KR20090104765A - Color filter - Google Patents

Abstract

PURPOSE: A color filter is provided to be proper to a chromatic purity so that the color filter may satisfy the standard for green and blue pixels overlapped with a visual acuity of other colors. CONSTITUTION: A color filter includes a green pixel region and a blue pixel region. The light transmittance rate of the green pixel region is over 15% for 600 nm~650 nm. The peak of the light transmittance rate of the green pixel region exist within 500 nm~550 nm. The light transmittance rate of the blue pixel region is below 30% for 500 nm~550 nm, and the peak of the light transmittance rate of the blue pixel region exits within 410 nm~470 nm.

Description

Color filter {COLOR FILTER}

The present invention relates to a color filter used for an organic EL display element.

As a method of manufacturing a full color organic EL display element, the following two methods are known.

The first method is a method of forming an organic EL light emitting layer for each color by separately applying an organic EL light emitting material for emitting each color to each pixel of red, green, and blue in a fine pattern (for example, Japanese Patent Laid-Open Publication). 9-167684, Japanese Patent Laid-Open No. 11-067454, etc.). This method includes, for example, photolithography, mask deposition, printing, inkjet, and the like.

First, the photolithography method is not suitable for the processing of thermally or chemically unstable organic EL light emitting materials because the processing temperature is high or a highly reactive chemical liquid treatment is required.

Next, the mask deposition method is a method of forming organic EL light emitting layers of respective colors by vacuum evaporation and patterning a low molecular weight organic EL light emitting material using a deposition mask, but it is not possible to produce a large size and excellent positional precision deposition mask. there is a problem. Therefore, the formation of a large surface and a fixed color pattern cannot be performed. In addition, since the characteristics such as luminance and lifespan of the organic EL light emitting layer constituting each pixel are different, the color balance changes with use time, and the characteristics of the display element are limited to the organic EL light emitting material having the lowest characteristics. have.

On the other hand, the printing method, in particular, the inkjet method, in which the organic EL light emitting material is inkized, dividedly applied by printing or inkjet to form an organic EL light emitting layer, has been noted in that a pattern of a fixed color can be formed. It becomes effective in the use of easy high molecular organic EL.

The second method is a method of extracting light emission of each color of red, green and blue by injecting white light from a white organic EL light emitting layer into a color filter (for example, Japanese Patent Application Laid-Open No. 8-321380, Japanese Patent). See Published Publication No. 2004-227854). In this method, since it is possible to use the pigment which is excellent in reliability and durability in a color filter, it becomes possible to manufacture the long life organic electroluminescent display element in which a color balance does not change. It is also possible to form in the color filter a pattern containing, for example, a fluorescent substance which absorbs blue light and emits green or red light instead of the pigment. Moreover, in the method using such a color filter, the color filter manufacturing technique of a liquid crystal display element can be diverted, and the large area and fixed organic EL display element can be manufactured.

In general, light emission from the organic EL light emitting layer tends to extend to the long wavelength side. As a result, especially for green pixels and blue pixels where the long wavelength side overlaps the visibility of different colors, even when the emission peaks of the organic EL light emitting layers of each color are matched to desired wavelengths, color purity that satisfies TV standards such as NTSC and EBU is achieved. It becomes difficult. Therefore, it is necessary to provide an appropriate color filter for each pixel of each color also in the organic electroluminescence display element produced by the 1st method, and the organic electroluminescence display element produced by the 2nd method.

This invention is made | formed in view of such a problem, and an object of this invention is to provide the color filter suitable for the improvement of the color purity of organic electroluminescent display element, and its manufacturing method.

In order to solve the above-mentioned problem, the 1st color filter of this invention is equipped with the green pixel area | region, and the light transmittance of a green pixel area | region is 15% or less over 600 nm-650 nm.

Moreover, the 2nd color filter of this invention is equipped with a blue pixel area | region, and the light transmittance of a blue pixel area | region is 30% or less over 500 nm-550 nm.

According to the present invention, the color purity of the pixel of the organic EL display element can be increased.

Here, it is preferable that the peak of the light transmittance of a green pixel area exists in the range of 500 nm-550 nm, and the light transmittance in the peak of a light transmittance is 50% or more.

Moreover, it is preferable that the peak of the light transmittance of a blue pixel area exists in the range of 410 nm-470 nm, and the light transmittance in the peak of a light transmittance is 50% or more.

According to these, the utilization efficiency of light becomes high.

Moreover, it is preferable for the high molecular organic EL display element. In particular, since the polymer organic EL display element has a large extension of the wavelength spectrum of the emitted light, the effect of the present invention is high.

Moreover, it is preferable to contain dye, a pigment, or these mixture as a coloring material of a pixel area.

Moreover, it is preferable that a coloring material is a coloring material which has a phthalocyanine, a quinophthalone, a dioxazine, a pyrimidine, barbituric acid, a polymethine, a triallyl methane, anthraquinone, a pyridone azo, or a xanthene frame | skeleton.

Specifically, the blue dye represented by following formula (1) or formula (2) is mentioned as a coloring material.

In the formulas (1) and (2), the ring Z ₁ to ring Z ₈ each independently represent a heterocycle that may have a substituent. X ^a- is a halogen anion, ClO ₄ ^- shows the organic carboxylic acid anion, organic acid anion, a boron anion or an organometallic complex anion ^-, OH. k is a valence of an anion and shows the integer of 1 or 2. _{1 ^Y-2} and Y ^- is a halogen anion, ClO _4, each ^{independently-represent} the, monovalent organic acid anion, a monovalent organic acid anion, a monovalent anion or a monovalent organic boron metal complex anion ^-, OH. l and l 'respectively independently represent the integer of 0 or more and 3 or less. L ₁ represents a hydrocarbon group which may be divalent.

Moreover, the blue dye represented by following formula (3) is mentioned as a coloring material.

In said Formula (3), ring Z <_9> and ring Z <_10> respectively independently represent the heterocyclic ring which may have a substituent. X <^-> represents a halogen anion, ClO <_4> ^- , OH <^-> , monovalent organic carboxylic acid anion, monovalent organic sulfonic acid anion, monovalent boron anion, or monovalent organometallic complex anion. l represents the integer of 0 or more and 3 or less.

Moreover, the dye represented by following formula (4) is mentioned as a coloring material.

In said Formula 4, R <^1> -R <^4> represents a hydrogen atom, -R <^6>, or a C6-C10 aromatic hydrocarbon group each independently. The hydrogen atom-containing aromatic hydrocarbon groups of 6 to 10 carbon atoms, a halogen ^{atom, -R 6, -OH, -OR 6} , -SO 3 -, -SO 3 H, -SO 3 M, -CO 2 -, -CO _{2 H, -CO 2 M, -CO} 2 R 6, -SO 3 R 6, -SO 2 NHR 8 or -SO may be substituted by ₂ NR ⁸ R ^9. R ⁵ is _{-SO 3 -, -SO 3 H,} -SO 3 M, -CO 2 -, -CO 2 H, -CO 2 M, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8 Or -SO ₂ NR ⁸ R ⁹ . m represents the integer of 0-5. When m is an integer of 2 or more, some R <^5> may be the same and may differ. X represents a halogen atom. a is R ¹ ~R -SO ₃ in any of the ^5- or -CO ₂ ^- represents 0 when a is contained, represents one when the other. R <^6> represents a C1-C10 saturated hydrocarbon group. The hydrogen atom contained in this C1-C10 saturated hydrocarbon group may be substituted by the halogen atom. The methylene-containing groups of the saturated hydrocarbon group having 1 to 10 carbon atoms an oxygen atom, a carbonyl group or -NR ⁶ - may be substituted with. R ⁸ and R ⁹ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms with an adjacent nitrogen atom. Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group and the aromatic heterocyclic group are -OH, R ⁶ , -OR ⁶ , -NO ₂ , It may be substituted by -CH = CH ₂ , -CH = CHR ⁶ or a halogen atom. The hydrogen atoms contained in the alkyl group and cycloalkyl group of 3 to 30 carbon atoms of straight or branched chain of 1 to 10 carbon atoms may be substituted by a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ^6. The carbon number of the methylene groups may be replaced by oxygen atoms contained in the straight-chain or alkyl group and cycloalkyl group of 3 to 30 carbon atoms in the branched chain of 1 to 10, a carbonyl group or -NR ⁶ - as may be substituted. The hydrogen atom contained in a C1-C10 heterocycle may be substituted by R <^6> , -OH or -Q. M represents a sodium atom or a potassium atom.

