JP6256221B2 - Colored composition, colored cured film, display element and solid-state image sensor - Google Patents

Description

  The present invention relates to a colored composition, a colored cured film, a display element, and a solid-state image sensor. More specifically, the present invention relates to a transmissive or reflective color liquid crystal display element, solid-state image sensor, organic EL display element, electronic paper, and the like. The present invention relates to a colored composition used for forming a colored cured film to be used, a colored cured film formed using the colored composition, and a display element and a solid-state imaging device including the colored cured film.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method (for example, see Patent Documents 1 and 2) in which pixels of three primary colors of red, green, and blue are arranged on a substrate by irradiation (hereinafter referred to as “exposure”) and development. In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

  As the colorant used for forming the pixel of the color filter, a pigment is often used from the viewpoint of heat resistance and solvent resistance. For example, when forming a green pixel, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Green pigments such as CI Pigment Green 58 are used. However, since it is difficult to obtain a desired spectral spectrum using only the green pigment, the spectral spectrum is adjusted by combining a yellow pigment (for example, see Patent Document 5).

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2010-26268 A

  However, together with the green pigment, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. When Pigment Yellow 185 is used, there is a problem that coloring power is low. Therefore, at present, development of a coloring composition suitable for forming a colored cured film having a good balance between coloring power and luminance is strongly demanded.

  Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film having a good balance between coloring power and luminance. Furthermore, the subject of this invention is providing the display element and solid-state image sensor which comprise the colored cured film formed using the said coloring composition, and this colored cured film.

  As a result of intensive studies, the present inventors have determined that C.I. I. It has been found that the above problem can be solved by using a specific yellow colorant together with CI Pigment Blue 16.

That is, the present invention
(A) C.I. I. A colorant comprising CI Pigment Blue 16;
(B) a binder resin, and (C) a coloring composition containing a polymerizable compound,
Further, (A) C.I. I. Pigment Yellow 185,
C. I. The present invention provides a colored composition in which the content of Pigment Yellow 185 is 16% by mass or more and 65% by mass or less with respect to the total colorant.

  The present invention also provides C.I. I. Pigment blue 16 and C.I. I. Pigment Yellow 185, C.I. I. The present invention provides a colored cured film in which the content of Pigment Yellow 185 is 16% by mass or more and 65% by mass or less based on the total colorant, and a display element and a solid-state imaging device including the colored cured film. Here, the “colored cured film” means each color pixel used for a display element or a solid-state imaging element.

By using the colored composition of the present invention, it is possible not only to form a colored cured film having a good balance between coloring power and luminance, but also to form a colored cured film excellent in spectral characteristics and color separation properties. is there.
Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described in detail components of the colored composition of the present invention.

-(A) Colorant-

  The coloring composition of the present invention includes C.I. I. Pigment blue 16 and C.I. I. It is essential to include CI Pigment Yellow 185. The colored cured film formed using the colored composition of the present invention has a good balance between coloring power and luminance, and is excellent in spectral characteristics and color separation properties. Therefore, it can be used as a color filter for organic EL display elements or solid-state imaging elements. Particularly suitable for forming a green cured film of a color filter used for an organic EL display element or a solid-state imaging element.

  The coloring composition of the present invention includes C.I. I. Although it is essential that the content ratio of Pigment Yellow 185 is 16% by mass or more and 65% by mass or less with respect to the total colorant, C.I. I. It is preferable to set the content ratio of Pigment Yellow 185 in the following manner.

For example, when the colored composition of the present invention is used for forming a green cured film of a color filter used in an organic EL display element, C.I. I. The content ratio of Pigment Yellow 185 is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, particularly preferably 35% by mass or more, and more preferably 40% by mass or more based on the total colorant. Is very preferable, 60% by mass or less is preferable, 55% by mass or less is more preferable, and 50% by mass or less is more preferable. According to such an embodiment, a colored cured film having a very good balance between coloring power and luminance can be formed.
In addition, when the colored composition of the present invention is used for forming a green cured film of a color filter used in a solid-state imaging device, C.I. I. The content ratio of Pigment Yellow 185 is preferably 20% by mass or more, more preferably 25% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass or less, based on the total colorant. Is more preferable. With such an embodiment, a solid-state imaging device with good spectral characteristics and color separation can be produced.

