TW201437696A - Color filter - Google Patents

Abstract

This invention provides a color filter that is suitable for enhancing color purity of organic EL display element, wherein a first color filter c for organic EL display element comprises green pixel area 4G, and the optical transmittance of green pixel area 4G through out 600 to 650nm is equal to or less than 15%. A second color filter c for organic EL display element comprises blue pixel area 4B, and the optical transmittance of blue pixel area 4B through out 500 to 550nm is equal to or less than 30%.

Description

Color filter

The present invention relates to a color filter 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 of various colors by applying an organic EL light-emitting material in which various colors of red, green, and blue pixels are applied to a fine pattern (for example, refer to Japanese Patent Publication No. 09). Japanese Patent Laid-Open No. Hei 11-067454, and the like. The method includes, for example, photolithography, mask evaporation, printing, inkjet, and the like.

First, the photolithography method is not suitable for processing of an organic EL luminescent material which is thermally unstable or chemically unstable because the processing temperature is high temperature or a chemical liquid treatment requiring high reactivity is required.

Next, the mask vapor deposition method is a method in which a low-molecular-type organic EL light-emitting material is vacuum-deposited using a vapor deposition mask to form a pattern, whereby an organic EL light-emitting layer of various colors can be formed, but it is not possible to produce a large-sized and A problem of a mask for vapor deposition that is excellent in positional accuracy. Therefore, it is impossible to form a large-screen, high-definition pattern. Moreover, due to the organic EL luminescence constituting each pixel The characteristics such as the brightness or the life of the layer are different. Therefore, the color balance varies depending on the use time, and there is a problem that the characteristics of the display element are limited by the organic EL luminescent material having the lowest characteristics.

On the other hand, a printing method, particularly an inkjet method, in which an organic EL luminescent material is inked and smeared by printing or inkjet to form an organic EL luminescent layer, in terms of a high definition pattern can be formed. It has been attracting attention, and it is considered to be effective especially in the use of a polymer organic EL which is easy to carry out ink formation.

The second method is a method in which white light from a white organic EL light-emitting layer is incident on a color filter to emit light of various colors of red, green, and blue (for example, refer to Japanese Patent Laid-Open Publication No. Hei 08-321380, No. Bulletin 2004-227854). In this method, since a pigment excellent in reliability and durability can be used in the color filter, it is possible to manufacture a long-life organic EL display element in which color balance does not change. Further, instead of the pigment, for example, a pattern containing a fluorescent substance that absorbs blue light and emits green light or red light may be formed in the color filter. Further, in the method of using such a color filter, a color filter manufacturing technique of a liquid crystal display element can be used, and a large-area, high-definition organic EL display element can be manufactured.

In general, the light emission from the organic EL light-emitting layer tends to smear toward the long wavelength side. As a result, in particular, the green pixel and the blue pixel in which the long-wavelength side is superimposed on the luminosity factor of the other color are difficult to satisfy even if the emission peaks of the organic EL light-emitting layers of the respective colors are made to coincide with the target wavelength. TV color of NTSC or EBU purity. Therefore, it is necessary to provide an appropriate color filter for pixels of various colors regardless of whether the organic EL display element produced by the first method or the organic EL display element produced by the second method.

The present invention has been made in view of such problems, and an object thereof is to provide a color filter suitable for improving the color purity of an organic EL display element and a method of manufacturing the same.

In order to solve the above problems, the first color filter of the present invention includes a green pixel region, and the light transmittance of the green pixel region is 15% or less in the range of 600 to 650 nm.

Further, the second color filter of the present invention includes a blue pixel region, and the light transmittance of the blue pixel region is 30% or less in the range of 500 to 550 nm.

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

Here, the peak of the light transmittance of the green pixel region is preferably in the range of 500 to 550 nm, and the light transmittance in the peak of the light transmittance is preferably 50% or more.

Further, the peak of the light transmittance of the blue pixel region is preferably in the range of 410 to 470 nm, and the light transmittance in the peak of the light transmittance is preferably 50% or more.

Thereby, the utilization efficiency of light can be improved.

Further, it is preferably used as a polymer organic EL display device. Since the wavelength spectrum of the light emitted from the polymer organic EL display element is large, the effect of the present invention is particularly excellent.

Further, the coloring material of the pixel region preferably contains a dye, a pigment, or a mixture thereof.

Further, the coloring material preferably has phthalocyanine, quinophthalone, and A coloring material of pyrimidine, barbituric acid, polymethine, triallyl methane, anthracene, pyridone azo or xanthene backbone.

Specifically, examples of the coloring material include a blue dye represented by the following formula (1) or (2).

In the formulae (1) and (2), the ring Z ₁ to the ring Z ₈ each independently represent a hetero ring which may have a substituent. X ^a- represents a halogen anion, ClO ₄ ^- , OH ^- , an organic carboxylic acid anion, an organic sulfonate anion, a boron anion or an organometallic complex anion. k is the valence of the anion and represents an integer of 1 or 2. Y ₁ ^- and Y ₂ ^- independently represent a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylic acid anion, a monovalent organic sulfonic acid anion, a monovalent boron anion or a monovalent organic metal Anion. l and l' each independently represent an integer of 0 or more and 3 or less. L ₁ represents a divalent hydrocarbon group which may be substituted].

Further, examples of the coloring material include a blue dye represented by the following formula (3).

[In the formula (3), the ring Z ₉ and the ring Z ₁₀ each independently represent a hetero ring which may have a substituent. X ^- represents a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylic anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organometallic complex anion. l represents an integer of 0 or more and 3 or less].

Further, examples of the coloring material include the dyes represented by the following formula (4).

In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be 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 ₂ NR ⁸ R ^{9 is} substituted. R ⁵ represents -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 from 0 to 5. When m is an integer of 2 or more, a plurality of R ^{5 's} may be the same or different. X represents a halogen atom. a represents 0 when -SO ₃ ^- or -CO ₂ ^- is contained in any of R ¹ to R ⁵ , and represents 1 in other cases. R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom. The methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group or -NR ⁶ -. 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 together 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 atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be -OH or -R ⁶ . -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ or a halogen atom substitution. A 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 a hydroxyl group, a halogen atom, -Q, -CH=CH ₂ or -CH=CHR ⁶ replaced. The methylene group contained in the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms may be substituted by an oxygen atom, a carbonyl group or -NR ⁶ -. The hydrogen atom contained in the hetero ring having 1 to 10 carbon atoms may be substituted by -R ⁶ , -OH or -Q. M represents a sodium atom or a potassium atom].