The manufacturing method of the color filter for organic electroluminescent display elements which concerns on this invention is a phthalocyanine, a quinophthalone, a dioxazine, a pyrimidine, barbituric acid, a polymethine, a triallyl methane, anthraquinone, a pyridone azo, or a xanthene frame | skeleton. The color filter for organic electroluminescent display elements mentioned above is manufactured by filling the opening of a black matrix with ink containing the coloring material which has.

According to this invention, the color filter suitable for the improvement of the color purity of organic electroluminescent display element, and its manufacturing method are provided.

Hereinafter, the color filter which concerns on embodiment is demonstrated. In addition, the same code | symbol is used for the same element, and the overlapping description is abbreviate | omitted.

(Schematic Structure of Color Filter and Organic EL Display Element)

1 is a plan view of a color filter c according to an embodiment, and FIG. 2 is a cross-sectional view taken along the II-II arrow of the color filter c shown in FIG. 1. 3 is a cross-sectional view of the organic EL display element d produced by bonding the color filter c shown in FIGS. 1 and 2 to the organic EL element e.

The color filter c shown in FIGS. 1 and 2 includes a transparent substrate 1, a black matrix 3 forming an opening corresponding to the pixel, and a red resin region 4R filling each opening of the black matrix 3. ), The green resin region 4G, the blue resin region 4B, the transparent protective film 5, and the spacer 6 are mainly provided.

In the organic EL display element d shown in FIG. 3, the color filter c and the organic EL element e of FIGS. 1 and 2 are joined to face each other via the resin layer 30. The organic EL element e is a pixel electrode 9, a TFT 10, a red organic EL layer 82R, a green organic EL layer 82G, a blue organic EL layer 82B, and a transparent layer on the transparent substrate 2. The electrode 81 and the transparent protective film 8 are laminated | stacked.

In the organic EL element e and the color filter c, the red organic EL layer 82R and the red resin region 4R face each other, and the green organic EL layer 82G and the green resin region 4G face each other. The blue organic EL layer 82B and the blue resin region 4B are disposed to face each other, and each of the colored resin regions 4R, 4G, and 4B includes red light, green light, and the like from each of the color organic EL layers 82R, 82G, and 82B. It transmits blue light.

(Color filter)

Hereinafter, the color filter c will be described in detail.

(Transparent board)

The material of the transparent substrate 1 is not particularly limited as long as it is transparent to visible light. For example, inorganic materials such as alkali free glass and low alkali glass, and transparent resin materials such as PET, PES, and PC can be used.

(Black matrix)

The black matrix 3 is a light shielding film, which prevents crosstalk between pixels. The black matrix 3 is patterned in a lattice pattern on the transparent substrate 1, and forms the opening 3a which forms a pixel. The black matrix 3 is formed of, for example, a light-shielding resin in which pigments having light shielding properties such as carbon black and metal oxides are dispersed (for example, black resist (TK-41 manufactured by Sumitomo Chemical Co., Ltd.), metal oxide / metal ( For example, a chromium oxide / metal chromium laminate). In addition, this black matrix 3 may be a multilayer structure called what is called a light shielding bank. For example, the light blocking bank may be formed by stacking a light blocking resin on a metal oxide / metal layer.

(Coloring resin area)

The red resin region 4R, the green resin region 4G, and the blue resin region 4B are provided to fill the inside of the opening 3a of the black matrix 3. Each colored resin area | region 4R, 4G, 4B in the opening 3a forms the pixel of each color of organic electroluminescent display element d, and each color organic EL layer 82R, 82G of organic electroluminescent element e is , 82B) absorbs light in a desired wavelength range from light emitted from the light. In addition, although the colored resin region may be spread over the black matrix 3, the spread portion does not contribute to light transmission.

It is also possible to form a spacer 6 to be described later by overlapping adjacent colored resin regions such as the red resin region 4R and the green resin region 4G on the black matrix 3 forming the boundary. Do.

It is preferable that colored resin area | region 4R, 4G, 4B is resin which mix | blended at least 1 sort (s) of coloring materials, such as an organic pigment, an inorganic pigment, or dye, in transparent resin. In particular, a so-called transparent coloring resist that gives photosensitivity to a transparent coloring resin is preferable, and a fine pattern can be formed by a photolithography method, an inkjet method, or a printing method, and in particular, when performing full color display of a fixed color, the photolithography method This is suitable.

Here, in a transparent coloring resist, coloring materials, such as a pigment, are disperse | distributed in a solvent, and binder resin, a photopolymerizable monomer, and a photoinitiator are melt | dissolved or disperse | distributed. In addition, other additives may be dissolved or dispersed.

The binder resin may be a binder resin in which the unexposed portion is developed by the alkaline solution or a binder resin that acts as a dispersion medium of the coloring material. For example, it is preferable to make a (meth) acrylate compound one monomer and to use the (meth) acrylic-type copolymer which has a carboxyl group in a molecule | numerator.

As a photopolymerizable monomer, unsaturated carboxylic acid and its ester are preferable, For example, acrylic acid, its ester, methacrylic acid, its ester, etc. are mentioned. Acrylic acid, methacrylic acid and each of these esters may be used alone or in combination with one or more of them, optionally further adding unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid or esters thereof. Also good.

As a photoinitiator, what is normally used in this field is acetophenone type, a benzoin type, a benzophenone type, a thioxanthone type, an s-triazine type photoinitiator, etc., These are respectively independently or two or more types are used. May be combined. The photopolymerization initiator is preferably contained in the range of 1 to 40 parts by weight based on 100 parts by weight of the total of the binder resin and the photopolymerizable monomer. In addition, when using a photoinitiator in addition to a photoinitiator, it is preferable that the total amount of a photoinitiator and a photoinitiator will be the said range (range of 1-40 weight part).

Although it does not restrict | limit especially as a solvent, Ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Diethylene glycol dialkyl ethers such as ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether Alkylene glycol alkyl ether acetates, such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate, aromatic hydrocarbons, such as benzene, toluene, xylene, and mesitylene, Aromatic aliphatic ethers such as sol, phentol, methylanisole, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclohexanone, etc. Ketones, ethanol, propanol, butanol, hexanol, cyclohexanol, alcohols such as ethylene glycol, glycerin, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, methyl 2-hydroxyisobutyrate Ester, such as these, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. Each of these solvents can be used alone or in combination with one or more other types, and the content of the solvent in the transparent colored resist is usually 20% by mass to 90% by mass, preferably 50% by mass or more 85 It is used so that it may become mass% or less.

The colored resin regions 4R, 4G, and 4B may be solidified colored ink, not colored resist. The coloring ink is composed of, for example, a solvent, a coloring material, a dispersant for ensuring stability in a solvent, a transparent resin for stably forming an ink film, a monomer, and other additives such as a polymerization initiator and a surfactant, if necessary.

As a coloring material, the organic pigment, inorganic pigment, and dye which are normally used for a transparent coloring resist and coloring ink can be used. Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts, and specifically, metal oxides or composite metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. And oxides. Examples of the organic pigments include compounds classified as pigments or dyes in the Color Index (C. I.) (published by The Society of Dyers and Colourists).