When the colored composition of the present invention is used for forming a green cured film of a color filter used in an organic EL display element, C.I. I. The content ratio of Pigment Blue 16 is preferably 4% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and preferably 15% by mass or less, and 14% by mass or less, based on the total colorant. Is more preferable, 13 mass% or less is still more preferable, and 12 mass% or less is especially preferable. According to such an embodiment, a colored cured film having a very good balance between coloring power and luminance can be formed.
In addition, when the colored composition of the present invention is used for forming a green cured film of a color filter used in a solid-state imaging device, C.I. I. The content ratio of Pigment Blue 16 is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 10% by mass or less, more preferably 7% by mass or less, and more preferably 5% by mass or less, based on the total colorant. Is more preferable. With such an embodiment, a solid-state imaging device with good spectral characteristics and color separation can be produced.

The coloring composition of the present invention includes C.I. I. A yellow colorant other than Pigment Yellow 185 may be contained.
Such yellow colorants include C.I. I. Examples thereof include yellow pigments other than pigment yellow 185 and yellow dyes. C. I. Examples of yellow pigments other than Pigment Yellow 185 include C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211, C.I. I. And CI Pigment Yellow 215.
As the yellow dye, a known dye exhibiting a yellow color, such as an anthraquinone dye, an azo dye, or a pyridone azo dye, can be used.

  C. I. C. in the case of containing a yellow colorant other than CI Pigment Yellow 185. I. The content ratio of Pigment Yellow 185 is all yellow when used for forming a green cured film of a color filter used for an organic EL display element and when forming a green cured film of a color filter used for a solid-state imaging element. The amount is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 85% by mass or more, and particularly preferably 90% by mass or more based on the agent. According to such an embodiment, a display element including a colored cured film having a very good balance between coloring power and luminance, or a solid-state imaging element having excellent spectral characteristics and color separation can be manufactured.

When using the coloring composition of this invention for formation of a green cured film, it is preferable that a green coloring agent is further included.
Examples of the green colorant include a green pigment and a green dye. As the green pigment, a halogenated metal phthalocyanine pigment is preferable, and examples thereof include a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, and an aluminum halide phthalocyanine pigment. Among these, from the viewpoint of coloring power and luminance, a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment are preferable.
Examples of the halogenated copper phthalocyanine pigment include C.I. I. Chlorinated copper phthalocyanine pigments such as CI Pigment Green 7; I. And chlorinated brominated copper phthalocyanine pigments such as CI Pigment Green 36. Examples of the halogenated zinc phthalocyanine pigment include C.I. I. And brominated chlorinated zinc phthalocyanine pigments such as CI Pigment Green 58.
Among these, chlorinated copper phthalocyanine pigments and brominated chlorinated zinc phthalocyanine pigments are preferable. I. Pigment green 7, C.I. I. Pigment Green 58 is more preferable.
As the green dye, a known dye exhibiting a green color can be used.

When using the coloring composition of this invention for formation of the green cured film of the color filter used for an organic EL display element, 25 mass% or more is preferable with respect to all the colorants, and the content rate of a green coloring agent is 30 masses. % Or more, more preferably 35% by weight or more, particularly preferably 40% by weight or more, and preferably 70% by weight or less, more preferably 65% by weight or less, and still more preferably 60% by weight or less. According to such an embodiment, a colored cured film having a very good balance between coloring power and luminance can be formed.
Moreover, when using the coloring composition of this invention for formation of the green cured film of the color filter used for a solid-state image sensor, the content rate of a green coloring agent has preferable 30 mass% or more with respect to all the coloring agents, 40 More preferably, it is more preferably 50% by weight or more, particularly preferably 60% by weight or more, more preferably 80% by weight or less, more preferably 75% by weight or less, and even more preferably 70% by weight or less. With such an embodiment, a solid-state imaging device with good spectral characteristics and color separation can be produced.

  The coloring composition of the present invention may contain other colorants other than those described above to the extent that the effects of the present invention are not affected. Specific examples include organic pigments, lake pigments, and dyes classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists).

The coloring composition of this invention is used suitably for formation of a green cured film.
Especially, the organic EL display element which has a high-intensity green pixel is producible with a thin film by using for formation of the green cured film of the color filter used for an organic EL display element. In addition, by using it for forming a green cured film of a color filter used for a solid-state image sensor, a solid-state image sensor having green pixels with good spectral characteristics and color separation can be produced with a thin film.

  In the present invention, C.I. I. Pigment blue 16, C.I. I. Pigment Yellow 185 and other pigments optionally mixed may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, these pigments may be used by modifying the particle surface with a resin, if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

In the present invention, C.I. I. Pigment blue 16, C.I. I. In addition to Pigment Yellow 185 and other colorants optionally mixed, known dispersants and dispersion aids can also be included.
Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester-based dispersants, (meth) acrylic-based dispersants and the like can be mentioned. Examples of commercially available products include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, Big Chemie ( BYK))) and other (meth) acrylic dispersants, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-17 , Dispersbyk-182 (above, manufactured by BYK Corporation), urethane dispersants such as Solsperse 76500 (manufactured by Lubrizol Corporation), and polyethyleneimine dispersions such as Solsperse 24000 (manufactured by Lubrizol Corporation) A polyester dispersant such as BYK-LPN21324 (manufactured by BYK), in addition to the agent, Azisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 (above, Ajinomoto Fine Techno Co., Ltd.) it can.

