JP2010237568A - Color filter and organic electroluminescent display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter enabling high transmittance while securing high color purity and effectively preventing dye and/or pigment color fade, and to provide a display using the color filter. <P>SOLUTION: The color filter includes: a base material; and a coloring layer formed on the base material and including dye and/or pigment as a color material. The coloring layer includes a metal complex non-contained antioxidant. In addition, the display includes the color filter. The color filter includes: the base material; and the coloring layer formed on the base material and including the dye and/or pigment as the color material. The coloring layer includes a metal complex non-contained antioxidant. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a color filter including a colored layer containing a metal complex-free antioxidant and an organic EL display including a color filter including a colored layer containing a metal complex-free antioxidant.

  In recent years, an EL display composed of an electroluminescence (hereinafter sometimes referred to as “EL”) element is expected as a next-generation display. There are two types of EL elements: inorganic EL elements and organic EL elements. Each EL element is self-luminous and has high visibility, and since it is a completely solid element, it has excellent impact resistance and is easy to handle. There is an advantage of being. For this reason, research and development and practical application as a pixel of a graphic display, a pixel of a television image display device, a surface light source, and the like are in progress.

  The organic EL element is composed of a light emitting layer made of a fluorescent organic solid such as anthracene and a hole injection layer made of a triphenylamine derivative, or an electron injection layer made of a light emitting layer and a perylene derivative, or a hole injection layer. And a laminated body of any one of the light emitting layer and the electron injecting layer between two electrodes (the light emitting surface side electrode is a transparent electrode). Such an organic EL element utilizes light emission generated when electrons and holes injected into the light emitting layer recombine. For this reason, the organic EL element has the advantage that it can be driven at a low voltage of, for example, 4.5 V and has a quick response by reducing the thickness of the light-emitting layer, and the luminance is proportional to the injected current. The EL element can be obtained. Further, by changing the type of the fluorescent organic solid used as the light emitting layer, light emission is obtained in all the visible colors of blue, green, yellow and red. Since the organic EL element has such advantages, in particular, that it can be driven at a low voltage, research for practical use is currently underway. Some small displays, such as display portions of mobile phones, which are relatively difficult to manufacture, have been put into practical use.

  As a color display method in the organic EL element, (1) a three-color coating method for forming a light emitting material of each color such as blue, red, and green, (2) a light emitting layer that emits blue, and blue → green and blue → CCM method that combines three color conversion layers (CCM layers) that convert each color to red, and (3) a method that combines light emitting layers that emit white light and color filters such as blue, red, and green. Is mentioned. Among these, from the viewpoint of luminous efficiency, the three-color painting method (1) is the most powerful and has been put to practical use in mobile phones, personal digital assistants (PDAs) and the like. Further, from the viewpoint of higher definition, the combination of white OLED + color filter (3), which does not require separate application of phosphors, is promising. Which method to select is determined by the nature of the device in which the display is incorporated.

  In these organic EL elements, since the electrode is made of a metal material and the light emitter itself is transparent, the display contrast is remarkably reduced due to reflection of external light when assumed to be used in a bright environment. There was a problem. Therefore, A. A. A circularly polarizing plate is attached to the outside light incident side of the organic EL element. Applying a color filter, C.I. Various measures such as coloring with an achromatic color or a color close to an achromatic color (so-called tint processing) are usually taken alone or in combination.

  Here, when the circularly polarizing plate of A is attached, although reflection of external light is completely suppressed in principle (depending on the incident angle of external light), more than half of the light emitted from the organic EL element is circular. It was absorbed by the polarizing plate and was not necessarily efficient. On the other hand, when the B color filter is applied, although the effect of suppressing the reflection of external light is inferior compared to the case of using a circularly polarizing plate, it is possible to adjust the color of the emission color from the organic EL element. Demonstrate the effect. Since there is a limit to the improvement in color purity due to light emission of the organic EL element itself, it can be said that the adjustment of the color by the color filter is very effective. Of course, it goes without saying that a color filter is indispensable for the colorization of white EL. Suppression of external light reflection by the color filter is achieved by absorbing a wavelength component unnecessary for display. That is, it is preferable from the viewpoint of improving contrast that the wavelength region where the OLED does not emit light or has almost no light is completely shielded from light.

  By the way, the lifetime of the organic EL element varies depending on the light emission luminance determined by the current value. That is, high luminance can be achieved by increasing the current value, but at the same time, the lifetime of the element is shortened. Therefore, after the light is emitted from the light emitter, suppressing the light absorption by the peripheral members as low as possible suppresses the current value, leading to a longer life. Therefore, it is desired to improve the transmittance of the color filter in each color pixel so as not to attenuate the emission of each color.

  Here, the transmittance of the color filter greatly depends on the performance of the color material used for the colored layer. For this reason, extensive research has been conducted on various color materials, particularly pigments, until now (see, for example, Patent Document 1), but it is required to use color materials having excellent transmittance. However, even a color material having excellent transmittance such as a dye has a problem of poor light resistance.