Specifically, although the compound of the following color index (C.I.) numbers is mentioned, It is not limited to these.

C. I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166 and 173;

C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;

C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242 and 254;

C. I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C. I. Solvent Violet 2, 8, 9, 11, 13, 14 and the like;

C. I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 28, 60, and 64;

C. I. Solvent Blue 25, 38, 64, 67, 70, 129;

C. I. pigment green 7, 10, 15, 25, 36, 47 and 58;

C. I. Solvent Greens 3, 28, 32, and 33;

C. I. Pigment Brown 28;

C. I. Pigment Black 1 and 7.

Examples of the organic colorant include colorants having at least one skeleton selected from the group consisting of phthalocyanine, quinophthalone, dioxazine, pyrimidine, barbituric acid, polymethine, triallyl methane, anthraquinone and pyridone azo. have.

Moreover, as an example of the dye which can be used suitably for a blue color filter in this invention, the cyanine dye (polymethine dye) represented by following formula (1) or formula (2) can be illustrated.

In the formulas (1) and (2), the ring Z ₁ to ring Z ₈ each independently represent a heterocycle that may have a substituent. X ^a- is a halogen anion, ClO ₄ ^- shows the organic carboxylic acid anion, organic acid anion, a boron anion or an organometallic complex anion ^-, OH. k is a valence of an anion and shows the integer of 1 or 2. _{1 ^Y-2} and Y ^- is a halogen anion, ClO _4, each ^{independently-represent} the, monovalent organic acid anion, a monovalent organic acid anion, a monovalent anion or a monovalent organic boron metal complex anion ^-, OH. l and l 'respectively independently represent the integer of 0 or more and 3 or less. L ₁ represents a hydrocarbon group which may be divalent.

The heterocycle represented by any of ring Z ₁ to ring Z ₈ contains one or a plurality of hetero atoms. The heterocycle may be monocyclic or may be polycyclic. The hetero atom may be an atom selected from Group 15 or Group 16 elements in the periodic table, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom and a tellurium atom. Examples of the heterocycle include indole ring, benzoindol ring, indolenin ring, benjoindolenine ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzoimidazole ring and quinoline ring. have.

Examples of the heterocyclic substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl and tert-pentyl groups. Aliphatic hydrocarbon groups such as these; Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group and p-cumenyl group; Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy groups; Aryloxy groups such as phenoxy group; Aralkyloxy groups such as benzyloxy group; Groups having ester bonds such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group; Methyl sulfamoyl group, dimethyl sulfamoyl group, ethyl sulfamoyl group, diethyl sulfamoyl group, n-propyl sulfamoyl group, di-n-propyl sulfamoyl group, isopropyl sulfamoyl group, diisopropyl sulfamoyl group, alkyl sulfamoyl groups such as n-butyl sulfamoyl group and di-n-butyl sulfamoyl group; Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group and tert-butylsulfonyl group; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Nitro group and cyano group are mentioned. In addition, when such a substituent has a hydrogen atom, this hydrogen atom is halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy groups; Aryloxy groups such as phenoxy group and benzyloxy group; Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group and p-cumenyl group; Carboxyl groups; Cyano group; Nitro group; It may be substituted by such.

Examples of the halogen anion represented by X ^a- include Cl ⁻ , Br ⁻ , I ⁻ , and the like. Examples of the organic carboxylic acid anion represented by X ^a -include benzene carboxylic acid ions, alkyl carboxylic acid ions, trihaloalkyl carboxylic acid ions, and nicotinic acid ions. Examples of the organic sulfonic acid anion include benzene sulfonic acid ion, benzene disulfonic acid ion, naphthalene sulfonic acid ion, naphthalene disulfonic acid ion, p-toluene sulfonic acid ion and alkyl sulfonic acid ion. As the boron anion represented by X ^a- for example BF ₄ ^- it may be mentioned. Examples of the organometallic complex anion represented by X ^a- include organometallic complex ions of azo, bisphenyldithiol, thiocatechol chelate, thiobisphenolate chelate, and bisdiol-α-diketone. In the organometallic complex ions, examples of the center metal include Group 3 to Group 11 transition elements of the periodic table. Examples of the transition metal include scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum , Copper, silver, gold, cadmium, mercury, and the like.

Y ₁ ^- Y ₂ or ^- for example, a halogen anion, a monovalent organic acid anion, a monovalent organic acid anion, a monovalent anion or 1 boron organometallic complex anion represented by the valency, the halogen anion represented by X ^a- , An organic carboxylic acid anion, an organic sulfonic acid anion, a boron anion or an organometallic complex anion are the same as those of the monovalent one.

Examples of the hydrocarbon group represented by L ¹ include divalent aliphatic hydrocarbon groups such as methylene group, ethylene group, vinylene group, trimethylene group, propylene group, propenylene group, tetramethylene group, pentamethylene group, and hexamethylene group; Divalent alicyclic hydrocarbon groups such as cyclopentylene group, cyclohexenylene group, and cyclohexadienylene group; divalent aromatic hydrocarbon groups such as o-phenylene group, m-phenylene group, p-phenylene group and naphthylene group; Etc. can be mentioned. One or more hydrogen atoms may be substituted by this hydrocarbon group by an amino group, a carboxy group, a cyano group, a nitro group, a halogen group, a hydroxyl group, etc. L ¹ is ring Z ₁ And ring Z ₃ You may couple to any position.

Moreover, as an example of the dye which can be used suitably for a blue color filter in this invention, the cyanine dye (polymethine dye) represented by following General formula (3) can also be illustrated.

In said Formula (3), ring Z <_9> and ring Z <_10> respectively independently represent the heterocyclic ring which may have a substituent. X <^-> represents a halogen anion, ClO <_4> ^- , OH <^-> , monovalent organic carboxylic acid anion, monovalent organic sulfonic acid anion, monovalent boron anion, or monovalent organometallic complex anion. l represents the integer of 0 or more and 3 or less.

Examples of the heterocycle which may have a substituent represented by ring Z ₉ or ring Z ₁₀ are the same as the examples of heterocycles which may have a substituent represented by any one of ring Z ₁ to ring Z ₈ in formulas (1) and (2). . Examples of the halogen anion represented by X ⁻ , monovalent organic carboxylic acid anion, monovalent organic sulfonic acid anion, monovalent boron anion or monovalent organometallic complex anion are halogen anion represented by X ^a- , monovalent organic carboxyl. It is the same as being monovalent in the example of an acid anion, monovalent organic sulfonic acid anion, monovalent boron anion, or monovalent organometallic complex anion.

Moreover, xanthene dye represented by following General formula (4) can also be illustrated as an example of the dye which can be used suitably for a blue color filter in this invention.