The method for producing a color filter for an organic EL display device of the present invention comprises containing phthalocyanine, quinacridone, and An ink of a coloring material of a pyrimidine, a barbituric acid, a polymethine, a triallyl methane, a hydrazine, a pyridone azo or a xanthene skeleton is ink-jet-filled into an opening of a black matrix. Further, the above-described color filter for an organic EL display element was produced.

According to the present invention, a color filter suitable for improving the color purity of an organic EL display element and a method of manufacturing the same are provided.

1, 2‧‧‧ Transparent substrate

3‧‧‧Black matrix

3a‧‧‧ openings

4B‧‧‧Blue resin area

4G‧‧‧Green Resin Area

4R‧‧‧Red Resin Area

5, 8‧‧‧ transparent protective film

6‧‧‧shims

9‧‧‧pixel electrode

10‧‧‧TFT

30‧‧‧ resin layer

61‧‧‧ Shield wall

81‧‧‧Transparent electrode

82R‧‧‧Red Organic EL Layer

82G‧‧‧Green Organic EL Layer

82B‧‧‧Blue organic EL layer

c‧‧‧Color filter

d‧‧‧Organic EL display components

e‧‧‧Organic EL components

Fig. 1 is an example of a plan view of a color filter of the present invention.

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

Fig. 3 is a cross-sectional view showing an organic EL display device produced by laminating the color filter shown in Fig. 1 and Fig. 2 to an organic EL device.

Fig. 4 is a transmission spectrum of the green color filter shown in Embodiments 1 to 7 of the present invention.

Fig. 5 is a transmission spectrum of the blue color filter shown in Examples 8 to 14 of the present invention.

Fig. 6 is a transmission spectrum of the green color filter shown in Comparative Example 1 to Comparative Example 3.

Fig. 7 is a transmission spectrum of the blue color filter shown in Comparative Example 4 to Comparative Example 5.

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

Hereinafter, the color filter according to the embodiment will be described. It is to be noted that the same elements are denoted by the same reference numerals and the description thereof will not be repeated.

(Summary structure of color filter and organic EL display element)

Fig. 1 is a plan view of a color filter c according to an embodiment, and Fig. 2 is a cross-sectional view taken along line II-II of the color filter c shown in Fig. 1. In addition, FIG. 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 mainly includes a transparent substrate 1; a black matrix 3 which forms an opening corresponding to the pixel; a red resin region 4R which fills each opening of the black matrix 3, and a green resin region 4G, blue resin region 4B; transparent protective film 5; and spacer 6.

The organic EL display element d shown in FIG. 3 is formed by bonding the color filter c of the first and second figures and the organic EL element e so as to face each other with the resin layer 30 interposed therebetween. The organic EL element e is formed by stacking 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, a transparent electrode 81, and a transparent protective layer on the transparent substrate 2. The film 8 is formed.

The organic EL element e and the color filter c are disposed such that the red organic EL layer 82R faces the red resin region 4R, and the green organic EL layer 82G faces the green resin region 4G, so that the blue organic EL layer 82B and The blue resin regions 4B are opposed to each other, and each of the colored resin regions 4R, 4G, and 4B transmits red light, green light, and blue light from the respective color organic EL layers 82R, 82G, and 82B.

(color filter)

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

(transparent substrate)

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

(black matrix)

The black matrix 3 is a light shielding film to prevent cross talk between pixels. The black matrix 3 is patterned into a lattice on the transparent substrate 1, and an opening 3a for forming a pixel is formed. The black matrix 3 may be, for example, a light-shielding resin in which a light-shielding pigment such as carbon black or a metal oxide is dispersed (for example, a black resist (TK-41 manufactured by Sumitomo Chemical Co., Ltd.), etc.), and metal oxidation. It consists of a substance/metal (for example, a chromium oxide/metal chromium laminate). It should be noted that the black matrix 3 may also be a multilayer structure called a so-called light-shielding bank. For example, the light-shielding bank may be formed by laminating a light-shielding resin on a metal oxide/metal layer.

(colored resin area)

The red resin region 4R, the green resin region 4G, and the blue resin region 4B are provided so as to fill the inside of the opening 3a of the black matrix 3. Each of the colored resin regions 4R, 4G, and 4B in the opening 3a is also formed from the light of the respective color organic EL layers 82R, 82G, and 82B of the organic EL element e while forming the pixels of the respective colors of the organic EL display element d. Absorbs light in the desired wavelength region. It should be noted that the colored resin region may be mounted on the black matrix 3, but the portion to be mounted does not contribute to the transmission of light.

Further, the spacer 6 to be described later may be formed by superimposing the adjacent colored resin regions, for example, the red resin region 4R and the green resin region 4G on the black matrix 3 on which the boundary is formed.

The colored resin regions 4R, 4G, and 4B are preferably resins prepared by blending at least one of an organic pigment or an inorganic pigment or a coloring material such as a dye in a transparent resin. Particularly, a so-called transparent coloring resist which imparts photosensitivity to a transparent colored resin can be formed into a fine pattern by a photolithography method, an inkjet method, or a printing method, and particularly when high-resolution full-color display is performed, light is used. Engraving is better.

Here, the transparent coloring resist is obtained by dispersing a coloring material such as a pigment in a solvent, and further dissolving or dispersing a binder resin, a photopolymerizable monomer, and a photopolymerization initiator. It should be noted that any other additives may be dissolved or dispersed.

The binder resin may be any binder resin that develops an unexposed portion with an alkaline solution or a binder resin that functions as a dispersion medium for the coloring material. It is preferred to use, for example, a (meth) acrylate compound as a monomer and a (meth) propyl group having a carboxyl group in the molecule. An olefinic copolymer.

The photopolymerizable monomer is preferably an unsaturated carboxylic acid or an ester thereof, and examples thereof include acrylic acid or an ester thereof, methacrylic acid or an ester thereof. Acrylic acid, methacrylic acid, and the like may be used singly or in combination with one or more other kinds. Further, an unsaturated carboxylic acid such as crotonic acid, itaconic acid, maleic acid or fumaric acid may be optionally added. Acid or its ester.

The photopolymerization initiator may be one commonly used in the art, and examples thereof include acetophenones, benzoin, benzophenones, thioxanthones, and s-three. The photopolymerization initiator or the like may be used singly or in combination of two or more. The content of the photopolymerization initiator is preferably 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 a photoinitiator is used in addition to a photoinitiator, the total amount of the photoinitiator and photoinitiator is preferably in the above range (1 to 40 parts by weight).

