JP2002175880A - Color conversion filter substrate, color conversion color display provided with the color conversion filter substrate, and their manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a design guide of an inorganic film layer which efficiently allows lights of an organic EL emitting element to pass through and a color conversion filter substrate and a color organic EL display where stable luminous properties is maintained over a long term. SOLUTION: This color conversion filter substrate is provided with at least with a transparent support substrate, a single or plural kinds of color conversion filter layers constituted, wherein a resin film containing fluorescent dyes is formed into a desired pattern, a transparent and flat polymer membrane layer, the transparent inorganic film layer, and a transparent electrode layer formed in a single or plural electrically independent regions, wherein concerning a wavelength λ within a range of 450 to 500 nm, a refractive index of the inorganic film layer that is a single layer is smaller than that of the transparent electrode layer and the equation the nd=sλ/2 (in the formula, n: the refractive index of the inorganic film layer, s: a natural number) is satisfied, in a film thickness d of the inorganic film layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color conversion filter substrate capable of high-definition multi-color display with excellent environmental resistance and productivity, and an organic multi-color light-emitting display having the color conversion color filter substrate. It relates to an element (display). Specifically, image sensors, personal computers, word processors, televisions, facsimile, audio,
The present invention relates to a color conversion filter substrate for display of a video, a car navigation, an electric desk calculator, a telephone, a portable terminal, an industrial measuring instrument, and the like, and an organic multicolor light emitting display element (display) including the color conversion filter substrate. In particular, the present invention relates to a multicolor light emitting display using a color conversion method.

[0002]

2. Description of the Related Art In recent years, information has been diversified. Among them, display devices in the information field, such as solid-state imaging devices, are required to have "beauty, lightness, thinness, and excellence", and active development for low power consumption and high-speed response is being promoted. In particular, high-definition full-color display devices have been widely devised.

As an element having characteristics such as high contrast, constant voltage driving, wide viewing angle, and high-speed response as compared with a liquid crystal display element or the like, in the late 1980's, an organic layer having an organic molecule thin film laminated structure was used. Electroluminescence (hereinafter, referred to as organic EL) elements have been proposed. Tang et al. Report a stacked EL device that emits light with a high luminance of 1000 cd / m ² or more at an applied voltage of 10 V (Appl. Phys. Le).
tt., 51, 913 (1987)), research for practical use has been actively conducted. Further, similar devices using organic polymer materials are also being actively developed.

[0004] Since organic EL elements can realize a high current density at a constant voltage, higher light emission luminance and light emission efficiency can be expected as compared with inorganic EL elements and LEDs. Organic EL devices include (1) high brightness and high contrast, (2) low voltage driving and high luminous efficiency, (3) high resolution, (4) wide viewing angle, (5) fast response speed, and (6) fine And (7) lightness and thinness, and other excellent characteristics as a display element. From the above points, "Beauty, light,
It is expected to be applied to thin and excellent flat panel displays.

[0005] Pioneer has already introduced a green monochrome organic EL display for use in a car in January 1997.
It has been commercialized since January, and in the future, to meet the diversifying needs of society, the practical use of organic EL displays capable of long-term stability, high-speed response, multicolor display, and high-definition full-color display is urgent. Is peeling.

[0006] Three methods have been studied as a method for multi-color or full-color organic EL displays. The first method is red (R), green (G), blue (B)
Are arranged separately on a matrix to emit light. See JP-A-57-157487, JP-A-58-147989, and JP-A-3-214593. This method is technically difficult because it is necessary to arrange three kinds of light-emitting materials of RGB on a matrix with high definition, and it is more difficult to manufacture it at low cost. In addition, 3
Since the lifetimes of the light emitting materials are different from each other, there is a drawback that the chromaticity shifts with time.

As a second method, there has been proposed a method of transmitting three primary colors of RGB by using a color filter in a backlight which emits white light. JP-A-1-315988
JP, JP-A-2-273496, JP-A-3-3-1
See No. 94885. In this method, a long-life, high-brightness white light-emitting organic EL used for a backlight necessary for obtaining RGB light of sufficient brightness.
Obtaining a light emitting element is a technically difficult task and has not yet been obtained.

In recent years, as a third method, a method has been disclosed in which light emitted from a luminous body is absorbed by phosphors which are separately arranged in a plane, and multicolor fluorescent light is emitted from each phosphor. JP-A-3-152897 and JP-A-5-2897
See 258860 and the like. In this method, since the emission color of the organic EL element is not limited to white, an organic EL element with higher luminance can be applied to the light source. JP-A-3-152897, JP-A-8-286033, JP-A-9-208944, etc. disclose a color using a blue light-emitting organic EL light-emitting element for converting blue light into green light and red light. A conversion scheme is disclosed. Here, if the fluorescence conversion film containing the fluorescent dye is patterned with high definition, it is possible to construct a full-color light-emitting display even using weak energy rays such as near-ultraviolet light or visible light of the luminous body.

As a method of patterning the fluorescence conversion film, (1) a fluorescent dye is dispersed in a liquid resist (photoreactive polymer) and then formed by a spin coating method or the like as in the case of the inorganic phosphor. After forming the film, patterning by photolithography (Japanese Patent Laid-Open No. 5-198921)
And JP-A-5-258860) or (2) a method of dispersing a fluorescent dye or a fluorescent pigment in a basic binder and etching it with an acidic aqueous solution (JP-A-9-208944). be able to.

What is important for practical use as a color display is to have not only a fine color display function but also long-term stability (for example,
Functional Materials, Vol. 18, No. 2, p. 96). However, the organic EL light emitting element has a drawback that when driven for a certain period, light emitting characteristics such as current-luminance characteristics are significantly reduced.

A typical cause of the deterioration of the light emission characteristics is the growth of dark spots. The dark spot is a light emission defect point. This dark spot is considered to be caused by oxidation or agglomeration of the laminated constituent material of the device due to oxygen or moisture in the device. The growth of the dark spot proceeds not only during energization (during driving) but also during storage, and in extreme cases spreads over the entire light emitting surface. In particular, the growth is accelerated by (1) oxygen or moisture existing around the device, (2) affected by oxygen or moisture existing as an adsorbate in the organic laminated film, and (3) maintaining the device operation. It is also considered that it is also affected by the moisture adsorbed on the part or the infiltration of the water at the time of manufacturing or the like.

In the color conversion type color organic EL display, color conversion filter layers 2, 3, and 4 are provided below the transparent electrode 7 as shown in FIG. As described above, the color conversion filter is obtained by mixing a dye for color conversion in a resin.
Drying cannot be performed at a temperature exceeding 0 ° C. From this,
There is a high possibility that the color conversion filter layer is formed in a state where the water contained in the coating liquid or the water mixed during the pattern forming step is held. The moisture retained in the color conversion filter layer reaches the device through the polymer film layer during storage or driving, and is a factor promoting the growth of dark spots.

As a method for preventing the penetration of moisture into the organic EL element, an insulating inorganic oxide film layer having a thickness of 0.01 to 200 μm is provided between the color conversion filter layer and the organic EL element.
The technique of arranging in m is known (JP-A-8-2793).
No. 94). The inorganic oxide film layer is required to have a high moisture-proof property to maintain the life of the organic light-emitting layer, and the gas permeability coefficient of water vapor or oxygen (JIS K7) in the inorganic oxide film layer is required.
126 according to the gas permeability test method)
^-13 cc · cm / cm ² · s · cmHg or less is desirable.

As disclosed in JP-A-7-146480 and JP-A-10-10518, a method for producing a color filter is to perform DC sputtering on a polymer film layer formed on a color filter layer. By S
There is a method of forming iO _x and SiN _x, and the effect of improving the adhesion of the transparent conductive film is known.

[0015]

In a color conversion type color organic EL display, an inorganic film layer efficiently transmits excitation light from an organic EL light emitting element in order to reduce power consumption and extend the life. Therefore, it is required to have a function of transmitting to the color conversion filter layer.

As shown in FIG. 2, a color conversion type color organic EL display has an inorganic film layer under a transparent electrode 7,
A polymer film layer and a color conversion filter layer are provided. Light from the organic light emitting layer passes through the interface between the organic layer and the transparent electrode, the interface between the transparent electrode and the inorganic film layer, and the interface between the inorganic film layer and the polymer film layer, and reaches the color conversion filter layer. . mainly,
Light in the blue to green region with a wavelength of 450 to 500 nm,
Converted to blue, green, red, etc. The light from the organic light emitting layer is
As a result of reflection or interference at the interface in the device as described above, the intensity of transmitted light varies. The intensity of the transmitted light intensity varies depending on the material and thickness of each layer.

