TW201344354A - Color filter, organic EL display element and colored composition - Google Patents

Abstract

The present invention provides a stable organic EL display element for a long time and a color filter used therefore and a colored composition of forming the color filter. The color filter 3 is having coloration layer 5 of a plurality of color for the colored composition. At least one of coloration layer 5 of a plurality of colors of color filter 3 which is configured to contain polyfunctional antioxidant and having superior stability. Organic EL display element 1 is configured to contain color filter 3 and organic EL layer 2. Organic EL display layer 2 has the tandem structure which can emit white light; organic EL display element 1 enables the display of color images by using color filter3.

Description

Color filter, organic EL display element, and coloring composition

The present invention relates to a color filter, an organic EL display element, and a coloring composition, and more particularly to a color filter for an organic EL display element, a coloring composition for forming the color filter, and An organic EL display element having the color filter.

The organic EL display element has an advantage of being highly visible due to its own color development, being lighter and lighter than a liquid crystal display element, having a high reaction speed, and having a wide viewing angle. The basic structure of the organic EL element constituting the organic EL display element is a simple structure in which the laminated structure of the anode/organic EL layer (light-emitting layer)/cathode is basic. As described above, light of various colors such as red, green, blue, or white can be emitted depending on the light-emitting characteristics of the organic EL layer serving as the light-emitting layer.

In recent years, such an organic EL display element has been used as a color display element in various applications such as a solid-state light source, a color display, or a full-color display.

Further, as an organic EL display element capable of color display, an object obtained by combining an organic EL element substrate having such an organic EL element and a color filter is known.

As the color filter used in the organic EL display element, for example, a color filter using a specific pigment disclosed in Patent Document 1 is known. In addition, as the organic EL element used in the organic EL display element, for example, a series structure disclosed in Patent Document 2 and Non-Patent Document 1 is known.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2010-26268

Patent Document 2 Japanese Patent Laid-Open Publication No. 2003-45676

Non-patent literature

Non-Patent Document 1 Sansei Mingyi Supervisor, "The forefront of organic EL technology development - high brightness, high precision, long life. 诀窍集-", Technical Information Association, pp. 326-328, 2008

However, the organic EL layer has a problem that it is easily deteriorated by various major factors such as moisture or oxygen. Therefore, the life of the organic EL display element is shorter than that of the liquid crystal display element. Therefore, in the development of a color filter used for an organic EL display element, it is also sought to design and configure such that the organic EL layer does not adversely affect the life of the organic EL display element. The present invention has been made in view of such circumstances, and an object thereof is to provide a long-term stable organic EL display element, a color filter for the organic EL display element, and a coloring composition used for forming the color filter.

As a result of intensive studies, the present inventors have found that the above problems can be solved by including an antioxidant in the coloring layer constituting the color filter, and the present invention has been completed.

That is, the first aspect of the present invention relates to a color filter characterized by having a coloring layer of a plurality of colors and a color filter for an organic EL display element, at least one of the coloring layers of the plurality of colors containing A multifunctional antioxidant.

In the first aspect of the invention, the polyfunctional antioxidant preferably contains at least one compound having at least one selected from the group consisting of a hindered phenol structure, a hindered amine structure, and an ethyl sulfide structure.

In the first aspect of the invention, it is preferred that the polyfunctional antioxidant contains a compound having a molecular weight of 300 or more.

In the first aspect of the invention, the polyfunctional antioxidant preferably contains at least one polymer having at least one selected from the group consisting of a hindered phenol structure, a hindered amine structure, and an ethyl sulfide structure.

In the first aspect of the invention, it is preferred that the copolymer has a copolymerization ratio of the repeating unit represented by the following formula (1) of from 30% by mass to 95% by mass.

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and X represents -COO-(*) or -CONR ³ -(*) (however, R ³ represents a hydrogen atom or a linear alkyl group, * A bond indicating a bond to R ² ), and R ² represents a linear aliphatic hydrocarbon group or an alicyclic hydrocarbon group).

In the first aspect of the present invention, the copolymerization ratio of the repeating unit represented by the following formula (2) (except for the repeating unit represented by the above formula (1)) of the polymer is preferably 30% by mass or less.

(In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a group having a branched structure or an aromatic group).

A second aspect of the invention relates to an organic EL display device characterized by comprising the color filter of the first aspect of the invention.

A third aspect of the invention relates to a coloring composition comprising a coloring agent, a polyfunctional antioxidant, and a crosslinking agent for forming a color filter used in an organic EL display element.

According to the first aspect of the present invention, a color filter which provides a long-term stable organic EL display element can be obtained.

According to the second aspect of the present invention, it is possible to provide a long-term stable organic EL display element.

According to the third aspect of the present invention, a coloring composition for forming a color filter which provides a long-term stable organic EL display element can be obtained.

1‧‧‧Organic EL display components

2‧‧‧Organic EL layer

3‧‧‧Color filters

4‧‧‧Substrate

5‧‧‧Colored layer

6‧‧‧Black matrix

8‧‧‧TFT

10‧‧‧ element substrate

11‧‧‧Component layer

12‧‧ ‧ flattening layer

13‧‧‧lower electrode

14‧‧‧ next door

15‧‧‧Upper electrode

16‧‧‧Protective layer

17‧‧‧Adhesive layer

Fig. 1 is a cross-sectional view schematically showing a configuration of a main part of an organic EL display element of the present embodiment.

Hereinafter, embodiments of the present invention will be described in detail.

<Color Filter>

The color filter of the embodiment of the present invention has a plurality of colored layers of different colors. It is particularly preferable that at least three colors of a red layer, a green layer, and a blue layer are formed as the three primary colors. Thus, it can be suitably applied to an organic EL display element having an organic EL layer (light emitting layer).

In the color filter of the present embodiment, at least one of the coloring layers of the plurality of colors constituting the color filter is characterized by containing a polyfunctional antioxidant. The colored layer is usually formed using a colored composition. The coloring composition contains at least a colorant, a binder resin, and a crosslinking agent, and if necessary, imparts a susceptibility to the coloring composition by containing a photopolymerization initiator. Further, in the present invention, the colored composition contains a polyfunctional antioxidant and is used. Further, the coloring composition is usually used in the form of a liquid composition in combination with a solvent. Hereinafter, each component will be described. Further, among the components constituting the coloring composition, it is preferable to exclude as much as possible the impurities which may cause the escape gas from the color filter.

[Multifunctional antioxidants]

At least one of the coloring layers constituting the plurality of colors of the color filter of the present embodiment contains a polyfunctional antioxidant. The polyfunctional antioxidant has a plurality of, that is, two or more, one showing an antioxidant capacity in one molecule. Base compound. Examples of the polyfunctional antioxidant include a compound having two or more hindered phenol structures, a compound having two or more hindered amine structures, a compound having two or more thioether structures, a compound having two or more phosphorus atoms, and the like. . In the present invention, the polyfunctional antioxidant preferably contains at least one compound selected from the group consisting of a hindered phenol structure, a hindered amine structure, and a thioether structure.

Polyfunctional antioxidants can be low molecular compounds, too It may be a polymer compound. Further, from the viewpoint of improving the desired effect, a compound having a molecular weight of 300 or more is preferable, and particularly preferably a polymerization having at least one selected from the group consisting of a hindered phenol structure, a hindered amine structure, and a thioether structure. (hereinafter, also referred to as "specific polymer"). If the molecular weight of the polyfunctional antioxidant is too small, an escape gas may be formed to deteriorate the combined organic EL layer. When the polyfunctional antioxidant is a specific polymer, it is also preferable from the viewpoint of allowing the polyfunctional antioxidant to function as a binder resin.

As the above polymer having a hindered phenol structure, for example, A polymer having a repeating unit derived from an ethylenically unsaturated monomer having a hindered phenol structure is exemplified. The ethylenically unsaturated monomer having a hindered phenol structure is preferably a (meth)acrylic monomer having a hindered phenol structure, and examples thereof include compounds represented by the following formulas.

(In the formula (3), R ¹³ each independently represents an alkyl group having 1 to 5 carbon atoms, R ¹⁴ each independently represents an alkyl group having 1 to 8 carbon atoms, and R ¹⁵ represents hydrogen or 1 to 8 carbon atoms. Alkyl, R ¹⁶ represents a hydrogen atom or a methyl group).

Among them, 2-tert-butyl-6-(3-tert-butyl-2-) is preferred Hydroxy-5-methylbenzyl)-4-methylphenyl (meth) acrylate, 2-[1-(2-hydroxy-3,5-ditripentylphenyl)ethyl]-4 , 6-di-3 pentylphenyl (meth) acrylate.

Further, as the above polymer having a hindered amine structure, For example, a polymer having a repeating unit derived from an ethylenically unsaturated monomer having a hindered amine structure can be mentioned. The ethylenically unsaturated monomer having a hindered amine structure may, for example, be an ethylenically unsaturated monomer having a group represented by the following formula (4).