  Further, in the organic EL display application, there is a problem that the light resistance of the coloring material is required due to the structure. Therefore, in order to improve light resistance, it has been proposed to laminate an ultraviolet cut film as an ultraviolet prevention layer on the display surface side of the display device (see, for example, Patent Document 2). For example, in an organic EL display, a technique of laminating an anti-reflection film (AR film) having an antireflection function on the display side is generally employed. In the AR film, an ultraviolet absorber is added to the TAC film as a base. Usually, the UV absorber added to the TAC film does not absorb in the visible light region or is suppressed to a slight extent so as not to adversely affect the display characteristics of the display (for example, patent document) 3). In addition, it has been proposed to use a protective layer having an absorption region in the visible light portion (see, for example, Patent Document 4), but it may be yellowish due to absorption of the visible light portion. These references do not propose the addition of antioxidants. In addition, in order to improve the light resistance of dye, adding a metal complex to the color pattern itself containing dye is proposed (for example, refer patent document 5). However, in this method, since a metal complex is added to a color pattern containing a considerable amount of a dye as a color material in advance, undesirable problems such as precipitation of the metal complex and gelation of the ink may occur. There is. In addition, in order to improve the light resistance of the coloring material itself, it has also been proposed to use a lake pigment, but the setting and evaluation of the light resistance test are insufficient, and practical light resistance is obtained. (For example, see Patent Document 6). However, there is still a strong demand for a color filter that can achieve high transmittance while ensuring high color purity and is excellent in light resistance.

JP 2004-85592 A JP 2005-222915 A JP 2005-43400 A JP 2007-234301 A Japanese Patent Laid-Open No. 11-223720 JP 2001-81348 A

1 is a typical cross-sectional view of a display device including a color filter of the present invention.

  The present invention has been made in view of the above-described background art, and an object of the present invention is to provide a color filter capable of increasing the transmittance while ensuring high color purity while improving the light resistance of the color filter. There is to do. Another object of the present invention is to provide a display device and an organic EL display capable of realizing sufficient performance for each color pixel by improving the light resistance, transmittance, and color purity of the color filter.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that the above problems can be solved by adding a metal complex-free antioxidant to the colored layer, and have completed the present invention. .

That is, the present invention
A substrate;
A colored layer formed on the base material and containing a dye and / or pigment as a coloring material,
A color filter in which the colored layer contains an antioxidant containing no metal complex is provided.

According to another aspect, the present invention provides:
A display device comprising a color filter,
The color filter comprises a base material and a colored layer formed on the base material and containing a dye and / or pigment as a coloring material,
A display device is provided in which the colored layer contains an antioxidant containing no metal complex.

According to another aspect, the present invention provides:
An organic EL display having a light emitting element including light emitters of three colors of blue, red, and green, and having a color filter,
The color filter comprises a base material and a colored layer formed on the base material and containing a dye and / or pigment as a coloring material,
An organic EL display in which the colored layer contains an antioxidant containing no metal complex is provided.

  According to the color filter of the present invention, it is possible to increase the transmittance while ensuring high color purity, and to effectively prevent the color material from fading. In addition, according to the display device and the organic EL display of the present invention, sufficient performance can be realized with respect to each color pixel by improving the light resistance, transmittance, and color purity of the color filter.

Color filter The color filter according to the present invention comprises a base material and a colored layer formed on the base material and containing a dye and / or pigment as a coloring material, and the colored layer is an oxidation free of a metal complex. It contains an inhibitor. By adding an antioxidant directly into the colored layer, the light resistance of the colored layer itself can be improved. This makes it possible to use a color material with low light resistance for the colored layer. Furthermore, since the antioxidant does not contain a metal complex, problems such as precipitation of a coloring material contained in the colored layer and gelation of the coating liquid can be prevented. Moreover, according to the preferable aspect of this invention, since a base material exists in the light-projection side, a transparent base material with high light transmittance is used. For example, the transparent base material which consists of material with high light transmittances, such as glass, quartz, or various resin, is mentioned.

Antioxidant In the present invention, an antioxidant refers to an antioxidant that prevents oxidative degradation of a target substance. Antioxidants include radical scavengers that have the function of invalidating radicals generated in materials by energy such as ultraviolet rays and heat, and the generated peroxides are decomposed into innocuous substances so that no new radicals are generated. There is a peroxide decomposition agent having a function of making it.

  According to a preferred aspect of the present invention, the colored layer preferably contains at least one antioxidant selected from the group consisting of hindered phenols, amines, and phenols. These antioxidants are so-called radical scavengers, and discoloration of the coloring material in the colored layer can be prevented by invalidating the generated radicals. A radical scavenger and a peroxide decomposer may be used in combination. Examples of the peroxide decomposing agent include phosphorus-based compounds and sulfur-based compounds.