For this reason, in order to efficiently transmit the excitation light to the color conversion filter, it is necessary to show an optical design guideline of the inorganic film layer. The present invention has been made in view of the above-described problems, and provides a design guideline of an inorganic film layer that efficiently transmits light of an organic EL light emitting element, and a color conversion filter substrate that maintains stable light emission characteristics for a long time. It is an object to provide a color organic EL display.

[0018]

According to a first aspect of the present invention, there is provided a color conversion filter substrate in which a transparent support substrate and a resin film containing a fluorescent dye disposed on the support substrate are formed in a desired pattern. A single or plural types of color conversion filter layers, a polymer film layer that covers the color conversion filter layer, is transparent and is formed flat, and is formed on the polymer film layer A color conversion filter substrate comprising at least a transparent inorganic film layer and a transparent electrode layer formed in one or a plurality of electrically independent regions on the inorganic film layer, wherein the inorganic film layer is a single layer. And 450 nm or more and 500
For a wavelength λ in the range of not more than nm, the refractive index of the inorganic film layer is smaller than the refractive index of the transparent electrode layer, and the film thickness d of the inorganic film layer is represented by the following formula: nd = sλ / 2 (where n is the refractive index of the inorganic film layer with respect to light having a wavelength λ, and s is a natural number).

A color conversion filter substrate according to a second aspect of the present invention comprises a transparent support substrate and a single or a transparent resin substrate formed on the support substrate and having a resin film containing a fluorescent dye formed in a desired pattern. A plurality of types of color conversion filter layers, a polymer film layer covering the color conversion filter layer, being transparent, and formed flat, and a transparent inorganic film layer formed on the polymer film layer; A transparent electrode layer formed in one or more electrically independent regions on the inorganic film layer, wherein the inorganic film layer is formed of a laminate of at least two layers. Is configured, and for a wavelength λ in the range of 450 nm or more and 500 nm or less, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and counted from the transparent electrode layer. 2p-1st and Layers constituting the 2p-th inorganic film layer (p is a natural _{number), n 2p-1> n 2p} ; n 2p-1 d 2p-1 = s 2p-1 λ / 2; and n _2p d _2p = (wherein, n _u is the refractive index of the u-th layer, d _u is u th layer of thickness, s _u is a natural number) s _2p λ / 4 and satisfying the following relationship.

According to a third aspect of the present invention, there is provided a color conversion filter substrate according to the second aspect, wherein the color conversion filter substrate is 450 nm or more and 500 nm or more.
m, the refractive index of the layer constituting the inorganic film layer is gradually reduced from the transparent electrode layer side toward the polymer film layer. .

A color conversion filter substrate according to a fourth aspect of the present invention is a single-layer or single-layer filter formed by forming a transparent support substrate and a resin film containing a fluorescent dye disposed on the support substrate in a desired pattern. A plurality of types of color conversion filter layers, a polymer film layer covering the color conversion filter layer, being transparent, and formed flat, and a transparent inorganic film layer formed on the polymer film layer; A color conversion filter substrate comprising at least a transparent electrode layer formed in one or a plurality of electrically independent regions on the inorganic film layer, wherein the inorganic film layer comprises a laminate of at least two layers And the wavelength λ in the range of 450 nm or more and 500 nm or less, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and counted from the transparent electrode layer 2
Layers constituting the (p-1) th and 2pth inorganic film layers (p
Is a natural number), but n _2p-1 <n _2p ; n _2p-1 d _2p-1 = s _2p-1 λ / 4; and n _{2pd 2p} = s _2p λ / 2 (where n _u is refractive index of u th layer, d _u is characterized by satisfying u th layer of thickness, s _u is a natural number) the relationship.

A color conversion filter substrate according to a fifth aspect of the present invention is a single-layer or multi-layer filter formed by forming a transparent support substrate and a resin film containing a fluorescent dye disposed on the support substrate in a desired pattern. A plurality of types of color conversion filter layers, a polymer film layer covering the color conversion filter layer, being transparent, and formed flat, and a transparent inorganic film layer formed on the polymer film layer; A color conversion filter substrate comprising at least a transparent electrode layer formed in one or more electrically independent regions on the inorganic film layer, wherein the inorganic film layer is a single layer, and The inorganic film layer has a continuously changed composition such that its refractive index decreases gradually from the transparent electrode layer toward the polymer film layer.

A color conversion filter substrate according to a sixth aspect of the present invention is the color conversion filter substrate according to any one of the first to fifth aspects, wherein the thickness d of the transparent electrode layer is within a range of 450 nm or more and 500 nm or less. With respect to λ, the following formula is satisfied: nd = sλ / 2 (where n is the refractive index of the transparent electrode layer with respect to light of wavelength λ, and s is a natural number).

A color conversion color display according to a seventh aspect of the present invention provides a color conversion filter substrate according to any one of the first to sixth aspects, wherein a light emitting layer containing at least a light emitting material, a second electrode layer, Are sequentially laminated.

In a method of manufacturing a color conversion filter substrate according to an eighth aspect of the present invention, a transparent support substrate is prepared, and a resin film containing a fluorescent dye disposed on the support substrate is formed in a desired pattern. Forming a single or plural types of color conversion filter layers, covering the color conversion filter layer, forming a transparent and flat polymer film layer, and forming the inorganic film layer as a single layer. And 450 nm or more and 500
For wavelengths λ that are in the range of nm or less, the thickness d satisfies the relationship: nd = sλ / 2, where n is the refractive index for light of wavelength λ and s is a natural number. And forming a transparent electrode layer formed in one or more electrically independent regions on the inorganic film layer and having a refractive index larger than the refractive index of the inorganic film layer. Characterized in that it is provided with at least

In a method of manufacturing a color conversion filter substrate according to a ninth aspect of the present invention, a transparent support substrate is prepared, and a resin film containing a fluorescent dye is formed on the support substrate in a desired pattern. Forming a single or plural types of color conversion filter layers, covering the color conversion filter layer, forming a polymer film layer that is transparent and flat, and the inorganic film layer is transparent. Preparing a support substrate, forming a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern, and covering the color conversion filter layer Forming a transparent and flat polymer film layer, wherein the inorganic film layer comprises a laminate of at least two layers; and 450
For a wavelength λ in the range of not less than nm and not more than 500 nm, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and 2p−1 counted from the transparent electrode layer. The layers constituting the 2nd and 2p-th inorganic film layers (p is a natural number) are n _2p-1 > n _2p ; n _2p-1 d _2p-1 = s _2p-1 λ / 2; and n _2p d _2p = s _{2p λ} / 4 (wherein, n _u is u-th refractive index of the layer, d _u is the film thickness, s _u of u th layer is a natural number) inorganic having a thickness d satisfying the relationship: Forming a film layer, and forming a transparent electrode layer formed in one or more electrically independent regions on the inorganic film layer and having a refractive index larger than the refractive index of the inorganic film layer. It is at least provided.

According to a tenth aspect of the present invention, there is provided a method for manufacturing a color conversion filter substrate according to the ninth aspect, wherein the inorganic film layer has a refractive index in the range of 450 nm or more and 500 nm or less with respect to the wavelength λ. The present invention is characterized in that the concentration decreases gradually from the electrode layer toward the polymer film layer.

In a method of manufacturing a color conversion filter substrate according to an eleventh aspect of the present invention, a transparent support substrate is prepared, and a resin film containing a fluorescent dye disposed on the support substrate is formed in a desired pattern. Forming one or more types of color conversion filter layers, covering the color conversion filter layers, forming a transparent and flat polymer film layer, wherein the inorganic film layer has at least 2 For a wavelength λ comprised of a laminate of two layers, and in the range of 450 nm or more and 500 nm or less, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and The layers constituting the 2p-1st and 2pth inorganic film layers counted from the transparent electrode layer (p is a natural number) are as follows: _n2p-1 <_n2p; _{n2p-1 d2p-1} = _{s2p -1} lambda / 4; and _{n 2p d 2p = s 2p λ} / 2 ( where n _u is the refractive index of the u-th layer, d _u forms a inorganic layer having a thickness d that satisfies u th layer of thickness, s _u is a natural number) the relationship, and inorganic film layers Forming at least one transparent electrode layer formed in one or more electrically independent regions and having a refractive index larger than the refractive index of the inorganic film layer.