The solvent is not particularly limited, and examples thereof include 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; Diethylene glycol dialkyl ethers such as dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl cellosolve acetate Ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetic acid Alkanediol alkyl ether acetates such as esters, methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; anisole, phenylethyl ether, methyl Aromatic aliphatic ethers such as anisole; acetone, 2-butanone, Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol Alcohols such as glycerin; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, methyl 2-hydroxyisobutyrate; and γ-butyrolactone Esters and the like. These solvents may be used singly or in combination of one or more kinds thereof, and the content of the solvent in the transparent coloring resist is usually 20% by mass or more and 90% by mass or less based on the mass fraction. It is 50% by mass or more and 85% by mass or less.

Further, the colored resin regions 4R, 4G, and 4B may be formed by curing the colored ink instead of curing the colored resist. The coloring ink is, for example, a solvent, a coloring material, a dispersing agent for ensuring stability in a solvent, a transparent resin for a film for stably forming an ink, a monomer, and a polymerization initiator or a surfactant as needed, and the like. The composition of the additive.

As the coloring material, an organic pigment or an inorganic pigment or a dye which is generally used for a transparent coloring resist or a coloring ink can be used. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specific examples thereof include oxidation of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Or composite metal oxide. As the organic pigment, for example, a compound classified as a pigment or a dye in a dye index (Colour Index: C.I.) (published by The Society of Dyers and Colourists) can be cited.

Specifically, the compound of the dye index (C.I.) number described below can be mentioned, but it is not limited to this.

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; CI Pigment Orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71; CI Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,215,216,224,242 and 254; CI Pigment Violet 14,19 , 23, 29, 32, 33, 36, 37 and 38; CI solvent violet 2, 8, 9, 11, 13, 14 etc.; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 22, 28, 60 and 64; CI Solvent Blue 25, 38, 64, 67, 70, 129; CI Pigment Green 7, 10, 15, 25, 36, 47 and 58; CI Solvent Green 3, 28, 32 and 33 CI Pigment Brown 28; CI Pigment Black 1 and 7.

As the coloring material of the organic type, it is exemplified by having a selected from the group consisting of phthalocyanine, quinacridone, and A coloring material for at least one of the groups of pyrimidine, barbituric acid, polymethine, triallyl methane, anthracene, and pyridone azo.

In addition, as an example of the dye which can be suitably used for the blue color filter in the present invention, a cyan dye (polymethine dye) represented by the following formula (1) or (2) can be exemplified.

In the formula (1) and the formula (2), the ring Z ₁ to the ring Z ₈ each independently represent a hetero ring which may have a substituent. X ^a- represents a halogen anion, ClO ₄ ^- , OH ^- , an organic carboxylic acid anion, an organic sulfonate anion, a boron anion or an organometallic complex anion. k is the valence of the anion and represents an integer of 1 or 2. Y ₁ ^- and Y ₂ ^- independently represent a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylic acid anion, a monovalent organic sulfonic acid anion, a monovalent boron anion or a monovalent organic metal Anion. l and l' each independently represent an integer of 0 or more and 3 or less. L ₁ represents a divalent hydrocarbon group which may be substituted].

The heterocyclic ring represented by any one of Ring Z ₁ to Ring Z ₈ contains one or more hetero atoms. The above heterocyclic ring may be a single ring or a polycyclic ring. The above hetero atom may be an atom selected from a group 15 element or a group 16 element of the periodic table, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom or a germanium atom. Examples of the above heterocyclic ring include an anthracene ring, a benzofluorene ring, an indolenine ring, and a benzofluorene ring. Oxazole ring, benzo An azole ring, a thiazole ring, a benzothiazole ring, a benzimidazole ring or a quinoline ring.

Examples of the substituent of the above heterocyclic ring include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, an isopentyl group, and a new one. An aliphatic hydrocarbon group such as a pentyl group or a third amyl group; a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, an o-isopropylphenyl group, a m-isopropylphenyl group, and a diastereomer An aromatic hydrocarbon group such as propylphenyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, tert-butoxy, pentyloxy, etc. An alkoxy group; an aryloxy group such as a phenoxy group; an aralkoxy group such as a benzyloxy group; a group having an ester bond such as a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, an ethyloxy group or a benzyl group. Methylamine sulfonate Mercapto, dimethylamine sulfonyl, ethylamine sulfonyl, diethylamine sulfonyl, n-propylamine sulfonyl, di-n-propylamine sulfonyl, isopropylamine sulfonate , alkyl sulfonyl group such as diisopropylamine sulfonyl, n-butylamine sulfonyl, di-n-butylamine sulfonyl; methylsulfonyl, ethylsulfonyl, propylsulfonate Alkylsulfonyl group such as isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, t-butylsulfonyl, tert-butylsulfonyl; fluorine atom; chlorine atom a halogen atom such as a bromine atom or an iodine atom; a nitro group or a cyano group. In addition, when these substituents have a hydrogen atom, the hydrogen atom may be substituted by a group such as a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methoxy group or an ethoxy group; An alkoxy group such as a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group or a pentyloxy group; an aryloxy group such as a phenoxy group or a benzyloxy group; An aromatic hydrocarbon group such as phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, mesityl, o-cumyl, m-isopropylphenyl or p-cumyl; carboxyl; cyano Nitro, etc.

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 a benzoic acid ion, an alkyl carboxylic acid ion, a trihaloalkyl carboxylic acid ion, and a nicotinic acid ion. Examples of the organic sulfonic acid anion include a benzenesulfonate ion, a benzenedisulfonic acid ion, a naphthalenesulfonic acid ion, a naphthalene disulfonate ion, a p-toluenesulfonic acid ion, and an alkylsulfonate ion. The boron anion represented by X ^a- may, for example, be BF ₄ ^- . Examples of the organometallic complex anion represented by X ^a- include azo, biphenyldithiol, thiocatechol chelate, thiobisphenolate chelate, and diammonium. Alcohol-α-diketone organometallic complex ion. Among the above organometallic complex ions, as the central metal, a transition element of Group 3 to Group 11 of the periodic table of the elements can be cited. Examples of the transition metal include ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, lanthanum, cerium, iron, lanthanum, cerium, cobalt, lanthanum, cerium, and nickel. , palladium, platinum, copper, silver, gold, cadmium, mercury, etc.

An example of a halogen anion represented by Y ₁ ^- or Y ₂ ^- , a monovalent organic carboxylic acid anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organometallic complex anion, and X ^a- The monovalent one in the examples of the halogen anion, the organic carboxylic acid anion, the organic sulfonic acid anion, the boron anion or the organometallic complex anion shown is the same.

Examples of the hydrocarbon group represented by L ₁ include a methylene group, an exoethyl group, a vinyl group, a trimethylene group, a propyl group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and the like. a divalent aliphatic hydrocarbon group; a divalent alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexylene group or a cyclohexylene group; an exophenyl group, an exophenyl group, a paraphenyl group, a naphthyl group, etc. A divalent aromatic hydrocarbon group or the like. One or more hydrogen atoms of the hydrocarbon group may be substituted with an amine group, a carboxyl group, a cyano group, a nitro group, a halogen group, a hydroxyl group or the like. L ₁ may be bonded to any position of the ring Z ₁ and the ring Z ₃ .