In the formula ^4, R ¹ ~R 4 each independently represents an aromatic hydrocarbon group of a hydrogen atom, -R ^6, or 6 to 10 carbon atoms. The hydrogen atom-containing aromatic hydrocarbon groups of 6 to 10 carbon atoms, a halogen ^{atom, -R 6, -OH, -OR 6} , -SO 3 -, -SO 3 H, -SO 3 M, -CO 2 -, -CO _{2 H, -CO 2 M, -CO} 2 R 6, -SO 3 R 6, -SO 2 NHR 8 or -SO may be substituted by ₂ NR ⁸ R ^9. R ⁵ is _{-SO 3 -, -SO 3 H,} -SO 3 M, -CO 2 -, -CO 2 H, -CO 2 M, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8 Or -SO ₂ NR ⁸ R ⁹ . m represents the integer of 0-5. When m is an integer of 2 or more, some R <^5> may be the same and may differ. X represents a halogen atom. a is R ¹ ~R -SO ₃ in any of the ^5- or -CO ₂ ^- represents 0 when a is contained, represents one when the other. R <^6> represents a C1-C10 saturated hydrocarbon group. The hydrogen atom contained in this C1-C10 saturated hydrocarbon group may be substituted by the halogen atom. The methylene-containing groups of the saturated hydrocarbon group having 1 to 10 carbon atoms an oxygen atom, a carbonyl group or -NR ⁶ - may be substituted with. R ⁸ and R ⁹ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms with an adjacent nitrogen atom. Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group and the aromatic heterocyclic group include -OH, R ⁶ , -OR ⁶ , -NO ₂ , It may be substituted by -CH = CH ₂ , -CH = CHR ⁶ or a halogen atom. The hydrogen atom contained in a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms may be substituted with a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ⁶ . . The carbon number of the methylene groups may be replaced by oxygen atoms contained in the straight-chain or alkyl group and cycloalkyl group of 3 to 30 carbon atoms in the branched chain of 1 to 10, a carbonyl group or -NR ⁶ - as may be substituted. The hydrogen atom contained in a C1-C10 heterocycle may be substituted by R <^6> , -OH or -Q. M represents a sodium atom or a potassium atom.

R ^{6 is} methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, nonyl, Decanyl, tricyclodecanyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl and the like.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl and naphthyl. Fluorine, chlorine, bromine etc. are mentioned as a halogen atom mentioned as a substituent of this C6-C10 aromatic hydrocarbon group. Examples of -SO ₃ R ⁶ include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decansulfonyl, and the like. -CO ₂ R ^{6 is} methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neo Pentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cy Clooctyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyloxycarbonyl, methoxypropyloxycarbonyl, ethoxypropyloxycarbonyl, hexyloxypropyloxycarbonyl, 2-ethylhexyl Oxypropyloxycarbonyl, methoxyhexyloxycarbonyl, and the like.

-SO ₂ NHR ^{8 is} sulfamoyl, methane sulfamoyl, ethane sulfamoyl, propane sulfamoyl, isopropane sulfamoyl, butane sulfamoyl, isobutane sulfamoyl, pentane sulfamoyl, isopentansulfamoyl, neopentane sulfamoyl, cyclo Pentane sulfamoyl, hexane sulfamoyl, cyclohexane sulfamoyl, heptane sulfamoyl, cycloheptanesulfamoyl, octane sulfamoyl, 2-ethylhexane sulfamoyl, 1,5-dimethylhexane sulfamoyl, cyclooctane sulfamoyl, nonan sulfamoyl , Decanesulfamoyl, tricyclodecanesulfamoyl, methoxy propanesulfamoyl, ethoxypropanesulfamoyl, propoxypropanesulfamoyl, isopropoxypropanesulfamoyl, hexyloxypropanesulfamoyl, 2-ethylhexyloxypropanesulfamoyl , Methoxyhexane sulfamoyl, 3-phenyl-1-methylpropanesulfamoyl and the like.

Examples of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ include groups represented by the following chemical formulas.

In the formula, X ¹ represents a halogen atom. Examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom and a bromine atom.

In said formula, X <^3> represents a C1-C3 alkyl group or a C1-C3 alkoxy group, and the hydrogen atom of this alkyl group and an alkoxy group may be substituted by the halogen atom. Methyl, ethyl, propyl, isopropyl, perfluoromethyl, etc. are mentioned as a C1-C3 alkyl group which may be substituted by the halogen atom. As a C1-C3 alkoxy group which may be substituted by the halogen atom, methoxy, ethoxy, propoxy, etc. are mentioned.

In said formula, X <^2> represents a C1-C3 alkyl group, a C1-C3 alkoxy group, a halogen atom, or a nitro group, and the hydrogen atom of this alkyl group and an alkoxy group may be substituted by the halogen atom. Examples of the halogen atom in X ² include a fluorine atom, a chlorine atom and a bromine atom. Methyl, ethyl, propyl, isopropyl, perfluoromethyl, etc. are mentioned as a C1-C3 alkyl group which may be substituted by the halogen atom. As a C1-C3 alkoxy group which may be substituted by the halogen atom, methoxy, ethoxy, propoxy, etc. are mentioned.

In said formula, X <^2> represents the same meaning as the above.

In said formula, X <^3> represents the same meaning as the above.

R ⁸ and R ⁹ contained in —SO ₂ NR ⁸ R ⁹ include a branched alkyl group having 6 to 8 carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, and a carbon group having 2 to 8 carbon atoms. The hydroxyl group containing alkyl and aryl group of 8, or the C2-C8 alkoxy group containing alkyl or aryl group are preferable, and it is especially preferable that it is 2-ethylhexyl.

The substituent of the aromatic hydrocarbon group of 6 to 10 carbon atoms, ethyl, propyl, phenyl, dimethylphenyl, a -SO ₃ R ^6, or -SO ₂ NHR ⁸ is preferred.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decanylphenyl, fluorophenyl, chlorophenyl, bromophenyl, hydroxyphenyl, methoxyphenyl and dimeth Oxyphenyl, ethoxyphenyl, hexyloxyphenyl, decanyloxyphenyl, trifluoromethylphenyl, and the like.

At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted. At least one of R ¹ and R ² , and at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted. At least one of R ¹ and R ² , and at least one of R ³ and R ⁴ are more preferably a C 6-10 aromatic hydrocarbon group which may be substituted. R ⁵ is carboxyl, ethyloxycarbonyl, sulfoxyl, 2-ethylhexyloxypropanesulfamoyl, 1,5-dimethylhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, isopropoxypropanesulfamoyl Is preferably.

The compound represented by the formula (4) is preferably a compound represented by the following formula (4-1).

In said Formula (4-1), R <^11> -R <^14> represents a hydrogen atom, -R <^6>, or a C6-C10 aromatic hydrocarbon group each independently. The hydrogen atom-containing aromatic hydrocarbon groups of 6 to 10 carbon atoms, a halogen ^{atom, -R 6, -OH, -OR 6} , -SO 3 -, -SO 3 H, -SO 3 Na, -CO 2 -, -CO _{2 H, -CO 2 Na, -CO} 2 R 6, -SO 3 R 6, -SO 2 NHR 8 or -SO may be substituted by ₂ NR ⁸ R ^9. R ¹⁵ represents a hydrogen atom, —SO ₃ ^— , —SO ₃ H, —CO ₂ ^— , —CO ₂ H, —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . R ¹⁶ represents —SO ₃ ^— , —SO ₃ H, —CO ₂ ^— , —CO ₂ H, —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . a 'is -SO ₃ R ¹¹ in any one of ~R ^{15 -} or -CO ₂ ^- represents 0 when a is contained, represents one when the other. R ⁶ , R ⁸ , R ⁹ , m and X have the same meanings as above.

It is preferable that the compound represented by General formula (4) is a compound represented by following General formula (4-2).

In Formula 4-2, R ²¹ ~R ²⁴ each independently represents an aromatic hydrocarbon group of a hydrogen atom, -R ^26, or 6 to 10 carbon atoms. The hydrogen atom-containing aromatic hydrocarbon groups of 6 to 10 carbon atoms, a halogen ^{atom, -R 26, -OH, -OR 26} , -SO 3 -, -SO 3 Na, -CO 2 -, -CO 2 Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ may be substituted. R ²⁵ represents —SO ₃ —, —SO ₃ Na, —CO ₂ ^— , —CO ₂ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H or SO ² NHR ²⁸ . R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in this C1-C10 saturated hydrocarbon group may be substituted by -OR <^26> or a halogen atom. R ²⁸ represents a hydrogen atom, -R ²⁶ , -CO ₂ R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon having 6 to 10 carbon atoms is substituted with -R ²⁶ or -OR ²⁶ May be. a "is R ²¹ -SO ₃ ~R in any one of ^{25 -} or -CO ₂ ^-. represents 0 when a is contained, represents one when the other of m and X have the same meanings as defined above.