In a method of manufacturing a color conversion filter substrate according to a twelfth aspect of the present invention, a transparent support substrate is prepared, and a resin film containing a fluorescent dye disposed on the support substrate is formed in a desired pattern. Forming a single or plural types of color conversion filter layers, covering the color conversion filter layers, forming a transparent and flat polymer film layer, and continuously changing the composition. Forming an inorganic film layer, and forming a transparent electrode layer formed in one or more electrically independent regions on the inorganic film layer and having a refractive index greater than the refractive index of the inorganic film layer At least.

According to a thirteenth aspect of the present invention, there is provided a method for manufacturing a color conversion color display, comprising preparing a transparent support substrate and forming a resin film containing a fluorescent dye on the support substrate into a desired pattern. Forming a single or plural types of color conversion filter layers, covering the color conversion filter layer, forming a transparent and flat polymer film layer,
The inorganic film layer is a single layer, and for a wavelength λ in the range of 450 nm or more and 500 nm or less, the following formula: nd = sλ / 2 (where n is a refractive index for light having a wavelength λ) And an s is a natural number) forming an inorganic film layer having a thickness d that satisfies the following relationship: formed in one or more electrically independent regions on the inorganic film layer; and , A transparent electrode layer having a refractive index larger than that of (a), an organic light emitting layer containing at least a light emitting material, and a second electrode layer are formed.

In a method of manufacturing a color conversion color display according to a fourteenth aspect of the present invention, a transparent support substrate is prepared, and a resin film containing a fluorescent dye disposed on the support substrate is formed in a desired pattern. Forming a single or plural types of color conversion filter layers, covering the color conversion filter layer, forming a transparent and flat polymer film layer,
The inorganic film layer is composed of a laminate of at least two layers, and for a wavelength λ in a range of 450 nm or more and 500 nm or less, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index, and the layers constituting the 2p-1 th and 2p-th inorganic film layer counted from the transparent electrode layer (p is a natural _{number), n 2p-1> n 2p} ; n 2p- ₁ d _2p-1 = s _2p-1 λ / 2; and n _{2pd 2p} = s _2p λ / 4 (where n _u is the refractive index of the u-th layer, and d _u is the thickness of the u-th layer) , S _u is a natural number) forming an inorganic film layer having a film thickness d satisfying the following relationship: formed in one or more electrically independent regions on the inorganic film layer; Forming a transparent electrode layer having a refractive index larger than the refractive index, forming an organic light emitting layer containing at least a light emitting material And characterized by comprising at least to the formation of the second electrode layer.

According to a fifteenth aspect of the present invention, there is provided a method for manufacturing a color conversion color display according to the fourteenth aspect, wherein the refractive index of the inorganic film layer is in the range of 450 nm or more and 500 nm or less. The present invention is characterized in that the concentration decreases gradually from the electrode layer toward the polymer film layer.

In a method of manufacturing a color conversion color display according to a sixteenth aspect of the present invention, a transparent support substrate is prepared, and a resin film containing a fluorescent dye disposed on the support substrate is formed in a desired pattern. Forming a single or plural types of color conversion filter layers, covering the color conversion filter layer, forming a transparent and flat polymer film layer,
The inorganic film layer is composed of a laminate of at least two layers, and for a wavelength λ in a range of 450 nm or more and 500 nm or less, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index, and the layers constituting the 2p-1 th and 2p-th inorganic film layer counted from the transparent electrode layer (p is a natural _{number), n 2p-1 <n 2p} ; n 2p- _{1 d 2p-1 = s 2p} -1 λ / 4; during and _{n 2p d 2p = s 2p λ} / 2 ( wherein, n _u is the refractive index of the u-th layer, d _u is the thickness of the u-th layer , S _u is a natural number) forming an inorganic film layer having a film thickness d satisfying the following relationship: formed in one or more electrically independent regions on the inorganic film layer; Forming a transparent electrode layer having a refractive index larger than the refractive index, forming an organic light emitting layer containing at least a light emitting material And characterized by comprising at least to the formation of the second electrode layer.

In a method of manufacturing a color conversion color display according to a seventeenth aspect of the present invention, a transparent support substrate is prepared, and a resin film containing a fluorescent dye disposed on the support substrate is formed in a desired pattern. Forming a single or plural types of color conversion filter layers, covering the color conversion filter layer, forming a transparent and flat polymer film layer,
Forming an inorganic film layer having a continuously changed composition, and being formed in one or more electrically independent regions on the inorganic film layer, and having a refractive index larger than the refractive index of the inorganic film layer. A transparent electrode layer having at least a light-emitting material, an organic light-emitting layer containing at least a light-emitting material, and a second electrode layer.

[0035]

DETAILED DESCRIPTION OF THE INVENTION 1. Color Conversion Filter Substrate An example of the color conversion filter substrate of the present invention is shown in FIG. In FIG. 1, a red conversion filter layer 2 is provided on a support substrate 1.
The green color conversion filter layer 3 and the blue color conversion filter layer 4 are each formed with a predetermined pattern. As described later, the green color conversion filter layer 3 may be a green color filter layer. Further, the blue conversion filter layer 4 is preferably a blue filter layer. Over these conversion filter layers,
A polymer film layer 5 is formed, and an inorganic film layer 6 is further formed thereon, and the upper surface thereof is flat. Inorganic film layer 6
Over one or more electrically independent transparent electrode layers 7
Is provided. Hereinafter, each layer will be described in detail.

1. Color Conversion Filter Layer 1) Organic Fluorescent Dye In the present invention, the organic fluorescent dye absorbs light in the near-ultraviolet region or visible region emitted from the luminous body, particularly light in the blue or blue-green region, and emits visible light of a different wavelength. It emits light as fluorescence. Preferably, at least one kind of fluorescent dye that emits fluorescence in the red region is used, and further, one or more kinds of fluorescent dyes that emit fluorescence in the green region may be combined.

That is, when an organic light emitting device that emits light in the blue or blue-green region is used as a light source, if light from the device is passed through a simple red filter to obtain light in the red region, the light in the red region is originally used. Since the light of the wavelength is small, the output light becomes extremely dark. Therefore, by converting light in the blue or blue-green region from the device into light in the red region by using a fluorescent dye, light in the red region having sufficient intensity can be output.

On the other hand, similarly to the light in the red region, the light in the green region may be converted into light in the green region by another organic fluorescent dye and output. Alternatively,
If the light emission of the device includes sufficient light in the green region, the light from the device may simply be output through a green filter.

Further, with respect to the light in the blue region, the light of the organic light emitting device may be converted and output using a fluorescent dye, but more preferably, the light of the organic light emitting device is output through a simple blue filter. Let it.

Examples of the fluorescent dye that absorbs light in the blue to blue-green region emitted from the luminous body and emits fluorescence in the red region include, for example, rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, sulforhodamine, and basic. Rhodamine dyes such as violet 11, basic red 2, cyanine dyes, 1-
Ethyl-2- [4- (p-dimethylaminophenyl)-
Examples thereof include pyridine dyes such as [1,3-butadienyl] -pyridinium perchlorate (pyridine 1), and oxazine dyes. Further, various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can also be used as long as they have fluorescence.

Examples of fluorescent dyes that emit light in the green region by absorbing light in the blue or blue-green region emitted from the illuminant include 3- (2′-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), -(2'-benzimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 7), 3- (2'-N-methylbenzimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 30), 2,3, 5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolidine (9,9a,
1-gh) Coumarin-based dyes such as coumarin (coumarin 153), and naphthalimide-based dyes such as Solvent Yellow 11 and Solvent Yellow 116, such as Basic Yellow 51, which is a coumarin dye-based dye. Further, various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can also be used as long as they have fluorescence.

The organic fluorescent dyes used in the present invention include polymethacrylic acid ester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer resin, alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, benzoguanamine resin and An organic fluorescent pigment may be prepared by kneading the resin mixture or the like in advance and forming a pigment. In addition, these organic fluorescent dyes and organic fluorescent pigments (the two are collectively referred to as an organic fluorescent dye in the present specification) may be used alone, and two or more kinds thereof may be used to adjust the hue of fluorescence. May be used in combination.

The organic fluorescent dye used in the present invention is contained in the color conversion filter layer in an amount of 0.01 to 5% by weight, more preferably 0.1 to 2% by weight, based on the weight of the color conversion filter layer. You. If the content of the organic fluorescent dye is 0.01
When the content is less than 5% by weight, sufficient wavelength conversion cannot be performed, or when the content exceeds 5%, the color conversion efficiency is lowered due to the effect of concentration quenching and the like.