In addition, as an example of the dye which can be suitably used for a blue color filter in the present invention, a cyanine dye (polymethine dye) represented by the following formula (3) can also be exemplified.

[In the formula (3), the ring Z ₉ and the ring Z ₁₀ each independently represent a hetero ring which may have a substituent. X ^- represents a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylic anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organometallic complex anion. l represents an integer of 0 or more and 3 or less].

An example of the heterocyclic ring which may have a substituent represented by the ring Z ₉ or the ring Z ₁₀ , and a heterocyclic ring which may have a substituent represented by any one of the ring Z ₁ to the ring Z ₈ in the formula (1) or the formula (2) The examples are the same. An example of a halogen anion represented by X ^- , a monovalent organic carboxylic acid anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organometallic complex anion, and a halogen anion represented by X ^a- The monovalent organic carboxylic acid anion, the monovalent organic sulfonic acid anion, the monovalent boron anion or the monovalent organic metal complex anion are the same as those of the monovalent one.

In addition, in the present invention, as an example of a dye which can be suitably used for a blue color filter, a xanthene dye represented by the following formula (4) can also be exemplified.

In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be 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 ₂ NR ⁸ R ^{9 is} substituted. R ⁵ represents -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 from 0 to 5. When m is an integer of 2 or more, a plurality of R ^{5 's} may be the same or different. X represents a halogen atom. a represents 0 when -SO ₃ ^- or -CO ₂ ^- is contained in any of R ¹ to R ⁵ , and represents 1 in other cases. R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom. The methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group or -NR ⁶ -. 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 together 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 atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be -OH or -R ⁶ . -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ or a halogen atom substitution. A 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 a hydroxyl group, a halogen atom, -Q, -CH=CH ₂ or -CH=CHR ⁶ replaced. The methylene group contained in the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms may be substituted with an oxygen atom, a carbonyl group or -NR ⁶ -. The hydrogen atom contained in the hetero ring having 1 to 10 carbon atoms may be substituted by -R ⁶ , -OH or -Q. M represents a sodium atom or a potassium atom].

Examples of R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a heptyl group. Cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, decyl, decyl, tricyclodecyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethyl Hexyloxypropyl, methoxyhexyl, ethoxypropyl and the like.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Examples of the halogen atom exemplified as the substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms include fluorine, chlorine, bromine and the like. Examples of the -SO ₃ R ⁶ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group, and a decanesulfonyl group. Examples of the -CO ₂ R ⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a pentyloxycarbonyl group, an isopentyloxycarbonyl group, a neopentyloxycarbonyl group, and the like. Cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptoxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, oxime oxycarbonyl, oxime oxycarbonyl, tricyclic Anthracenyloxycarbonyl, methoxypropoxycarbonyl, ethoxypropoxycarbonyl, hexyloxypropoxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, methoxyhexyloxycarbonyl, and the like.

Examples of -SO ₂ NHR ⁸ include an amine sulfonyl group, a methanesulfonyl group, an ethaneamine sulfonyl group, a propanyl sulfonyl group, an isopropanyl sulfonyl group, a butane sulfonyl group, and an isobutyl group. Alkylsulfonyl, pentamaminesulfonyl, isoamylamine sulfonyl, neopentylamine sulfonyl, cyclopentylamine sulfonyl, hexylamine sulfonyl, cyclohexylamine sulfonate Base, heptanesulfonyl, cycloheptylamine sulfonyl, octylamine sulfonyl, 2-ethylhexylamine sulfonyl, 1,5-dimethylhexylsulfonyl, ring Octanesulfonyl, decylamine sulfonyl, decylamine sulfonyl, tricyclodecylamine sulfonyl, methoxypropane sulfonyl, ethoxypropane sulfonyl, propoxy Propylamine sulfonyl, isopropoxypropanylsulfonyl, hexyloxypropanylsulfonyl, 2-ethylhexyloxypropanylsulfonyl, methoxyhexaneaminesulfonyl, 3 -Phenyl-1-methylpropanaminesulfonyl and the like.

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

In the above 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 the above formula, X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and a hydrogen atom of the alkyl group and the alkoxy group may be substituted by a halogen atom. The alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a perfluoromethyl group. Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted by a halogen atom include a methoxy group, an ethoxy group, a propoxy group and the like.

In the above formula, X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and a hydrogen atom of the alkyl group and the alkoxy group may be substituted by a halogen atom. Examples of the halogen atom in X ² include a fluorine atom, a chlorine atom and a bromine atom. The alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a perfluoromethyl group. Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted by a halogen atom include a methoxy group, an ethoxy group, a propoxy group and the like.

In the above formula, the meaning of X ² is the same as described above.

In the above formula, the meaning of X ³ is the same as described above.

R ⁸ and R ⁹ contained in -SO ₂ NR ⁸ R ⁹ are preferably a branched alkyl group having 6 to 8 carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, an allyl group or a benzene group. a group, an aralkyl group having 8 to 10 carbon atoms, a hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, and an aryl group or an alkoxy group-containing alkyl group or aryl group having 2 to 8 carbon atoms, particularly preferably 2-ethylhexyl.

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

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent include a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a hexylphenyl group, and a nonylphenyl group. Fluorophenyl, chlorophenyl, bromophenyl, hydroxyphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decyloxyphenyl, trifluoromethyl Phenyl group 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 an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted. R ^{5 is} preferably a carboxyl group, an ethoxycarbonyl group, a fluorenyloxy group, a 2-ethylhexyloxypropanylsulfonyl group, a 1,5-dimethylhexylsulfonyl group, or a 3-phenyl-1 group. -methylpropanolsulfonyl, isopropoxypropanesulfonyl.

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

[In the formula (4-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be 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 ₂ NR ⁸ R ^{9 is} substituted. 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' represents 0 when -SO ₃ ^- or -CO ₂ ^- is contained in any one of R ¹¹ to R ¹⁵ , and represents 1 in other cases. R ⁶ , R ⁸ , R ⁹ , m and X have the same meanings as described above].

The compound represented by the formula (4) is preferably a compound represented by the formula (4-2).

In the formula (4-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be 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 are} 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 the saturated hydrocarbon group having 1 to 10 carbon atoms 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 group having 6 to 10 carbon atoms may be -R ²⁶ or - OR ²⁶ replaced. a" represents 0 when -SO ₃ ^- or -CO ₂ ^- is contained in any one of R ²¹ to R ²⁵ , and in other cases, the meanings of 1, m and X are the same as above].

