosensitive insulating layer coating solution having the following composition was prepared using the above black dispersant.
(Coating solution for insulating layer)
・ Ester of 1,2-naphthoquinone- (2) -diazide-5-sulfonic acid and 2,3,4-trihydroxybenzophenone 30 parts by weight ・ Co-methacrylic acid / methyl methacrylate / 2-hydroxyethyl methacrylate / cyclohexyl methacrylate Polymer (composition ratio 22: 26: 30: 22, molecular weight 15000) 100 parts by weight Black dispersion liquid 40 parts by weight

An organic EL image display device of the present invention was produced in the same manner as in Reference Example 1 , except that this insulating layer coating solution was used.
As a result of measuring the optical density OD value and the volume resistivity of the obtained insulating layer in the same manner as in Example 1, the optical density OD value was 0.9, and the volume resistivity was 10 ¹⁵ Ω · cm.

[Comparative Example 1]
An organic EL image display device was produced in the same manner as in Example 2 except that the insulating layer was formed using the transparent smoothing layer coating solution as an insulating layer coating solution.
That is, a transparent smoothing layer coating solution was applied by spin coating so as to cover the transparent electrode layer, and then baked (100 ° C., 30 minutes) to form an insulating film (thickness 1.2 μm). Next, a photosensitive resist was applied on the insulating film, mask exposure and development were performed to form a resist pattern. Using this resist pattern as a mask, the exposed insulating film was removed by spray etching using an organic developer to form an insulating layer.
As a result of measuring the optical density OD value and volume resistivity of this insulating layer in the same manner as in Example 1, the optical density OD value was 0.2 and the volume resistivity was 10 ¹⁵ Ω · cm.

[Comparative Example 2]
In the same manner as in Comparative Example 2, an organic EL image display device was produced. However, the thickness of the insulating layer was set so that the optical density OD value measured in the same manner as in Example 1 was 0.4.
The volume resistivity of the obtained insulating layer was measured in the same manner as in Example 1. As a result, it was 10 ¹⁵ Ω · cm.

[Comparative Example 3]
In the step of forming the insulating layer, instead of forming the titanium nitride thin film, a chromium thin film (thickness 0.3 μm) was formed by sputtering to form a three-layer insulating layer. Thus, an organic EL image display device was produced.
As a result of measuring the optical density OD value and the volume resistivity of this insulating layer in the same manner as in Example 1, the optical density OD value was 4.0 and the volume resistivity was 10 ⁹ Ω · cm.

[Evaluation]
A voltage of DC 8.5 V is constant at 10 mA / cm ² on the transparent electrode layer and the back electrode layer of the organic EL image display device (Example 1 , Reference Examples 1 and 2 , Comparative Examples 1 to 3) manufactured as described above. The voltage was applied at the current density, the contrast was evaluated by the following evaluation method, and the results are shown in Table 1 below.
(Contrast evaluation method)
Brightness Y _ON when irradiated external light irradiated to the insulating layer portion, _and the brightness Y _OFF when not _irradiated, defined as _YOFF / Y _{ON contrast,} the contrast is determined as good 0.8 or more .

The presence or absence of crosstalk between adjacent picture elements was determined by the following evaluation method, and the results are shown in Table 1 below.
(Judgment method of crosstalk)
If the brightness of the selected picture element is Y _ON and the brightness of the non-selected picture element adjacent to it is Y _OFF , if Y _OFF > Y _ON / 100 is satisfied, it is determined that there is crosstalk. .

Industrial applicability

  It is useful in the manufacture of an organic electroluminescent image display device.

It is a partial top view which shows one Embodiment of the organic electroluminescent image display apparatus of this invention. It is a longitudinal cross-sectional view in the AA line of the organic electroluminescent image display apparatus shown by FIG. It is a longitudinal cross-sectional view in the BB line of the organic electroluminescent image display apparatus shown by FIG. It is a longitudinal cross-sectional view equivalent to FIG. 3 which shows other embodiment of the organic electroluminescent image display apparatus of this invention. FIG. 5 is a partial plan view showing another embodiment of the organic electroluminescent image display device of the present invention and showing a state in which a color filter layer is formed on a transparent substrate via a black matrix. It is a fragmentary sectional view which shows an example of the conventional organic electroluminescent image display apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,21 ... Organic electroluminescent image display device 2,22 ... Transparent substrate 3 ... Black matrix 4,24 ... Color filter layer 4R, 4G, 4B, 24R, 24G, 24B ... Colored layer 6,26 ... Transparent smooth 7, 27 ... auxiliary electrode 8, 28 ... transparent electrode layer 10, 30 ... organic electroluminescence element layer 11, 31 ... back electrode layer 13, 33 ... insulating layer 15, 35 ... partition wall 10 ', 30' ... dummy organic Electroluminescence element layer 11 ', 31' ... dummy back electrode layer 25 ... color conversion phosphor layer 25G ... green conversion phosphor layer

Claims (7)

A pair of electrodes composed of a hole injection electrode and an electron injection electrode, an organic electroluminescence element layer disposed between the electrodes, and an insulating layer disposed in a matrix in a non-light emitting region, the insulating layer Is a multilayer structure comprising at least one layer containing no organic component and having an optical density OD value of 0.5 or more , and has a volume resistivity of 10 ¹⁴ Ω · cm or more and a thickness of 0.2. An organic electroluminescent image display device having a range of ˜1 μm . The insulating layer is formed by laminating two or more thin films made of a titanium black pigment which is any one of titanium nitride, titanium oxide, and titanium oxynitride , or a thin film made of the titanium black pigment 2. The organic electroluminescent image display device according to claim 1, wherein a thin film and an insulating thin film are laminated . 3. The organic electroluminescent image display device according to claim 2 , wherein the insulating layer is a three-layer thin film of silicon dioxide, titanium nitride, and silicon dioxide. The organic electroluminescent image display device according to any one of claims 1 to 3 , further comprising a color filter layer. The organic electroluminescent image display device according to claim 4 , further comprising a color conversion phosphor layer between the color filter layer and the electrode. The organic electroluminescence element layer is any one of white light emission, blue light emission, red light emission, and green light emission, or a combination of blue light emission, red light emission, and green light emission in a predetermined pattern. The organic electroluminescent image display apparatus according to any one of claims 1 to 5 . The organic electroluminescence element layer emits blue light, and the color conversion phosphor layer emits light by converting blue light into green fluorescence, and a red conversion layer that emits light by converting blue light into red fluorescence. The organic electroluminescent image display device according to claim 5 , comprising:

Images