2) Matrix Resin Next, the matrix resin used in the color conversion filter layer of the present invention is obtained by subjecting a photo-curable or photo-curable curable resin (resist) to light and / or heat treatment to obtain radical species or It is insoluble and infusible by generating ionic species to polymerize or crosslink. In order to perform patterning of the color conversion filter layer, it is desirable that the photo-curable or photo-thermo-curable resin is soluble in an organic solvent or an alkaline solution in an unexposed state.

Specifically, the photo-curable or photo-heat-curable resin is composed of (1) a composition comprising an acrylic polyfunctional monomer or oligomer having a plurality of acroyl groups or methacryloyl groups, and a photo- or thermal polymerization initiator. (2) a composition comprising a polyvinylcinnamate and a sensitizer;
(3) a composition comprising a chain or cyclic olefin and a bisazide; and (4) a composition comprising a monomer having an epoxy group and an acid generator. In particular, the composition comprising the acrylic polyfunctional monomer or oligomer of (1) and a photo- or thermal polymerization initiator is capable of high-definition patterning and has high reliability such as solvent resistance and heat resistance. Is preferred. As described above, the matrix resin is formed by applying light and / or heat to the photo-curable or photo-thermo-curable resin.

The photopolymerization initiator, sensitizer and acid generator which can be used in the present invention are preferably those which initiate polymerization by light having a wavelength not absorbed by the contained fluorescent conversion dye. In the fluorescence conversion filter layer of the present invention, a photopolymerization initiator and a thermal polymerization initiator are added when the resin itself in the photocurable or photothermal curable resin can be polymerized by light or heat. It is also possible not to do it.

As the matrix resin, a solution or dispersion containing a photo-curable or photo-heat-curable resin and an organic fluorescent dye is applied on a support substrate to form a resin layer,
Then, a desired portion of the photo-curable or photo-thermo-curable resin is exposed to light and polymerized by exposure. After exposing a desired portion to insolubilize the photo-curable or photo-thermo-curable resin, patterning is performed.
The patterning can be performed by a conventional method such as removal using an organic solvent or an alkaline solution that dissolves or disperses the resin in the unexposed portion.

2. Polymer Film Layer 5 Preferred materials for the polymer film layer 5 have high transparency in the visible region (transmittance of 50% or more in a range of 400 to 700 nm), Tg of 100 ° C. or more, and a pencil hardness of 2H. It is a material having the above surface hardness, capable of forming a coating film smoothly on the color conversion filter layer, and not deteriorating the functions of the color conversion filter layers 2 to 4. Such a material is, for example, an imide-modified silicone resin (Japanese Unexamined Patent Publication No.
-134112 and JP reference Hei 7-218717 and JP Laid-Open No. 7-306311, etc.), dispersing acrylic, polyimide, an inorganic metal compound in a silicone resin or the like _{(TiO, Al 2 O 3,} SiO 2 , etc.) Materials (JP-A-5-119306, JP-A-7-104114)
Reference). Examples of the ultraviolet curable resin that can be used in the polymer film layer 5 include an epoxy-modified acrylate resin (see JP-A-7-48424).
Resins having acrylate monomer / oligomer / polymer reactive vinyl groups, resist resins (JP-A-6-30)
0910, JP-A-7-128519, JP-A-8-273394, JP-A-9-330793, etc.), fluororesin (JP-A-5-36475, JP-A-9-330793) And / or a thermosetting resin. Alternatively, an inorganic compound formed by a sol-gel method (described in Monthly Display 1997, Vol. 3, No. 7, JP-A-8-27934, etc.) can also be used.

The method for forming the polymer film layer 5 is not particularly limited. For example, a dry method (sputtering method, vapor deposition method, CVD method, etc.) or a wet method (spin coating method, roll coating method, casting method) It can be formed by conventional means such as.

3. Inorganic film layer 6 The inorganic film layer 6 has electric insulation, barrier properties against gas and organic solvent, and high transparency in the visible region (transmittance 50% in the range of 400 to 700 nm).
As described above, it is desirable to use a material having a hardness (preferably a pencil hardness of 2H or more) that can withstand the formation of the transparent electrode layer 7 on the inorganic film layer 6. For example, SiO _x , Al
Inorganic oxides such as O _x , TiO _x , TaO _x , SiN _x , S
An inorganic nitride such as iC: N or an inorganic material such as SiN _x O _y or diamond-like carbon (DLC) can be used. The method for forming the inorganic film layer 6 is not particularly limited, and can be formed by a conventional method such as a sputtering method, a CVD method, a vacuum evaporation method, and a dipping method.

The inorganic film layer 6 may be a single layer or a laminate of a plurality of layers.

When applying the inorganic film layer 6 to a color conversion type organic light emitting display, there are important factors to be considered. That is, consideration is given to the influence of the refractive index and the thickness of the inorganic film layer on the display performance.

In general, assuming a homogeneous material, the target wavelength is λ, the refractive index and film thickness of the p-th material are n _p and d _p , respectively, and the (p−1) -th layer and the p-th When the amplitude reflectivity and the energy reflectivity with respect to the layer are denoted by ρ _{p, p-1} and R _{p, p-1} , respectively, the transmittance t _n when light is incident perpendicularly to the film is: It is shown by the following equation. In addition,
Where γ _p is the phase of light transmitted through the p-th film, and γ _{p , p−1} is the phase of light transmitted through the p-th film taking into account the phase in the p−1 layer. is there.

[0054]

(Equation 1)

Here, when the inorganic film layer 6 is a single layer, the inorganic film layer which is in contact with the transparent electrode layer 7 with respect to the light having the target wavelength λ within the range of 450 to 500 nm emitted from the organic EL light emitting element. 6 is smaller than the refractive index of the transparent electrode layer 7, and the thickness of the inorganic film layer 6 is nd = sλ / 2 (n:
Refractive index, d: film thickness, s: natural number),
It is possible to increase the transmittance of light having the target wavelength λ and increase the half width of the interference peak. It is desirable that the refractive index of the inorganic film layer 6 is smaller than that of the transparent electrode layer 7 and larger than that of the polymer film layer 5.

Generally, the material of the transparent electrode layer 7 is IT
O (indium-tin oxide) or In ₂ O ₃ —Zn
An O-based material is used. Wavelength of these materials 450-5
The refractive index for light of 00 nm is about 2.0 and 2.1, respectively. The refractive index of the inorganic film layer 6 is 1.6 to
It is desirable that the value be about 1.8. In order to realize such a refractive index, a material such as SiO _x , SiO _x N _y , or Al _x O _y is selected.

In addition, at least two inorganic film layers 6
Can be used. Transparent in this case
The refractive index of the constituent layer in contact with the electrode layer 7 is set to that of the transparent electrode layer 7.
Smaller and higher refractive index materials
By alternately laminating the material with
Increases light transmittance and increases half width of interference peak
Can be done. Use a laminate of at least two layers
In this case, the odd-numbered layers from the transparent electrode layer 7 side
It is composed of a large material, and is evenly arranged from the transparent electrode layer 7 side.
The number-th layer may be made of a material having a low refractive index.
No. Alternatively, the odd-numbered layers from the transparent electrode layer 7 side
A transparent electrode layer made of a material having a small refractive index;
The even-numbered layers from the side are made of a material with a high refractive index
You may. In any of the above cases, the organic EL
Wavelength in the range of 450 to 500 nm emitted by the optical element
For light of λ, the film thickness of a material having a large refractive index is nd =
Satisfies sλ / 2 (n: refractive index, d: film thickness, s: natural number)
The thickness of the material having a small refractive index is nd = sλ / 4 (n:
Refractive index, d: film thickness, s: natural number)
No. For example, two inorganic film layers 6 using two kinds of materials are used.
If present, SiO _xAnd SiN_xOr DLC
And Al_xO_yEtc. can be used. In addition, three kinds
When three inorganic film layers 6 using materials are used, Si is used.
O_x, SiO_xN _yAnd SiN_xEtc. can be used
You. In particular, the refractive index of the constituent layers of the inorganic film layer 6 is determined by changing the refractive index of the transparent electrode layer.
From 7 side to polymer film layer 5 side
A configuration is preferred.

Also, the transmittance of light of a specific wavelength can be increased by a method of continuously decreasing the refractive index of the inorganic film layer 6 from the transparent electrode layer 7 side to the polymer film layer 5 side.
In addition, it is possible to increase the half width of the interference peak. For example, by continuously decreasing x (the ratio of N to Si) of SiN _x , the refractive index of the inorganic film layer 6 can be continuously reduced, and the above effect can be exhibited.