The compound represented by the formula (4) includes, for example, a compound represented by the formula (4a) to the formula (4f).

[In the formula (4a), R ^b and R ^c each independently represent a hydrogen atom, -SO ₃ ^- , -CO ₂ ^- , -CO ₂ H or -SO ₂ NHR ^a . R ^a represents 2-ethylhexyl. a"' represents 0 when -SO ₃ ^- or -CO ₂ ^- is contained in any of R ^b or R ^c , and otherwise represents 1. X has the same meaning as described above].

[In the 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 the formula (4b) is a tautomer of the compound represented by the formula (4b').

[In the formula (4b'), R ^{b '} has the same meaning as described above].

[In the formula (4c), R ^d , R ^e and R ^f each independently represent -SO ₃ ^- , -SO ₃ Na, -SO ₃ H, -SO ₂ NHR ^a , -CO ₂ ^- , -CO ₂ Na or -CO ₂ H. R ^a represents 2-ethylhexyl, but any of R ^d , R ^e and R ^f is -SO ₃ ^- or -CO ₂ ^- ].

The compound represented by the formula (4c) is a tautomer of the compound represented by the formula (4c').

[In the 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, but any of R ^{d '} , R ^{e '} and R ^{f '} is -SO ₃ H or -CO ₂ H].

[In the formula (4d), R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ^a , -CO ₂ ^- or -CO ₂ H. R ^a represents 2-ethylhexyl. However, any of R ^g , R ^h and R ⁱ is -SO ₃ ^- or -CO ₂ ^- ].

The compound represented by the formula (4d) is a tautomer of the compound represented by the formula (4d').

[In the formula (4d'), R ^{g '} , R ^{h '} and R ^{i '} each independently represent a hydrogen atom, -SO ₃ H, -SO ₂ NHR ^a or -CO ₂ H. R ^a represents 2-ethylhexyl, but any of R ^{g '} , R ^{f '} and R ^{i '} is -SO ₃ H or -CO ₂ H].

The compound represented by the formula (4) can be chlorinated by a usual method, for example, by using a dye or a dye intermediate having -SO ₃ H, and the resulting dye or pigment intermediate having -SO ₂ Cl and R ⁸ -NH The amine shown in ₂ is produced by a reaction. In addition, the dye produced by the method described in the upper right column to the lower left column of the third page of the Japanese Patent Publication No. 3-78702 can be produced by chlorinating in the same manner as described above and reacting with an amine.

These coloring materials may be used singly or in combination of two or more, whereby color development can be adjusted. Further, it is preferable that the coloring resin contains 10 to 50% by weight of the coloring material based on the total solid content of the colored 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 a The transmittance of light in the range of 550 nm is an absorption spectrum of 30% or less. Thereby, the blue resin region 4B sufficiently absorbs light in the vicinity of green. When the blue resin region 4B has a portion having a transmittance of more than 30% in the range of 500 to 550 nm, the green color mixed in the light emission from the blue organic EL layer 82B, particularly the blue polymer organic EL layer, cannot be sufficiently removed. Light, therefore, it is difficult to visualize sufficient color purity. In addition, the blue resin region 4B preferably has a high transmittance for blue light, particularly, the peak of the transmittance is 410 to 470 nm, and the transmittance at the peak is preferably 50% or more.

In addition, the green resin region 4G for wavelength selection of the light emitted from the green organic EL layer 82G also has an absorption spectrum having a transmittance of 15% or less in the range of 600 to 650 nm. Thereby, the light in the range near the orange is sufficiently absorbed. When the green resin region 4G has a portion having a transmittance of more than 15% in the range of 600 to 650 nm, the orange light which is mixed in the light emission from the green organic EL layer 82G, particularly the green polymer organic EL layer, cannot be sufficiently removed. Therefore, it is difficult to develop sufficient color purity. In addition, the green resin region 4B preferably has a high transmittance for green light, and has a peak of transmittance of 500 to 550 nm and a transmittance of 50% or more at a peak of transmittance.

In other words, each of the green resin region 4G and the blue resin region 4B of the color filter c of the present embodiment has a green organic EL layer 82G and a blue organic EL layer 82B that can sufficiently absorb the corresponding organic EL element e. A trailing light absorption spectrum on the long wavelength side of the luminescence spectrum.

Thereby, light emitted from each of the organic EL layers 82R, 82G, and 82B can be emitted. The light in an unnecessary wavelength range is sufficiently removed, so that the color purity can be improved. Thereby, the color of the pixel can be made close 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, the green resin region 4G and the blue resin region 4B are respectively in a wavelength region outside the above-described wavelength range, that is, for the green resin region 4G. In the wavelength region of 480 nm or less and 620 nm or more, the blue resin region 4B is preferably a wavelength region of 520 nm or more, and preferably has a transmittance 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 the light having a longer wavelength than the red wavelength is not a problem, it is only required to be a known material that can absorb light other than red. Further, the red resin region R can be produced by using a red coloring material for liquid crystal according to a known method.

The absorption spectra of the respective color resin regions 4R, 4G, and 4B can be easily adjusted by blending or changing the pigment or dye with respect to the concentration of the resin. Further, the thickness of the colored resin regions 4R, 4G, and 4B is not particularly limited, and may be, for example, 0.5 to 5 μm.

(transparent protective film)

The transparent protective film 5 is a film that coats the black matrix 3 and the colored resin regions 4R, 4G, and 4B. As the transparent protective film 5, a film made of an organic transparent resin or an inorganic transparent material can be used, whereby moisture, reaction products, and the like generated from the black matrix 3 or the colored resin regions 4R, 4G, and 4B can be reduced. Floating in the organic EL layer 82 of the organic EL element e The possibility. It should be noted that the present invention can be carried out even without the transparent protective film 5.

The transparent protective film 5 is a film of a transparent inorganic material such as an oxide such as ruthenium or aluminum, a nitride, an oxynitride or a diamond-like carbon (DLC film), and/or a polyvinyl alcohol, an ethylene vinyl alcohol resin, or an acrylic resin. A transparent resin film such as a methacrylic resin is used alone or laminated. The thickness is, for example, about 1 to 10 μm. For example, HC-501 manufactured by Sumitomo Chemical Co., Ltd. can be used.

(gasket)

As shown in FIGS. 1 to 3, the spacer 6 is formed on the black matrix 3. As a result, as shown in FIG. 3, the light emission from the organic EL layers 82R, G, and B is not blocked by the spacer 6, but is output to the outside through the colored resin regions 4R, 4G, and 4B. The height of the spacer 6 can be set to, for example, 3 to 20 μm.