In this invention, a dispersing agent can be used individually or in mixture of 2 or more types.
In the present invention, the content of the dispersant is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, still more preferably 20 to 100 parts by weight, with respect to 100 parts by weight of the colorant (A). -50 mass parts is still more preferable.

  Examples of the dispersion aid include pigment derivatives. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

  (A) The content of the colorant is usually 5 to 70% by mass, preferably 5 to 60% by mass, more preferably 5% to 60% by mass in the solid content of the colored composition from the viewpoint of forming a pixel having high luminance and excellent coloring power. Is 10-50 mass%, and 20-50 mass% is particularly preferable. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2)”). .

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. By setting it as such an aspect, the remaining-film rate of a film, a pattern shape, heat resistance, an electrical property, and the resolution can be improved further, and generation | occurrence | production of the dry foreign material at the time of application | coating can be suppressed at a high level.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts, More preferably, it is 30-150 mass parts. . By setting it as such an aspect, in addition to the further improvement of coloring power and a brightness | luminance, alkali developability, the storage stability of a coloring composition, pattern shape, and chromaticity characteristic can be improved.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and 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, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, and 30 to 150 parts by mass with respect to 100 parts by mass of the (A) colorant. Is preferred. By adopting such an embodiment, curability and alkali developability are further improved, and in addition to further improvement in coloring power and brightness, background stains, film residue, etc. on the unexposed substrate or on the light shielding layer Occurrence can be suppressed at a high level.

-(D) Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, A diazo compound, an imide sulfonate compound, etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-acyloxime compound.

  Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2, 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be mentioned.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  Specific examples of the biimidazole compound include 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 Examples include ', 5,5'-tetraphenyl-1,2'-biimidazole.

  In addition, when using a biimidazole compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The term “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, and 4,4′-bis (diethylamino) benzophenone. Mention may be made of amine hydrogen donors. In the present invention, hydrogen donors can be used alone or in admixture of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. Is preferable in that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-eth Triazine compounds having a halomethyl group such as cistyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- And dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime). As commercially available O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daito Chemix Corporation), and the like can also be used. .

  In this invention, when using photoinitiators other than biimidazole compounds, such as an acetophenone compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In the present invention, the content of (D) the photopolymerization initiator is preferably 0.01 to 120 parts by weight, more preferably 1 to 100 parts by weight, with respect to 100 parts by weight of (C) the polymerizable compound. More preferred is 40 parts by weight. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be improved more and coloring power and a brightness | luminance can be improved further.

-(E) Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
(E) As a solvent, as long as (A)-(C) component and other components which comprise a coloring composition are disperse | distributed or melt | dissolved, and it does not react with these components, but has moderate volatility. Can be appropriately selected and used.

Among such solvents, for example
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Of these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, and other ethers from the viewpoints of solubility, pigment dispersibility, coatability, etc. , Ketones, diacetates, alkoxycarboxylic acid esters, and other esters are preferred, especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-hept Non, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3- Methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl pyruvate and the like are preferable.

  In this invention, a solvent can be used individually or in mixture of 2 or more types.

  (E) Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and it is 10-40 mass%. Is more preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di- antioxidants such as t-butyl-4-hydroxyphenyl) propionate]; 2- (3-t-butyl-5-methyl-2-hydroxy Nyl) -5-chlorobenzotriazole, alkoxybenzophenones, etc .; anti-aggregation agents 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-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol Residue improving agents such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. An improving agent etc. can be mentioned.

  The coloring composition of the present invention can be prepared by an appropriate method. Examples of the preparation method include (A) to (C) components together with (E) a solvent and other components optionally added. , Can be prepared by mixing. Among them, C.I. I. Pigment blue 16 and C.I. I. (A) Colorant containing Pigment Yellow 185 (E) In the presence of a dispersant in a solvent, optionally mixed with (B) part of the binder resin, for example, using a bead mill, roll mill, etc. Disperse to obtain a pigment dispersion, and then to this pigment dispersion, (C) a polymerizable compound and, if necessary, (B) a binder resin, (D) a photopolymerization initiator, an additional (E) solvent, A method in which other components are added and mixed is preferred.