  Examples of the phenol-based antioxidant include 2,6-di-tert-butyl-p-cresol (Yosinox BHT manufactured by API Corporation), 4,4′-butylidenebis- (6-tert-butyl-3). -Methylphenol) (Yoshinox BB, manufactured by API Corporation), 2,2'-methylenebis- (4-methyl-6-tert-butylphenol) (Yoshinox 2246G, manufactured by API Corporation), 2,2'-methylenebis- ( 4-ethyl-6-tert-butylphenol (Yoshinox 425 manufactured by API Corporation), 2,6-di-tert-butyl-4-ethylphenol (250 manufactured by API Corporation), 1,1,3-tris ( 2-Methyl-4hydroxy- -Butylphenyl) butane (Yoshinox 930 manufactured by API Corporation), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Tominox SS manufactured by API Corporation), tetrakis [Methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Tominox TT manufactured by API Corporation), triethylene glycol bis [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionate] (Tominox 917 manufactured by API Corporation) and tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (API Corporation) Yoshinox 314), and the like.

  Examples of the amine antioxidant include dilauryl thiodipropionate (DLTP manufactured by API Corporation), distearyl thiodipropionate (DSTP manufactured by API Corporation), and dimyristyl thiodipropionate (AP). Sulfur-based antioxidants such as DMTP (manufactured by I Corporation) and ditridecylthiodipropionate (DTTP manufactured by AP Corporation), N-isopropyl-N'-phenyl-p-phenylenediamine (Antage 3C manufactured by Kawaguchi Chemical Co., Ltd.) ), N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (Antage 6C manufactured by Kawaguchi Chemical Co., Ltd.), and 6-ethoxy-2,2,4-trimethyl-1,2-dihydro Quinoline (An manufactured by Kawaguchi Chemical Industry Co., Ltd. tag AW) and the like.

  Examples of the hindered phenol antioxidant include 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (trade name: IRGANOX 1330 manufactured by Ciba Japan), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010 manufactured by Ciba Japan), 2- t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer GM, manufactured by Sumitomo Chemical Co., Ltd.), 2- [1- (2-hydroxy- 3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate (trade name: Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), N, N′-hexa Tylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (trade name: IRGANOX 1098, manufactured by Ciba Japan), 1,6-hexanediol-bis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 259 manufactured by Ciba Japan), 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propionyloxy] 1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.), Tris- (3,5 -Di-t-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114, manufactured by Ciba Japan), isooctyl-3- (3,5-di-t-butyl-4-hydroxyph) Nil) propionate (trade name: IRGANOX 1135, manufactured by Ciba Japan), 4,4′-thiobis (6-tert-butyl-3-methylphenol) (trade name: Sumilizer WX-R, manufactured by Sumitomo Chemical Co., Ltd.), and 6 -[3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxa Phosfepin (trade name: Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  In the present invention, the light resistance of the colored layer can be improved by adding an antioxidant to the colored layer of the color filter. In addition, although this invention is not restrained by any theory, it is thought that it is as follows as a mechanism of the light resistance improvement of a colored layer. However, it goes without saying that the present invention should not be limited by the following description. First, when a radical is generated in the colored layer by light irradiation, it becomes a base point and a new radical or peroxide (R—O—O—H) is generated. Peroxide is unstable and can be easily decomposed by heat and light to create new radicals. Thus, once oxidation starts, oxidative degradation occurs in sequence. Therefore, if the generated radical can be invalidated, chain oxidation deterioration can be suppressed. Therefore, it is considered that fading due to oxidative deterioration of the coloring material in the colored layer can be effectively suppressed by directly adding an antioxidant (particularly a radical scavenger) to the colored layer. Further, by using a lake pigment and / or a dye in the colored layer, the transmittance can be increased as compared with a conventional pigment-based color filter. Conventionally, it was a material that could not be used because of insufficient light resistance, but by using it together with the above antioxidant (particularly a hindered phenol), light resistance that can withstand practical use can be obtained. The content of the antioxidant is 3.0 to 50.0% by mass with respect to the color material amount in the color material-containing photoresist.

  According to a preferred embodiment of the present invention, the colored layer preferably includes colored layers of each color, and includes, for example, a blue colored layer, a red colored layer, and a green colored layer. According to a preferred embodiment of the present invention, the blue colored layer preferably contains a dye as a colorant, and includes a methine dye, an anthraquinone dye, an azo dye, a metal-containing azo dye, a triarylmethane dye, and More preferably, it contains at least one dye selected from the group consisting of phthalocyanine dyes. According to such a dye, high transmittance can be realized while ensuring high color purity for the blue pixel of the color filter. In the present invention, commercially available dyes can also be used. For example, Basonyl Blue 636 (a triarylmethane dye manufactured by BASF) and Basacid Blue 750 (a phthalocyanine dye manufactured by BASF) are preferably used. In a preferred embodiment, the content of the dye is 5 to 40% by mass with respect to the total amount of the colorant-containing photoresist.