Examples of the compound represented by the formula (4) include compounds represented by the following formulas (4a, 4b, 4b ', 4c, 4c', 4d and 4d ').

Of Formula 4a, R ^b and R ^c are independently hydrogen atom, -SO _3, respectively ^-, -CO ₂ ^-, represents a -CO ₂ H or -SO ₂ NHR ^a. R ^a represents 2-ethylhexyl. a "'is -SO ₃ to any one of the R ^c ~R ^{b -} or -CO ₂ ^-. represents 0 when a is contained, represents one when the other X have the same meanings as defined above.

In said Formula (4b), R ^{b '} represents a hydrogen atom, -CO ₂ H or -SO ₂ NHR ^a . R ^a represents 2-ethylhexyl.

The compound represented by Chemical Formula 4b is a tautomer of the compound represented by the following Chemical Formula 4b '.

In said Formula (4b '), Rb ^' shows the same meaning as the above.

In the formula 4c, R ^d, R ^e and R ^f are each independently a _{^{-SO 3 -, -SO 3 Na,}} -SO 3 H, -SO 2 NHR a, -CO 2 -, -CO 2 Na , or -CO ₂ represents the H. R ^a represents 2-ethylhexyl. Provided that any one of R ^d, R ^e and R ^f is -SO ₃ ^- or -CO ₂ ^- a.

The compound represented by Formula 4c is a tautomer of the compound represented by Formula 4c '.

In Formula 4c ', R ^d' , R ^{e '} and R ^f' each independently represent -SO ₃ Na, -SO ₃ H, -SO ₂ NHR ^a , -CO ₂ Na or -CO ₂ H. R ^a represents 2-ethylhexyl. With the proviso that any one of R ^{d '} , R ^e' and R ^{f '} is -SO ₃ H or -CO ₂ H.

Formula 4d of R ^g, R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- or represents a _{^{-CO 2 H -, -SO 3 H}} , -SO 2 NHR a, -CO 2. R ^a represents 2-ethylhexyl. Any one stage, R ^g, R ^h and R ⁱ are -dndSO ₃ ^- or -CO ₂ ^- a.

The compound represented by Chemical Formula 4d is a tautomer of the compound represented by Chemical Formula 4d ′.

R ^{g '} , R ^h' and R ^{i '} in Formula 4d' each independently represent a hydrogen atom, -SO ₃ H, -SO ₂ NHR ^a or -CO ₂ H. R ^a represents 2-ethylhexyl. With the proviso that any one of R ^{d '} , R ^e' and R ^{f '} is -SO ₃ H or -CO ₂ H.

The compound represented by the formula (4) is reacted with, for example, a dye or a dye intermediate having -SO ₂ Cl obtained by chlorination of a dye or a dye intermediate having -SO ₃ H with an amine represented by R ⁸ -NH ² . It can manufacture. Moreover, it can manufacture by reacting with the amine after coloring the pigment | dye manufactured by the method described in the upper right column to the lower left column of Unexamined-Japanese-Patent No. 3-78702 page 3 similarly to the above.

These coloring materials may be individual or it may combine them 2 or more types, and color development can be adjusted by this. Moreover, it is preferable to contain 10-50 weight% of coloring materials in a coloring resin based on the total solid amount in a coloring resin.

In particular, in the present embodiment, the blue resin region 4B for wavelength selection of light emitted from the blue organic EL layer 82B has an absorption spectrum such that light transmittance becomes 30% or less over a range of 500 nm to 550 nm. . As a result, the blue resin region 4B sufficiently absorbs light in a range close to green. When the blue resin region 4B has a portion in which the transmittance exceeds 30% in the range of 500 nm to 550 nm, green mixed with light emitted from the blue organic EL layer 82B, especially the blue polymer organic EL layer Since the light cannot be sufficiently removed, it becomes difficult to express sufficient color purity. In addition, it is preferable that the blue resin region 4B has a high transmittance with respect to blue light, particularly, the peak of transmittance is at 410 nm to 470 nm, and the transmittance at the peak is preferably 50% or more.

Similarly, the green resin region 4G having wavelength selection of light emitted from the green organic EL layer 82G has an absorption spectrum in which transmittance is 15% or less over a range of 600 nm to 650 nm. As a result, light in the range close to orange is sufficiently absorbed. When the green resin region 4G is in the range of 600 nm to 650 nm, and there is a portion where the transmittance is 15%, the orange mixed in the light emission from the green organic EL layer 82G, especially the green polymer organic EL layer Since the light of the system cannot be sufficiently removed, it becomes difficult to express sufficient color purity. In addition, it is preferable that the green resin region 4B has a high transmittance with respect to the green light, the peak of transmittance is at 500 nm to 550 nm, and the transmittance at the peak of transmittance is preferably 50% or more.

That is, the green resin region 4G and the blue resin region 4B of the color filter c according to the present embodiment are composed of the green organic EL layer 82G and the blue organic EL layer 82B of the corresponding organic EL element e. And a light absorption spectrum capable of sufficiently absorbing tails on the long wavelength side of each emission spectrum.

Thereby, the light of an unnecessary wavelength range can be fully removed from the light which generate | occur | produces in each organic EL layer 82R, 82G, and 82B, and color purity can be improved. As a result, the color of the pixel can be made closer to the three primary colors of the NTSC standard.

In addition, from the viewpoint of preventing reflection of ambient light in the organic EL display element d, wavelength regions other than the above-described wavelength ranges for the green resin region 4G and the blue resin region 4B are respectively, that is, green resins. It is preferable that the wavelength range of 480 nm or less and 620 nm or more with respect to the area | region 4G, and the wavelength range of 520 nm or more with respect to the blue resin area | region 4B preferably have a transmittance | permeability of 10% or less. When the transmittance exceeds 10%, the reflectance of the color filter becomes 1% or more, which is not preferable.

In the red resin region 4R, since light on the longer wavelength side is not a problem than red, a known one capable of absorbing light other than red may be used. In addition, about red resin region R, it can manufacture by a well-known method using the red coloring material for liquid crystals.

The absorption spectrum of each color resin area | region 4R, 4G, 4B can be easily adjusted by changing a density | concentration with respect to resin mix | blending of a pigment or dye. The thickness of the colored resin regions 4R, 4G, and 4B is not particularly limited, but may be, for example, 0.5 µm to 5 µm.

(Transparent shield)

The transparent protective film 5 is a film covering the black matrix 3 and the colored resin regions 4R, 4G, and 4B. As the transparent protective film 5, it is possible to use a thin film made of an organic transparent resin or an inorganic transparent material, whereby water or reaction products generated from the black matrix 3 or the colored resin regions 4R, 4G, 4B, or the like can be used. Floating and mixing into the organic EL layer 82 of the organic EL element e can be reduced. Moreover, even if there is no transparent protective film 5, implementation of this invention is possible.

The transparent protective film 5 is a film of a transparent inorganic material such as an oxide such as silicon, aluminum, nitride, oxynitride, diamond-like carbon (DLC film), or polyvinyl alcohol, ethylene vinyl alcohol resin, acrylic resin or methacryl resin. It is made by laminating or laminating transparent resin films such as these. The thickness is, for example, about 1 µm to 10 µm. For example, the one manufactured by HC-501: Sumitomo Chemical Co., Ltd. can be used.

(Spacer)

The spacer 6 is formed on the black matrix 3 as shown in Figs. Accordingly, as shown in FIG. 3, light emission from the organic EL layers 82R, 82G, and 82B is output to the outside through the colored resin regions 4R, 4G, and 4B without being blocked by the spacers 6. . The height of the spacer 6 can be 3-20 micrometers, for example.