4. Transparent Electrode Layer 7 The material of the transparent electrode layer 7 is the excitation light emitted from the organic EL light emitting element (that is, light in the near ultraviolet to visible range, preferably blue to blue).
Blue-green light) must be transmitted efficiently. As such a material, ITO (indium-tin oxide) or In ₂ O ₃ —ZnO-based material can be used as described above. In addition, 450 to 450 emitted from the organic EL light-emitting element.
For light having a wavelength λ in the range of 500 nm, the thickness of the transparent electrode layer desirably satisfies the formula nd = sλ / 2 (n: refractive index, d: film thickness, s: natural number).

The conditions regarding the thickness of the inorganic film layer 6 described above,
By satisfying the condition regarding the thickness of the transparent electrode layer 7, the inorganic film layer 6 and the transparent electrode layer 7 of the present invention can
The excitation light emitted from the L light emitting element can be transmitted efficiently.

Since the shape of the transparent electrode layer 7 depends on the design of the organic EL element formed thereon,
It will be described later in the section of the element.

[0062] 5. Support substrate 1 Support substrate 1 used for the color conversion filter substrate of the present invention
Needs to be transparent to the light emitted from the color conversion filter layers 2 to 4 described above. In addition, the support substrate 1
It should withstand the conditions (solvent, temperature, etc.) used for forming the color conversion filter layers 2 to 4 and the polymer film layer 5, and preferably have excellent dimensional stability.

Preferred materials for the support substrate 1 are as follows:
It includes resins such as glass, polyethylene terephthalate, and polymethyl methacrylate. Fusion glass is particularly preferred.

6. Color Conversion Filter Substrate The color conversion filter substrate of the present invention is formed by forming one or more types of color conversion filter layers in a desired pattern on the support substrate 1 described above. The color conversion filter layer is formed by applying the composition including the above-described fluorescence conversion dye and resist onto the support substrate 1, exposing through a mask for forming a desired pattern, and patterning to have a desired pattern. Created. The color conversion filter layer has a thickness of 5 μm or more, preferably 8 to 15 μm.

When creating a color display,
It is preferable to form three types of color conversion filter layers of red, green and blue. In the case of using a light-emitting body that emits blue or blue-green light, as described above, the red and green color conversion filter layers and the blue filter layer, or the red color conversion filter layer and the green and blue It is also possible to form a filter layer.

The desired pattern of the color conversion filter layer and the filter layer depends on the application used. A set of red, green, and blue rectangular or circular areas may be formed on the entire support substrate. Alternatively, parallel red, green and blue stripes (having the desired width,
An area having a length corresponding to the length of the support substrate 1) may be set as one set and formed on the entire surface of the support substrate. It is also possible to arrange more (numerically and in terms of area) the specific color conversion filter layers than the color conversion filter layers of other colors.

B. Color conversion type organic EL color display The color conversion type color display of the present invention includes the above-mentioned color conversion filter substrate and the organic EL light emitting element provided on the transparent electrode layer 6 of the filter substrate. That is, light in the near-ultraviolet to visible region, preferably light in the blue to blue-green region, emitted from the light-emitting element enters the color conversion filter layer, and emits visible light of a different wavelength from the color conversion filter layer. It was made.

The organic EL device comprises a transparent electrode layer 7 and a second
It has a structure in which at least an organic light emitting layer is supported between an electrode layer and a hole injection layer or an electron injection layer as necessary. Specifically, a layer having the following layer configuration is employed.

(1) anode / organic light emitting layer / cathode (2) anode / hole injection layer / organic light emitting layer / cathode (3) anode / organic light emitting layer / electron injection layer / cathode (4) anode / hole injection Layer / organic light emitting layer / electron injection layer / cathode (5) anode / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode In the above layer structure, at least one of the anode and the cathode is as described above. The transparent electrode layer 7 on the color conversion filter substrate is used. In the present invention, preferably, the transparent electrode layer 7 is used as an anode.

FIG. 2 shows an example of the organic EL color display of the present invention. FIG. 2 shows a portion corresponding to one pixel of an organic light-emitting element having a plurality of pixels for use as a multi-color or full-color display of a color conversion system. Each color conversion filter layer 2 on the transparent electrode layer 7 of the color conversion filter substrate shown in FIG.
At positions corresponding to 3 and 4, a hole injection layer 8, a hole transport layer 9, an organic light emitting layer 10, an electron injection layer 11, and a cathode (second electrode layer) 12 are sequentially stacked.

Known materials are used as the materials for the respective layers. In order to obtain blue to blue-green light emission, the organic light emitting layer 10 includes, for example, a benzothiazole-based, benzimidazole-based, benzoxazole-based fluorescent whitening agent, a metal chelated oxonium compound, a styrylbenzene-based compound, Aromatic dimethylidin compounds are preferably used.

The cathode 12 is formed from a metal electrode. The patterns of the anode 7 and the cathode 12 may be formed in parallel stripes and cross each other.
In that case, the organic light emitting device of the present invention can perform matrix driving, that is, when a voltage is applied to a specific stripe of the anode 7 and a specific stripe of the cathode 12, the organic light emitting element 10 A portion where these stripes intersect emits light. Therefore, by applying a voltage to selected stripes of the anode 7 and the cathode 12, only a portion where a specific fluorescent color conversion filter layer and / or a simple filter layer is located can emit light.

The anode 7 may be a uniform flat electrode having no stripe pattern, and the cathode 12 may be patterned so as to correspond to each pixel. In that case, a so-called active matrix drive can be performed by providing a switching element corresponding to each pixel.

[0074]

EXAMPLES In the following examples, the thickness of the inorganic film layer was measured by using a scanning electron microscope (SEM) and calibrating with a standard sample. The measurement error at this time is ± 10 nm
Met. The refractive index of the inorganic film layer was calculated from a value measured by a spectroscopic ellipsometer. In order to improve the accuracy of the refractive index measurement, a plurality of samples having different film thicknesses were measured. The measurement error at this time was ± 0.05.

Example 1 A UV curable resin (epoxy-modified acrylate) was applied on a glass substrate by spin coating, and irradiated with light from a high-pressure mercury lamp to form a polymer film layer having a thickness of 8 μm. . On this polymer film layer, boron-doped Si is used as a target and 20% O ₂ is mixed.
An SiO _x film having a thickness of about 300 nm was formed by an RF sputtering method in a r atmosphere without heating the substrate. As a result of measuring the refractive index of this SiO _x film with respect to light having a wavelength of 475 nm using an ellipsometer, the refractive index was about 1.6. This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 2).

On the SiO _x film thus formed, I
20% O ₂ using DIXO (made by Idemitsu Kosan) target
A 220 nm-thick In ₂ O ₃ -ZnO-based transparent electrode layer was formed by a DC sputtering method in an atmosphere of an Ar atmosphere in which was mixed. The wavelength of this transparent electrode layer is 475n.
The refractive index for light of m was about 2.1. This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 2).

(Example 2) As in Example 1, a polymer film layer was formed on a glass substrate. On the polymer film layer,
30% N ₂ with boron-doped Si as target
Not heating substrate in Ar atmosphere mixed with
A SiN _x film having a thickness of about 120 nm was formed by a sputtering method. As a result of measuring the refractive index of this SiN _x film with respect to light having a wavelength of 475 nm by an ellipsometer, the refractive index was about 2.0. This film has the aforementioned nd = sλ / 2 (s =
Satisfies the relationship of 1).

On the thus-formed SiN _x film, a SiO 2 film having a thickness of about 75 nm was formed by RF sputtering using a boron-doped Si target as a target in an Ar atmosphere containing 20% O ₂ without heating the substrate. _{An x} film was formed. As a result of measuring the refractive index of this SiO _x film with respect to light having a wavelength of 475 nm using an ellipsometer, the refractive index was about 1.
It was 6. This film has the above-mentioned nd = sλ / 4 (s = 1)
Satisfy the relationship.

Finally, an IDIXO (manufactured by Idemitsu Kosan) target was used on the SiO _x film thus formed,
By a DC sputtering method in an Ar atmosphere containing 0% O ₂ , a 220 nm-thick In ₂ O ₃ —Z
An nO-based transparent electrode layer was formed. The refractive index of this transparent electrode layer with respect to light having a wavelength of 475 nm was about 2.1.
This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 2).

Example 3 As in Example 1, a glass substrate was used.
A polymer film layer was formed on the plate. On this polymer film layer,
U-doped Si, 20% O_TwoTo
RF switches that do not heat the substrate in a mixed Ar atmosphere
By the putter method, a SiO film having a thickness of about 75 nm _xTo form a film
Was. This SiO for light of wavelength 475 nm_xFilm refraction
The refractive index was measured with an ellipsometer, and as a result, the refractive index was about 1.
It was 6. This film has the above-mentioned nd = sλ / 4 (s = 1)
Satisfy the relationship.