Colored cured film and method for producing the same The colored cured film of the present invention comprises C.I. I. Pigment blue 16 and C.I. I. Pigment Yellow 185, C.I. I. The pigment yellow 185 content is 16% by mass or more and 65% by mass or less based on the total colorant, and the pigment yellow 185 can be formed using the colored composition of the present invention. As the colored cured film of the present invention, for example, there is a green cured film used for a color filter constituting a display element or a solid-state imaging element.

Hereinafter, a colored cured film used for a color filter and a method for forming the same will be described.
As a method for forming the colored cured film constituting the color filter, the following method is first exemplified. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a green liquid composition of the radiation-sensitive colored composition of the present invention on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which green pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, each radiation-sensitive colored composition of red or blue is used, and the radiation-sensitive colored composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the red pixel array and blue Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition.

Examples of the substrate used when forming the colored cured film include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness in the case of forming a cured film of a color filter used in the organic EL display element is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying. Moreover, the coating thickness in the case of setting it as the cured film of the color filter used for a solid-state image sensor is 0.3-5 micrometers normally as a film thickness after drying, Preferably it is 0.5-2 micrometers.

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

  Further, as a second method for forming a colored cured film constituting a color filter, a method for obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723, JP-A-2000-310706, etc. Can be adopted. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a green liquid composition of the thermosetting coloring composition of the present invention is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a green pixel pattern.

  Subsequently, red or blue thermosetting coloring compositions are used to sequentially form a red pixel pattern and a blue pixel pattern on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used for forming the colored cured film, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used.

  Since the color filter including the colored cured film of the present invention thus formed has extremely high luminance, contrast, and coloring power, a color liquid crystal display element, a color imaging tube element, a color sensor, an organic EL display element, and electronic paper It is extremely useful for such as.

Display element The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (tin-doped indium oxide) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

Moreover, the organic EL display element provided with the colored cured film of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
Moreover, the electronic paper provided with the colored cured film of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Solid-state image sensor The solid-state image sensor of the present invention comprises the colored cured film of the present invention. In addition, the solid-state imaging device of the present invention can take an appropriate structure. For example, as one embodiment, by using the colored composition of the present invention to form a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, in particular, spectral characteristics. In addition, a solid-state imaging device having excellent color separation can be manufactured.

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

<Synthesis of binder resin>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by weight of propylene glycol monomethyl ether acetate, 25 parts by weight of benzyl methacrylate, 10 parts by weight of styrene, 20 parts by weight of N-phenylmaleimide, 5 parts by weight of glycerol monomethacrylate, 10 parts by weight of methacrylic acid A mixed solution of 30 parts by mass of ω-carboxypolycaprolactone monoacrylate and 3 parts by mass of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour, and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 40% by mass). The obtained binder resin had Mw of 9,800 and Mn of 6,000. This binder resin solution is referred to as “binder resin solution (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by mass of 2,2′-azobisisobutyronitrile and 100 parts by mass of propylene glycol monomethyl ether acetate, and subsequently 12 parts by mass of N-phenylmaleimide, 10 parts by mass of styrene, Methacrylic acid 20 parts by mass, 2-hydroxyethyl methacrylate 15 parts by mass, 2-ethylhexyl methacrylate 29 parts by mass, benzyl methacrylate 14 parts by mass and pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) 5 A mass part was charged and the atmosphere was replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 3 hours for polymerization. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 34% by mass). The obtained binder resin had Mw of 9,700 and Mn of 5,700. This binder resin solution is referred to as “binder resin solution (B-2)”.

<Synthesis of dispersant>
Synthesis example 3
A block copolymer comprising an A block having a repeating unit derived from dimethylaminoethyl methacrylate and a B block having a repeating unit derived from butyl methacrylate, methyl methacrylate and methacrylic acid, according to Example 1 of WO 2012/001945. Was synthesized. The copolymerization ratio of each repeating unit is dimethylaminoethyl methacrylate / butyl methacrylate / methyl methacrylate / methacrylic acid = 22/50/23/5, Mw is 12,720, and Mw / Mn is 1.46. This block copolymer is referred to as “dispersant (1)”.

<Preparation of colorant dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 12 parts by weight of Pigment Blue 16, 13 parts by weight of BYK-LPN21116 (produced by Big Chemie, solid concentration = 40% by weight) as a dispersant, and 10 parts by weight (solid content) of a binder resin solution (B-1) as a binder resin Concentration 40% by mass), 57 parts by mass of propylene glycol monomethyl ether acetate and 8 parts by mass of propylene glycol monoethyl ether as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a colorant dispersion (B1).

Preparation Examples 2 to 10
In Preparation Example 1, a colorant dispersion was prepared by changing the type and amount of each component as shown in Table 1.