The spacer 6 can be easily formed by the photolithography method using photosensitive resin. As photosensitive resin, microfabrication is possible, and what is necessary is just a resin composition in which the formed structure has sufficient adhesive force and pressure-resistant strength with respect to a lower material, Preferably, a large elastic deformation area is large. For example, a composition containing an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, an epoxy group-containing unsaturated compound and a copolymer of other olefinically unsaturated compounds, a polymerizable compound having an ethylenically unsaturated bond, a radiation sensitive polymerization initiator and a colorant. Can be mentioned.

In addition, as shown in FIG. 1, a light shielding wall 61 may be provided at the boundary between each of the colored resin regions 4R, 4G, and 4B on the black matrix 3. As a result, the light transmitted through the adjacent colored resin regions 4R, 4G, and 4B is not mixed even when the display element is observed at a high viewing angle. In addition, when the light shielding wall 61 is arrange | positioned on the black matrix 3 at the time of bonding the color filter c to the organic electroluminescent element e, the light emission part of each color organic EL layer 82R, 82G, and 82B will be Since it is not opposed to, it is difficult to damage the organic EL layer 82 by pressing. The light shielding wall 1 can be manufactured from the same material as the spacer 6.

(Organic EL device)

Subsequently, the organic EL element e will be briefly described.

The transparent substrate 2 is the same as the transparent substrate 1.

Known organic EL materials can be used for the colored organic EL layers 82R, 82G, and 82B. In particular, it is preferable to use a polymer EL material. Specifically, LUMATION type polymer light emitting material (made by Sumation Corporation) is mentioned.

The pixel electrode 9 is, for example, a thin film of metal or the like.

The TFT 10 can use a well-known thing.

The transparent protective film 8 can use the same thing as the transparent protective film 5.

In addition, the resin layer 30 filled between the organic EL element e and the color filter c is not particularly limited as long as it is a transparent material. Examples thereof include photocurable resins such as ultraviolet curable acrylic resins.

(Production method)

Next, the manufacturing method of a color filter (c) and an organic electroluminescent display element (d) is demonstrated. By sequentially performing the following steps (1) to (6), the color filter (c) and the organic EL display element (d) can be manufactured.

Process (1) Black Matrix Formation Process

First, a light shielding film (for example, a light shielding resin film or a metal light shielding film) is formed on the transparent substrate 1, and a resist is applied using a spin coater, a roll coater, a die coater, or the like. Next, light such as ultraviolet rays is irradiated onto the transparent substrate 1 to which the resist is applied through a photomask having an opening corresponding to the shape of the black matrix 3 and developed to form a resist pattern.

Further, the black matrix 3 is formed on the transparent substrate 1 by being immersed in a liquid having a corrosiveness to the light shielding film, corrosion removal of the light shielding film not protected by the resist, and then peeling off the resist.

Process (2) colored resin area formation process

Next, for example, a blue transparent colored resist is coated on the transparent substrate 1 on which the black matrix 3 is formed by using a spin coater, a die coater, and the like and prebaked at 70 ° C to 120 ° C. Furthermore, by irradiating light, such as an ultraviolet-ray, through the photomask which has a pattern corresponding to the blue resin area | region 4B, and immersing in alkaline solution, the blue resin area | region 4B of the area | region to which light is not irradiated is removed and removed. After sufficiently washing with pure water, it is heated to 160 ° C to 250 ° C using an oven, a hot plate or the like to cure and bake the remaining blue resin region 4B.

 This process is further patterned twice, i.e., red resin region 4R for red and green resin region 4G for green, by the same patterning, red, green and blue colored resin regions 4R, 4G, 4B. A stripe array is formed periodically.

At this time, at the boundary between adjacent colored resin regions 4G and 4B, 4B and 4R, and 4R and 4G, the spacer 6 may be formed by overlapping the photosensitive resin material. In addition, you may use the electrodeposition method or the printing method in addition to the photolithographic method for a colored resin area formation process.

Instead of using a transparent coloring resist, you may form colored resin area | region 4R, 4G, 4B by the inkjet method or the printing method. In the printing method, after forming the black matrix 3 using light-shielding photosensitive resin, it can form by overprinting the ink pattern corresponding to a colored resin area | region. In particular, the reverse printing method has a feature capable of simultaneously forming a black matrix and a colored resin region. On the other hand, the inkjet method forms a black matrix covering the periphery with a light-shielding bank structure using a light-shielding photosensitive resin, and then, after filling the openings with ink colored with a color material, the ink is dried and cured by heat treatment or the like. The color filter c can be obtained. Since the inkjet method has less heating stress than the photolithography method, a heat sensitive colorant can be suitably used.

And by any method, the coloring resin area | region of the absorption spectrum which satisfy | fills the above-mentioned transmittance | permeability can be formed by appropriately adjusting the component of the coloring material contained in a colored resin area | region, and the density | concentration with respect to the resin.

Process (3) transparent protective film formation process

Thereafter, the transparent protective film 5 may be formed on the transparent substrate on which the colored resin region is formed so as to cover the black matrix 3 and the colored resin regions 4R, 4G, and 4B. The transparent protective film 5 may be a method of applying a light or thermosetting transparent resin film by using a spin coater or a spinless coater and then curing with light and / or heat. When the transparent protective film 5 is an inorganic material such as metal oxide, nitride, oxynitride or DLC film, it can be formed by, for example, sputtering, plasma CVD or vapor deposition.

Process (4) spacer formation process

In addition, for example, an acrylic photocurable thermosetting resin is applied to the transparent substrate 1 having the transparent protective film 5 formed thereon using a spin coater or the like to prebak, and the photo has a pattern corresponding to the shape of the spacer 6. It exposes using a mask and removes a non-exposed part by developing by aqueous alkali solution, and bakes. As a result, the spacer 6 is formed. The spacer may be formed by laminating a black matrix or a transparent colored resist pattern.

Process (5) bonding process

A photocurable resin, for example, an ultraviolet curable resin, is applied onto the organic EL element e prepared in advance using a spin coater or the like. Moreover, the above-mentioned color filter (c) is aligned (aligned) with a bonding apparatus, and is bonded so that it may oppose the organic electroluminescent element (e) to which photocurable resin was apply | coated.

Process (6) bonding process

Finally, light is irradiated and hardened | cured about the photocurable resin filled in the clearance gap between organic electroluminescent element (e) and color filter (c). Thereby, the color filter c and the organic EL element e can be adhered and fixed, and the organic EL display element d is completed.

(Action)

Subsequently, the operation of the color filter c according to the present embodiment will be described. Light emitted from the organic EL layers 82G and 82B of the organic EL element e is incident on the color filter c. Light incident on the color filter is shielded by the black matrix 3 to pass through the colored resin regions 4G and 4B, and green light and blue light are wavelength-selected. Thus, each colored resin region constitutes a pixel that emits light of a specific wavelength.

In the color filter according to the present embodiment, the transmittance of the green resin region 4G and the transmittance of the blue resin region 4B are set as described above. Therefore, the green pixel emits light of the light wavelength side extension part of the light spectrum generated from the green organic EL layer 82G of the organic EL element e or the light wavelength side extension part of the light spectrum generated from the blue organic EL layer 82B. The blue pixels can be suppressed respectively. Therefore, the color purity of the light emitted from each pixel can be improved.

In addition, this invention is not limited to the said embodiment, A various form is possible. For example, in the said embodiment, although the above-mentioned transmittance | permeability condition is satisfy | filled each so that both of the green resin area | region 4G and the blue resin area | region 4B may absorb an extended part, either colored resin area | region satisfies the transmittance | permeability condition mentioned above. If it does, one color purity will improve at least.