The spacer 6 can be easily formed by photolithography using a photosensitive resin or the like. The photosensitive resin may be a photosensitive resin having a structure that can be finely processed and has a sufficient adhesion to the underlayer and a pressure-resistant strength, and is preferably a resin composition having a large elastic deformation region. For example, a composition comprising an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, an epoxy group-containing unsaturated compound, and a copolymer of an olefinic unsaturated compound other than the above may be mentioned, and has an ethylene property. A polymerizable compound having a saturated bond, a radiation-sensitive polymerization initiator, and a color former.

In addition, as shown in FIG. 1, the light shielding wall 61 can be provided in the boundary of each colored resin region 4R, 4G, and 4B on the black matrix 3. Thereby, even if the display element is viewed from a high angle of view, the adjacent colored resin region is transmitted through The light of 4R, 4G, and 4B will not be mixed in. When the color filter c is placed on the organic EL element e, when the light shielding wall 61 is disposed on the black matrix 3, the light-emitting portions of the organic EL layers 82R, 82G, and 82B do not face each other. It is not easy to damage the organic EL layer 82 by extrusion. The light shielding wall 1 can be made of the same material as the spacer 6.

(Organic EL device)

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

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

A well-known organic EL material can be used for the colored organic EL layers 82R, 82G, and 82B. It is particularly preferable to use a polymer EL material. Specific examples include a LUMATION-based polymer light-emitting material (manufactured by Sumation Co., Ltd.).

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

The TFT 10 can utilize a well-known substance.

The transparent protective film 8 can be made of the same material as the transparent protective film 5.

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

(Production method)

Next, a method of manufacturing the color filter c and the organic EL display element d will be described. The color filter c and the organic EL display element d can be manufactured by sequentially performing the following steps (1) to (6).

Step (1): Black matrix forming step

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 the resist is applied by a spin coater, a roll coater, a die coater or the like. Agent. Then, the transparent substrate 1 coated with the resist is irradiated with light such as ultraviolet rays through a light mask having an opening corresponding to the shape of the black matrix 3, and developed to form a resist pattern. .

Further, by immersing in a liquid which is corrosive to the light-shielding film, the light-shielding film which is not protected by the resist is removed by etching, and then the resist is removed by peeling off, whereby the black matrix 3 is formed on the transparent substrate 1.

Step (2): Colored resin region forming step

Next, on the transparent substrate 1 on which the black matrix 3 is formed, for example, a blue transparent colored resist is applied using a spin coater, a die coater or the like, and prebaked at 70 ° C to 120 ° C. Further, a light mask having a pattern corresponding to the blue resin region 4 B is irradiated with light such as ultraviolet rays, and immersed in an alkali solution to dissolve and dissolve the blue resin region 4B in a region where the light is not irradiated, and pure water is used. After sufficiently washing, it is heated to 160 to 250 ° C using an oven, a hot plate, or the like, and the remaining blue resin region 4B is cured and sintered.

This step is further performed twice, that is, the red resin region 4R is similarly patterned in red, and the green resin region 4G is patterned in green, thereby periodically forming red, green, and blue colored resin regions. Stripe arrangement of 4R, 4G, 4B.

At this time, the spacer 6 may be formed by superposing a photosensitive resin material on the boundary between the adjacent colored resin regions 4G and 4B, 4B and 4R, and 4R and 4G. In addition, in the colored resin region forming step, in addition to the photolithography method, an electroplating method or a printing method may be used.

Instead of using a transparent colored resist, the colored resin regions 4R, 4G, and 4B may be formed by an inkjet method or a printing method. In the printing method, After the black matrix 3 is formed of the light-shielding photosensitive resin, the ink patterns corresponding to the colored resin regions are superimposed and printed, whereby the colored resin regions 4R, 4G, and 4B can be formed. In particular, in the reverse printing method, there is a feature that a black matrix and a colored resin region can be simultaneously formed. On the other hand, in the inkjet method, after the black matrix surrounding the light-shielding bank structure is formed using the light-shielding photosensitive resin, the ink colored by the color material is filled in the opening, and then the ink is dried and given. The color filter c can be obtained by heat treatment or the like to cure it. Since the inkjet method has less heating stress than the photolithography method, a heat-resistant coloring material can be suitably used.

Further, in any of the methods, the colored resin region satisfying the absorption spectrum of the above transmittance can be formed by appropriately adjusting the components of the coloring material contained in the colored resin region and the concentration thereof with respect to the resin.

Step (3): transparent protective film forming step

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

Step (4): gasket forming step

Further, on the transparent substrate 1 on which the transparent protective film 5 is formed, for example, an acrylic photocurable/thermosetting resin is applied by a spin coater or the like. Prebaking is performed by using a photomask having a pattern corresponding to the shape of the spacer 6, and developing with an alkaline aqueous solution, thereby removing the non-exposed portion, and then baking. Thereby, the spacer 6 is formed. Alternatively, the spacer may be formed by laminating a black matrix or a transparent colored resist pattern.

Step (5): lamination step

A photocurable resin such as an ultraviolet curable resin is applied onto the organic EL element e prepared in advance using a spin coater or the like. In addition, the color filter c is placed in alignment with the organic EL element e to which the photocurable resin is applied, and the color filter c is adjusted in position (alignment) by a bonding apparatus.

Step (6): bonding step

Finally, the photocurable resin filled in the gap between the organic EL element e and the color filter c is irradiated with light and cured. Thereby, the color filter c and the organic EL element e can be bonded and fixed, and the organic EL display element d can be completed.

(effect)

Next, the action of the color filter c of the present embodiment will be described. The light emitted from the organic EL layers 82G and 82B of the organic EL element e is incident on the color filter c. The light incident on the color filter is shielded by the black matrix 3 and transmitted through the colored resin regions 4G and 4B, and the green light and the blue light are wavelength-selected. Therefore, each of the colored resin regions constitutes a pixel that emits light of a specific wavelength.

Further, in the color filter of 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 organic EL element can be suppressed in the green pixel and the blue pixel, respectively. The trailing portion on the light wavelength side of the spectrum generated by the green organic EL layer 82G of the piece e or the trailing portion on the light wavelength side of the spectrum generated from the blue organic EL layer 82B. Therefore, the color purity of the light emitted from each pixel can be improved.

It should be noted that the present invention is not limited to the above embodiment, and may be various forms. For example, in the above embodiment, both of the green resin region 4G and the blue resin region 4B satisfy the above-described transmittance conditions that should absorb the trailing portion, but if at least one of the colored resin regions satisfies the above-described transmittance conditions, at least one is increased. The color purity of the colored resin region.