In Table 1, each component is as follows.
PB16: C.I. I. Pigment Blue 16
PG7: C.I. I. Pigment Green 7
PG36: C.I. I. Pigment Green 36
PG58: C.I. I. Pigment Green 58
PY129: C.I. I. Pigment Yellow 129
PY139: C.I. I. Pigment Yellow 139
PY150: C.I. I. Pigment Yellow 150
PY185: C.I. I. Pigment Yellow 185
LPN21116: BYK-LPN21116 ((meth) acrylic dispersant, manufactured by Big Chemie, solid content concentration = 40% by mass)
α: quinophthalone pigment derivative S5000: Solsperse S5000
PGMEA: Propylene glycol monomethyl ether acetate PGEE: Propylene glycol monoethyl ether

<Preparation and evaluation of coloring composition>
Example 1
Colorant dispersion (B1) 50 parts by mass as a colorant, colorant dispersion (G1) 206 parts by mass and colorant dispersion (Y4) 244 parts by mass, binder resin solution (B-1) 24.6 as a binder resin 29.9 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as a polymerizable compound (product name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) and 2-benzyl-2-dimethyl as a photopolymerization initiator Amino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, trade name Irgacure 369) 2.0 parts by mass and NCI-930 (manufactured by ADEKA Corporation) 2.0 Mass part, Megafac F-554 (manufactured by DIC Corporation) 0.31 as a fluorosurfactant As a solvent, 143.7 parts by mass of propylene glycol monomethyl ether acetate, 255 parts by mass of 3-methoxybutyl acetate and 42.5 parts by mass of dipropylene glycol methyl ether acetate as a solvent were mixed, and the solid content concentration was 15% by mass. A coloring composition (GS-1) was prepared. The colorant concentration is 40% by mass.

Evaluation of Film Thickness and Luminance Colored composition (GS-1) was applied on a glass substrate using a slit die coater, and then pre-baked on a 90 ° C. hot plate for 1 minute to form a coating film. The same operation was performed by changing the coating conditions of the slit die coater to form three coating films having different film thicknesses.
Next, after cooling these substrates to room temperature, the coating film on the substrates was exposed to radiation containing each wavelength of 365 nm, 405 nm, and 436 nm at 600 J / m ² without using a high pressure mercury lamp. Exposed in quantity. After that, shower development was performed on these substrates by discharging a developer composed of a 0.04% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, these substrates were washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 20 minutes to produce a green cured film.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinates (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three green cured films obtained. (Y) was measured. From the measurement result, the stimulus value (Y) when the chromaticity coordinate value y = 0.690 was obtained. The evaluation results are shown in Table 4.
It can be said that the greater the stimulus value (Y), the higher the luminance, and the thinner the film thickness, the greater the coloring power of the colorant. The chromaticity coordinate value x = 0.220.

<Production of color filter>
The coloring composition (GS-1) was applied onto a glass substrate on which a black matrix was formed using a slit coater, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film. Next, after the substrate on which the coating film is formed is cooled to room temperature, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film through a striped photomask using a high-pressure mercury lamp at 1,000 J / m. The exposure amount was ² . Thereafter, after alkali development, the substrate was washed with ultrapure water and further post-baked at 230 ° C. for 20 minutes to form a green striped colored layer having a thickness of 2.0 μm on the substrate.
Next, a red striped colored layer having a thickness of 2.0 μm was formed next to the green striped colored layer using the red composition (RS-1) described later by the same method. Further, a blue striped colored layer having a thickness of 2.0 μm adjacent to the green and red colored layers was similarly formed using the blue composition (BS-1) described later.
Next, a protective film was formed using a photocurable resin composition on a colored layer composed of three colors of color, green, and blue. In this way, a color filter substrate was produced.

A red composition (RS-1) was prepared by the following method.
As a coloring agent, C.I. I. Pigment Red 254, 2.5 parts by mass, C.I. I. 9.8 parts by mass of CI Pigment Red 177, and C.I. I. 0.8 parts by mass of Pigment Yellow 150, 6.3 parts by mass (solid content concentration = 40% by mass) of BYK-LPN22102 (produced by BYK) as a dispersant, and 6 of a binder resin solution (B-2) .3 parts by mass, and 63.0 parts by mass of propylene glycol monomethyl ether acetate and 1.5 parts by mass of propylene glycol monomethyl ether as a solvent were mixed and dispersed by a bead mill to prepare a red pigment dispersion.
1600 parts by weight of the red pigment dispersion prepared above, 25 parts by weight of the binder resin solution (B-1) as the binder resin, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as the polymerizable compound (Nippon Kayaku Co., Ltd.) 70 parts by mass, trade name KAYARAD MAX-3510, manufactured by the company, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by BASF, trade name Irgacure as a photopolymerization initiator) 369) 30 parts by mass, 5 parts by mass of 2,4-diethylthioxanthone, 10 parts by mass of a 5% by mass propylene glycol monomethyl ether acetate solution of nonionic surfactant Emulgen A-60 (manufactured by Kao Corporation), and 3- Ethyl ethoxypropionate 650 mass Part and 890 parts by mass of methoxybutyl acetate were mixed to prepare a liquid red composition (RS-1).
BYK-LPN22102 is a (meth) acrylic dispersant, and the (meth) acrylic dispersant is a modified (meth) acrylic block copolymer propylene glycol methyl ether acetate / propylene glycol methyl ether = 1/1. (Mass ratio) 40% by mass solution (acid value = 0, amine value = 29 mgKOH / g). The modified (meth) acrylic block copolymer comprises a block having repeating units derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethyl methacrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and triethylene. It consists of a block having repeating units derived from glycol ethyl ether methacrylate.