(In the formula (4), R ²¹ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 12 carbon atoms. Aralkyl group, fluorenyl group, oxygen radical or OR ²⁴ , R ²⁴ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and an aromatic group having 6 to 20 carbon atoms. An aralkyl group or a fluorenyl group having 7 to 12 carbon atoms, and R ²² and R ²³ independently of each other represent a methyl group, an ethyl group or a phenyl group, or are bonded to each other to form an aliphatic ring having 4 to 12 carbon atoms. "*" indicates the binding site).

In the above formula (4), examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms of R ²¹ and R ²⁴ include a linear chain having 1 to 18 carbon atoms. Or a branched alkyl group and a cyclic alkyl group having 3 to 8 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, and a tertiary butyl group. Is n-hexyl, cyclohexyl, n-octyl, hexadecyl and the like. In the above formula (4), examples of the aryl group having 6 to 20 carbon atoms of R ²¹ and R ²⁴ include a phenyl group, an α-naphthyl group, and a β-naphthyl group. In the above formula (4), examples of the aralkyl group having 7 to 12 carbon atoms of R ²¹ and R ²⁴ include an alkyl group having 1 to 8 carbon atoms and an aromatic group having 6 to 10 carbon atoms. Specific examples of the group of the base bond include a benzyl group, a phenethyl group, an α -methylbenzyl group, and a 2-phenylpropan-2-yl group. Further, in the above formula (4), examples of the fluorenyl group of R ²¹ and R ²⁴ include an alkanoyl group having 2 to 8 carbon atoms and an aryl group, and specific examples thereof include an ethyl sulfonyl group and a benzoic acid group.醯基等.

In the present embodiment, R ^{21 is} preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an oxygen radical, and particularly preferably a hydrogen atom, an oxygen radical or a methyl group.

In the above formula (4), examples of the aliphatic ring formed by bonding R ²² and R ^{23 to} each other include cyclopentane, cyclohexane and the like. As these R ²² and R ²³ , a methyl group is preferred.

As the ethylenic unsaturated having the group represented by the above formula (4) Specific examples of the monomer and the monomer include a compound represented by the following formula (4-1), a compound represented by the following formula (4-2), and the like.

(In the formula (4-1) and the formula (4-2), R ²⁵ and R ²⁷ each independently represent a hydrogen atom or a methyl group, and R ²⁶ represents a methylene group or an alkylene group having 2 to 5 carbon atoms; A each independently represents a group represented by the above formula (4), and Y represents -CONH-(*), -SO ₂ -(*), -SO ₂ NH-(*) (wherein the binding site of the mark "*" and A key), n represents an integer from 0 to 9.)

R ^{26 is} preferably a vinyl group or a propylene group, and particularly preferably a vinyl group. n is an integer from 0 to 8, and particularly preferably an integer from 0 to 6.

Specific examples of the monomer represented by the above formula (4-1) include compounds represented by the following formulas (4-1-1) to (4-1-7).

(In the formula (4-1-1) to (4-1-7), R ²⁵ and n in the above formula (4-1) R ²⁵ and n are the same).

In addition, specific examples of the monomer represented by the above formula (4-2) include compounds represented by the following formulas (4-2-1) to (4-2-4).

(In the formula (4-2-1) to (4-2-4), R ²⁷ and ²⁷ defined in the formula (4-2) R the same).

Wherein 2,2,6,6-tetramethylpiperidinyl methacrylate (a compound in which R ²⁵ is a methyl group in the above formula (4-1-1)), 1, 2, 2, 6, and 6 - pentamethylpiperidinyl methacrylate (a compound in which R ²⁵ is a methyl group in the above formula (4-1-2)) is sold as FA-712HM and FA-711MM, respectively, by Hitachi Chemical Co., Ltd.

In the present embodiment, the compound represented by the above formula (4-1) and the compound represented by the above formula (4-2) may be used alone or in combination of two or more.

In addition, examples of the polymer having a thioether structure include a polymer obtained by radically polymerizing an arbitrary ethylenically unsaturated monomer in the presence of a polyfunctional thiol compound. The polyfunctional thiol compound is, for example, a polyfunctional thiol compound represented by the following formula (5).

(In the formula (5), Z represents an n-valent organic group, R ³¹ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 2 to 10).

In addition, as the polyfunctional thiol compound of the above formula (5), for example, a compound represented by the following formula (5-1) is preferable.

(In the formula (5-1), Z ¹ represents an n-valent organic group, R ³¹ and n in the formula (. 5) R ³¹ and n are the same as defined above).

Examples of the above-mentioned polyfunctional thiol compound include mercaptocarboxylic acids such as indole acetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and 3-mercaptovaleric acid, and ethylene glycol, tetraethylene glycol, and dibutyl phthalate. Polyols such as alcohol, trimethylolpropane, neopentyl alcohol, dipentaerythritol, tripentenol, 1,3,5-tris(2-hydroxyethyl) cyanurate, sorbitol Esterified esters and the like.

In the present embodiment, specific examples of the preferred polyfunctional thiol compound include trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate). , tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(mercaptoacetate), 1,4-double (3- Mercaptobutyloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-tri -2,4,6(1H,3H,5H)-trione and the like.

These polyfunctional thiol compounds can be used individually or in mixture of 2 or more types.

In the manufacture of the above specific polymers, hindered phenol The ethylenically unsaturated monomer or the like of the structure may be used alone or in combination of two or more. The specific polymer may be a polymer obtained by polymerizing any one of an ethylenically unsaturated monomer having a hindered phenol structure and an ethylenically unsaturated monomer having a hindered amine structure, or may be an ethylenic group having a hindered phenol structure. A copolymer of an unsaturated monomer and an ethylenically unsaturated monomer having a hindered amine structure. Further, a polymerization obtained by radically polymerizing an ethylenically unsaturated monomer having a hindered phenol structure and/or an ethylenically unsaturated monomer having a hindered amine structure in the presence of the above polyfunctional thiol compound may be used. Things.

Ethylene with hindered phenol structure in a specific polymer The total copolymerization ratio of the unsaturated monomer and the ethylenically unsaturated monomer having a hindered amine structure is preferably from 0.1% by mass to 20% by mass, more preferably from 0.1% by mass to 10% by mass, particularly preferably from 0.5% by mass to 5% by mass. quality%. If the copolymerization ratio of the ethylenically unsaturated monomer having a hindered phenol structure is too small, the desired effect may not be obtained. On the other hand, if it is too large, then When the coloring composition imparts susceptibility to radiation, the sensitivity of the radiation is low.

The specific polymer may have any structure in addition to the hindered phenol structure or the like, but preferably has a repeating unit represented by the following formula (1).

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and X represents -COO-(*) or -CONR ³ -(*) (however, R ³ represents a hydrogen atom or a linear alkyl group, * R ² represents the bonding site bonded), R ² represents a linear aliphatic hydrocarbon group or alicyclic hydrocarbon group).

In the above formula (1), the linear aliphatic hydrocarbon group represented by R ² is preferably a linear aliphatic hydrocarbon group having 1 to 20 (preferably 1 to 15) carbon atoms, particularly preferably A linear alkyl group or an alkenyl group. Further, the alicyclic hydrocarbon group represented by R ² is preferably an alicyclic hydrocarbon group having 3 to 20 (preferably 4 to 15) carbon atoms, particularly preferably a cycloalkyl group, a condensed polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group. , a cyclic decylene group.

Examples of the monomer which provides the repeating unit represented by the above formula (1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Dodecyl (meth)acrylate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (methyl) Acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, decahydro-2-naphthyl (meth) acrylate, pentacyclic fifteen Alkyl (meth) acrylate, tricyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- Butyl (meth) acrylamide and the like.

These monomers may be used alone or in combination of two or more.

In a specific polymer, the repeating unit represented by the above formula (1) The copolymerization ratio is preferably from 30% by mass to 95% by mass, more preferably from 35% by mass to 80% by mass, particularly preferably from 50% by mass to 70% by mass. By copolymerizing the repeating unit represented by the above formula (1) in such a ratio, the desired effect can be further enhanced.

In addition, in the specific polymer, to further improve the Greek From the viewpoint of the effect of the viewpoint, the copolymerization ratio of the repeating unit represented by the following formula (2) (excluding the repeating unit represented by the above formula (1)) is preferably 30% by mass or less, more preferably 20% by mass. Hereinafter, it is particularly preferably 5% by mass or less, and most preferably zero.

(In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a group having a branched structure or an aromatic group).

Examples of the monomer which provides the repeating unit represented by the above formula (2) include isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tertiary butyl (meth)acrylate, and (methyl). ) 2-ethylhexyl acrylate, isodecyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, Ethylene oxide of phenol is modified by (meth) acrylate or the like.

Further, the specific polymer preferably has an acid such as a carboxyl group or a sulfo group. Sexual functional group. By having an acidic functional group, it is possible to impart alkaline solubility. As the acidic functional group, a carboxyl group is preferred. Examples of the monomer which provides an acidic functional group include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl) propylene methoxyethyl ester], and ω-carboxy condensed polyethylene. Lactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These monomers may be used alone or in combination of two or more.