An SiN _x film having a thickness of about 120 nm is formed on the SiO _x film by RF sputtering without heating the substrate in an Ar atmosphere mixed with 30% N ₂ using boron-doped Si as a target. did. Wavelength 4
As a result of measuring the refractive index of this SiN _x film with respect to light of 75 nm by an ellipsometer, the refractive index was about 2.0. This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 1).

Further, on the SiN _x film thus formed, boron-doped Si was
A SiO _x film having a thickness of about 75 nm was formed by an RF sputtering method in which the substrate was not heated in an Ar atmosphere mixed with% O ₂ . This SiO _x for light with a wavelength of 475 nm
As a result of measuring the refractive index of the film with an ellipsometer, the refractive index was about 1.6. This film has the above-mentioned nd = sλ / 4.
(S = 1) is satisfied.

Finally, an IDIXO (manufactured by Idemitsu Kosan) target was used on the SiO _x film thus formed.
By a DC sputtering method in an Ar atmosphere containing 0% O ₂ , a 220 nm-thick In ₂ O ₃ —Z
An nO-based transparent electrode layer was formed. The refractive index of this transparent electrode layer with respect to light having a wavelength of 475 nm was about 2.1.
This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 2).

Example 4 As in Example 1, a glass substrate was used.
A polymer film layer was formed on the plate. On top of this polymer membrane layer,
SiH at a substrate temperature of 180 ° C_FourAnd NH_ThreeUse gas
Plasma SiN_xA film was formed.
At the beginning of this film formation, SiH_Four: NH _ThreeFlow rate ratio
The raw material gas was introduced at 15.0, and S
iN_xA film was formed. Then, SiH_Four: NH_ThreeFlow ratio
Film formation is continued while gradually increasing 180 nm (total
240 nm thick SiN_xA film was formed. Ultimate
SiH_Four: NH_ThreeWas 20.0.

On the SiN _x film thus formed, I
20% O ₂ using DIXO (made by Idemitsu Kosan) target
A 220 nm-thick In ₂ O ₃ -ZnO-based transparent electrode layer was formed by a DC sputtering method in an atmosphere of an Ar atmosphere in which was mixed. The wavelength of this transparent electrode layer is 475n.
The refractive index for light of m was about 2.1. This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 2).

(Comparative Example 1) In the same manner as in Example 1,
A polymer film layer was formed on the plate. On this polymer film layer,
U-doped Si, 20% O_TwoTo
RF switches that do not heat the substrate in a mixed Ar atmosphere
By the putter method, a SiO film having a thickness of about 75 nm _xTo form a film
Was. This SiO for light of wavelength 475 nm_xFilm refraction
The refractive index was measured with an ellipsometer, and as a result, the refractive index was about 1.
It was 6. This film has the above-mentioned nd = sλ / 2 (s: self
Does not satisfy the relationship of nd = sλ / 4 (s =
Satisfies the relationship of 1).

On the SiO _x film thus formed, I
20% O ₂ using DIXO (made by Idemitsu Kosan) target
A 220 nm-thick In ₂ O ₃ -ZnO-based transparent electrode layer was formed by a DC sputtering method in an atmosphere of an Ar atmosphere in which was mixed. The wavelength of this transparent electrode layer is 475n.
The refractive index for light of m was about 2.1. This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 2).

[Evaluation of Inorganic Film Layer] The samples prepared in Examples 1 to 4 and Comparative Example 1 were measured at a wavelength of 300 to 700 nm using a UV-PC2100 ultraviolet-visible light transmittance meter (manufactured by Shimadzu Corporation). The light transmittance within the range was measured.
FIG. 3 shows the measurement results.

As compared with Comparative Example 1, Examples 1 to 5 of the present invention
It was confirmed that the sample No. 4 had an improved transmittance at a wavelength of 475 nm or a wider transmission curve peak. The transmittances of the samples of the examples at the wavelengths of 450 nm and 500 nm are reduced within 3% of the maximum transmittances of the respective samples. From the above results, it was found that the inorganic film layer of the present invention was useful for producing a color organic EL display.

The effect of the first embodiment is that the refractive index of the inorganic film layer is smaller than the refractive index of the transparent electrode layer, and nd = sλ / 2.
This is because the relationship of (s = 2) was satisfied. The effects of Examples 2 and 3 are that the inorganic film layer formed by alternately laminating materials having a large refractive index and a material having a small refractive index is nd = sλ / 2 (s: natural number) for a material having a large refractive index.
And for low index materials n
This is because the relationship of d = sλ / 4 (s: natural number) was satisfied. The effect of Example 4 is attributable to changing the composition of the inorganic film layer so that the refractive index of the transparent electrode and the inorganic film layer adjacent to the transparent electrode decreases toward the polymer film layer.

(Embodiment 5) One example in which the laminated inorganic film layer of the present invention is applied will be described below with reference to the drawings.

FIG. 1 is a sectional view of an example of a color conversion filter substrate. A red conversion filter layer 2, a green conversion filter layer 3, and a blue conversion filter layer 4 are formed on a transparent support substrate 1 with a predetermined pattern. In addition,
The blue conversion filter layer 4 in this embodiment is a simple blue filter layer having no color conversion function. A polymer film layer 5 and an inorganic film layer 6 are formed on these conversion filter layers, and one or more electrically independent transparent electrode layers 7 are further provided thereon.

FIG. 2 is a cross-sectional view of an example of a color conversion type color organic EL display, in which required layers including an organic EL light emitting layer are formed on the color conversion filter substrate.

[Preparation of Blue Filter Layer 4] Fusion glass (50 × 50 × 1.1 mm) as transparent substrate 1
On top, a blue filter material (Fuji Hunt Electronics Technology: Color Mosaic CB-7001)
It was applied using a spin coating method. The coating film is patterned by a photolithographic method, and has a line width of 0.1.
Thus, a blue filter 4 having a stripe pattern having a thickness of 6 mm and a pitch (period) of 0.33 mm was obtained.

[Preparation of Green Conversion Filter Layer 3] Coumarin 6 (0.7 parts by mass) was used as a fluorescent dye, and propylene glycol monoethyl acetate (PEGMA) 12 as a solvent was used.
It was dissolved in 0 parts by mass. To this solution, 100 parts by mass of a photopolymerizable resin "V259PA / P5" (trade name, Nippon Steel Chemical Co., Ltd.) was added and dissolved to obtain a coating liquid.

On the transparent support substrate on which the blue filter layer has been formed, the coating solution prepared as described above is applied by spin coating, patterned by photolithography, and has a line width of 0.1 mm and a pitch ( Cycle) 0.33 mm,
A green color conversion filter 3 having a 10 μm-thick stripe pattern was obtained.

[Preparation of red conversion filter layer 2] Coumarin 6 (0.6 parts by mass), rhodamine 6G
(0.3 parts by mass), Basic Violet 11 (0.
3 parts by mass) were dissolved in 120 parts by mass of propylene glycol monoethyl acetate (PEGMA) as a solvent. For the solution, the photopolymerizable resin “V259PA /
P5 "(trade name, Nippon Steel Chemical Co., Ltd.) was added and dissolved to obtain a coating liquid.

On the transparent support substrate on which the blue filter layer 4 and the green conversion filter layer 3 are formed, the coating solution prepared as described above is applied by a spin coating method, and is patterned by a photolithographic method. Width 0.1mm,
A red conversion filter 2 having a stripe pattern with a pitch (period) of 0.33 mm and a film thickness of 10 μm was obtained.

The linear pattern of the red conversion filter layer 2, the green conversion filter layer 3, and the blue filter layer 4 formed as described above has a gap width of 0.01 between each.
mm.

[Preparation of Polymer Film Layer 5] A UV-curable resin (epoxy-modified acrylate) was applied on the above-mentioned fluorescence conversion filter layers 2 to 4 by a spin coating method, and irradiated with a high-pressure mercury lamp. An 8 μm thick polymer film layer 5 was formed. At this time, the pattern of the fluorescence conversion filter has no deformation,
Further, the upper surface of the polymer film layer was flat.

[Preparation of Inorganic Film Layer 6] The aforementioned polymer film layer 5
A boron-doped Si as a target, a deposition pressure of 0.45 Pa, a deposition power of 1.5 W, and 20%
A 120 nm-thick SiN _x film was formed by a reactive RF sputtering method in an Ar atmosphere mixed with N ₂ . The refractive index of this SiN _x film with respect to light having a wavelength of 475 nm is
As a result of measurement with an ellipsometer, the refractive index was about 2.1. This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 1).