The blue composition (BS-1) was prepared by the following method.
As a coloring agent, C.I. I. Pigment Blue 15: 6 (12.1 parts by mass) and dye (1) described below (0.9 parts by mass), and BYK-LPN21116 (by Big Chemy (BYK)) as a dispersant (10.5 parts by mass (solid content concentration) = 40% by mass), 12.5 parts by mass of the binder resin solution (B-1), 42.5 parts by mass of propylene glycol monomethyl ether acetate, 1.5 parts by mass of propylene glycol monomethyl ether and 21.0 parts by mass of ethyl lactate as a solvent. A blue colorant dispersion was prepared by mixing and dispersing with a bead mill.
330 parts by weight of the blue colorant dispersion prepared above, 160 parts by weight of the binder resin solution (B-1) as the binder resin, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as the polymerizable compound (Nippon Kayaku) Product name KAYARAD (registered trademark) MAX-3510) 70 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (BASF) as a photopolymerization initiator Manufactured by 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 Corporation) 5% by mass solution of propylene glycol monomethyl ether acetate 10 parts by mass and 3-ethoxypropyl as solvent A liquid blue composition (BS-1) was prepared by mixing 380 parts by mass of ethyl lopionate, 400 parts by mass of methoxybutyl acetate and 125 parts by mass of propylene glycol monomethyl ether acetate.
The dye (1) is compound No. 1 synthesized according to Synthesis Example 1 of JP2012-083552A. 1 and C.I. I. It is a salt of a cationic triarylmethane chromophore derived from Basic Blue 7 and a bistrifluoromethanesulfonylimide anion.

<Production and Evaluation of Organic EL Display Device>
With reference to Example 2 of JP-T-2010-527108, an organic EL device emitting white light was produced. The emission spectrum of the obtained organic EL device showed maximum emission peaks 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). This organic EL element and the color filter were bonded together to produce an organic EL display element.
Then, a voltage was applied between both electrodes of the obtained organic EL display element to irradiate the color filter with light, and color reproducibility and luminance were evaluated. The evaluation results are shown in Table 4.

Examples 2-12 and Comparative Examples 1-12
In Example 1, the kind and quantity of each component were changed as shown in Tables 2-3, and colored compositions (GS-2) to (GS-24) were prepared. The coloring agent density | concentration in coloring composition (GS-2)-(GS-24) is all 40 mass%.
Subsequently, the colored composition was evaluated in the same manner as in Example 1 except that the colored compositions (GS-2) to (GS-24) were used instead of the colored composition (GS-1). In both cases, the chromaticity coordinate value is x = 0.220. The evaluation results are shown in Tables 4-5.
In Example 1, a color filter was prepared in the same manner as in Example 1 except that the colored compositions (GS-2) to (GS-24) were used instead of the colored composition (GS-1). Subsequently, an organic EL display element was produced. Then, a voltage was applied between both electrodes of the obtained organic EL display element to irradiate the color filter with light, and color reproducibility and luminance were evaluated. The evaluation results are shown in Tables 4-5.

In Tables 2-3, each component is as follows.
C-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)
D-1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (product name: Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-2: NCI-831 (made by ADEKA Corporation)
F-1: Megafuck F-554 (manufactured by DIC Corporation)
MBA: 3-methoxybutyl acetate DPMA: dipropylene glycol methyl ether acetate

From Tables 4 and 5, when the green cured film formed using the colored compositions (GS-1) to (GS-12) is thin and has high luminance, the balance between coloring power and luminance is good. I can say that.
Moreover, the organic EL display element which comprises the color filter which has the green cured film formed using coloring composition (GS-1)-(GS-12) showed all the outstanding color reproducibility and brightness | luminance.