  According to the preferable aspect of this invention, it is preferable that a blue colored layer contains a pigment as a coloring material, and it is more preferable that a lake pigment is included. For example, C.I. I. Disazo pigments such as C.I. Pigment Blue 25 (Dianisidine Blue, etc.); I. Phthalocyanine pigments such as C.I. Pigment Blue 15 (phthalocyanine blue, etc.); I. Anthraquinone pigments such as C.I. Pigment Blue 60 (Indantron Blue, etc.); I. As an alkali blue pigment such as CI Pigment Blue 18 (Alkali Blue V-5: 1), and a lake pigment, C.I. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment blue 14 and C.I. I. And CI Pigment Blue 24. According to such a pigment, high transmittance and light resistance can be realized while ensuring high color purity with respect to the blue pixel of the color filter.

  According to a preferred embodiment of the present invention, the blue colored layer further preferably contains a pigment raked with a complex acid as a coloring material. Examples of the complex acid include phosphotungstic acid, phosphomolybdic acid, and phosphotungsten / molybdic acid. Among the above pigments, complex acid is used as a precipitant and exists as a counter ion in the molecule. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment Blue 14 and the like are preferable in terms of light resistance, and C.I. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment Blue 10 is particularly preferable. Light resistance can be further improved by using a pigment raked with such complex acid. In a preferred embodiment, the pigment content is 5 to 40% by mass based on the total amount of the pigment photoresist.

  According to the preferable aspect of this invention, it is preferable that a red colored layer or a green colored layer contains a pigment and / or dye as a coloring material. For example, C.I. I. Monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.); I. Disazo pigments such as C.I. Pigment Red 38 (Pyrazolone Red B, etc.); I. Pigment Red 53: 1 (Lake Red C, etc.) and C.I. I. Azo lake pigments such as C.I. Pigment Red 57: 1 (Brilliant Carmine 6B); I. Condensed azo pigments such as C.I. Pigment Red 144 (condensed azo red BR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Red 174 (Phloxine B Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Red 81 (Rhodamine 6G 'lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Red 177 (eg, dianthraquinonyl red); I. Thioindigo pigments such as C.I. Pigment Red 88 (Thioindigo Bordeaux, etc.); I. Perinone pigments such as C.I. Pigment Red 194 (perinone red, etc.); I. Perylene pigments such as C.I. Pigment Red 149 (perylene scarlet, etc.); I. Pigment violet 19 (unsubstituted quinacridone), C.I. I. Quinacridone pigments such as CI Pigment Red 122 (quinacridone magenta, etc.); I. Isoindolinone pigments such as C.I. Pigment Red 180 (Isoindolinone Red 2BLT, etc.); I. And alizarin lake pigments such as CI Pigment Red 83 (Mada Lake, etc.). Further, as a pigment exhibiting green, C.I. I. Pigment green 7 (phthalocyanine green), C.I. I. Phthalocyanine pigments such as CI Pigment Green 36 (phthalocyanine green), and C.I. I. And azo metal complex pigments such as CI Pigment Green 8 (Nitroso Green). Furthermore, examples of the dye include organic dyes such as acid dyes, direct dyes, disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes, and sublimable dyes. Specific examples include azo, anthraquinone, benzodifuran, and condensed methine. In such a red or green colored layer, a higher transmittance of the color filter can be obtained by including a dye, and higher light resistance and heat resistance can be obtained by including a pigment.

  According to a preferred aspect of the present invention, the color filter may further include an ultraviolet blocking layer formed on the surface of the substrate opposite to the colored layer. The ultraviolet blocking layer is preferably formed from an ultraviolet protective film. In the present invention, a commercially available UV protection film can also be used. For example, examples of the TAC film include KC4UX2M manufactured by Konica Minolta and Fujitac manufactured by Fuji Film. Examples of the UV cut film include a UV guard manufactured by Fuji Film, Lumicool 1501 manufactured by Lintec. Moreover, as an ultraviolet absorber, Ciba Japan Tinuvin series etc. can be used. According to such an ultraviolet prevention film, since the incidence of ultraviolet rays from the display surface can be blocked, the fading of the color material (pigment and / or dye) contained in the color filter can be more effectively prevented. it can. When the ultraviolet blocking layer is a film type, it is preferable to further include an adhesive layer between the substrate and the ultraviolet blocking layer. The adhesive layer can be formed using an adhesive layer forming material such as an ultraviolet curable acrylic resin adhesive, a two-component cross-linking acrylic resin adhesive, and a thermosetting epoxy resin adhesive.

  According to a preferred aspect of the present invention, a color filter for a display device is preferred, which is composed of finely patterned pixels including red, green, and blue, and each color pixel is constituted by the color filter described above.