In a specific polymer, a monomer providing an acidic functional group The copolymerization ratio is preferably from 3% by mass to 65% by mass, more preferably from 5% by mass to 60% by mass, particularly preferably from 10% by mass to 45% by mass. By copolymerizing a monomer which provides an acidic functional group in this ratio, moderate alkali developability can be provided.

As a specific polymer, further, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, 2-hydroxyethyl (meth)acrylate, 4-hydroxyl (meth)acrylate Butyl ester, 1,4-cyclohexane dimethanol monoacrylate, 2-hydroxyethyl acrylamide, N-butoxymethyl acrylamide, N-methylol methacrylamide, N-A Oxymethyl (meth) acrylamide, polyethylene glycol methyl ether (meth) acrylate, polypropylene glycol methyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol Mono(meth)acrylate, glycerol mono(meth)acrylate, 3-[(meth)acryloxymethyl]oxetane, 3-[(meth)acryloxyloxy Methyl]-3-ethyloxetane, γ-butyrolactone (meth) acrylate, propylene oxime A well-known monomer such as a phenyl group is copolymerized.

GPC for specific polymers (gel permeation chromatography, Gel Permeation Chromatography) (eluent solvent: tetrahydrofuran) The polystyrene-converted weight average molecular weight is usually from 1,000 to 100,000, preferably from 3,000 to 50,000.

Specific polymers can be produced by well-known polymerization methods. It is preferably produced so that an unreacted monomer, a polymerization initiator, and the like which may cause exhaust gas are not left as much as possible. Further, when the ethylenically unsaturated monomer having a hindered phenol structure and/or the ethylenically unsaturated monomer having a hindered amine structure are subjected to radical polymerization, if polymerization is carried out in the presence of a monofunctional thiol compound, it can be introduced. The thioether structure is therefore preferred.

In the present embodiment, the specific polymer may be used alone or in combination. Two or more types are used.

As a polyfunctional antioxidant other than a specific polymer The agent is exemplified by the following compounds. Examples of the phenolic antioxidant having two or more hindered phenol structures include a compound having at least two or more groups represented by the following formula (6) (hydroxyphenylpropionate compound), and polyhydroxybenzyl. A base compound, a thiobisphenol compound, an alkanediyl polyphenol compound, or the like. Among them, a hydroxyphenylpropionate-based compound is preferred from the viewpoint of improving the desired effect.

In the formula (6), R ⁴¹ and R ⁴² each independently represent an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms). The alkyl group may be any of a straight chain, a branched chain, and a cyclic group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, and an isobutyl group. , pentyl, tertiary pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, trioctyl, 2-ethylhexyl and the like.

Specific examples of the hydroxyphenylpropionate compound can be used Let 3,9-bis[2-[3-(3-tris-butyl-4-hydroxy-5-methylphenyl)propenyloxy]-1,1-dimethylethoxy] -2,4,8,10-tetraoxaspiro[5.5]undecane, neopentyltetrakis[3-(3,5-ditributyl-4-hydroxyphenyl)propionate] , triethylene glycol-bis[3-(3-tri-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-ditributyl-4-hydroxyphenyl) Propionate], tetrakis[methylene-3-(3,5'-ditributyl-4-c-hydroxyphenylpropionate)]methane, and the like.

Specific examples of the polyhydroxybenzyl compound include 1,3,5-trimethyl-2,4,6-tris(3',5'-ditributyl-4-hydroxybenzyl). Benzene, tris-(3,5-ditributyl-4-hydroxybenzyl)-isocyanate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2, 6-Dimethylbenzyl)-isocyanate or the like.

Specific examples of the thiobisphenol compound include 4,4'-thiobis(6-tributylbutyl-3-methylphenol).

Specific examples of the alkanediylpolyphenol-based compound include N,N'-hexamethylenebis(3,5-ditributylbutyl-4-hydroxy-hydroxycinnamoamine), 2,2' -methylenebis(4-methyl-6-tertiary butylphenol), 4,4'-butylene-bis(3-methyl-6-tertiary butylphenol), 1,1,3- Tris(2-methyl-4-hydroxy-5-tributylphenyl)butane and the like.

In addition, as a subject having two or more hindered amine structures Examples of the amine-blocking antioxidant include sebacic acid-bis(2,2,6,6-tetramethyl-4-piperidyl ester) and sebacic acid-bis(N-methyl-2,2, 6,6-tetramethyl-4-piperidyl ester), sebacic acid-bis(1,2,2,6,6-pentamethyl-4-piperidyl ester) and the like.

Further, examples of the phosphorus-based antioxidant having two or more phosphorus atoms include 3,9-bis(2,6-ditributyl-4-methylphenoxy)-2,4,8. 10-four (tetraoxane)-3,9-diphosphaspiro[5.5]undecane, diisodecyl neopentyl alcohol diphosphite, bis(2,4-ditributylphenyl)nepentaerythritol Alcohol diphosphite and the like.

In addition, as a sulfur system having two or more thioether structures The antioxidant may, for example, be a compound having at least two or more groups represented by the following formula (7).

In the formula (7), R ⁵¹ represents an alkyl group having 1 to 30 carbon atoms, and is preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group may be the same alkyl group as R ⁴¹ and R ^{42 of the} above formula (6), and examples thereof include dodecyl group, tetradecyl group, hexadecyl group and octadecyl group.

Specific examples of such a compound include 2,2- Bis[{[3-(dodecylthio)propenyl)oxy}methyl]-1,3-propanediyl-bis[3-(dodecylthio)propionate], neopenta Tetraol tetrakis(3-dodecylthiopropionate) and the like.

In the present embodiment, anti-oxidation other than a specific polymer The agent may be used alone or in combination of two or more.

In the present embodiment, as the polyfunctional antioxidant, it is preferred to contain (1) at least one selected from the group consisting of a hindered phenol structure and a hindered amine structure and a thioether structure from the viewpoint of improving a desired effect. (2) a combination of a polymer having at least one selected from the group consisting of a hindered phenol structure and a hindered amine structure and a sulfur-based antioxidant having the above two or more thioether structures. More specifically, it is preferred to contain (1) in the presence of a monomer including an ethylenically unsaturated monomer having a hindered phenol structure and/or an ethylenically unsaturated monomer having a hindered amine structure, and a thiol compound. a polymer obtained by radical polymerization; (2) a polymer comprising a monomer having a hindered phenol structure and/or an ethylenically unsaturated monomer having a hindered amine structure, and having the above 2 A combination of sulfur-based antioxidants of more than one thioether structure.

In the present embodiment, the polyfunctional antioxidant is specific In the case of a polymer, the content of the polyfunctional antioxidant is preferably from 10 parts by mass to 1000 parts by mass, particularly preferably from 20 parts by mass to 500 parts by mass, based on the mass of the coloring agent 100 to be described later. On the other hand, in the case of a polyfunctional antioxidant other than the specific polymer, the quality of the coloring agent 100 to be described later is preferably 0.01 mass% to 20 mass%, particularly preferably 0.1 mass% to 10 mass%.

[Colorant]

The coloring agent constituting the color filter of the present embodiment is not particularly limited as long as it has coloring property, and the color and material can be appropriately selected in accordance with the luminescence spectrum from the organic EL layer. Specifically, as the coloring agent, any of a pigment, a dye, and a natural coloring matter can be used, but the color filter of the present embodiment used in the organic EL display element can be used. Colors, brightness, heat resistance, and the like are required, and therefore, pigments and/or dyes are preferred.

As a red layer constituting the color filter of the present embodiment The coloring agent used in the color index (CI) name, for example, CI Pigment Red 7, CI Pigment Red 14, CI Pigment Red 41, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48:4, CI Pigment Red 81:1, CI Pigment Red 81:2, CI Pigment Red 81:3, CI Pigment Red 81:4, CI Pigment Red 146, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 208, CI Pigment Red 210, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 246, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 279, and the like. Preferably, it contains at least one selected from the group consisting of CI Pigment Red 177, CI Pigment Red 242, CI Pigment Red 254, and CI Pigment Red 264, and particularly preferably contains CI Pigment Red 177, CI Pigment Red 254, and CI Pigment Red. At least one of 264. Further, in the formation of the red layer, it is possible to appropriately color the toner together with the red coloring agent and with a yellow coloring agent. The yellow coloring agent used in the red layer preferably contains at least one selected from the group consisting of C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185. As the coloring agent used in the red layer, a combination of CI Pigment Red 177 and CI Pigment Red 254, a combination of CI Pigment Red 177 and CI Pigment Yellow 185, CI Pigment Red 177 and CI Pigment Red 254 and CI Pigment Yellow 150 are preferred. Combination, CI Pigment Red 177 and CI Pigment Red 254 Combination with CI Pigment Red 242, Combination of Pigment Red 177 and CI Pigment Red 242 and CI Pigment Yellow 139, Combination of CI Pigment Red 264 and CI Pigment Yellow 139, Combination of CI Pigment Red 264 and CI Pigment Yellow 150, CI Pigment Combination of Red 264 and CI Pigment Yellow 185, CI Pigment Red 177 and CI Pigment Red 264 and CI Pigment Yellow 139, CI Pigment Red 177 and CI Pigment Red 264 and CI Pigment Yellow 185.