<Preparation and evaluation of colored cured film for solid-state imaging device>
Preparation Example 101
(Preparation of composition for forming undercoat film)
After the atmosphere in the flask was replaced with nitrogen, 200 parts by mass of a methyl-3-methoxypropionate solution in which 0.6 parts by mass of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 37.5 parts by mass of tert-butyl methacrylate and 62.5 parts by mass of glycidyl methacrylate were charged, stirred, and heated at 70 ° C. for 6 hours. After cooling, a resin solution containing a polymer was obtained.
Next, after diluting 33.3 parts by mass (containing 10 parts of the polymer) of this resin solution, 31.9 parts by mass of methyl-3-methoxypropionate, and 3.4 parts by mass of propylene glycol monomethyl ether. , 0.3 parts by mass of trimellitic acid, 0.5 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 0.005 parts by mass of the trade name “FC-4432” (manufactured by Sumitomo 3M Limited) Then, a composition for forming a base film was prepared.

<Preparation of colorant dispersion>
Preparation Example 102
As a coloring agent, C.I. I. Pigment blue 16 in an amount of 0.36 parts by mass, C.I. I. Pigment Green 58 (8.16 parts by mass), C.I. I. 3.48 parts by weight of Pigment Yellow 185, 3 parts by weight of a dispersant (1) (solid content concentration = 100% by weight) as a dispersant, 0.6 parts by weight of a quinophthalone pigment derivative as a dispersion aid, and a binder resin Binder resin solution (B-2) (solid content concentration: 34% by mass) is mixed and dispersed in a bead mill for 12 hours using 8.82 parts by mass and 75.58 parts by mass of propylene glycol monomethyl ether acetate as a solvent. An agent dispersion (G11) was prepared.

Preparation Examples 103-106
In Preparation Example 1, colorant dispersions (G12) to (G15) were prepared by changing the type and amount of each component as shown in Table 6.

Example 101
12 parts by weight of the colorant dispersion (G11) as the colorant, 1.481 parts by weight of the binder resin solution (B-2) (solid content concentration 34% by weight) as the binder resin, and Kayrad DPEA-12 ( Nippon Kayaku Co., Ltd., ethylene oxide-modified dipentaerythritol hexaacrylate) 0.66 parts by mass, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O -Benzoyl oxime) (Ciba Specialty Chemicals Co., Ltd., Irgacure OXE01) 0.203 parts by mass, 1% by mass propylene glycol monomethyl ether acetate solution of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant 0.102 parts by mass and propylene glycol monomer 5.554 parts by mass of tilether acetate was mixed to obtain a colored composition (GS-101) having a solid concentration of 18% by mass. In addition, the coloring agent density | concentration in a coloring composition (GS-101) is 40 mass%.

Evaluation of transmittance A colored composition (GS-101) was applied on a glass substrate by a spin coating method, and then heated at 100 ° C. for 180 seconds to form a coating film. Subsequently, the entire surface of the coating film on the substrate was exposed (exposure amount of 1,000 mJ / cm ² at a wavelength of 365 nm). Next, the coating film was brought into contact with an aqueous solution containing 0.05% by mass of tetramethylammonium hydroxide for 15 seconds, and then the coating film was washed with water. Then, the glass wafer which has a colored cured film with a film thickness of 0.8 micrometer was obtained by heating for 300 second with a 200 degreeC hotplate.
Using a spectrophotometer (manufactured by JASCO Corporation, V-7300), the transmittance (% T) of the glass wafer having the colored cured film was measured, and the transmittance at the following measurement points was determined. The results are shown in Table 8. However, the transmittance in Table 8 is a value relative to the glass substrate, and the film thickness is a value measured with a stylus type step gauge (manufactured by Yamato Scientific Co., Ltd., Alpha Step IQ).

Evaluation method Measurement point 1: Transmittance at 450 nm. If it is 10% or less, purple to blue light can be efficiently shielded.
Measurement point 2: transmittance at 530 nm. If it is 90% or more, green light can be efficiently transmitted.
Measurement point 3: transmittance at 590 nm. If it is 50% or less, yellow to orange light can be efficiently shielded.
Measurement point 4: transmittance at 650 nm. If it is 10% or less, red light can be efficiently shielded.

  In addition, if it is a green cured film which satisfy | fills all the evaluation criteria in the measurement points 1-4, it can be said that it is a green cured film for solid-state image sensors with favorable spectral characteristics.