Method for Producing Color Filter The method for producing a color filter according to the present invention is not particularly limited, but can be carried out according to a preferred embodiment shown below. That is, according to a preferred embodiment of the present invention, first, a colorant (dye and / or pigment) -containing photoresist is applied on a substrate, dried under reduced pressure, and pre-baked to remove the solvent. Conventionally known methods can be used for applying the colorant-containing photoresist, for example, spin coating, printing, ink jet, bar coating, spraying, die coating, bead coating, and slit & spin coating. Etc. In any method, in order to obtain a uniform coating film, dilution / viscosity adjustment with a solvent may be performed so that the coating solution has a constant viscosity. Subsequently, ultraviolet light is exposed to cure the colorant-containing photoresist. When patterning is performed, pattern exposure is performed through a photomask, followed by spray development using a 0.05 to 0.5% KOH aqueous solution. Furthermore, a colored layer can be formed on a base material by baking. In addition, it is preferable to perform prebaking on 70-120 degreeC and the conditions for 1 to 10 minutes, and it is preferable to perform exposure of an ultraviolet-ray with the exposure amount of 30-3000 mJ / cm < ² > by the ultraviolet-ray which has a 254-360 nm emission peak. The colorant-containing photoresist includes a dye and / or a pigment, a monomer, a polymer, a solvent, and optionally a surfactant, a photopolymerization initiator, a pigment derivative, and a dispersant. Can be included.

  Examples of the monomer include allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2 Hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1 , 4-Butanegio Diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate Acrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane Triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triac 2,2,4-trimethyl-1,3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the above acrylate groups Substituted with a methacrylate group, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, 2-hydroxyethylacryloyl phosphate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 3-butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate ester neopent Glycol diacrylate, phenol-ethylene oxide modified acrylate, phenol-propylene oxide modified acrylate, N-vinyl-2-pyrrolidone, bisphenol A-ethylene oxide modified diacrylate, pentaerythritol diacrylate monostearate, tetraethylene glycol diacrylate, polypropylene Acrylate monomers such as glycol diacrylate, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate , And those obtained by substituting these acrylate groups with methacrylate groups, urethane acrylate oligomers in which an acrylate group is bonded to an oligomer having a polyurethane structure, polyester acrylate oligomers in which an acrylate group is bonded to an oligomer having a polyester structure, and having an epoxy group Epoxy acrylate oligomers with acrylate groups bonded to oligomers, urethane methacrylate oligomers with methacrylate groups bonded to oligomers with polyurethane structures, polyester methacrylate oligomers with methacrylate groups bonded to oligomers with polyester structures, and oligomers with epoxy groups Epoxy methacrylate oligomer bonded with methacrylate group, Polyureta having acrylate group Acrylate, polyester acrylate having an acrylate group, epoxy acrylate resin having an acrylate group, polyurethane methacrylate having a methacrylate group, polyester methacrylate having a methacrylate group, and epoxy methacrylate resin having a methacrylate group. In the present invention, commercially available monomers can also be used. For example, SR399 (manufactured by Sartomer Co., Ltd.) is preferable. In a preferred embodiment, the monomer content is 2.0 to 10.0 mass% with respect to the total amount of the colorant-containing photoresist.

  Examples of the polymer include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid resin, ethylene methacrylic acid. Resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether ether Ketone, polyethersulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, polyamide Resin, polyamic acid resin, polyetherimide resin, phenol resin, urea resin, etc., and polymerizable monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl Acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl One or more of methacrylate, n-decyl acrylate, n-decyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, styrene, α-methyl styrene, N-vinyl-2-pyrrolidone, glycidyl (meth) acrylate, acrylic acid, Examples thereof include methacrylic acid and dimers of acrylic acid (for example, M-5600 manufactured by Toa Gosei Chemical Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. In a preferred embodiment, the content of the polymer is 2.0 to 5.0% by mass with respect to the total amount of the colorant-containing photoresist, and examples of the polymer include benzyl methacrylate, styrene, acrylic acid, and 2-hydroxyethyl methacrylate. A copolymer obtained by adding 2-methacryloyloxyethyl isocyanate to the copolymer is used. Preferably, the molar ratio of each component of the copolymer is benzyl methacrylate: styrene: acrylic acid: 2-hydroxyethyl methacrylate = 10-20: 30-40: 25-35: 10-20, 10-20 mol of 2-methacryloyloxyethyl isocyanate is added to 100 mol of the copolymer.

  Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, n-butylbenzene, diethylbenzene, and tetralin, ethers such as methoxybenzene, 1,2-dimethoxybenzene, and diethylene glycol dimethyl ether, acetone, and methyl ethyl ketone. Ketones such as methyl isobutyl ketone, cyclohexanone, and 2,4-pentanedione, esters such as ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone, Amido solvents such as 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide, chloroform , Dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, tritrichloroethylene, tetrachloroethylene, chlorobenzene, and orthodichlorobenzene, and other halogenated solvents, t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene Examples include at least one selected from the group consisting of alcohols such as glycol, ethylene glycol monomethyl ether, ethyl cellosolve, and butyl cellosolve, and phenols such as phenol and parachlorophenol. In a preferred embodiment, the content of the solvent is 50 to 90% by mass with respect to the total amount of the colorant-containing photoresist. In addition, the use of a single solvent alone may cause the material to be coated (the material that constitutes the substrate) to be eroded when the solubility of the photoresist composition is insufficient or when the photoresist is applied. These disadvantages can be avoided by using a mixture of two or more solvents.