In the above embodiment, the organic EL element e has a red organic EL layer 82R, a green organic EL layer 82G, and a blue organic EL layer 82B, and emits red light, green light, and blue light. Instead, it may have a white organic EL layer which emits white light. Although the white organic EL layer emits white light by containing a plurality of organic EL materials, the same is true for extending to the longer wavelength side than the peak wavelength in the light emission from each organic EL material. Therefore, the color filter of this invention has the same color purity improvement effect also about the organic electroluminescent element which has a white organic electroluminescent layer.

In the above embodiment, the red pixel region is composed of a resin colored in red to be a red resin region 4R, and the green pixel region is composed of a resin colored in green to be a green resin region 4G, and blue The pixel region is composed of a resin colored in blue to form a blue resin region 4B, and by doing so, reflection of unnecessary external light can be suppressed, but as long as the required wavelength absorption characteristics are satisfied, The color is not limited to the above.

Example

(Production of Organic EL Device)

After fabricating a TFT substrate on which a bank frame was formed, a buffer film (PEDT: poly (3,4) ethylenedioxythiophene / polystyrenesulfonic acid (Steve Vtech Co., Ltd., product name: BaytronPCH8000) was manufactured using an inkjet printing machine, Similarly, a red phosphor ink [LUMATION RP-221 (manufactured by Summon Corporation) on red pixels and a green phosphor ink [LUMATION GP-1200 (Summer Co., Ltd.) on green pixels using an inkjet printer. (Manufactured by LUMATION BP-105), and then the solvent was removed to form a phosphor layer. Charge the charge injection layer (IL40) by using, to remove the solvent, and to form a high-purity Al-Mg film as a cathode to form a silicon nitride film by CVD to obtain an organic EL device (e) The.

(Preparation of colored resin raw material liquid)

Preparation of Photosensitive Coloring Resist

(Example 1 to Example 6, Example 9 to Example 11, Example 15 to Example 18, Comparative Example 5)

15 parts by weight of the colorant shown in Table 1, a dispersant (40% by weight relative to the pigment) and 36 parts by weight of the solvent (propylene glycol monomethyl ether acetate / 3-ethoxypropionate = 70/30 (weight ratio)) were mixed to obtain a colorant dispersion. It prepared. Copolymer of binder resin (benzyl methacrylate / methacrylic acid = 70/30 (molar ratio)) to this colorant dispersion: 28 parts by weight of a polyfunctional acrylate monomer (dipenta) with an acid value of 113 and a polystyrene equivalent weight average molecular weight of 30,000 8 parts by weight of erythritol hexaacrylate), 2 parts by weight of a polymerization initiator (Ilgacure 907: manufactured by Chiba Japan Co., Ltd.), 2 parts by weight of surfactant (F477: manufactured by DIK), and 180 parts by weight of a solvent (same as above). After the addition, the mixture was sufficiently mixed, followed by filtration with a 3 μm filter to obtain a photosensitive colored resist.

(Example 7, Example 8, Example 12, Comparative Examples 1 to 4)

The color material (photosensitive coloring resist) for commercially available color filters for liquid crystal displays shown in Table 1 was used.

Preparation of coloring ink

(Examples 13 to 14)

15 weight part of a coloring material shown in Table 1, a dispersing agent (40 weight% with respect to pigment), and 36 weight part of solvents (dipropylene glycol methyl ether acetate) were mixed, and the coloring material dispersion liquid was prepared. To this colorant dispersion, 3 parts by weight of binder resin (same as above), 1 part by weight of polyfunctional acrylate monomer (same as above) and 1 part by weight of polymerization initiator (same as above) were added, and the mixture was sufficiently mixed. The colored ink was obtained by filtering by the micrometer filter, adding 30 weight part of polyfunctional acrylate monomers (trimethylol propane triacrylate) further, and adjusting the viscosity to 15 mPa * s.

Here, Examples 1 to 7 and Comparative Examples 1 to 3 are colored resin raw materials for forming green resin regions, and Examples 8 to 18 and Comparative Examples 4 to 5 are used for forming blue resin regions. It is a coloring resin raw material liquid. In Table 1, PG is Pigment Green, PV is Pigment Violet, PB is Pigment Blue, PY is Pigment Yellow, and phthalocyanine dye (* 1) is a compound represented by the following Chemical Formula 5, Cyanine Dye (* 2) Is a compound of formula (6), cyanine dye (※ 3) is a compound of formula (7), xanthene dye (※ 4) is a compound of formula (8), YG800, YB800, B111 are all Dongwoo Finechem Co., Ltd. The brand name of the color material for filters (photosensitive coloring resist) is shown.

^{_{R = -SO 3 -, -SO 2}} NHCH (C 2 H 5) C 5 H 11, -SO 2 N (CH 3) 2

(Production of Color Filters)

(Green filter: Examples 1 to 7, Comparative Examples 1 to 3), (Blue filter: Examples 8 to 12, Examples 15 to 18, Comparative Examples 4 to 5)

The photosensitive coloring resist obtained as mentioned above was apply | coated to the clean alkali free glass (E2K thickness 0.63mm by Corning) with a spin coater. Post-baking after 220 degreeC x 20 minute (s) after whole surface exposure, and in Example 5 thru | or Example 7 and Example 10, the above application | coating, whole surface exposure, and post-baking are repeated 2 to 5 times, and the thickness shown in Table 2 or Table 3 is carried out. A pseudo color filter having a colored resin region was produced.

(Blue Filter: Examples 13-14)

The above-mentioned coloring ink was apply | coated to the alkali free glass wash | cleaned as a transparent substrate (E2K thickness 0.63mm by Corning Corporation) using an inkjet printing machine, and after prebaking (90 degreeC, 1 minute), it post-baked (220 degreeC, 20 minutes) to produce a pseudo color filter having a blue resin region having a thickness shown in Table 3.

(Manufacture of Organic EL Display Element)

A photocurable resin (Smiflash XR-98, manufactured by Sumitomo Chemical Co., Ltd.) was applied onto the organic EL device by a spin coater, and the pressure was reduced to degas the photocurable resin. Each color filter was subjected to an organic EL. It laminated | stacked on the element, pressurized by pressurization with the gas pressure of 1 atmosphere, and irradiated with ultraviolet-ray using a high pressure mercury lamp, and further heat-processed 80 degreeC * 2 hours, hardened | cured the photocurable resin and obtained the organic electroluminescence display element.

(Evaluation and results)

Before bonding each color filter with organic electroluminescent element, the transmittance | permeability in the 400 nm-700 nm range of each color filter is measured, and each color filter is measured by measuring the transmittance | permeability only of the alkali free glass which is a transparent substrate beforehand. The transmittance curve of the colored resin region was obtained. In addition, from this transmittance curve, the transmittance | permeability (maximum transmittance | permeability in 600 nm-650 nm) in 600 nm is calculated | required about the green filter (Example 1-Example 7, Comparative Examples 1-3), and blue About filters (Examples 8-18, Comparative Examples 4-5), the transmittance | permeability (maximum transmittance | permeability in 500 nm-550 nm) at 500 nm is calculated | required, and the wavelength whose transmittance becomes a peak, and the The transmittance of the peak was obtained and the results are shown in Table 2 or Table 3.

In addition, the green organic EL layer is turned on for the green filter (Example 1 to Example 7, Comparative Example 1 to Comparative Example 3) with respect to the organic EL display element in which the color filter and the organic EL element are bonded together, and the blue filter ( In Examples 8 to 18 and Comparative Examples 4 to 5, the blue organic EL layer was turned on to measure the emission spectrum and chromaticity (x, y) of emission, respectively, and the chromaticities are shown in Table 2 or Table 3. It was. Further, the emission spectrum of 400 nm to 700 nm of the light emitted from the green organic EL layer and the blue organic EL layer of the organic EL element in the state without providing the color filter is measured, and the organic EL with respect to the emission spectrum of the organic EL element is measured. The intensity ratio (area ratio) of the emission spectrum of a display element is shown in Table 2 or Table 3 as light utilization efficiency.