On this SiN _x film, reactive RF sputtering was performed in an Ar atmosphere in which boron-doped Si was used as a target, a film forming pressure of 0.45 Pa, a film forming power of 1.5 W, and 20% O ₂ were mixed. As a result, a 75 nm-thick SiO _x film was formed. As a result of measuring the refractive index of this SiO _x film with respect to light having a wavelength of 475 nm using an ellipsometer, the refractive index was about 1.6. This film has the aforementioned nd =
The relationship of sλ / 4 (s = 1) is satisfied.

[Production of Transparent Electrode Layer 7] On the inorganic film layer 6 thus formed, a transparent electrode (ID
IXO). After applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka) on the IDIXO, patterning is performed by a photolithographic method, and a width corresponding to each of the fluorescence conversion filter layers 2 to 4 is set. Transparent electrode layer 7 having a 0.094 mm gap 0.016 mm and a line pattern having a thickness of 100 nm
Was formed to obtain a color conversion filter substrate. The refractive index of this transparent electrode layer with respect to light having a wavelength of 475 nm was about 2.1. This film satisfies the aforementioned relationship of nd = sλ / 2 (s = 1). This transparent electrode layer 7 is used as an anode.

[Preparation of Organic EL Element] As shown in FIG. 2, a hole injection layer 8 / a hole transport layer 9 / an organic light emitting layer 10 / electrons were formed on the color conversion filter substrate manufactured as described above. The injection layer 11 / cathode 12 was formed, and an organic EL light emitting device having a six-layer structure was formed together with the transparent electrode layer 7.

The color conversion filter substrate was mounted in a resistance heating evaporation apparatus, and the hole injection layer 8, the hole transport layer 9, the organic light emitting layer 1
0, the electron injection layer 11 was sequentially formed on the entire surface without breaking vacuum. During the film formation, the internal pressure of the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. Copper phthalocyanine (Cu
Pc) was laminated to a thickness of 100 nm. As the hole transport layer 9,
4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was laminated to a thickness of 20 nm. As the organic light emitting layer 10, 4,4′-bis (2,2 ′)
-Diphenylvinyl) biphenyl (DPVBi) to 30
nm. As the electron injection layer 11, an aluminum chelate (tris (8-hydroxyquinoline) aluminum complex, Alq) was laminated to a thickness of 20 nm. Table 1 shows the structural formula of the material used for each layer.

[0106]

[Table 1]

Next, without breaking vacuum, the anode (transparent electrode layer) 7 has a width of 0.30
Mg / Ag (mass ratio of 10 /
1) A cathode 12 composed of a layer was formed.

The organic light-emitting device thus obtained was sealed in a sealing glass (not shown) under a dry nitrogen atmosphere (both oxygen and moisture concentrations were 10 ppm or less) in a glove box.
And a UV curable adhesive to obtain a color organic EL display.

Example 6 A color organic EL display was manufactured in the same manner as in Example 5, except that the inorganic film layer 6 was manufactured by the method described below.

As the inorganic film layer 6, a SiN _x film was formed at a substrate temperature of 180 ° C. by a plasma CVD method using SiH ₄ and NH ₃ gases. At the beginning of this film formation, a source gas was introduced at a flow rate ratio of SiH ₄ : NH ₃ of 15.0, and a SiN _x film having a thickness of about 60 nm was formed.
Thereafter, film formation was continued while gradually increasing the flow rate ratio of SiH ₄ : NH ₃ to form a SiN _x film having a total thickness of 240 nm. The final flow rate ratio of SiH ₄ : NH ₃ is 20.0
Met.

Comparative Example 2 A color organic EL display was produced in the same manner as in Example 5, except that the inorganic film layer 6 was produced by the method described below.

As the inorganic film layer 6, boron-doped S
An SiO _x film having a thickness of about 60 nm was formed by RF sputtering without heating the substrate in an Ar atmosphere containing 20% O ₂ using i as a target. Wavelength 475nm
As a result of measuring the refractive index of this SiO _x film with respect to the light of the above by an ellipsometer, the refractive index was about 1.6. This film does not satisfy the aforementioned relationship of nd = sλ / 2 (s: natural number).

[Evaluation of Color Organic EL Display] A driving test was performed on the displays manufactured in Examples 5 and 6 and Comparative Example 2. Drive frequency 6
The area luminance was compared by driving by line sequential scanning at 0 Hz, a duty ratio of 1/60, and a current amount per pixel of 2 mA, and lighting only green. The results are shown in Table 2 below.

[0114]

[Table 2]

Color organic EL using inorganic film layer of the present invention
It was found that the display improved the brightness by 10% or more.

[0116]

By using an inorganic film layer satisfying the refractive index and the film thickness of the additive according to the present invention, the light of the organic EL light emitting element can be transmitted efficiently, and the organic EL light emitting element By suppressing the generation of moisture that causes a deterioration in characteristics, it is possible to provide a color organic EL display that maintains stable light-emitting characteristics for a long time. According to the present invention, an organic EL display of a color conversion system having excellent reliability is realized.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a color conversion filter substrate of the present invention.

FIG. 2 shows an organic EL using the color conversion filter substrate of the present invention.
It is a schematic sectional drawing of a color display.

FIG. 3 is a graph showing the light transmittance of the samples of Examples 1 to 4 and Comparative Example 1.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 transparent support substrate 2 red conversion filter 3 green conversion filter 4 blue conversion filter 5 polymer film layer 6 inorganic film layer 7 transparent electrode layer 8 hole injection layer 9 hole transport layer 10 organic light emitting layer 11 electron injection layer 12 cathode

[Procedure amendment]

[Submission date] December 18, 2000 (200.12.
18)

[Procedure amendment 1]

[Document name to be amended] Drawing

[Correction target item name] Fig. 1

[Correction method] Change

[Correction contents]

FIG.

[Procedure amendment 2]

[Document name to be amended] Drawing

[Correction target item name] Figure 2

[Correction method] Change

[Correction contents]

FIG. 2

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H048 BA02 BA45 BB02 BB10 BB14 BB41 CA04 CA14 CA19 CA23 CA24 3K007 AB02 AB04 AB11 AB18 BA06 BB06 CA01 CB01 DA01 DB03 EA04 EB00 FA01

Claims (17)