  Examples of the surfactant include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, and an anionic surfactant. In a preferred embodiment, the content of the surfactant is 0.03 to 3.0% by mass with respect to the total amount of the colorant-containing photoresist.

  As the photopolymerization initiator, a radical polymerizable initiator can be used. The radical polymerizable initiator generates free radicals by energy such as ultraviolet rays. For example, benzyl (also called bibenzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 -Benzoyl-4'-methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminomethylbenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3'-dimethyl-4-methoxy Benzophenone, methylobenzoyl formate, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-mol Olinophenyl) -butan-1-one, 1- (4-dodecylphenyl) -2hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone , Isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like. In the present invention, a commercially available photopolymerization initiator can also be used. For example, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907 (all manufactured by Ciba Specialty Chemicals), Darocur (Merck) , Adeka 1717 (manufactured by Asahi Denka Kogyo Co., Ltd.) and the like, and 2,2′-bis (o-chlorophenyl) -4,5,4′-tetraphenyl-1,2′biimidazole (black gold chemical) Biimidazole compounds such as those manufactured by KK are preferred. In a preferred embodiment, the content of the photopolymerization initiator is 1.0 to 5.0% by mass with respect to the total amount of the colorant-containing photoresist.

  Examples of the pigment derivative include those having a sulfonic acid group, a sulfonic acid amide group, a carboxylic acid group, an amide group, and an imide group in the pigment skeleton. In addition, a pigment derivative has an effect which improves the dispersibility of a pigment. In the present invention, commercially available pigment derivatives can also be used. For example, Solsperse 12000 (manufactured by Geneca), Solsperse 5000 (manufactured by Avisia), and Solsperse 22000 (manufactured by Abyssia) are preferable. In a preferred embodiment, the content of the pigment derivative is 0.05 to 10% by mass with respect to the total amount of the colorant-containing photoresist.

  Examples of the dispersant include cationic, anionic, nonionic, amphoteric, and polymer dispersants. In the present invention, commercially available dispersants can also be used, for example, Solsperse 24000 (manufactured by Geneca Corporation), Solsperse 20000 (manufactured by Geneca Corporation), and Disperbyk-160 (manufactured by Big Chemie Japan Corporation). Is preferred. In a preferred embodiment, the content of the dispersant is 0.1 to 50% by mass with respect to the total amount of the colorant-containing photoresist. These dispersants can be used alone or in admixture of two or more.

Display device The display device according to the present invention comprises a substrate and a colored layer formed on the substrate and containing a dye and / or pigment as a coloring material, and the colored layer is an oxidation free of a metal complex. A color filter including an inhibitor is provided. According to a preferred embodiment, the display device is an organic EL display. The organic EL display preferably has a light emitting element including three color light emitters of blue, red, and green. According to a preferred embodiment of the present invention, the organic EL display is obtained by bonding a color filter and an organic EL light emitter with an adhesive. As the adhesive, the above-mentioned adhesive layer forming material can be used, for example, a two-component mixed type of a main agent (SK Dyne 2094, manufactured by Soken Chemical Co., Ltd.) and a curing agent (E-AX, manufactured by Soken Chemical Co., Ltd.). An acrylic adhesive can be used. According to such an organic EL display, sufficient performance can be realized with respect to each color pixel by improving the light resistance, transmittance, and color purity of the color filter.

  Here, FIG. 1 shows a typical sectional view of a display device having the color filter of the present invention. The organic EL display shown in FIG. 1 has a blue colored layer (2), a green colored layer (3), and a red colored layer (4) on a substrate (1), and a black stripe layer (5) between each color. A color filter (6) formed in a predetermined pattern, and a light emitting element (10) including three color light emitters of a blue light emitter (7), a green light emitter (8), and a red light emitter (9) Are laminated via an adhesive layer (11).

Manufacturing method of organic EL light- emitting body The manufacturing method of the organic EL light-emitting body is not particularly limited, but can be carried out according to the preferred embodiments shown below. That is, a blue light emitting layer is formed by patterning a reflective anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer in this order on a substrate. . This is repeated twice later to form a green light emitting layer and a red light emitting layer. Furthermore, a semitransparent cathode and a protective layer are sequentially formed and laminated in this order on the blue light emitting layer, the green light emitting layer, and the red light emitting layer, and an organic EL light emitting body can be manufactured.