In addition, the transmittance curves of the color filters of Examples 1 to 7 are shown in FIG. 4, the transmittance curves of the color filters of Examples 8 to 14 are shown in FIG. 5, and Comparative Examples 1 to 6 are shown in FIG. 6. 3 shows the transmittance curve of the color filter, FIG. 7 shows the transmittance curve of the color filters of Comparative Examples 4 to 5, and FIG. 9 shows the light and green organic EL layers emitted from the blue organic EL layer of the organic EL element. The wavelength spectrum of the emitted light is shown.

(result)

The color filters of Examples 1 to 7 having a green resin region having a transmittance of 15% or less over 600 nm to 650 nm compared with Comparative Examples 1 to 1 having a region where the transmittance was not 15% or less over 600 nm to 650 nm. Compared with the color filter of Example 3, the color purity was closer to (0.21, 0.71), which is the chromaticity of the green light of the NTSC chromaticity coordinates.

Further, the color filters of Examples 8 to 18 having a blue resin region having a transmittance of 30% or less over 500 nm to 550 nm had a comparative example 4 having a region where the transmittance was not 30% or less over 500 nm to 550 nm. Compared with the color filter of the comparative example 5, it is closer to (0.14, 0.08) which is chromaticity of blue light of NTSC chromaticity coordinate, and color purity improved.

Therefore, by using the color filter of this invention, the area | region of the color reproduced by the light of RGB3 color can be enlarged significantly.

1 is an example of a top view of a color filter according to the invention.

FIG. 2 is a cross-sectional view of the color filter shown in FIG. 1.

3 is a cross-sectional view of an organic EL display element produced by bonding the color filters shown in FIGS. 1 and 2 to an organic EL element.

4 is a transmission spectrum of the green color filter shown in the first to seventh embodiments of the present invention.

5 is a transmission spectrum of the blue color filter shown in the eighth to fourteenth embodiments of the present invention.

6 is a transmission spectrum of the green color filters shown in the first to third comparative examples.

7 is a transmission spectrum of the blue color filter shown in the fourth comparative example to the fifth comparative example.

8 is an emission spectrum of a green or blue organic EL light emitting element.

Claims (11)

The color filter for organic electroluminescent display elements provided with a green pixel area | region, and the light transmittance of the said green pixel area | region is 15% or less over 600 nm-650 nm. The color filter for organic electroluminescent display elements of Claim 1 whose peak of the light transmittance of the said green pixel area exists in the range of 500 nm-550 nm, and the light transmittance in the peak of the said light transmittance is 50% or more. The color filter for organic electroluminescent display elements provided with a blue pixel area | region, and the light transmittance of the said blue pixel area | region is 30% or less over 500 nm-550 nm. The color filter for organic electroluminescent display elements of Claim 3 whose peak of the light transmittance of the said blue pixel area exists in the range of 410 nm-470 nm, and the light transmittance in the peak of a light transmittance is 50% or more. The color filter for organic electroluminescent display elements of any one of Claims 1-4 which is for polymer organic electroluminescent display elements. The color filter for organic electroluminescent display elements of any one of Claims 1-4 which contains dye, a pigment, or these mixture as a coloring material of the said pixel area | region. The coloring material according to claim 6, wherein the coloring material has at least one skeleton selected from the group consisting of phthalocyanine, quinophthalone, dioxazine, pyrimidine, barbituric acid, polymethine, triallyl methane, anthraquinone and pyridoneazo. Color filter for phosphorescent organic EL display elements. The color filter for organic electroluminescent display elements of Claim 3 or 4 containing the blue dye represented by following formula (1) or following formula (2):

In the formula (1), (2), the ring Z ₁ ~ Z ₈ ring which may have a substituent, each independently represents a good heterocyclic ring, X ^a- is a halogen anion, ClO ₄ ^-, OH ^-, organic acid anion, organic represents an acid anion, a boron anion or an organometallic complex anion, and k is a valence of the anion, a denotes an integer of 1 or 2, Y ₁ ^-, and Y ₂ ^- is a halogen anion, each independently, ClO ₄ ^-, OH ^-, 1 A valent organic carboxylic acid anion, a monovalent organic sulfonic acid anion, a monovalent boron anion, or a monovalent organometallic complex anion, each independently represents an integer of 0 or more and 3 or less, and L ₁ represents a divalent substitution. The hydrocarbon group which may be used is shown. The color filter for organic electroluminescent display elements of Claim 3 or 4 containing the blue dye represented by following General formula (3):

In said Formula (3), ring Z <_9> and ring Z <_10> respectively independently represent the heterocyclic ring which may have a substituent, X <^-> represents halogen anion, ClO <_4> ^- , OH <^-> , monovalent organic carboxylic acid anion, monovalent organic The sulfonic acid anion, monovalent boron anion, or monovalent organometallic complex anion is represented, and l represents an integer of 0 or more and 3 or less. The color filter for organic electroluminescent display elements of Claim 3 or 4 containing the dye represented by following General formula (4):

In the formula (4), each of R ¹ to R ⁴ independently represents a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, -R ^{6, -OH, -OR 6, -SO} 3 -, -SO 3 H, -SO 3 M, -CO 2 -, -CO 2 H, -CO 2 M, -CO 2 R 6, -SO 3 R 6 , -SO ₂ NHR ⁸ or -SO good optionally substituted by a ₂ NR ⁸ R ^9, R ⁵ is _{-SO 3 -, -SO 3 H,} -SO 3 M, -CO 2 -, -CO 2 H, -CO ₂ M, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ^8, or -SO ₂ NR ⁸ R ⁹ , m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different and X represents a halogen atom, a represents 0 when -SO ₃ ^- or -CO ₂ ^- is contained in any one of R ¹ to R ⁵ , and when otherwise, represents 1, R ⁶ represents a saturated hydrocarbon group of 1 to 10 carbon atoms, where the saturated hydrocarbon group of 1 to 10 carbon atoms The hydrogen atoms contained in the purge may be substituted with a halogen atom, a methylene-containing groups, saturated hydrocarbon groups having 1 to 10 carbon atoms an oxygen atom, a carbonyl group or -NR ⁶ - good optionally substituted by, R ⁸ and R ⁹ are each independently A straight or branched chain alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 30 carbon atoms, or -Q, or R ⁸ and R ⁹ combine to form a heterocyclic ring of 1 to 10 carbon atoms with adjacent nitrogen atoms; Q may represent an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, wherein the hydrogen atoms contained in the aromatic hydrocarbon group and the aromatic heterocyclic group include -OH, R ⁶ , -OR ⁶ , _{-NO 2, -CH = CH 2,} -CH = CHR 6 , or may be substituted with halogen atoms, the hydrogen atoms contained in the alkyl group and cycloalkyl group of 3 to 30 carbon atoms of straight or branched chain of 1 to 10 carbon atoms is Group, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ⁶ good optionally substituted with, the methylene groups may be replaced by oxygen contained in the alkyl group and cycloalkyl group of 3 to 30 carbon atoms of straight or branched chain of 1 to 10 carbon atoms May be substituted with an atom, a carbonyl group, or -NR ^6- , the hydrogen atom contained in a C1-10 heterocycle may be substituted with R ⁶ , -OH or -Q, and M represents a sodium atom or a potassium atom . The group according to any one of claims 1 to 4, which consists of phthalocyanine, quinophthalone, dioxazine, pyrimidine, barbituric acid, polymethine, triallyl methane, anthraquinone, pyridoneazo, and xanthene. The manufacturing method of the color filter for organic electroluminescent display elements which fills the opening of a black matrix with inkjet ink containing the pigment or dye which has any frame | skeleton selected from the following.

Images