Further, in the above-described embodiment, the organic EL element e has the red organic EL layer 82R, the green organic EL layer 82G, and the blue organic EL layer 82B to emit red light, green light, or blue light, but may also emit white light. In place of the above organic EL element e, an organic EL element of a white organic EL layer is used. The white organic EL layer emits white light by including a plurality of organic EL materials, and the tailing on the long wavelength side longer than the peak wavelength is the same in the light emission from each organic EL material. Therefore, the color filter of the present invention has the same effect of improving color purity even for an organic EL element having a white organic EL layer.

Further, in the above-described embodiment, the red pixel region is formed of a resin colored in red as the red resin region 4R, and the green pixel region is formed by resin colored in green as the green resin region 4G and the resin colored in blue. The blue pixel region serves as the blue resin region 4B, whereby reflection of unnecessary external light can be suppressed, but the color of the resin constituting each pixel region is not limited to the above as long as the necessary wavelength absorption characteristics are satisfied. Said.

Example (production of organic EL device)

After the TFT substrate having the bank frame was formed, a buffer film (PEDT: poly(3,4)-extended ethyldioxythiophene/polystyrenesulfonic acid (Starck V tech) was formed by an ink jet printer at a film thickness of 0.1 μm. Made by the company, trade name: Baytron PCH8000)). In the same manner, the red pixel is filled with red phosphor ink (LUMATION RP-221 (manufactured by Sumation Co., Ltd.)), and the green pixel is filled with green phosphor ink (LUMATION GP-1200 (Sumation Co., Ltd.)) After the blue pixel is filled with blue phosphor ink (LUMATION BP-105 (manufactured by Sumation Co., Ltd.)), the solvent is removed to form a phosphor layer. After the solvent is sufficiently removed in a vacuum, the charge injection layer (IL40) is filled with an inkjet printer, the solvent is dried and removed, and a high-purity Al-Mg film is formed by vapor deposition as a cathode, and then a tantalum nitride film is formed by CVD. The organic EL element e was obtained.

(Preparation of colored resin raw material liquid) Preparation of photosensitive color resist (Examples 1 to 6, 9 to 11, 15 to 18, and Comparative Example 5)

15 parts by weight of the color material shown in Table 1, dispersant (40% by weight relative to the pigment), and solvent (propylene glycol monomethyl ether acetate / ethyl 3-glycolate = 70/30 (weight ratio) 36 parts by weight, a color material dispersion was prepared. A binder resin (benzyl methacrylate/methacrylic acid = 70/30 (mole ratio) copolymer) having an acid value of 113 and a polystyrene-equivalent weight average molecular weight of 30,000 was added to the color material dispersion. Parts by weight, multifunctional acrylate monomer (dipenta 8 parts by weight of a tetraol hexaacrylate, 2 parts by weight of a polymerization initiator (Irgacure 907, manufactured by Ciba Japan Co., Ltd.), 2 parts by weight of a surfactant (F477, manufactured by DIK Co., Ltd.), and 180 parts by solvent (ibid.) The mixture was thoroughly mixed, and then filtered through a 3 μm filter to obtain a photosensitive colored resist.

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

A commercially available color material (photosensitive coloring resist) for a color filter for liquid crystal display shown in Table 1 was used.

Preparation of pigmented ink (Examples 13 to 14)

15 parts by weight of the color material shown in Table 1, a dispersing agent (40% by weight based on the pigment), and 36 parts by weight of a solvent (dipropylene glycol methyl ether acetate) were mixed to prepare a color material dispersion. 3 parts by weight of a binder resin (same as above), 1 part by weight of a polyfunctional acrylate monomer (same as above), and 1 part by weight of a polymerization initiator (same as above) were added to the color material dispersion, and after mixing well, filtration was carried out by 3 μm. Filter, add 30 parts by weight of polyfunctional acrylate monomer (trimethylolpropane triacrylate), adjust the viscosity to 15mPa. s, thereby obtaining a colored ink.

Here, Examples 1 to 7 and Comparative Examples 1 to 3 are colored resin raw material liquids for forming green resin regions, and Examples 8 to 18 and Comparative Examples 4 to 5 are colored resin raw material liquids for forming blue resin regions. In the table 1, PG means pigment green, PV means pigment purple, PB means pigment blue, PY means pigment yellow, and phthalocyanine dye (*1) means a compound of the following formula (5), a cyanine dye (※ 2) The compound of the following formula (6), the cyanine dye (*3), the compound of the following formula (7), and the xanthene dye (*4) represent the compound of the following formula (8), YG800, YB800, B111 Each of them is a trade name of a color material (photosensitive coloring resist) used for a color filter for liquid crystal displays by Toho Chemical Co., Ltd.

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

(manufacture of color filters) (Green filter: Examples 1 to 7, Comparative Examples 1 to 3), (blue filter: Examples 8 to 12, 15 to 18, and Comparative Examples 4 to 5)

The photosensitive colored resist obtained as described above was applied onto the cleaned alkali-free glass (E2K manufactured by Corning Co., Ltd., thickness: 0.63 mm) by a spin coater. After the full exposure, post-baking was carried out under the conditions of 220 ° C × 20 minutes, and the above coating, full exposure and post-baking were further repeated 2 to 5 times in Examples 5 to 7, 10, thereby preparing Table 2 or An analog color filter of the colored resin region of the thickness shown in Table 3.

(Blue filter: Examples 13 to 14)

The colored ink was applied onto the cleaned alkali-free glass (E2K manufactured by Corning Co., Ltd., thickness: 0.63 mm) as a transparent substrate by an inkjet printer, and pre-baked (90 ° C, 1 minute), and then Baking (220 ° C, 20 minutes), an analog color filter having a blue resin region having a thickness shown in Table 3 was prepared.

(Manufacture of organic EL display elements)

A photocurable resin (Sumiflash XR-98, manufactured by Sumitomo Chemical Co., Ltd.) was applied to the organic EL device by a spin coater, and the photocurable resin was defoamed under reduced pressure, and each color filter was laminated on the organic EL device. In the above, the film was pressed and pressed at a pressure of 1 atm, and the ultraviolet ray was irradiated with a high-pressure mercury lamp, and further heat-treated at 80 ° C for 2 hours to cure the photocurable resin to obtain an organic EL display device.

(evaluation and results)

For each color filter, the transmittance of each color filter in the range of 400 to 700 nm is measured before bonding with the organic EL element, and only the transmittance of the alkali-free glass as a transparent substrate is measured in advance. The transmittance curve of the colored resin region in each color filter was obtained. In addition, according to the transmittance Curve, the transmittance of the green filter (Examples 1 to 7, Comparative Examples 1 to 3) at 600 nm (maximum transmittance in 600 to 650 nm), blue filter (Examples 8 to 18, Comparative Example) were determined. 4 to 5) Transmittance at 500 nm (maximum transmittance in 500 to 550 nm), and the wavelength at which the transmittance became a peak and the transmittance at the peak thereof were obtained, and the results are shown in Table 2 or Table 3.