As said board | substrate, the alkali free glass substrate which has TFT as a switching element can be used, The thickness of a alkali free glass substrate becomes like this. Preferably it is 0.5-1.1 mm. As the reflection type anode, a reflection type anode having a laminated structure of ITO / Ag / ITO can be used. Preferably, the thickness of each layer of the laminated structure is 10 to 150 nm, preferably the reflection type electrode. The thickness is 50 to 300 nm. The hole injection layer is a hole made of a co-deposited thin film of bis (N- (1-naphthyl-N-phenyl) benzidine) (α-NPD) and MoO ₃ (volume concentration of MoO ₃ : 20%). An injection layer can be used, and preferably the thickness of the hole injection layer is 10 to 400 nm. As said hole transport layer, the hole transport layer which consists of (alpha) -NPD can be used, Preferably the thickness of a hole transport layer is 5-200 nm. As the above light emitting layer, a light emitting layer using 9,10-di-2-naphthylanthracene (DNA) as a host material and 1-tert-butyl-perylene (TBP) as a guest material can be used, and preferably The light emitting layer has a thickness of 20 to 60 nm, and is preferably adjusted so that the mixing ratio of the host material and the guest material is 10: 1 to 100: 1. As said electron carrying layer, the electron carrying layer which consists of a tris (8-quinolinolato) aluminum complex (Alq3) can be used, Preferably the thickness of an electron carrying layer is 5-200 nm. As said electron injection layer, the electron injection layer which consists of LiF can be used, Preferably the thickness of an electron injection layer is 0.1-1 nm. As the translucent cathode, a translucent cathode made of MgAg can be used, and the thickness of the translucent cathode is preferably 1 to 100 nm. As said protective layer, the protective layer which consists of SiON can be used, Preferably the thickness of a protective layer is 50-400 nm.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

  In the following examples and comparative examples, glass (substitute for organic EL elements) and a color filter were laminated and integrated to manufacture a pseudo panel (substitute for organic EL display). Subsequently, a light resistance test was performed on the manufactured pseudo panel.

Example 1
Manufacture of pseudo panel First, a pigment photoresist for a blue pattern was prepared using the following composition.

Blue pattern pigment photoresist / blue pigment (lake pigment manufactured by BASF, Pigment Blue 1): 6.0 parts by mass pigment derivative (manufactured by Zeneca Co., Ltd., Solsperse 12000): 0.6 parts by mass dispersant Zeneca Co., Ltd., Solsperse 24000): 2.4 parts by mass / monomer (Sartomer Co., Ltd., SR399): 4.0 parts by mass / polymer: 5.0 parts by mass / photopolymerization initiator (Ciba Geigy Corporation) Irgacure 907): 1.4 parts by mass / photopolymerization initiator (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole): 0 .6 parts by mass / solvent (propylene glycol monomethyl ether acetate): 80.0 parts by mass / antioxidant (hindered phenol, Sumitizer GP manufactured by Sumitomo Chemical): 1.0 part by mass In addition, the above-mentioned polymer is 2 with respect to 100 mol of the copolymer of benzyl methacrylate: styrene: acrylic acid: 2-hydroxyethyl methacrylate = 15.6: 37.0: 30.5: 16.9 (molar ratio). -16.9 mol of methacryloyloxyethyl isocyanate is added, and the weight average molecular weight is 42500.

The pigment photoresist prepared above is applied by spin coating on a 0.7 mm thick glass substrate (Corning Corp., 1737) as a base material, dried under reduced pressure, and pre-baked at 80 ° C. for 5 minutes. The solvent was removed. Subsequently, ultraviolet rays having an emission peak of 365 nm were solid-exposed with an exposure amount of 300 mJ / cm ² to cure the coating film. Furthermore, by baking for 30 minutes in a 180 degreeC clean oven, the colored layer was formed in the thickness of 1.8 micrometers on the glass substrate, and the color filter was obtained.

  The pigment photoresist could be patterned on the order of 10 μm by pattern exposure through a photomask and subsequent spray development using a 0.1% KOH aqueous solution. Thereby, sufficient resolution for a color filter application was confirmed.

  Next, as an adhesive, an acrylic adhesive that is a two-component mixture of a main agent (SK Dyne 2094, manufactured by Soken Chemical Co., Ltd.) and a curing agent (E-AX, manufactured by Soken Chemical Co., Ltd.) is prepared. On the other hand, 0.27% by mass of a curing agent was added, and methyl ethyl ketone as a dilution solvent was further added at a rate of 30% by mass. The prepared adhesive composition was applied to 0.1 mm-thick non-alkali glass (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G) using a bar coater, and the solvent component was reduced to 200 Pa by reduced pressure drying. Was removed. Next, this glass was laminated on the colored layer side of the color filter and bonded to obtain a pseudo panel of Example 1.

  One TAC film (trade name: TF80UL, manufactured by Fuji Film Co., Ltd.) was laminated on the glass surface opposite to the 0.7 mm-thick colored layer as an ultraviolet protection film and subjected to the following evaluation. Note that the TAC film was laminated only during the light resistance test, and peeled off during the spectroscopic measurement.