As a green layer constituting the color filter of the present embodiment The coloring agent to be used preferably contains at least one selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 58, and particularly preferably C.I. Pigment Green 7. Further, in the formation of the green layer, it is preferred to perform coloring together with a green coloring agent together with a yellow coloring agent. The yellow coloring agent used in the green layer preferably contains at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185, and particularly preferably contains a coloring agent selected from the group consisting of CI Pigment At least one of yellow 139, CI pigment yellow 150, and CI pigment yellow 185. As the coloring agent used in the green layer, a combination of CI Pigment Green 7 and CI Pigment Yellow 185, a combination of CI Pigment Green 7 and CI Pigment Yellow 139, a combination of CI Pigment Green 7 and CI Pigment Yellow 150, and a CI Pigment are preferred. Combination of Green 7 and CI Pigment Yellow 139 and CI Pigment Yellow 185, CI Pigment Green 7 and CI Pigment Yellow 139 and CI Pigment Yellow 150, CI Pigment Green 7 and CI Pigment Green 36 and CI Pigment Yellow 185.

As a blue layer constituting the color filter of the present embodiment Examples of the coloring agent used include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 22, CI Pigment Blue 60, C.I. Pigment Blue 64, and the like. Among them, it is preferred to contain C.I. Pigment Blue 15:6. Further, in the formation of the blue layer, it is preferred to perform coloring together with a blue coloring agent together with a purple coloring agent. As the purple coloring agent used in the blue layer, C.I. Pigment Violet 23 is preferably contained. As the blue or violet coloring agent used in the blue layer, a triarylmethane-based lake pigment, a triarylmethane-based dye, and a dibenzopyran dye are preferable. As the coloring agent used in the blue layer, CI pigment blue 15:6 alone, CI pigment blue 15:6 and CI pigment violet 23 combination, CI pigment blue 15:6 and triarylmethane-based lake pigment are preferred. Combination, combination of CI Pigment Blue 15:6 and triarylmethane dyes, combination of CI Pigment Blue 15:6 and dibenzopyran dye, CI Pigment Blue 15:6 and CI Pigment Violet 23 and Dibenzopyran A combination of dyes.

Coloring of each color constituting the color filter of the present embodiment In the layer, the coloring agent may be used singly or in combination of two or more.

In the present embodiment, when a pigment is used as the colorant, If necessary, the surface of the particles may be modified with a resin to be used. Examples of the resin for modifying the surface of the pigment particles include a vehicle resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments. Further, the pigment is preferably used by refining the primary particles by salt milling. As a method of salt milling, for example, the method disclosed in JP-A-08-179111 can be employed. Further, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof.

[Binder Resin]

The colored composition for forming the colored layers of the respective colors constituting the color filter of the embodiment of the present invention may contain a binder resin. When a specific polymer is used as the above-mentioned polyfunctional antioxidant, the specific polymer functions as a binder resin, but by using a binder resin other than the specific polymer, adhesion to the substrate and alkali developability can be improved. The storage stability of the colored composition. The binder resin is not particularly limited, but is preferably a resin having a carboxyl group.

A preferred embodiment of the resin having a carboxyl group is exemplified. A copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer. As a preferable example of the copolymer, for example, JP-A-7-140654, JP-A-H08-259876, JP-A-H09-311444, and JP-A No. 10-31308 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The copolymer disclosed in 101728 et al.

Further, in the present invention, for example, it is also possible to use like Japan. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain disclosed in Japanese Laid-Open Patent Publication No. Hei.

In the present embodiment, the binder resin may be used alone or in combination. Two or more types are used.

When a specific polymer and a binder resin other than the specific polymer are used in combination, the mixing ratio (specific polymer: binder resin other than the specific polymer, mass ratio) is preferably 20:80 to 100:0, more preferably It is 50:50~100:0, especially 80:20~100:0.

[crosslinking agent]

The coloring composition for forming the colored layers of the respective colors constituting the color filter of the embodiment of the present invention may contain a crosslinking agent. Thereby, it has curability accompanying exposure and/or heating.

The crosslinking agent is not particularly limited as long as it is a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxirane group, an oxypropylene group, and an N-alkoxymethylamino group. In the present invention, as the crosslinking agent, a compound having two or more (meth)acrylinyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

As the above, having two or more (meth) acrylonitrile groups Specific examples of the compound include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and a polyfunctional (meth) acrylate modified by caprolactone. a polyfunctional (meth) acrylate modified with an alkylene oxide, a polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, and having A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a hydroxy (meth) acrylate with an acid anhydride.

Here, as the above aliphatic polyhydroxy compound, for example, A dihydric aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol; such as glycerin or trimethylolpropane, may be mentioned. A ternary or higher aliphatic polyhydroxy compound such as pentaerythritol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(methyl). Acrylate, dipentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. The acid anhydride may, for example, be an acid anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride or hexahydrophthalic anhydride, such as benzene tetra A tetrabasic acid dianhydride such as an acid anhydride, a biphenyltetracarboxylic dianhydride, or a benzophenone tetracarboxylic dianhydride.

In addition, as the above polyfunctional (methyl) modified by caprolactone The acrylate is, for example, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The polyfunctional (meth) acrylate modified by the alkylene oxide may, for example, be bisphenol A di(meth)acrylate modified from at least one selected from the group consisting of ethylene oxide and propylene oxide. And at least one modified iso-trisocyanate selected from ethylene oxide and propylene oxide, modified by at least one selected from the group consisting of ethylene oxide and propylene oxide a trimethylolpropane tri(meth)acrylate, at least one modified pentaerythritol tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from the group consisting of At least one modified neopentyltetrakis(meth)acrylate of oxyethane and propylene oxide, and at least one modified dipentaerythritol selected from the group consisting of ethylene oxide and propylene oxide An alcohol penta (meth) acrylate or a dipentaerythritol hexa(meth)acrylate modified from at least one selected from the group consisting of ethylene oxide and propylene oxide.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Moreover, the melamine structure and the benzoguanamine structure refer to one or more than three The chemical structure of the ring as a basic skeleton is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, and N. , N, N', N'-tetrakis(alkoxymethyl)benzoguanamine, N, N, N', N'-tetrakis(alkoxymethyl) glycoluril, and the like.

Among these crosslinking agents, it is preferably a trivalent or higher aliphatic group. An ester of a polyhydroxy compound with (meth)acrylic acid, a polyfunctional (meth) acrylate modified by caprolactone, a polyfunctional urethane (meth) acrylate, a polyfunctional group having a carboxyl group (methyl) Acrylate, N, N, N', N', N", N"-hexa(alkoxymethyl) melamine, N, N, N', N'-tetrakis (alkoxymethyl) benzo Guanamine. From the viewpoint of the high strength of the colored layer and the excellent surface smoothness of the colored layer, in the trivalent or higher aliphatic polyhydroxy compound and the (meth)acrylic acid ester, trimethylolpropane triacrylate is particularly preferable. , pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, in a polyfunctional (meth) acrylate having a carboxyl group, particularly preferably to make pentaerythritol three A compound obtained by reacting an acrylate with succinic anhydride, or a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride.

In the present embodiment, the crosslinking agent may be used alone or in combination 2 More than one kind.

In the coloring composition for forming the colored layers of the respective colors constituting the color filter of the embodiment of the present invention, the content of the crosslinking agent is usually 5 parts by mass to 500 parts by mass based on 100 parts by mass of the binder resin, preferably 50 mass points ~ 300 mass points. At this time, if the content of the crosslinking agent is too small, sufficient curability is not obtained. On the other hand, when the content of the crosslinking agent is too large, the alkali developability tends to be lowered when the alkali developing property is imparted to the colored composition of the present embodiment.

[Photopolymerization initiator]

The coloring composition for forming the colored layers of the respective colors constituting the color filter of the embodiment of the present invention can impart radiation sensitivity by containing a photopolymerization initiator. The photopolymerization initiator is a compound capable of generating an active species capable of initiating a curing reaction of the above polyfunctional monomer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, benzophenone compound, α -diketone compound, polynuclear guanidine compound, diazo compound, quinone a sulfonate compound or the like.

In the present embodiment, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a compound and an O-mercapto lanthanide compound.

In the preferred photopolymerization initiator of the present embodiment, Specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Polinylphenyl)butan-1-one and the like.

Further, as a specific example of the biimidazole-based compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4- Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-biimidazole.

Further, when a biimidazole-based compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. a thiol-based hydrogen donor such as azole; an amine-based hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone . In the present invention, the hydrogen donor may be used alone or in combination of two or more. However, from the viewpoint of further improving the sensitivity, it is preferred to combine one or more kinds of thiol-based hydrogen donors and one or more amines. Hydrogen is used as a precursor.

In addition, as the above three Specific examples of the compound include 2,4,6-tris(trichloromethyl)-all. 2-methyl-4,6-bis(trichloromethyl)-all three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-all three Three with a halogenated methyl group a compound.