In addition, for the organic EL display element to which the color filter and the organic EL element are bonded, the green organic EL layer is illuminated for the green filter (Examples 1 to 7, Comparative Examples 1 to 3), and the blue filter is applied. (Examples 8 to 18 and Comparative Examples 4 to 5) The blue organic EL layer was illuminated, and the luminosity spectrum and the chromaticity (x, y) of the luminescence were measured, respectively, and the chromaticity is shown in Table 2 or Table 3. In addition, in the state where the color filter is not provided, the light emission spectrum of 400 to 700 nm of the light emitted from the green organic EL layer and the blue organic EL layer of the organic EL element is measured, and the light emission spectrum of the organic EL display element is compared with The intensity ratio (area ratio) of the emission spectrum of the organic EL device is shown in Table 2 or Table 3 as the light use efficiency.

Further, Fig. 4 shows the transmittance curves of the color filters of Examples 1 to 7, the fifth chart shows the transmittance curves of the color filters of Examples 8 to 14, and the sixth figure shows the color filters of Comparative Examples 1 to 3. Transmittance curve of the device, Fig. 7 shows the transmittance curve of the color filters of Comparative Examples 4 to 5, and Fig. 8 shows the presence of A wavelength spectrum of light emitted from the blue organic EL layer of the EL element and light emitted from the green organic EL layer.

(result)

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

Further, the color filters of Examples 8 to 18 having a blue resin region having a transmittance of 30% or less in the range of 500 to 550 nm, and those having a transmittance of not more than 30% in the range of 500 to 550 nm In comparison with the color filters of Comparative Examples 4 to 5, the chromaticity (0.14, 0.08) of the blue light closer to the NTSC chromaticity coordinates was improved, and the color purity was improved.

Therefore, by using the color filter of the present invention, it is possible to greatly expand the color gamut which is reproduced by light of RGB three colors.

3‧‧‧Black matrix

3a‧‧‧ openings

4B‧‧‧Blue resin area

4G‧‧‧Green Resin Area

4R‧‧‧Red Resin Area

6‧‧‧shims

61‧‧‧ Shield wall

c‧‧‧Color filter

Claims (9)

A color filter for an organic EL display element having a blue pixel region, and the light transmittance of the blue pixel region is 30% or less in a range of 500 to 550 nm. The color filter for an organic EL display device according to the first aspect of the invention, wherein the peak of the light transmittance of the blue pixel region is in the range of 410 to 470 nm, and the light transmittance in the peak of the light transmittance is above 50. A color filter for an organic EL display device according to claim 1 or 2, which is used for a polymer organic EL display device. A color filter for an organic EL display element according to claim 1 or 2, wherein the coloring material as the pixel region contains a dye, a pigment or a mixture thereof. The color filter for an organic EL display device according to the fourth aspect of the invention, wherein the coloring material is selected from the group consisting of phthalocyanine, quinophthalone, and A coloring material for at least one of the groups of pyrimidine, barbituric acid, polymethine, triallyl methane, anthracene, and pyridone azo. A color filter for an organic EL display element according to claim 1 or 2, which contains a blue dye represented by the following formula (1) or (2), [In the formulae (1) and (2), the ring Z ₁ to the ring Z ₈ each independently represent a hetero ring which may have a substituent; X ^a- represents a halogen anion, ClO ₄ ^- , OH ^- , an organic carboxylic acid anion, An organic sulfonic acid anion, a boron anion or an organometallic complex anion; k is a valence of an anion, representing an integer of 1 or 2; and Y ₁ ^- and Y ₂ ^- independently represent a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylic acid anion, a monovalent organic sulfonic acid anion, a monovalent boron anion or a monovalent organic metal complex anion; and l and l' each independently represent an integer of 0 or more and 3 or less; L ₁ Represents a divalent hydrocarbon group which may be substituted]. A color filter for an organic EL display element according to claim 1 or 2, which contains a blue dye represented by the following formula (3), [In the formula (3), the ring Z ₉ and the ring Z ₁₀ each independently represent a hetero ring which may have a substituent; X ^- represents a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylic acid anion, monovalent An organic sulfonic acid anion, a monovalent boron anion or a monovalent organic metal complex anion]. The color filter for an organic EL display device according to claim 1 or 2, which contains the dye represented by the following formula (4), [In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms; and a hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms; It may be 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 ₂ NR ⁸ R ⁹ substituted; R ⁵ represents -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; when m is an integer of 2 or more, plural R ^{5 is the} same or different; X represents a halogen atom; a represents 0 in the case of -SO ₃ ^- or -CO ₂ ^- in any of R ¹ to R ⁵ , and represents 1 in other cases; R ⁶ represents a carbon number of 1 to a saturated hydrocarbon group of 10; a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom; and the methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be an oxygen atom, a carbonyl group or NR ⁶ - substituted; R ⁸ and R ⁹ each independently represents a linear or branched alkyl group, carbon atoms, a cycloalkyl group or a -Q 1 to 10 carbon atoms, 3 to 30; or R ⁸ and R ⁹ also Together with the adjacent nitrogen atom, a heterocyclic ring having 1 to 10 carbon atoms; 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 aromatic hydrocarbon group and The hydrogen atom contained in the aromatic heterocyclic group may be substituted by -OH, -R ⁶ , -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ or a halogen atom; the number of carbon atoms is 1 to 10. The hydrogen atom contained in the linear or branched alkyl group and the cycloalkyl group having 3 to 30 carbon atoms may be substituted by a hydroxyl group, a halogen atom, -Q, -CH=CH ₂ or -CH=CHR ⁶ ; The methylene group contained in the linear or branched alkyl group to 10 and the cycloalkyl group having 3 to 30 carbon atoms may be substituted by an oxygen atom, a carbonyl group or -NR ⁶ -; in a heterocyclic ring having 1 to 10 carbon atoms; The hydrogen atom contained may be substituted by -R ⁶ , -OH or -Q; M represents a sodium atom or a potassium atom]. A method for producing a color filter for an organic EL display element according to any one of claims 1 to 2, wherein the method comprising the selected one selected from the group consisting of phthalocyanine, quinophthalone, and An ink of a pigment or dye of any one of a group of pyrimidine, barbituric acid, polymethine, triallyl methane, anthracene, pyridone azo, and xanthene is filled by inkjet Go into the opening of the black matrix.