Evaluation of Pattern Shape and Residue A colored composition (GS-101) was applied on a silicon wafer by a spin coating method, and then heated at 100 ° C. for 180 seconds to form a coating film. Exposure was performed by reduced projection exposure (manufactured by Nikon Corporation, NSR-2005i10D, exposure amount of 1,000 mJ / cm ² at a wavelength of 365 nm) through a mask. Next, the coating film was developed by bringing it into contact with an aqueous solution containing 0.05% by mass of tetramethylammonium hydroxide for 15 seconds. Next, the silicon wafer having the developed coating film was heated on a hot plate at 200 ° C. for 300 seconds to obtain a silicon wafer having a square colored cured film having a side of 3 μm.
By observing this silicon wafer with an electron microscope, the resolution of the colored composition (GS-101) was evaluated. The evaluation criteria are as follows, and the results are shown in Table 8.

Evaluation criteria ○: The cross-sectional shape of the pattern is rectangular, and no residue is observed between the patterns.
(Triangle | delta): The cross-sectional shape of a pattern is not a rectangle, or a residue is recognized between patterns.
X: The cross-sectional shape of a pattern is not a rectangle, and a residue is recognized between patterns.

  In addition, if the evaluation result is “◯” or “Δ”, it can be said that the green cured film for the solid-state imaging device is excellent in color separation.

Example 102 and Comparative Examples 101-104
In Example 101, the type and amount of each component were changed as shown in Table 7 to prepare colored compositions (GS-102) to (GS-106). The solid content concentrations of the colored compositions (GS-102) to (GS-106) are all 18% by mass.
Subsequently, evaluation was performed in the same manner as in Example 101 except that the colored compositions (GS-102) to (GS-106) were used instead of the colored composition (GS-101). The evaluation results are shown in Table 8.

In Table 7, each component is as follows.
C-2: Kayalad DPEA-12 (Nippon Kayaku Co., Ltd., ethylene oxide modified dipentaerythritol hexaacrylate)
D-3: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (Irgacure OXE01, manufactured by Ciba Specialty Chemicals Co., Ltd.)
F-2: 1% by mass propylene glycol monomethyl ether acetate solution of MegaFac F-554 (manufactured by DIC Corporation)

  From Table 8, it can be said that the green cured films of Examples 101 to 102 have good spectral characteristics and color separation, and are therefore suitable for solid-state imaging devices.

Claims (11)

(A) C.I. I. A coloring composition comprising a pigment blue 16 pigment, (B) a binder resin, and (C) a polymerizable compound,
Further, (A) C.I. I. Pigment yellow 185 and a green colorant ,
C. I. Der content ratio 65 mass% 16 mass% or more based on the total colorant Pigment Yellow 185 is, and
The content ratio of the green colorant is 22% by mass or more and 74% by mass or less with respect to the total colorant.
A colored composition for forming a green cured film of a color filter used in an organic EL display element . Content of the green colorant is 70 wt% or less than 30% by weight, based on the total colorant, the colored composition of claim 1. The green colorant is C.I. I. Pigment green 7 and C.I. I. The coloring composition according to claim 1 or 2 , which is at least one selected from the group consisting of CI Pigment Green 58. C. I. The content of CI Pigment Yellow 185 is 60 wt% or more based on the total yellow colorant, the colored composition according to any one of claims 1 to 3. C. I. Content of Pigment Blue 16 is not more than 13 wt% 5 wt% or more based on the total coloring agent, a coloring composition according to any one of claims 1-4. (A) C.I. I. A coloring composition comprising a pigment blue 16 pigment, (B) a binder resin, and (C) a polymerizable compound,
Further, (A) C.I. I. Pigment yellow 185 and a green colorant,
C. I. Pigment Yellow 185 is contained in an amount of 20% by mass or more and 30% by mass or less based on the total colorant, and
The content ratio of the green colorant is 68% by mass or more and 71% by mass or less with respect to the total colorant.
Green cured film formed Wear color composition of the color filter used in solid-state imaging device. C. I. The coloring composition of Claim 6 whose content rate of pigment blue 16 is 1 mass% or more and 5 mass% or less with respect to all the coloring agents. C. I. Pigment blue 16 and C.I. I. Pigment yellow 185 and a green colorant ,
C. I. Der content ratio 65 mass% 16 mass% or more based on the total colorant Pigment Yellow 185 is, and
The content ratio of the green colorant is 22% by mass or more and 74% by mass or less with respect to the total colorant.
A green cured film of a color filter used in an organic EL display element . C. I. Pigment blue 16, C.I. I. Pigment yellow 185 and a green colorant,
C. I. Pigment Yellow 185 is contained in an amount of 20% by mass or more and 30% by mass or less based on the total colorant, and
The content ratio of the green colorant is 68% by mass or more and 71% by mass or less with respect to the total colorant
Green cured film for color filters used in solid-state image sensors. An organic EL display device comprising the green cured film according to claim 8 . A solid-state imaging device comprising the green cured film according to claim 9.