Further, as a specific example of the O-indenyl lanthanide compound, Take 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1-[9-ethyl-6-(2-A Benzomethane)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl) Oxylbenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6-{2-methyl-4-(2 , 2-Dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-ethanone 1-(O-acetyl) and the like. Examples of commercially available products of the O-mercapto fluorene-based compound include NCI-831 and NCI-930 (all manufactured by ADEKA Co., Ltd.).

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4- Diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5 - double (4-two Ethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)cha Ketones, etc.

Used to form color filters constituting an embodiment of the present invention In the colored composition of the colored layers of the respective sheets, the content of the photopolymerization initiator is usually from 0.01 to 120 parts by mass, preferably from 1 to 100 parts by mass, per 100 parts by mass of the crosslinking agent.

[solvent]

The coloring composition for forming the colored layers of the respective colors constituting the color filter of the embodiment of the present invention is usually prepared into a liquid composition in combination with a solvent. The solvent can be appropriately selected and used as long as the components constituting the colored composition are dispersed or dissolved, and do not react with these components, and have appropriate volatility.

As such a solvent, for example, propylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethyl Glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate And isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate and the like.

These solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but the color obtained is obtained. From the viewpoint of coatability, stability, and the like of the composition, it is preferred from the group The total concentration of each component of the product removal solvent is 5% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass.

[Other additives]

The coloring composition for forming the colored layers of the respective colors constituting the color filter of the embodiment of the present invention may further contain other additives as needed.

Examples of the above additives include glass, alumina, and the like. Filler; polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); surfactant such as nonionic surfactant, cationic surfactant, anionic surfactant; vinyl trimethoxy Decane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3- Glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3- a adhesion promoter such as chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane; a dispersing agent such as sodium polyacrylate; malonic acid, Adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino group -1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc. Residue improver; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, ω-carboxy polycap A developability improving agent such as ester mono(meth)acrylate.

Next, a color filter of an embodiment of the present invention The manufacturing method will be described.

As a method of producing a color filter, photolithography is preferred. In the photolithography method, first, a black matrix is formed on the surface of the substrate as needed. Next, a liquid composition of a red radiation-sensitive coloring composition is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, a pattern of a red layer was formed by hard baking.

Next, use a green or blue sensed radiation coloring set The liquid material of the product was subjected to coating, prebaking, exposure, development, and hard baking of each liquid material in the same manner as described above, and a green layer pattern and a blue layer pattern were sequentially formed on the same substrate. Thereby, a color filter in which patterns of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present embodiment, the order in which the respective colored layers are formed is not limited to the above order.

As the substrate used in forming the coloring layer, for example, A transparent substrate of glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamidimide, polyimine or the like is exemplified. On these transparent substrates, a thin film transistor for driving an organic EL element can be formed.

When a liquid material having a radiation-sensitive coloring composition is applied onto a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, or a bar coating method may be employed. It is particularly preferable to use a spin coating method or a slit die coating method.

The pre-baking is usually carried out by combining drying under reduced pressure and drying by heating. Drying under reduced pressure is usually carried out at 0.1 Torr to 1 Torr. Further, the conditions of heat drying are usually from 70 ° C to 110 ° C for about 1 minute to 10 minutes.

As the radiation used when forming the color layer, for example, For example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, etc. or argon ion laser, YAG laser, XeCl excimer thunder Laser light sources such as lasers and nitrogen lasers. As the exposure light source, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 nm to 450 nm is preferred.

The exposure amount of the radiation is preferably from 10 J/m ² to 10000 J/m ² .

Further, as the alkaline developing solution, for example, carbonic acid is preferred. Sodium, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo- [4.3.0] An aqueous solution of -5-pinene or the like.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer in an appropriate amount. However, it is usually washed with water after alkaline development.

As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be used. The developing conditions are preferably from 5 seconds to 300 seconds at normal temperature.

The conditions for hard roasting are usually from 180 ° C to 280 ° C for about 10 minutes to 40 minutes.

The film thickness of the coloring layer thus formed is usually 0.5 μm to 5.0 μm, preferably 1.0 μm to 3.0 μm.

In addition, as the color filter of the present embodiment is manufactured In addition to the photolithography method, an inkjet method can be employed. In the inkjet method, a thermosetting coloring composition is usually used.

On the color filter thus obtained, a protective film is formed as needed. The protective film may, for example, be an organic film formed of a thermosetting resin composition, an inorganic film such as a SiN _x film or a SiO _x film.

<Organic EL display element>

The organic EL display device of the embodiment of the present invention preferably has an organic EL layer (light emitting layer) and has a color filter of an embodiment of the present invention. Further, the organic EL display device according to the embodiment of the present invention is preferably configured to include the color filter of the embodiment of the present invention and the organic EL element that emits white light.

The organic EL element emitting white light is preferably a series junction Structure. The above-described Patent Document 2 and Non-Patent Document 1 disclose a series structure of organic EL elements. For example, the organic EL element has a structure in which an organic EL layer is provided between one of the lower electrode having light reflectivity and the upper electrode having light transmissivity on one surface of the substrate. At this time, the lower electrode is preferably made of a material having a sufficient reflectance in a wavelength region of visible light. Further, in order to function as an anode, the lower electrode is preferably made of a material having a sufficiently large work function so that holes can be efficiently injected into the organic EL layer. Specific examples of the constituent material of the lower electrode at this time include nickel (Ni), silver (Ag), gold (Au), platinum (Pt), palladium (Pd), selenium (Se), and rhodium (Rh). ), a metal such as ruthenium (Ru), iridium (Ir), ruthenium (Re), tungsten (W), molybdenum (Mo), chromium (Cr), ruthenium (Ta), or niobium (Nb), or an alloy of these metals. Further, the lower electrode may be made of the same light transmissive material as the upper electrode, and the light reflecting layer may be provided under the layer.

In order to function as a cathode, the upper electrode is preferably made of a material having a sufficiently small work function to efficiently inject electrons into the organic EL layer. Specific examples of the upper electrode constituent material include relatively active metals such as lithium (Li), magnesium (Mg), and calcium (Ca), and silver (Ag), aluminum (Al), or indium (In). An alloy of a relatively inactive metal or a light-transmitting conductive material such as tin oxide (SnO ₂ ), indium tin oxide (ITO), zinc oxide (ZnO) or titanium oxide (TiO ₂ ). Further, the upper electrode may have, for example, a laminated structure in which the above two kinds of metals (relatively active metals and relatively inactive metals) are laminated.

The organic EL layer contains a plurality of light-emitting layers and has a laminate A laminated structure (series structure) of these plurality of light emitting layers. The organic EL layer may include, for example, a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer among the plurality of light-emitting layers. Further, it is preferable to have a plurality of light-emitting auxiliary layers for causing the light-emitting layer to emit light together with the plurality of light-emitting layers. The organic EL layer may be, for example, a laminated structure in which a light-emitting layer and a light-emitting auxiliary layer are alternately laminated.

The organic EL element having the organic EL layer having such a structure can be To emit white light. In this case, the spectrum of the white light emitted from the organic EL element is preferably in the blue region (430 nm - 485 nm) and green as disclosed in FIG. 3 of Non-Patent Document 1, page 328, and JP-A-2010-527108. The region (530 nm - 580 nm) and the yellow region (580 nm - 620 nm) have strong maximum luminescence peaks. In addition to these luminescence peaks, it is further preferred to have a large luminescence peak in the red region (650 nm - 700 nm). By combining such an organic EL element that emits white light and a color filter having a coloring layer of each color containing the coloring agent, an organic EL display element having a high NTSC ratio can be obtained.

FIG. 1 is a view schematically showing an organic EL of the present embodiment A cross-sectional view of the structure of the main part of the display element.

The organic EL display element 1 of the present embodiment shown in FIG. The organic EL layer 2 is provided and has the above-described color filter 3 of the present embodiment. The organic EL layer 2 has the above-described series structure and constitutes an organic EL element that emits white light. Further, the color filter 3 is formed, for example, on a transparent substrate 4 such as a glass substrate including alkali-free glass, and has a plurality of colored layers 5 of different colors and a black matrix 6 provided between the respective colored layers 5. For example, it is preferable that the color filter 3 has a coloring layer 5 of three colors of a red colored layer, a green colored layer, and a blue colored layer.

In addition, the characteristics of the color filter 3 constitute the color filter At least one of the coloring layers 5 of the plurality of colors of the light sheet contains a polyfunctional antioxidant. The colored layer 5 is formed using a coloring composition as described above. In the present invention, a polyfunctional antioxidant is used in the colored composition.