Example 2
A light resistance test was performed in the same manner as in Example 1 except that the blue pigment was changed to Pigment Blue 11.

Example 3
The light resistance test was performed in the same manner as in Example 1 except that the antioxidant was changed to Sumitizer GA-80 manufactured by Sumitomo Chemical Co., Ltd., which is a hindered phenol antioxidant.

Example 4
A light resistance test was performed in the same manner as in Example 1 except that the antioxidant was changed to Antage 3C manufactured by Kawaguchi Chemical Industry Co., Ltd., which is an amine-based antioxidant.

Example 5
The light resistance test was conducted in the same manner as in Example 1 except that the antioxidant was changed to Yoshinox BHT manufactured by API Corporation, which is a phenolic antioxidant.

Example 6
A light resistance test was conducted in the same manner as in Example 1 except that a dye photoresist prepared as follows was used instead of the blue pattern pigment photoresist.
Blue pattern dye photoresist / blue dye (BASF triarylmethane dye, Basonyl Blue 636): 6.0 parts by mass / monomer (Sartomer Co., Ltd., SR399): 4.0 parts by mass / polymer: 5 0.0 part by mass / photopolymerization initiator (manufactured by Ciba Geigy, Irgacure 907): 1.4 parts by mass / photopolymerization initiator (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5 ′ -Tetraphenyl-1,2'-biimidazole): 0.6 parts by mass / solvent (propylene glycol monomethyl ether acetate): 80.0 parts by mass / antioxidant (hindered phenol, Sumilizer GP manufactured by Sumitomo Chemical): 1.0 part by mass The above-mentioned polymer is benzyl methacrylate: styrene: acrylic acid: 2-hydroxyethyl methacrylate = 15. 6: 37.0: 30.5: 16.9 (molar ratio) of 16.9 mol of 2-methacryloyloxyethyl isocyanate to 100 mol of copolymer, and the weight average molecular weight is 42500. is there.

Comparative Example 1
A light resistance test was performed in the same manner as in Example 1 except that the antioxidant was not used.

Comparative Example 2
A light resistance test was conducted in the same manner as in Example 6 except that the antioxidant was not used.

Light Resistance Test Next, a light resistance test was performed on the pseudo panels manufactured in the above examples and comparative examples. As a light resistance test, a xenon fade meter using xenon arc lamp (product name: Suntest XLS +, manufactured by Toyo Seiki Co., Ltd.) was used to continuously irradiate 100 hours from the UV protection film side of the pseudo panel at an output of 310 W for 100 minutes Evaluation was performed. The test light was irradiated from the glass surface assuming actual use. The color difference was evaluated by ΔE * _ab color difference color. The color difference is measured by spectrophotometry using a microspectrophotometer (Model name: OSP-SP200, manufactured by Olympus) before laminating the UV protection film, and then the UV protection film is peeled off after the light resistance test is completed. It is a value obtained from the chromaticity before and after the light resistance test by measuring. The smaller the numerical value, the higher the light resistance. Standard light C was used as a light source for color difference evaluation. For the reference at the time of spectroscopic measurement, a 0.7 mm thick glass substrate (Corning Corp., 1737) without a colored layer and a 0.1 mm thick non-alkali glass (Nippon Electric Glass) in the same procedure as in the example. A product name: OA-10G) is pasted with an acrylic adhesive that is a two-component mixed type of a main agent (SK Dyne 2094, manufactured by Soken Chemical Co., Ltd.) and a curing agent (E-AX, manufactured by Soken Chemical Co., Ltd.). The combined ones were used.

The results of the color difference evaluation are as shown in Table 1. In the pseudo panel using the color filter satisfying the composition of the present invention of Examples 1 to 6, the color difference value before and after the test is small, and the light resistance is excellent. I understand.

DESCRIPTION OF SYMBOLS 1 Base material 2 Blue colored layer 3 Green colored layer 4 Red colored layer 5 Black stripe layer 6 Color filter 7 Blue light emitter 8 Green light emitter 9 Red light emitter 10 Light emitting element 11 Adhesive layer

Claims (4)

A substrate;
A colored layer formed on the base material and containing a dye and / or pigment as a coloring material,
The color filter in which the colored layer contains an antioxidant containing no metal complex.   2. The color filter according to claim 1, wherein the colored layer includes at least one antioxidant selected from the group consisting of hindered phenols, amines, and phenols. A display device comprising a color filter,
The color filter comprises a base material and a colored layer formed on the base material and containing a dye and / or pigment as a coloring material,
A display device, wherein the colored layer includes an antioxidant containing no metal complex. An organic EL display having a light emitting element including light emitters of three colors of blue, red, and green, and having a color filter,
The color filter comprises a base material and a colored layer formed on the base material and containing a dye and / or pigment as a coloring material,
An organic EL display in which the colored layer contains an antioxidant containing no metal complex.

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