[Claims] 1. A transparent support substrate, a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern, and the color conversion filter A polymer film layer covering the layer and being transparent and formed flat; a transparent inorganic film layer formed on the polymer film layer; and one or more electrical films on the inorganic film layer A color conversion filter substrate comprising at least a transparent electrode layer formed in an independent region, wherein the inorganic film layer is a single layer;
For a wavelength λ within the range of 00 nm or less, the refractive index of the inorganic film layer is smaller than the refractive index of the transparent electrode layer, and the film thickness d of the inorganic film layer is represented by the following formula: nd = sλ / 2. A color conversion filter substrate which satisfies the following relationship: 2 where n is a refractive index of the inorganic film layer with respect to light having a wavelength λ, and s is a natural number. 2. A transparent support substrate, a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern, and the color conversion filter A polymer film layer covering the layer and being transparent and formed flat; a transparent inorganic film layer formed on the polymer film layer; and one or more electrical films on the inorganic film layer A color conversion filter substrate comprising at least a transparent electrode layer formed in an independent region, wherein the inorganic film layer is composed of a laminate of at least two layers, and is in a range of 450 nm or more and 500 nm or less. With respect to the wavelength λ, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and the 2p−1th and 2pth inorganic film layers counted from the transparent electrode layer. Constituent layers (p is natural In a) it _{is, n 2p-1> n 2p} ; n 2p-1 d 2p-1 = s 2p-1 λ / 2; and in _{n 2p d 2p = s 2p λ} / 4 ( wherein, n _u is u th , And _du is the film thickness of the u-th layer, and s _u is a natural number. 3. The color conversion filter substrate according to claim 2, wherein, for a wavelength λ in a range of 450 nm or more and 500 nm or less, the refractive index of a layer constituting the inorganic film layer is higher than that of the transparent electrode layer. A color conversion filter substrate characterized in that the size of the color conversion filter gradually decreases toward the polymer film layer. 4. A single or plural kinds of color conversion filter layers formed by forming a transparent support substrate, a resin film containing a fluorescent dye disposed on the support substrate in a desired pattern, and the color conversion filter. A polymer film layer covering the layer and being transparent and formed flat; a transparent inorganic film layer formed on the polymer film layer; and one or more electrical films on the inorganic film layer A color conversion filter substrate comprising at least a transparent electrode layer formed in an independent region, wherein the inorganic film layer is composed of a laminate of at least two layers, and is in a range of 450 nm or more and 500 nm or less. With respect to the wavelength λ, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and the 2p−1th and 2pth inorganic film layers counted from the transparent electrode layer. Constituent layers (p is natural In a) it _{is, n 2p-1 <n 2p} ; n 2p-1 d 2p-1 = s 2p-1 λ / 4; during and _{n 2p d 2p = s 2p λ} / 2 ( wherein, n _u is u th , And _du are the thickness of the u-th layer, and s _u is a natural number. 5. A transparent support substrate, a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern, and the color conversion filter A polymer film layer covering the layer and being transparent and formed flat; a transparent inorganic film layer formed on the polymer film layer; and one or more electrical films on the inorganic film layer A color conversion filter substrate comprising at least a transparent electrode layer formed in an independent region, wherein the inorganic film layer is a single layer, and the inorganic film layer comprises:
A color conversion filter substrate having a composition that is continuously changed such that the refractive index decreases gradually from the transparent electrode layer toward the polymer film layer. 6. For a wavelength λ where the thickness d of the transparent electrode layer is in a range of 450 nm or more and 500 nm or less, the following formula: nd = sλ / 2 (where n is the transparent property to light having a wavelength λ) The color conversion filter substrate according to any one of claims 1 to 5, wherein the refractive index of the electrode layer and s is a natural number are satisfied. 7. A color obtained by sequentially laminating a light emitting layer containing at least a light emitting material and a second electrode layer on the color conversion filter substrate according to any one of claims 1 to 6. Conversion type color display. 8. A transparent support substrate is prepared, and a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern are formed. The color conversion filter layer is coated to form a transparent and flat polymer film layer, and the inorganic film layer is a single layer and is in a range of 450 nm or more and 500 nm or less. With respect to the wavelength λ, an inorganic film layer having a film thickness d that satisfies the following formula: nd = sλ / 2 (where n is a refractive index for light having a wavelength λ, and s is a natural number) And forming at least one transparent electrode layer formed in one or more electrically independent regions on the inorganic film layer and having a refractive index larger than the refractive index of the inorganic film layer. Characterized by a color conversion filter substrate Production method. 9. A transparent support substrate is prepared, and a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern are formed. The color conversion filter layer is coated to form a transparent and flat polymer film layer, and the inorganic film layer is composed of a laminate of at least two layers, and has a thickness of 450 nm or more and 500 nm or less. For a wavelength λ in the range, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and the 2p−1th and 2pth numbers counted from the transparent electrode layer. layers constituting the inorganic layer (p is a natural _{number), n 2p-1> n 2p} ; n 2p-1 d 2p-1 = s 2p-1 λ / 2; and n _2p d _2p = s _2p λ / 4 (where, n _u is the refractive index of the u-th layer, d _u is the u-th layer thickness, s _u Is a natural number), and an inorganic film layer having a film thickness d satisfying the following relationship is formed in one or more electrically independent regions on the inorganic film layer, and the refractive index of the inorganic film layer is A method for manufacturing a color conversion filter substrate, comprising at least forming a transparent electrode layer having a larger refractive index. 10. The method according to claim 1, wherein the refractive index of the inorganic film layer is gradually decreased from the transparent electrode layer toward the polymer film layer for a wavelength λ in a range of 450 nm or more and 500 nm or less. The method for manufacturing a color conversion filter substrate according to claim 9. 11. A transparent support substrate is prepared, and a single or plural kinds of color conversion filter layers are formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern, The color conversion filter layer is coated to form a transparent and flat polymer film layer, and the inorganic film layer is composed of a laminate of at least two layers, and has a thickness of 450 nm or more and 500 nm or less. For a wavelength λ in the range, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and the 2p−1th and 2pth numbers counted from the transparent electrode layer. The layers constituting the inorganic film layer (p is a natural number) include: n _2p-1 <n _2p ; n _2p-1 d _2p-1 = s _2p-1 λ / 4; and n _{2pd 2p} = s _2p λ / 2 (wherein, n _u is the refractive index of the u-th layer, d _u is the u-th layer thickness, _u forms a inorganic layer having a thickness d that satisfies a is) the relationship natural number, and is formed into one or more electrically independent region on the inorganic layer, and the refraction of the inorganic membrane layer At least forming a transparent electrode layer having a refractive index higher than the refractive index. 12. A transparent support substrate is prepared, and a single or plural types of color conversion filter layers are formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern. Forming a transparent and flat polymer film layer, forming an inorganic film layer having a continuously changed composition, and forming an inorganic film layer on the inorganic film layer. Or manufacturing a color conversion filter substrate at least comprising forming a transparent electrode layer formed in a plurality of electrically independent regions and having a refractive index larger than the refractive index of the inorganic film layer. Method. 13. A transparent support substrate is prepared, and a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern are formed. The color conversion filter layer is coated to form a transparent and flat polymer film layer, and the inorganic film layer is a single layer and is in a range of 450 nm or more and 500 nm or less. With respect to the wavelength λ, an inorganic film layer having a film thickness d that satisfies the following formula: nd = sλ / 2 (where n is a refractive index for light having a wavelength λ, and s is a natural number) Forming a transparent electrode layer formed in one or more electrically independent regions on the inorganic film layer and having a refractive index larger than the refractive index of the inorganic film layer, and containing at least a luminescent material; Forming an organic light emitting layer; The color conversion color display manufacturing method characterized by comprising at least that to form a layer. 14. A transparent support substrate is prepared, and a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern are formed; The color conversion filter layer is coated to form a transparent and flat polymer film layer, and the inorganic film layer is composed of a laminate of at least two layers, and has a thickness of 450 nm or more and 500 nm or less. For a wavelength λ in the range, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and the 2p−1th and 2pth numbers counted from the transparent electrode layer. layers constituting the inorganic layer (p is a natural _{number), n 2p-1> n 2p} ; n 2p-1 d 2p-1 = s 2p-1 λ / 2; and n _2p d _2p = s _2p λ / 4 (where, n _u is the refractive index of the u-th layer, the d _u of u th layer thickness, _u is formed in a region forming the inorganic layer having a thickness d, independent one or more electrically on inorganic film layer satisfying a is) the relationship natural number, and the refractive index of the inorganic membrane layer Forming a transparent electrode layer having a refractive index larger than that of at least a light emitting material, forming an organic light emitting layer containing at least a light emitting material, and forming a second electrode layer. Production method. 15. The method according to claim 1, wherein the refractive index of the inorganic film layer is sequentially reduced from the transparent electrode layer toward the polymer film layer for a wavelength λ in a range of 450 nm or more and 500 nm or less. The method of manufacturing a color conversion color display according to claim 14. 16. A transparent support substrate is prepared, and a single or plural types of color conversion filter layers are formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern. The color conversion filter layer is coated to form a transparent and flat polymer film layer, and the inorganic film layer is composed of a laminate of at least two layers, and has a thickness of 450 nm or more and 500 nm or less. For a wavelength λ in the range, the refractive index of the inorganic film layer adjacent to the transparent electrode layer is smaller than the refractive index of the transparent electrode layer, and the 2p−1th and 2pth numbers counted from the transparent electrode layer. The layers constituting the inorganic film layer (p is a natural number) include: n _2p-1 <n _2p ; n _2p-1 d _2p-1 = s _2p-1 λ / 4; and n _{2pd 2p} = s _2p λ / 2 (wherein, n _u is the refractive index of the u-th layer, d _u is the u-th layer thickness, _u is formed in a region forming the inorganic layer having a thickness d, independent one or more electrically on inorganic film layer satisfying a is) the relationship natural number, and the refractive index of the inorganic membrane layer Forming a transparent electrode layer having a refractive index larger than that of at least a light emitting material, forming an organic light emitting layer containing at least a light emitting material, and forming a second electrode layer. Production method. 17. A transparent support substrate is prepared, and a single or plural types of color conversion filter layers formed by forming a resin film containing a fluorescent dye on the support substrate in a desired pattern are formed; Forming a transparent and flat polymer film layer, forming an inorganic film layer having a continuously changed composition, and forming an inorganic film layer on the inorganic film layer. Or forming a transparent electrode layer formed in a plurality of electrically independent regions and having a refractive index larger than the refractive index of the inorganic film layer, forming an organic light emitting layer containing at least a light emitting material, and A method for producing a color conversion color display, comprising at least forming two electrode layers.