The organic EL display element 1 of the present embodiment has a formation The element substrate 10 which the organic EL layer 2 has. As the element substrate 10, a glass substrate such as an alkali-free glass can be used, and a resin substrate can also be used. On the element substrate 10, a pixel circuit (not shown) is formed in each pixel of the image display unit of the organic EL display element 1, and the element layer 11 is formed. The pixel circuit of the element layer 11 is a thin film transistor (TFT: Thin Film Transistor) 8 that emits light by driving the organic EL layer 2, a driving wiring (not shown) connected thereto, and an interlayer insulating layer (not shown). And so on. The TFT 8 can be formed by using low-temperature polycrystalline germanium or amorphous germanium as an active layer. The drive wiring can be made of, for example, a conductive material such as aluminum (Al) or aluminum-copper alloy (AlCu).

An insulating planarization layer 12 is disposed on the element layer 11. The planarization layer 12 is a layer that electrically separates the TFT 8 of the element layer 11 and the driving wiring from the organic EL layer 2, and planarizes the substrate on which the organic EL layer 2 is disposed. The planarization layer 12 is made of, for example, an inorganic insulating material such as cerium oxide (SiO ₂ ) or an organic insulating material such as an acrylic resin.

In the upper layer of the planarization layer 12, the configuration is divided into each The above-described light-reflecting lower electrode 13 of the organic EL element is formed of a pixel.

The lower electrode 13 is connected to a contact hole (not shown) penetrating the planarization layer 12 by a drain (not shown) of the TFT 8 of the element layer 11 for each pixel.

The partition wall 14 divides each pixel into a lattice shape on a plane. In order to prevent malfunction due to light, the TFTs 8 in the element layer 11 are configured to be disposed on the lower layer of the partition walls 14. The partition 14 is made of, for example, polyimide, polybenzo An organic insulating material such as azole or acrylic resin or an inorganic insulating material such as cerium oxide.

The organic EL layer 2 covers the lower electrode 13 and the partition wall 14 The way is formed as one side. In addition, in FIG. 1, the organic EL layer 2 is shown in a single layer, but actually, as described above, a laminated structure including light-emitting layers of respective colors such as red, green, and blue is formed. Further, the organic EL layer 2 includes the above-described light-emitting auxiliary layer, and if necessary, a hole injection layer, an electron injection layer, and the like are also included.

In the upper layer of the organic EL layer 2, the above-mentioned upper electricity is disposed Extreme 15.

A protective layer 16 is provided on the upper layer of the upper electrode 15. The protective layer 16 is mainly used for protecting an organic EL element, for example, a passivation film made of a light-transmitting dielectric material such as tantalum nitride (SiN).

On the upper layer of the protective layer 16, that is, the protective layer 16 and the color filter Between the light sheets 3, an adhesive layer 17 is disposed. In the organic EL display element 1 of the present embodiment, the organic EL element and the color filter 3 which are formed by sandwiching the organic EL layer 2 by the lower electrode 13 and the upper electrode 15 are attached by using the adhesive layer 17. They are combined to form one. The adhesive layer 17 can be formed, for example, by using a translucent thermosetting resin such as an epoxy resin.

Organic EL display of the present embodiment having the above constitution Each pixel of the display element 1 emits image light corresponding to the color tone of the color filter 3. For example, when the red pixel having the red coloring layer 5 is provided, the white light emitted from the organic EL element is incident on the red coloring layer 5 of the color filter 3 as described above. In this way, red light is selected by the red coloring layer 5 to form red image light, which is emitted from the substrate 4 side. The same applies to the pixels having the green and blue coloring layers 5. Thereby, in the organic EL display element 1, it is possible to perform full-color image display by image light emitted from a plurality of pixels of respective colors.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited to the following examples.

<Synthesis of a binder resin other than a specific polymer and a specific polymer> Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, and 12 parts by mass of methyl methacrylate were charged. , 20 parts by mass of cyclohexyl methacrylate, 25 parts by mass of butyl methacrylate, 12 parts by mass of mono(2-propenyloxyethyl) succinate, 1,2,2,6,6-pentamethyl Piperidinyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-711MM) 1 mass fraction, 2,2'-azobis(2,4-dimethylvaleronitrile) 3 mass fraction and new A mixed solution of pentaerythritol tetrakis(3-mercaptopropionate) 3 parts by mass was subjected to nitrogen substitution, and polymerization was carried out at 80 ° C for 3 hours. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). The obtained resin was Mw = 11,000, Mn = 5,600, and Mw / Mn = 1.96. This resin was designated as a specific polymer (B-1).

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, and 12 parts by mass of methyl methacrylate were charged. , 20 parts by mass of cyclohexyl methacrylate, 25 parts by mass of butyl methacrylate, 12 parts by mass of succinic acid mono(2-propenyloxyethyl ester), 2-tert-butyl butyl-6-(3-three Grade butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer (registered trademark) GM) 1 mass fraction, tertiary butyl peroxy-2-ethylhexanoate (manufactured by Nippon Oil Co., Ltd., trade name: PERBUTYL (registered trademark) O) 1 mass fraction, 2,2'-azo double (2,4-dimethyl A mixed solution of 3 parts by mass of valeronitrile and 3 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) was subjected to nitrogen substitution, and polymerization was carried out at 80 ° C for 3 hours. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). The obtained resin was Mw=11300, Mn=5700, and Mw/Mn=1.98. This resin was designated as a specific polymer (B-2).

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was placed and replaced with nitrogen. Heating to 80 ° C, adding 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, cyclohexyl methacrylate 22 at the same temperature over 2 hours. Mass, 22 parts by mass of dodecyl methacrylate, 20 parts by mass of mono(2-propenyloxyethyl) succinate, 1,2,2,6,6-pentamethylpiperidinylmethyl a mixed solution of 1 part by mass of acrylate, 3 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 3 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate), kept This temperature was carried out for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). The obtained resin was Mw = 10,800, Mn = 5,200, and Mw / Mn = 2.08. This resin was designated as a specific polymer (B-3).

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, and dicyclopentyl methacrylate were charged. 22 parts by mass, octadecyl methacrylate 22 parts by mass, succinic acid single (2- Propylene methoxyethyl ester) 20 parts by mass, 1,2,2,6,6-pentamethylpiperidyl methacrylate 1 part by mass, 2,2'-azobis(2,4-dimethyl A mixed solution of 3 parts by mass of valeronitrile and 3 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) was subjected to nitrogen substitution, and polymerization was carried out at 80 ° C for 3 hours. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). The obtained resin was Mw = 11,000, Mn = 5,400, and Mw / Mn = 2.04. This resin was designated as a specific polymer (B-4).

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, and 12 parts by mass of methyl methacrylate were charged. , 20 parts by mass of cyclohexyl methacrylate, 25 parts by mass of butyl methacrylate, 12 parts by mass of succinic acid mono(2-propenyloxyethyl ester), 2,2,6,6-tetramethylpiperidine Base methacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-712HM) 1 part by mass, 2,2'-azobis(2,4-dimethylvaleronitrile) 3 parts by mass and having a mercaptan A propylene glycol monomethyl ether acetate solution (available from Arakawa Chemical Industries, Ltd., COMPOCERAN (registered trademark) SQ SERIES, solid content concentration = 25% by mass) of a 12-mass mixed solution for nitrogen substitution The polymerization was carried out at 80 ° C for 3 hours. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). The obtained resin was Mw = 12100, Mn = 5100, and Mw / Mn = 2.37. This resin was designated as a specific polymer (B-5).

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 39 parts by mass of 2-hydroxyethyl methacrylate, and 15 parts by mass of cyclohexyl methacrylate were charged. 10 parts by mass of methyl methacrylate, 10 parts by mass of 3-ethyl-3-propenyloxymethyloxetane, 15 parts by mass of mono(2-propenyloxyethyl) succinate, 1,2,2,6,6-pentamethylpiperidinyl methacrylate 1 mass fraction, 2,2'-azobis(2,4-dimethylvaleronitrile) 3 mass fraction and neopenta tetra A mixed solution of tetrakis(3-mercaptopropionate) 4 parts by mass was subjected to nitrogen substitution, and polymerization was carried out at 80 ° C for 3 hours. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin solution. To the resin solution, 56 parts by mass of 2-isocyanoethyl methacrylate and 85 parts by mass of propylene glycol monomethyl ether acetate were added, and the mixture was reacted at a temperature of 110 ° C for 9 hours. The resin solution after completion of the reaction was washed twice with water, and concentrated under reduced pressure to obtain a resin solution having a solid concentration of 40% by weight. The obtained resin was Mw=11600, Mn=5700, and Mw/Mn=2.03. This resin was designated as a specific polymer (B-6).

Synthesis Example 7

In a flask equipped with a cooling tube and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, and 12 parts by mass of methyl methacrylate were charged. , 22 parts by mass of cyclohexyl methacrylate, 23 parts by mass of butyl methacrylate, 12 parts by mass of mono(2-propenyloxyethyl) succinate, 1,2,2,6,6-pentamethyl Piperidinyl methacrylate 1 part by mass, 2,2'-azobis(2,4-dimethylvaleronitrile) 3 parts by mass and pyrazole-1-dithiocarbamic acid cyano group The mixed solution of 4 parts by mass of methyl ester was subjected to nitrogen substitution, and polymerization was carried out at 80 ° C for 3 hours. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). The obtained resin was Mw = 9800, Mn = 7600, and Mw / Mn = 1.29. This resin was designated as a specific polymer (B-7).

Synthesis Example 8

In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was placed and replaced with nitrogen. Heating to 80 ° C, at the same temperature, adding 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 15 parts by mass of 2-hydroxyethyl methacrylate at 2 hours, 2-Ethylhexyl methacrylate 28 parts by mass, N-phenylmaleimide 12 parts by mass, succinic acid mono(2-propenyloxyethyl ester) 15 parts by mass, and 2,2'-azo A mixed solution of bis(2,4-dimethylvaleronitrile) 6 parts by mass was maintained at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). The obtained resin was Mw = 10,500, Mn = 7,900, and Mw / Mn = 1.33. This resin was used as a binder resin (B-8).

Synthesis Example 9

In a flask equipped with a cooling tube, 150 parts by mass of propylene glycol monomethyl ether acetate, 8 parts by mass of N-phenylmaleimide, 15 parts by mass of styrene, 15 parts by mass of benzyl methacrylate, and methacrylic acid were placed. 32 parts by mass of 2-ethylhexyl ester, 15 parts by mass of 2-hydroxyethyl methacrylate, 15 parts by mass of methacrylic acid, 3 parts by mass of azobisisobutyronitrile, and 4 mass of α -methylstyrene dimer 4 After the polymerization was carried out at 90 ° C for 4 hours, 0.5 parts by mass of azobisisobutyronitrile was added thereto, and further polymerization was carried out for 1 hour. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and the mixture was stirred for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). The obtained resin was Mw = 11,500, Mn = 6,800, and Mw / Mn = 1.68. This resin was used as a binder resin (B-9).

Synthesis Example 10

In a flask equipped with a cooling tube, propylene glycol monomethyl ether acetate 150 parts by mass, 2-tris-butyl-6-(3-tert-butyl-6-(3-tert-butyl-2-hydroxyl) -5-Methylbenzyl)-4-methylphenyl acrylate 100 parts by mass, tertiary butyl peroxy-2-ethylhexanoate (manufactured by Nippon Oil & Fat Co., Ltd., trade name: PERBUTYL (registered trademark O) The nitrogen substitution was carried out, and the polymerization was carried out at 90 ° C for 4 hours. Thereafter, the temperature of the reaction solution was raised to 110 ° C, and the mixture was stirred for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). As a specific polymer (B-10).

Synthesis Example 11

In a flask equipped with a cooling tube, 150 parts by mass of propylene glycol monomethyl ether acetate, 100 parts by mass of 1,2,2,6,6-pentamethylpiperidyl methacrylate, and tertiary butyl peroxidation were charged. 2-Ethylhexanoate (manufactured by Nippon Oil & Fat Co., Ltd., trade name: PERBUTYL (registered trademark) O) was replaced with nitrogen, and polymerization was carried out at 90 ° C for 4 hours. Thereafter, the temperature of the reaction solution was raised to 110 ° C, and the mixture was stirred for 1 hour to obtain a resin solution (solid content concentration = 40% by mass). This resin was designated as a specific polymer (B-11).

<Preparation of Red Pigment Dispersion> Pigment dispersion preparation example 1

13 mass parts of CI Pigment Red 254 as a coloring agent, 11.5 parts by mass (solid content concentration = 40% by mass) BYK-LPN21116 (manufactured by BYK-Chemie (BYK) Co., Ltd.), and 11.0 parts by mass of a specific polymer (as a dispersing agent) were used. B-1), propylene glycol monomethyl ether acetate as solvent, 64.5 mass parts and propylene glycol monomethyl ether 1.5 mass parts, mixed by a bead mill. Disperse to prepare a red pigment dispersion (A-1).

Pigment dispersion preparation example 2~11

In the pigment dispersion preparation example 1, a red pigment dispersion liquid (A-2) was prepared in the same manner as in the pigment dispersion preparation example 1 except that the type and amount of each component were changed as shown in Table 1. ~(A-11).

In Table 1, "R254" means C.I. Pigment Red 254, "R242" means CI Pigment Red 242, "R177" means CI Pigment Red 177, "R264" means CI Pigment Red 264, "Y150" means CI Pigment Yellow 150, and "Y139" means CI Pigment Yellow 139. "LPN21116" means BYK-LPN21116 (BYK-Chemie (BYK) company), "PGMEA" means propylene glycol monomethyl ether acetate, and "PGME" means propylene glycol monomethyl ether.

<Preparation of Radiation-Linear Red Composition> Radiation-sensitive coloring composition preparation example 1

600 parts by mass of the pigment dispersion (A-1), 137.5 parts by mass of a specific polymer (B-1) solution as a binder resin, dipentaerythritol hexaacrylate and dipentaerythritol as a crosslinking agent a mixture of pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD (registered trademark) MAX-3510) 70 parts by mass, 2-benzyl-2-dimethylamino-1- as a photopolymerization initiator (4- Phenyl phenyl)butan-1-one (manufactured by BASF Corporation, trade name IRGACURE (registered trademark) 369) 30 parts by mass, 2,4-diethyl thioxanthone 5 parts by mass, 矽 times with thiol group A propylene glycol monomethyl ether acetate solution of a hemi-oxyalkylene (manufactured by Arakawa Chemical Co., Ltd., COMPOCERAN (registered trademark) SQ SERIES, solid content concentration = 25% by mass), 1 part by mass, and 3-ethoxy group as a solvent A liquid red component (R-1) was prepared by mixing 230 parts by mass of ethyl propionate and 790 parts by mass of methoxybutyl acetate.

Radiation-sensitive coloring composition preparation example 2~11

In the preparation example 1 of the radiation sensitive coloring composition, the types and blending amounts of the respective components were changed as shown in Table 2, and In the radioactive coloring composition preparation example 1, liquid red compositions (R-2) to (R-11) were prepared in the same manner.

In Table 2, each component is as follows.

C-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD (registered trademark) MAX-3510)

D-1: 2-benzyl-2-dimethylamino-1-(4- Olefinophenyl)butan-1-one (manufactured by BASF Corporation, trade name IRGACURE (registered trademark) 369)

D-2: 2,4-diethylthioxanthone

G-1: a propylene glycol monomethyl ether acetate 5% by mass solution of a sesquioxane having a thiol group (COMPOCERAN (registered trademark) SQ SERIES, manufactured by Arakawa Chemical Industries, Ltd.)

E-1: pentaerythritol tetrakis[3-(3,5-ditributyl-4-hydroxyphenyl)propionate] (manufactured by ADEKA Co., Ltd., trade name ADK STAB) Booklet) AO-60)

E-2: pentaerythritol tetrakis(3-dodecylthiopropionate) (manufactured by ADEKA Co., Ltd., trade name AO-412S)

E-3: Tert-butyl catechol

F-1: ethyl 3-ethoxypropionate

F-2: methoxybutyl acetate

<Preparation of Green Pigment Dispersion> Pigment Dispersion Preparation Example 12

6.8 parts by mass of CI pigment green 58, 6.2 parts by mass of CI pigment yellow 150, and BYK-LPN 21116 (manufactured by BYK-Chemie (BYK)) as a dispersing agent were used as a coloring agent (solid content concentration = 40% by mass) 13.0 parts by mass of a specific polymer (B-1) solution, 61.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and 1.7 parts by mass of propylene glycol monomethyl ether, and mixed by a bead mill. Dispersion, preparation of a green pigment dispersion (A-12).

Pigment Dispersion Preparation Examples 13~23

In the pigment dispersion preparation example 12, a green pigment dispersion liquid (A-13) was prepared in the same manner as in the pigment dispersion preparation example 12 except that the type and amount of each component were changed as shown in Table 3. ~(A-23).

In Table 3, "G58" means CI Pigment Green 58, "Y150" means CI Pigment Yellow 150, "Y138" means CI Pigment Yellow 138, "G7" means CI Pigment Green 7, and "Y185" means CI Pigment Yellow 185, "Y139" refers to CI Pigment Yellow 139, "LPN21116" refers to BYK-LPN21116 (BYK-Chemie (BYK)), "PGMEA" refers to propylene glycol monomethyl ether acetate, and "PGME" is Refers to propylene glycol monomethyl ether, "PGEE" refers to propylene glycol monoethyl ether.

<Preparation of Radiation-Linear Green Composition> Radiation-sensitive coloring composition preparation example 12

1025 parts by mass of the pigment dispersion (A-12), 65 parts by mass of a specific polymer (B-1) solution as a binder resin, dipentaerythritol hexaacrylate and dipentaerythritol as a crosslinking agent a mixture of pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD (registered trademark) MAX-3510) 70 parts by mass, 2-benzyl-2-dimethylamino-1- as a photopolymerization initiator (4- Phenyl phenyl)butan-1-one (manufactured by BASF Corporation under the trade name IRGACURE (registered trademark) 369) 25 parts by mass, 2,4-diethyl thioxanthone 5 parts by mass, and half of a thiol group Propylene glycol monomethyl ether acetate solution of decane (COMPOCERAN (registered trademark) SQ SERIES, solid content concentration = 25% by mass) 1 mass point, nonionic surfactant EMULGEN A- 60 (manufactured by Kao Co., Ltd.) propylene glycol monomethyl ether acetate 5 mass% solution 10 parts by mass and ethyl 3-ethoxypropionate 200 parts by mass and methoxybutyl acetate 1050 parts by mass The mixture was mixed to prepare a liquid green composition (G-1).

Radiation-sensitive coloring composition preparation examples 13 to 23

In the preparation example 12 of the radiation-sensitive coloring composition, liquid green was prepared in the same manner as in the preparation of the radiation-sensitive coloring composition, except that the type and amount of each component were changed as shown in Table 4. Composition (G-2) ~ (G-12).

In Table 4, each component is as follows.

D-3: ADEKA ARKLS NCI-831 (made by ADEKA Co., Ltd.)

E-4: bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate/1-methyl-8-(1,2,2,6,6-five Mixture of methyl-4-piperidinyl) sebacate (manufactured by BASF Corporation, trade name TINUVIN (registered trademark) 292)

G-2: EMULGEN A-60 (made by Kao Co., Ltd.) propylene glycol monomethyl ether acetate 5 mass% solution

<Preparation of Blue Pigment Dispersion> Pigment Dispersion Preparation Example 24

13 parts by mass of C.I. Pigment Blue 15:6 as a coloring agent, BYK-LPN21116 (manufactured by BYK-Chemie (BYK) Co., Ltd.) as a dispersing agent, 11.3 parts by mass (solid content concentration = 40% by mass), specific polymer (B-1) 12.5 parts by mass of the solution, propylene glycol monomethyl ether acetate 62.5 parts by mass and 1.5 parts by mass of propylene glycol monomethyl ether as a solvent, and mixed by a bead mill. Dispersion, a blue pigment dispersion (A-24) was prepared.

Pigment dispersion preparation examples 25~38

In the pigment dispersion preparation example 24, a blue pigment dispersion liquid (A-25) was prepared in the same manner as in the pigment dispersion preparation example 24 except that the type and amount of each component were changed as shown in Table 5. )~(A-38).

In Table 5, "B15:6" means C.I. Pigment Blue 15:6, "V23" means CI Pigment Violet 23, "Dye (1)" means a triarylmethane dye represented by the following formula (8), and "dye (2)" means a diphenyl represented by the following formula (9) In the case of the penta-based dye, the "lake pigment (1)" is a triarylmethane-based lake pigment represented by the following formula (10), and "LPN21116" means BYK-LPN21116 (BYK-Chemie (BYK)) "PGMEA" means propylene glycol monomethyl ether acetate, "PGME" means propylene glycol monomethyl ether, "EL" means ethyl lactate, and "CHN" means cyclohexanone.

<Preparation of Radiation-Linear Blue Composition> Radiation-sensitive coloring composition preparation example 24

330 parts by mass of the pigment dispersion (A-24), 160 parts by mass of a specific polymer (B-1) solution as a binder resin, dipentaerythritol hexaacrylate and dipentaerythritol as a crosslinking agent a mixture of pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD (registered trademark) MAX-3510) 70 parts by mass, 2-benzyl-2-dimethylamino-1- as a photopolymerization initiator (4- Phenylphenyl)butan-1-one (manufactured by BASF Corporation under the trade name IRGACURE (registered trademark) 369) 15 parts by mass, 2,4-diethylthioxanthone 5 parts by mass, nonionic surfactant EMULGEN A-60 (manufactured by Kao Co., Ltd.) propylene glycol monomethyl ether acetate 5 mass% solution 10 parts by mass and ethyl 3-ethoxypropionate 380 parts by mass and methoxybutyl acetate 400 as a solvent The mass fraction and 125 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a liquid blue composition (B-1).

Radiation-sensitive coloring composition preparation examples 25 to 38

In the preparation example 24 of the radiation-sensitive coloring composition, liquid blue was prepared in the same manner as in the preparation of the radiation-sensitive coloring composition, except that the type and amount of each component were changed as shown in Table 6. Color composition (B-2) ~ (B-15).

In Table 6, each component is as follows.

F-3: propylene glycol monomethyl ether acetate

F-4: ethyl lactate

F-5: cyclohexanone

Example 1 <Production of color filter>

The red composition (R-1) was applied onto a glass substrate on which a black matrix was formed using a slit coater, and then prebaked in a hot plate at 90 ° C for 2 minutes to form a coating film. Next, after cooling the substrate on which the coating film was formed to room temperature, the coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at a exposure amount of 1000 J/m ² using a high pressure mercury lamp. . Thereafter, the mixture was subjected to alkaline development, washed with ultrapure water, and further baked at 230 ° C for 20 minutes to form a red striped colored layer having a thickness of 2.0 μm on the substrate.

Next, by using the green composition (G-1) by the same method, a green striped colored layer having a film thickness of 2.0 μm was formed beside the red striped colored layer. Further, a blue striped colored layer having a film thickness of 2.0 μm adjacent to the red and green colored layers was formed in the same manner using the blue composition (B-1).

Next, a photocurable resin composition is used on a coloring layer containing three colors of red, green, and blue to form a protective film. The color filter substrate was fabricated in this manner.

<Production and Evaluation of Organic EL Display Elements>

Referring to Example 2 of JP-A-2010-527108, an organic EL element emitting white light was produced. Light emission of the obtained organic EL element The spectrum showed a large luminescence peak in the blue region (near 460 nm), the green region (near 570 nm), the yellow region (near 610 nm), and the red region (near 660 nm). The organic EL element and the color filter were bonded together to form an organic EL display element.

When a voltage is applied between the electrodes of the organic EL display element thus obtained, and the color filter is irradiated with light, excellent color reproducibility and brightness are exhibited. In addition, the number of occurrences of the initial dark spots was zero, and the initial defects were zero. Next, the organic EL display element was allowed to stand in an environment of 95 ° C for 50 hours as an acceleration test, and after the color filter was irradiated again, the number of dark spots was zero, and there was no newly generated dark spot. That is, no new defects are generated. Thereafter, the light was irradiated every 50 hours until the heating time of 95 ° C was accumulated for 1000 hours, and no new dark spots were generated.

Examples 2 to 17 and Comparative Examples 1 to 2

In the first embodiment, each of the organic EL display elements was produced in the same manner as in the first embodiment except that a red, green, and blue striped colored layer was formed in accordance with the combination shown in Table 7 to form a color filter. Conduct an evaluation. Excellent color reproducibility and brightness were exhibited in all of the examples. In addition, the number of generation of dark spots is shown in Table 7. It is understood that the organic EL display element of the present embodiment has no dark spots or a smaller number of dark spots than the organic EL display element of the comparative example.

[Industrial availability]

The color filter of the present invention can provide a long-term stable color display element, and in particular, can provide an organic EL display element. Further, it can be suitably used for various organic EL display elements such as a monitor of a PC, a display of a mobile phone, a notebook PC, a handheld terminal, and a television.

1‧‧‧Organic EL display components

2‧‧‧Organic EL layer

3‧‧‧Color filters

4‧‧‧Substrate

5‧‧‧Colored layer

6‧‧‧Black matrix

8‧‧‧TFT

10‧‧‧ element substrate

11‧‧‧Component layer

12‧‧ ‧ flattening layer

13‧‧‧lower electrode

14‧‧‧ next door

15‧‧‧Upper electrode

16‧‧‧Protective layer

17‧‧‧Adhesive layer

Claims (8)

A color filter characterized by a color filter having a plurality of colors and a color filter for an organic EL display element, at least one of which is a polyfunctional antioxidant. The color filter of claim 1, characterized in that the polyfunctional antioxidant contains a compound having at least one structure selected from the group consisting of a hindered phenol structure, a hindered amine structure, and a thioether structure. The color filter of claim 1, characterized in that the polyfunctional antioxidant contains a compound having a molecular weight of 300 or more. The color filter of claim 3, characterized in that the polyfunctional antioxidant contains a polymer having at least one structure selected from the group consisting of a hindered phenol structure, a hindered amine structure, and a thioether structure. . The color filter of claim 4, characterized in that the copolymerization ratio of the repeating unit represented by the following formula (1) of the polymer is 30% by mass to 95% by mass, [In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and X represents -COO-(*) or -CONR ³ -(*), wherein R ³ represents a hydrogen atom or a linear alkyl group, and * represents A binding site bonded to R ² , and R ² represents a linear aliphatic hydrocarbon group or an alicyclic hydrocarbon group]. The color filter of claim 5, characterized in that the copolymerization ratio of the repeating unit represented by the following formula (2) of the polymer is 30% by mass or less, wherein the repeating unit represented by the formula (2) does not include The repeating unit represented by the formula (1), In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a group having a branched structure or an aromatic group. An organic EL display element characterized by having the color filter of any one of claims 1 to 6. A colored composition comprising a colorant, a polyfunctional antioxidant, and a crosslinking agent for forming a color filter used in an organic EL display device.